Enbridge Line 8B MP 608 Pipeline Release
Marshall, Michigan
Sampling and Analysis Plan
Prepared: August 2, 2010
(Revised August 17, 2010 per U.S. EP.A. August 17, 2010 letter)
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Enbridge Line 6B MP 608 Pipeline Release
Marshall, Michigan
Sampling and Analysis Plan
Prepared: August 2, 2010
(Revised August 17, 2010 per U.S. E.P.A. August 17, 2010 letter)
Table of Contents
Background, Spill Release Area Description, and Location
1.1 Spill Release Area Description and Location
1.2 Area Physical Features
1.3 Adaptive Management
1.4 General Scope of SAP
Current Conditions
Project Organization
3.1 Federal On-Seene Coordinator
3.2 Company Environmental Unit Leader
3.3 Sampling and Analysis Manager
3.4 Quality Assurance Officer (QAO)
3.5 Field Manager
3.6 Sample/Technical Manager
3.7 Data Manager
3.8 Third Party Data Validator
Overview of Sampling Activities
4.1 Data Quality Objectives
4.2 Objectives, Endpoints & Metrics
4.2.1 Riparian Zones and Stream Banks
4.2.2 Soil. Sand and Gravel
4.2.3 Man-made structures
4.3 Surface Water Sampling
4.3.1 Overview and Rationale
4.3.2 Location and Frequenev
4.3.3 Surface Water Monitoring and Analysis
4 4 Sediment Sampling
4.4.1 Overview and Rationale
4.4.2 Location and Frequency
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4,4,3 Sediment Analysis 21
4.5 Groundwater Sampling/Monitoring Approach 21
4.5.1 Location and Frequency 22
4.5.2 Groundwater Sample Analyses 22
4.6 Soil Sampling 23
4.6.1 Overview and Rationale 23
4.6.2 Location and Frequency 24
4.6.3 Soil Sample Analyses..... 24
4.7 Waste Characterization Sampling ......24
4.7.1 Overview and Rationale 24
4.7.2 Location and Frequency 25
4.7.3 Soil Sample Analyses 25
4.7.4 Waste Characterization Analysis 25
4.8 Product Sampling 26
5.0 Sample Management 28
5.1 Sample Labeling 29
5.2 Chain of Custody Procedures 29
6.0 Analytical Approach 31
7.0 Quality Assurance 32
7.1 Initial Field Evaluation 32
7.1.1 Surface Water Samples 32
7.1.2 Sediment 32
7.1.3 Groundwater 32
7.1.4 Soil 33
7.2 Field Duplicate Sample 33
7.3 Equipment Kinsate Sample 33
7.4 Trip Blanks 33
7.5 Field Split Samples 34
7.6 Laboratory QA 34
7.7 Matrix Spike/Matrix Spike Duplicate Sample ,...34
7.8 Data Validation 34
8.0 Sampling Equipment Decontamination Procedures 36
9.0 Waste Disposal and Investigative Derived Waste 37
10.0 Data Management .38
10.1 Sampling and Analytical Data 38
10.2 SI ERA Data 38
10.3 Data Flow 38
10.4 Data Backup ...................38
11.0 Records Management 39
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List of Tables
Table 4.1 Surface water parameters, methods, and container types 17
Table 4.2 Proposed Actionable Values 19
Table 4.3 Sediment parameters, methods, and container types 21
Table 4.4 Groundwater parameters, methods, and container types 23
Table 4.5 Soil parameters, methods, and container types 24
Table 4.6 Waste characterization parameters, methods, and container types 25
Table 4.7 Product Parameters/Forensic Fingerprinting (may change as needed} 27
List of Figures
Figure 1 Site Location
Figure 2 Division Designation Map
Figure 3 Division A - Multiple Media Sampling Locations
Figure 4 Division B - Multiple Media Sampling Locations
Figure 5 Division € - Multiple Media Sampling Locations
Figure 6 Di\ ision D - Multiple Media Sampling Locations
Figure 7 Division U Multiple Media Sampling Locations
Figure 8 Downstream Surface Water Locations From Morrow Lake to MP 76
Figure 9 Downstream Surface Water Locations From MP 74 to Lake Michigan
Figure 10 Proposed Sediment Sample Locations
Figure 1 1 Organizational Chart
List of Appendices
Appendix A Air Sampling and Monitoring Plan
Appendix B Crude MSDS
Appendix C Sampling SOPs
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List of Acronyms/Definitions
bbcl - barrels per dav
Company - Enbridge Energy. Limited Partnership
DNAPL - Dense Non-Aqueous Phase Liquid - A liquid w ith a Specific Gravity > 1.0
DO - Dissolved Oxygen
POSC - Federal On-Scene Coordinator
LNAPL - Light Non-Aqueous Phase Liquid - A liquid with a Specific Gravity < 1,0
MDNRE - Michigan Department of Natural Resources and Environment
NOAA - National Oceanic and Atmospheric Administration
NRDA - National Resource Damage Assessment
NREPA - Natural Resources and Environmental Protection Act
Oil Saturated Soil - Soils containing free-phase product capable of flowing or migrating as an oil
OSC - On Scene Coordinator
Remediation - Future long term corrective actions bevond those included as an initial response
Response - The initial response to remove and'or abate \ isible oil and/or sheen that is either
currently affecting navigable waterways and/or poses the threat of release of a visible oil and/or
sheen to navigable waterways.
RPIMA - Response Plan for Downstream Impacted Areas
SAP - Sampling and Analysis Plan
SAR - Source Area Response Plan
SCAT - Shoreline Cleanup Assessment Technique also known as SCAT Assessment or SCAT
Process - A systematic approach that uses standard terminology to collect data on impacted areas,
support decision-making for cleanup; reference HAZMAT Report No, 2000-1; Office of Response
and Restoration. Hazardous Materials Response Division, National Ocean Service. National Oceanic
& Atmospheric Administration. Shoreline Assessment Manual - Third Edition, August 2000.
SCAT Team - A team of qualified individuals using SCAT, organized and reporting to the FOSC
and comprised of representatives from USER A as the FOSC. MDNRE (as the SOSC and state NRDA
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trustee), NOAA or USFWS (as federal NRDA trustees) and Company to assess impacted areas and
recommend cleanup methods and priorities. At least one member should have sufficient expertise in
wetland and aquatic ecology to evaluate the sensitivity of impacted areas.
SCRIBE - U.S. EPA's database for warehousing environmental data
SGSC - State On-Scene Coordinator
Source Area - The primary locations impacted by the crude oil release, includes Division A (i.e. the
wetland area impacted b\ the release due to overland flow of oil) referred lo herein as the Spill
Release Area and. Division B (i.e.. the portion of Talmadge Creek impacted by the oil spill) referred
to herein as the Creek
SAR PLAN - Source Area Response Plan - A work plan describing interim response actions
designed to protect navigable waters from the crude oil release
Spill Release Area (Division A) - Area of primary spill release into wetland
Talmadge Creek (Division B) - Initial navigable water body impacted by release
U.S. EPA - Unites States Environmental Protection Agencv
U.S. FWS - United States Fish and Wildlife Service
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Sampling and Analysis Plan
Marshall Response to Pipeline Release
August 17, 2010
This Sampling and Analysis Plan (SAP) describes the sampling/analysis and quality assurance
programs that the Company will adhere to in the short term during realization of the primary
objective, which is the removal and/or abatement of visible oil and/or sheen that is either currently
affecting navigable waterways and/or poses the threat of release of a visible oil and/or sheen
discharge to navigable waterways. It is to be implemented in conjunction with response plans
described herein. Changes to the plan should be anticipated to reflect the changing conditions durin
the response and the information gained as the work progresses.
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1.0 Background, Spill Release Area Description,
and Location
On July 26. 20 ] 0, Enbridge Energy. Limited Partnership ("Company") discovered a release of heavy
crude oil (Cold Lake Blend) from Line 6B just west of milepost 608 in the vicinity its pump station
located in Marshall, Calhoun County. Michigan (N'/S Section 2, T3S, R6W). Line 6B is a 30-inch.
190,000 barrels per day (bpd) line transporting light synthetics, heavy and medium crude oil from
Griffith. IN, to Sarnia, Ontario. The location of the release from Line 6B is located in an
undeveloped area in the outskirts of town with coordinates of Latitude: 42.2395273. Longitude: -
84.9662018. For the purposes of this Plan, the "Spill Release Area" is defined as the location of the
pipeline breech that caused the release (Spill Release Area) and the Talmadge Creek. The Spill
Release Area has limited vehicle access from Division Drive (approximate address is 16000 Division
Drive).
Upon discovery of the release the pipeline was shut down and isolation valves closed, stopping the
source of the oil; however, initial estimates are that approximately I1),500 barrels of crude oil ma\
have been released.
The release entered Talmadge Creek and the Kalamazoo River. These waterways are considered to
be navigable waters. Approximately 35 miles of the Kalamazoo River have been impacted. Two
work plans have been prepared to control the response activities; "Enbridge Line 6B MP 608 Pipeline
Release. Marshall. Michigan. Source Area Response (SAR) Plan, dated August 2. 2010, revised
August 17. 2010 per U.S. EPA August 17, 2010 letter", and "Enbridge Line 6B MP 608 Pipeline
Release. Marshall, Michigan, Response Plan for Do\rnsireai>i Impacted Area fRPDlA), revised
August 17, 2010 per U.S. EPA August 17. 2010 letter". The SAR has been ordered by the FOSC to
control the response activities from the Spill Release Area along Talmadge Creek downstream to the
confluence with the Kalamazoo River. The RPDIA has been ordered by the FOSC to control the
response activities from the confluence of Talmadge Creek and the Kalamazoo River to the limit of
the impact. These impacted areas have been divided into Divisions for cleanup operations and
sampling described as follows:
• Division A - the Spill Release Area (to the constructed Flume where the release entered
Talmadge Creek):
• Division B - Talmadge Creek from the Flume site to the confluence with the Kalamazoo
River);
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• Division C - The confluence of the Taimadge Creek and the Kalamazoo River to the Angell
Street Bridge:
• Division D - Angell Street Bridge to the Kalamazoo County line; and
• Division E - Kalamazoo Count)' Line to Morrow Lake Dam.
Copies of the SAR and RPDIA are available upon request.
The Company recognizes the health issues associated with spill contact and has published a notice
explaining a suggested evacuation area and is also furnishing temporary housing for concerned
residents.
Access to the Spill Release Area is now restricted by a fence and twenty-four hour security. Access
to surface water is being limited by security control measures at crossings, signs, and fencing at river
access points. These measures address unauthorized access to the impacted areas w here practicable.
1.1 Spill Release Area Description and Location
The Spill Release Area is an approximate 5-acre parcel adjacent to the pipeline release location.
(Figures I, 2, and 3), The majority of the Spill Release Area is within a wetland adjacent to
Taimadge Creek. Vegetation consists of herbaceous emergent wetland plants in low lying areas, as
well as brush and trees in upland areas. Approximately five acres have been impacted by o\ erland
flow of oil in the Spill Release Area.
1.2 Area Physical Features
The surflcial deposits in the area of the Spill Release Area consist of glacial outwash sand and gravel
as well as post-glacial alluvium with occasional thin clay lenses. The glacial deposits in areas of the
Spill Release Area are generally underlain by the Mississippian Marshall Sandstone and Coldwater
Shale in Calhoun Count} and Coldwater Shale in Kalamazoo County. Ml. The bedrock surface was
mapped at 50-feet below ground surface (bgs) in much of Calhoun County and up to 200 feet in
Kalamazoo County based on the State of Michigan Department of Conservation, Geological Sun ey
Division, Drift Thickness Map, 1938.
Most of the Spill Release Area can be characterized as rural, including undeveloped and agricultural
areas. The Spill Release Area and impacted sections of Taimadge Creek (Tributary) and the
Kalamazoo River also include villages and cities, including developed areas.
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1.3 Adaptive Management
Throughout this plan there are various forward looking statements or content, as well as, associated
text that may indicate specific details may need to be worked out with relevant agencies as work
progresses. It is understood that the FOSC will provide sufficient technical staff to facilitate
supplementing or changing parts of the response plan (e.g., changes in sampling locations and
frequencies) and strategies as such situations arise, and will work with the Company to review and
approve alterations.
1.4 General Scope of SAP
The SAP will address the primarx objective of the response activities in the Spill Release Area and
Talmadge Creek, (collectively the Source Area), and the Downstream Impacted Area (Kalamazoo
River to Morrow Lake) that are outlined in the Source Area Response (SAR) Plan and Response Plan
for Downstream Area (RPDIAj. The primary objectives include: I) removal of free phase crude oil
and heavily impacted crude oil media (oil saturated soil and vegetation) from the overall Source
Area; and 2) to removal and/or abatement of visible oil and/or sheen that is either currently affecting
navigable water w a\ s and/or poses a threat of a release of visible oil or sheen discharge to navigable
waterways.
Within five days of an approved SAP, the Company will engage the Michigan Department of Natural
Resources and Environment (MDNRE) and other agencies that may have jurisdiction over future
remedial actions regarding the post-SAR and RPDIA activities consistent with Part 201
(Environmental Remediation) of the Natural Resources and Environmental Protection Act
(TsREPA)(l994 PA 451). as amended.
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2.0 Current Conditions
The Company has mobilized to the Spill Release Area the following resources in the support of
sample collection, analysis, data validation, and reporting:
• Air monitoring and data management professionals,
• Surface water, potable water, and sediment collection and data reporting professionals.
• Onsite area chemists and a mobile laboratory for on-going analytical services for rapid
assessment purposes.
To date, the Company has collected the following types of discrete samples in the appropriate sample
containers:
• crude oil:
• sediment:
• soil;
• groundwater
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completed to allow for heavy equipment traffic related to response activities and pipeline
repair. Timber mat access roads are also being constructed adjacent to Talmadge Creek.
• Site Clearing and Grubbing: Clearing and grubbing of site trees and vegetation has been
performed as necessary to allow construction of access roads and removal of soils impacted
by the overland flow of oil. The trees and brush will be chipped and the material mixed with
excavated soil for offsite disposal.
• Shallow Soil Excavation; Shallow soil in the Spill Release Area (primarily peat) impacted
by the overland flow of crude oil is being excavated and staged for offsite disposal. The
objective associated with shallow soil excavation is to prevent further migration of oii to
surface water. Spill Release Area excavation activities involve the use of a long reach
backhoe staged on the access road to remove the top 6-inehes to 1-foot of impacted soil/peat
material. The material is direct loaded into off-road trucks and transported to the staging area
where it is allowed to dewater prior to disposal. Talmadge Creek area excavation (i.e.. along
the banks of the Talmadge Creek) involve removal of primarily oil impacted vegetation and
shallow soil/root zone material as described in the Shoreline Cleanup Assessment Technique
(SCAT) Plan for Talmadge Creek. At the time this document was prepared, approximately 80
percent of the Spill Release Area excavation has been completed and 25 percent of Talmadge
Creek area has been mechanically cleaned.
• Staging Area Construction: An approximate 2.3 acre staging area was constructed at the
boundary of the exclusion zone to the north of the Spill Release Area. The staging area was
constructed using Class 5 gra\el to allow heavy equipment access and minimize erosion. Silt
fencing and other storm water control measures were implemented as needed. Material from
the Spill Release Area and Talmadge Creek is currently being transported to the main staging
area using off-road trucks.
• Berms: Three temporary soil berms have been constructed to remove the migration pathway
for crude oil from the Spill Release Area to Talmadge Creek. The basic design of the
temporary soil berms is an elongated earthen mound used to prevent the flow of water and
oil. Clean on-site soils and clean granular soils were used to construct the berms. The length
and height of the berms correspond with the volume of flow and drainage area required to be
controlled in the Spill Release Area. All berm heights are less than five feet from the toe of
the berm to the upstream bottom elevation. This berm height will ensure that the berms are
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not considered "dams" under Part 3 15 Dam Safety, of the Natural Resources and
Environment Protection Acl (NREPA), 1994 PA 451, as amended. As of July 30, 2010, flow
of crude oil to Talmadge Creek from the Spill Release Area has not been observed.
• Flumes: Numerous flumes (i.e., underflow weirs) were constructed downgradient of the
Spill Release Area to minimize further migration of crude oil. The basic design of a flume is
a pipe, or series of pipes, that extend through a temporary How control structure such as a
berm or dam. For a crude oil release to surface water, the pipe intakes are submerged on the
upstream side of the berm to allow oil-free water to How through the pipe. This prevents the
crude oi! floating on top of the water from migrating further downstream. Crude oil pools on
the upstream side of the berm or dam and is captured and containerized using sorbent booms,
pads and vacuum trucks.
• Oil and Water Containment and Recovery: Oil containment and recovery operations using
flumes, berms and vacuum trucks in the Source Area (i.e.. from both the Spill Release Area
and Talmadge Creek). Recovered oil is being reclaimed at the Company's Griffith, Indiana
oil storage terminal and wastewater is being treated on-site and disposed of at the Battle
Creek Publicl} Owned Treatment Works (POTW),
• Initial Receptor Survey: An initial receptor survey was implemented and will be updated
during post response activ ities to effectively identify potential migration pathways and
potential receptors within the Source Area. The receptor survey is conducted to identify the
presence and location of surface waters, water wells and surface water intakes which could be
impacted b> the crude oil release.
• Federal and State Approvals: The Company has coordinated efforts with all Federal and
Stale level environmental stakeholders identified at the site including:
o U.S. EPA. U.S. Fish and Wildlife Service (USFWS);
o Michigan Department of Natural Resources and Environment (MDNRE);
o U.S. Coast Guard;
o Michigan Department of Agriculture (MDA);
o Michigan Department of Commuuit) Health (MDCH);
o Calhoun County Public Health Department (CCPHD);
o Kalamazoo County Health and Community Sen ices Department (KCHCSD):
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A Joint Permit Application to IVIDNRE and USACE for Part 303/30] and Part 31 has been
submitted for general permit activities within the Spill Release Area with the SAR under a
separate cover.
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3 J Project Organization
This plan describes the duties and responsibilities of the Company and its Contractors. This section
provides information on project organization for the project. The project organization and the
responsibilities of key personnel are defined in subsequent sections. Figure 1-1 presents the program
lines of authority and the project organization.
3.1 Federal On-Scene Coordinator
Federal On-Scene Coordinator (FOSC) has regulatory oversight responsibilities for the development
and approval of the documents and reports for this project. The responsibilities of FOSC include, but
are not limited to, the following:
• Schedule meetings, if necessary, between agencies, and representatives of the Company:
• Review and approve proposed schedules; and,
• Review and approve documents and reports.
3.2 Company Environmental Unit Leader
Robert Steede, Enbridge Energy, Limited Partnership
The Company Environmental Unit Leader (EUL) is responsible for implementing the project, and has
the authority to commit the resources necessan to meet project objectives and requirements. The
EUL will comprise a rotation of project managers who will provide continuous management
activities. The EUL will report to the U.S. EPA FOSC. All communication and reporting will be
conducted through the EUL. The F.UL's primary function is to ensure that technical, financial, and
scheduling objectives are achieved successfully. The EUL will:
• Oversee project objectives and develop a detailed work schedule;
• Establish project policy and procedures to address the specific needs of the project as a
whole, as well as the objectives of each task:
• Acquire and apply technical and corporate resources as needed to ensure performance within
schedule constraints;
• Orient all field leaders and support staff concerning the project's special considerations;
• Monitor and direct the field leaders;
• Develop and meet ongoing project and/or task staffing requirements, including mechanisms
to review and evaluate each task product;
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• Review the work performed on each task to ensure its quality, responsiveness, and timeliness;
• Review and analyze overall task performance with respect to planned requirements and
authorizations;
• Approve all reports (deliverables) before their submission to FOSC;
• Ultimately be responsible for the preparation and quality of interim and final reports; and.
• Represent the project team at meetings and public hearing,
3.3 Sampling and Analysis Manager
The Sampling and Analysis Manager (SAM) is responsible for establishing projeet scope and
objectives and for communicating to the project team. The SAM is also responsible for identifying
internal, regulator)', and procedural requirements pertinent to the work that may differ from accepted
industry standards of" work. The SAM is responsible for assuring that projects are properly staffed
and is ultimately responsible for the technical direction and quality of the work. He is responsible
for establishing appropriate budgets and schedules, making available appropriate forms or equivalent
of training, and monitoring the performance of the staff. The SAM may talk with regulatory agencies
regarding methodologies and requirements. He is also responsible for monitoring the implementation
of the quality assurance program.
Specific responsibilities include:
• Assure the pro\ ision of necessary resources including personnel, facilities, and equipment;
• Rex iew and approve standard operating procedures and other project documents;
• Monitoring offsite area and on site area laboratories for proper turnaround times;
• Support the efforts of the Field Manager, Quality Assurance Officers (QAO). and Data
Manager(s) in all matters concerning the quality of work products;
• Assure effective response to corrective action requirements identified by any member of the
project team of staff;
• Plan the activ ities of and ensure proper equipment, personnel, and subcontractor resources
are allocated;
• Provide a liaison between the client, field, laboratory staff, and any other subcontractors;
• Effectively carry out the QA Program and this SAP: and.
• Assure completion of corrective actions, as needed.
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3.4 Quality Assurance Officer (QAO)
The Qualit) Assurance Offer (QAO) is responsible for implementation of the QAPP in both field and
laboratory operations. The QAO reports to the EUL and has the authority to take any actions
necessary to ensure the reliability and validity of work and deliverables according to the QAPP, The
QAO is responsible for developing and implementing procedures to appropriately document all
project activities, to provide specific means of measuring conformance to specifications, to manage
the corrective actions program, and to provide periodic reports to management. Specific
responsibilities include:
• Develop, document, and carry out QA activities to ensure thai appropriate Quality Control
(QC) measures are being carried out and documented:
• Ensure all records related to quality assurance are documented and maintained securely and
retrievably;
• Conduct periodic performance audits and/or surveillances to measure conformance lo
specifications:
• Prepare periodic quality reports and QA sections of final reports;
• Ensure corrective actions are carried out and documented in a way that precludes future
occurrences:
• Re\ iew and approve SOPs. training records, and purchasing actions: and.
• Acquire and maintain required certifications and manage performance evaluation tests.
3.5 Field Manager
The Field Manager is responsible for implementing the SAP. The Field Manager's responsibilities
include:
• Overseeing field equipment calibration, sample collection teams, field documentation,
submission of samples to laboratories, and preparation of a summary report:
• Leading and coordinating the day-to-day activities of the various sample teams under their
supervision;
• Implementing QC for technical data provided by the field staff including field measurement
data:
• Schedule compliance, and adherence to management-developed study requirements; and,
• Identifying problems at the field team level, resolving difficulties in consultation with the
SAM, implementing and documenting corrective action procedures, and provision of
communication between team and upper management.
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3.8 Sample/Technical Manager
The Sample/Technical Manager will be responsible for all sample collection and processing to the
project organization in accordance with the QAPP. These tasks include;
• Development of the laboratory SOW;
• Procurement of laboratory ser\ ices;
• Daily communication with the laboratory;
• Process samples for laboratory submittal;
• Address any chain-of-custody discrepancies or laboratory QA/QC anomalies; and,
• Logistically support Operations in the collection of samples.
3.7 Data Manager
The Data Manager is responsible for all data reporting, quality checking and reporting to the project
organization in accordance with the QAPP. These tasks include:
• Receiving analytical data; checking for completeness, and making sure that appropriate QA
checks have been performed;
• Performing summary validation on all samples not assigned for full validation;
• Assigning 10% of Level IV data packages for full data validation by the third party data
validator:
• Entering and maintenance of sample location data;
• Entering data into databases, including US.EPA's SCRIBE system; and,
• Maintenance of appropriate security measures to ensure data integrity.
3.8 Third Party Data Validator
The Third Party Data Validator is independent from the collection of samples and will be performed
by an entity not otherwise invoked w ith the project. Level IV data packages will be provided to
allow full validation of results, Full \ alidation will be conducted on 10% of chemistry samples.
Summary validation will occur on remaining samples, unless significant issues are identified on full
validation.
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4.0 Overview of Sampling Activities
Sampling activities will be conducted to address surface water, groundwater, sediment and soil
impacts. Background samples will be collected from all media to distinguish between pollutants
related to this incident and historical conditions. The data obtained from all sampling, along with
any significant field observations from the collection points (e.g., sheen, odor, etc) will be
summarized and provided daily to Operations. Data and observations will be evaluated regularly
during the operational period to determine if the level of effort is appropriate. A summary of
information and discussions with the state and federal regulatory agencies, as appropriate, will be
conducted as needed to increase or decrease the scope, including sample location, sample frequency
and analyte list. All plan modifications will be approved by the FOSC and the appropriate agencies.
4.1 Data Quality Objectives
The primary objective of the environmental sampling program is to assess the natural resources and
ecosystems along the potentially-affected waterways, (e.g.. Talmadge Creek, Kalamazoo River, and
Morrow Lake) and the source/spill area for the presence, or threat of release, of visible oil and/or
sheen to navigable waterways. The secondary goal is to obtain sufficient data to support a
comparison of the water and sediment quality to appropriate regulatory benchmarks.
The Data Quality Objectives (DQOs) include both qualitative and quantitative descriptions for
endpoint determinations. Qualitatively, for example, sediments in must be able to be disturbed at
regular intervals (e.g., 50") from the Spill Release Area through the affected waterways of Talmadge
Creek and in the immediate vicinity of the Spill Release Area using a rod, stick, or similar implement
without producing visible oil and/or sheen, especially from high sediment depositional areas.
Surface water will be continuously monitored for presence of crude oil constituents at multiple
locations using remote, telemeting water quality sensors. For qualitatively evaluating visible oil
and/or sheen along the Talmadge Creek banks, the primary method utilized will be the petroleum
sheen test, because of the reliability and consistency of the results and the speed with which the test
can be conducted. The petroleum sheen test consists of mixing a small aliquot of soil with deionized
water in a glass sample container and noting if any sheen is present. Soil with a rainbow sheen is
considered impacted with free-phase product. The petroleum sheen test is conducted to direct
excavation activities after initial excavation of soil with \ isible free-phase impacts are completed.
Quantitatively, the qualitative "results" of the sediment and surface water visual and water quality
monitoring evaluation must be able to be confirmed by submitting an appropriate number of
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representative sediment and surface water (e.g.. v4-mile and 1-mile sample intervals, respectively)
along the Talmadge Creek for confirmatory analysis.
In keeping with the objective of protection of public health, during the oil/sheen removal process,
community air monitoring activities described in the Air Sampling and Monitoring Plan (Appendix
A) will continue. As described in Section 5 therein, if community air monitoring reveals real-time
benzene detections above 200 ppb. confirmation testing involving grab analytical air samples will be
obtained to determine if levels in areas where community members may be exposed exceed 60 ppb.
If levels in excess of 60 ppb are documented with analytical grab sampling, longer-term sampling (8
- 24 hours) will be performed. Results of these tests will be reviewed by the Public Health Unit for
evaluation of actions, if any, that should be taken to address community exposure concerns. The
health-based benchmark for longer-term community exposure levels is the Agency for Toxic
Substances and Disease Registry "s Intermediate Minimal Risk Level for benzene of 6 ppb.
4.2 Objectives, Endpoints & Metrics
The objective of this Sampling and Analysis Plan (SAP) is to evaluate and identify \ isible oil and or
sheen that is either current!) affecting navigable water ways and/or poses the threat of release of a
visible oil or sheen discharge to na\ igable waterways. This objective will be accomplished by
meeting the target endpoints for each shoreline type described below. T he endpoints are based on
visual field screening for the presence of materials capable of producing a release of oil or sheen to
navigable water. Visual screening does not include soil that exhibits a petroleum odor and/or organic
headspace. These residual impacts will be addressed as part of the long-term assessment and
remediation efforts for the site.
4.2.1 Riparian Zones and Stream Banks
1. Shorelines no longer release sheens that affect navigable waterways.
2. Oil no longer rubs off on contact.
3. Oil removal to the point where recovery/re-colonization can occur without causing more
harm than leaving the oil in place. Heavy oil generally weathers to a dry coat within weeks.
4.2.2 Soil, Sand arid Gravel
1. Oil is no longer visible on surface.
2. No oil layers in test pits dug by inspection teams.
3. No longer release sheens that affect navigable waterway's.
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4,2,3 Man-made structures
1. Structure no longer generates liquid oil or sheen,
2. Oil no longer rubs off on contact.
Metric
Marshes
Soil,
Sand and
Gravel
Man-
made
Structures
Sheens no longer released to waterways
X
X
X
Oil no longer visible on surface or in test
pits dug for observation purposes
X
X
Oil no longer rubs off on contact
X
X
Recovery/recolonization can occur without
harm to incoming flora and fauna
4.3 Surface Water Sampling
4.3.1 Overview and Rationale
This section of the SAP describes the specific surface water sampling and monitoring procedures to
be utilized and implemented during response actions to remove \ isihle oil and/or sheen that may
affect navigable water ways or pose a threat of release of a visible oil or sheen discharge to navigable
waterways.
4.3.2 Location and Frequency
Surface water samples will be collected where and as frequent as necessary, to assess the affect of
visible oil and/or sheen to navigable water ways. The scope and frequency of the sampling may
increase, as needed, based on an evaluation of the data as it is produced; or in response to "wet""
weather conditions (i.e.. Vi-inch over a 24-hour period). It is initially anticipated that surface water
sampling will be conducted twice per week, however, "wet" weather may require an increased
frequency to ensure that the visible oil/sheen is contained, and does not exacerbate the extent of
impact.
Surface water sampling, when scheduled, will be conducted in conjunction with sediment sampling at
an initial spatial distribution of approximately one sample every two river miles starting from the
Spill Release Area and heading downstream. Original sample locations will be retained and
supplemented, as needed, with additional locations, which will be selected to be representative of
surface water quality and for accessibility and distribution. At the request of the Kalamazoo County
Health Department, additional samples w ill be collected at the following locations:
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• Upstream on the Kalamazoo River at 23 Mile Road:
• 35th Street in Galesburg;
• River Street in Comstock;
• D Avenue in Kalamazoo;
• Downstream of Morrow Lake at M-89 in Allegan,
• M~% Bridge in Augusta.
• H Avenue in Kalamazoo Township,
• Star Road in Plainwell.
• North Street in Otsego.
• Swan Creek and M-89,
• Kalamazoo Lake at Washington Street,
In addition to the defined areas listed above, surface water samples will be collected at sediment
deposition areas along the affected waterway as they are identified and/or determined to be relevant.
Qualitative determinations of oil content of samples will be made with respect LNAPL/DNAPL
characteristics. Oil and/or sheens observed floating on the surface will automatically be classified as
LNAPL. With respect to soil and/or sediment samples, a representative sample, (not to exceed 1:4
volumetricalK) of the subject matrix will he placed in a clear glass jar. and the jar filled with water.
LNAPLs will be observed floating on the surface of the water. Non-floating oils will be classified as
DNAPLs.
Surface water and subsurface water (i.e.. water column) samples will be collected at each sample
location to establish concentration changes with depth over time and to assure that no visible oil
[light non-aqueous phase liquids (LNAPL) or dense non-aqueous phase liquids (DNAPL)J or sheen is
present within the water column. For sample locations with a total river depth of six feet or less, two
samples will be collected and submitted for laboratory analysis: surface and immediately above the
bottom. For sample locations with a total rher depth greater than six feet, three samples will be
collected and submitted for laboratory analysis: surface, middle, and bottom. Additional, targeted,
surface or water column sampling locations will be implemented at the request of the FOSC.
Surface water and column samples will be collected in accordance writh the methods outlined in the
appended SOPs (SOP-*1!). Sample locations are presented on Figures 3-7, by operational division
(e.g.. A. R, C, D. and E).
16
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4.3.3 Surface Water Monitoring and Analysis
Water quality parameters (DO, Turbidity, temperature. pH, and conductivity) will be measured in the
field at every sample location. Physical conditions such as water depth and velocity will be
measured; visual observations, (including aquatic vegetation and the presence of sheen, and presence
of oil/tar-like flecks) will be made at each surface water sampling location and electronically noted
using a hand-held data collection device or recorded in a log dedicated to this project in accordance
with SOP-4. Samples will be collected and submitted for laboratory analysis as indicated in
Table 4.1,
Table 4.1 Surface water parameters, methods, and container types
Parameter
Method
Container Number,
Size, and Type
Sample
Preservatives
Volatile organic
compounds (VOC)
EPA 8280B
3 x 40 ml VOA vials
Hydrochloric acid
(HCI) to pH < 2; ice
Semi-volatile organic
compounds (SVOC)
EPA 8270A
2 x 1 L Amber glass
Ice
Total Petroleum
Hydrocarbons (TPH),
diesel range organics
TPH (DRO), oil range
organics TPH (ORO)
EPA 8015B
1x11 Amber glass
Ice
Gas range organics
TPH (GRO)
EPA 8015B
2 x 40 ml VOA vials
HCI to pH < 2; ice
Michigan Metals: (Sb,
As, Ba, Be, Cd, Cr, Hg,
Cu, Co, Fe, Pb, Mn,
Mo, Ni, Se, Ag, Tl, Va,
and Zn)
EPA 6010
EPA 7470 (Hg)
1 x 150 ml HOPE
bottle
Nitric Acid (HN03) to
pH < 2; ice
Polychlorinated
biphenyls (PCBs)
EPA 8082
1x11 Amber glass
Ice
Total Organic Carbon
(Toe)
EPA 415.3
1x11 Amber glass
Ice
Specific Gravity
NA
Total Suspended Solids
2540D
Hardness
EPA 130.1
The Company has additionally established a protocol for monitoring visible oil and/or sheen on
Morrow Lake and at other locations downstream of the Spill Release consisting of the deployment of
direct reading instruments and daily inspections of surface water quality from multiple boats and
coordinated over flights.
17
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In order to determine that water quality (as qualitatively measured by the presence of visible oil
and/or sheen) is maintained for the duration of response activities upstream, continuous monitoring
of various downstream locations, including four to six locations within Morrow Lake, will be
conducted. The non-Morrow Lake downstream locations will be selected with concurrence of the
FOSC and are anticipated to include at a minimum six additional locations. In order to determine that
water quality is maintained for the duration of response activities upstream. Company, under the
procedures proposed herein, proposes to conduct continuous monitoring at and routine sampling of
Morrow Lake,
Water quality parameters of Morrow Lake will be continuously collected at two established locations
using a Eureka Environmental Manta 2 multi-parameter water quality real-time monitor. The data
collected will be electronically logged on 15 minute intervals and will include:
• Temperature (oC)
• pll (0-14 standard units)
• Conductivity (Siemens/meter)
• Dissolved Oxygen (milligrams/liter)
• Turbidity (NTU)
• Crude Oil/Oil and Grease (parts per billion)
Continuous, remote monitoring of water quality parameters with satellite telemetry of data to a
database accessible by various stakeholders including Company personnel and federal and state
regulators will be performed. The water quality meters will be calibrated in accordance with
manufacturer's specifications and set to alert (via text and/or email) appropriate individuals should
surface water quality parameters fall outside specified ranges (i.e.. "actionable" values). Proposed
actionable values are presented in Table 4.2. Please refer to the appendix to the SOPs for product
information on Eureka Environmental Manta 2 multi-parameter water quality real-time monitor.
18
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Table 4,2 Proposed Actionable Values
Parameter
Proposed Actionable Value
Units
Temperature
~
™
pH
6.5 < x > 9.0
Standard Units
Conductivity
~
Siemens/m
Dissolved Oxygen
5,0
mg/L
Turbidity
300 or 30% greater than
background, whichever is
greater
NTUs
Crude Oil
Instrument detection Level
(i.e., any detection)
ppb
In the event that an alert is received, the results will be confirmed using a hand-held, properly
calibrated multi-parameter water quality meter, A re-evaluation of the controls and containment
measures deployed upstream of the alarming water quality meter would occur in the event of a
confirmed reading.
To demonstrate acceptability of data obtained by the remote surface water monitoring units, discrete
confirmation samples will be collected and submitted for laboratory analyses. It is anticipated that
initial samples will be collected daii\ from locations immediately adjacent to the water quality
monitoring units and the results expedited; however, as the initial analytical results are reviewed, is
anticipated that sampling frequency sample turn around, and/or sample locations may be revised
with concurrence of the FOSC. Samples will be submitted for analysis of parameters identified in
Table 4.1 above. Sampling will be documented in field notebooks and/or with hand-held data
collectors in accordance with Sample Handling Procedures outlined in the attached SOPs. A map of
current established sampling locations is available in the attached Figures, The FOSC will be
consulted if deviations are made to the above-described protocols noted above.
In addition to the water quality meters in Morrow Lake, water column sampling will be collected at
two grid nodes approximately one-third of the distance from the east and west ends of the lake on the
long axis. Buoys will be placed at those locations and logged by GPS. This will aid in replicability
of the sampling locations if the buoys are damaged or moved. These sample points will be accessed
and column sampling (surface, mid depth, and bottom) will be conducted on a twice weekly basis, as
per the analysis outlined below. The Company will adjust the number, analyses and frequency of
sampling based on the results of the analyzed samples, in conjunction with the FOSC.
19
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Fieid sampling will be carried out according to SOP-4 which is appended to this Plan. Surface water
sample parameters are presented on Tabic 4.1.
4,4 Sediment Sampling
4.4.1 Overview and Rationale
Sediment sampling will provide a base-line evaluation of the current conditions as well as confirm
the presence or absence crude oil impacts. Sediment samples will be collected using hand-operated
equipment in accordance with SOP-4.
4.4.2 Location and Frequency
Sediment samples will be collected at a minimum once weekly from Taimadge Creek, the Kalamazoo
River. Morrow Lake. Wenke Park, immediately upstream of C'eresco Dam. M-96 Bridge in Augusta,
and various background locations (e.g., several locations upstream of the Spill Release Area on
Taimadge Creek and the Kalamazoo River). The specific locations will be selected in the field based
on topography, erosion features, water depth, water velocity, and other indicators of sediment
deposition. Conceptually, the spatial distribution of sediment sample locations is anticipated to be
approximately ever}1 2 miles from the Spill Release Area to Morrow Lake; however, in actuality, an
assessment of the features of the affected waterways and location of sediment deposition will
determine the actual sediment sample locations. In areas of low potential for sediment deposition
(i.e., straight, narrow-, and/or swiftly moving waterwa)s) sediment samples will be collected from the
surface sediments to 2 inches in depth. At locations with a high potential for sediment deposition
(i.e., meandering, broad, and/or slowly moving waterways) sediment samples will be collected from
the surface sediments to 6 inches in depth to assess the potential for dense non-aqueous phase liquids
(DNAPL) impacts.
In the affected waterway immediately upstream of the Ceresco Dam, the initial sediment deposition
at the confluence of Morrow Lake, and any other locations of obvious sediment deposition between
the Spill Release Area and Morrow Lake, representative sediment samples, consisting of transect
and/or grid samples, will be collected. The transect and/or grid sample distribution/interval will be
determined following the qualitative assessment of the Kalamazoo River and Morrow Lake
sediments, as described in the RPD1A, Sections 4.1.1 and 4.1.2, respectively, dated August 2, 2010,
revised August 15. 2010 and submitted for the FOSC approval.
Results will be evaluated upon receipt of analytical results and further actions (e.g., increasing or
decreasing sample locations) will be made with concurrence of the FOSC.
20
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Coordinates at sediment sample locations will be recorded to allow subsequent sampling from the
same location to establish concentration changes over time. Sediment samples will be collected from
the fine sediment column in accordance with SOP-4.
4.4.3 Sediment Analysis
Collected samples will be transported to a fixed-base laboratory and analyzed as indicated in
Table 4,3, Excess material generated during sampling will managed in accordance with Section 2,3
of the Waste Treatment, Transportation, Disposal Plan (WTTP).
Table 4.3 Sediment parameters, methods, and container types
Parameter
Method
Container Number,
Size, and Type
Sample
Preservatives
Volatile organic
compounds (VOC)*
EPA 82608
Methanol; ice
Method 5035A
Semi-volatile organic
compounds (SVOC)
EPA 8270A
Total Petroleum
Hydrocarbons (TPH),
diesel range organics
TPH (DRO), oil range
organics TPH (ORO)
EPA 8015B
3 x 4 oz wide-mouth
Gas range organics
TPH (GRO)
EPA 8015B
glass
Ice
Michigan Metals; (Sb,
As, Ba, Be, Cd, Cr,
Hg, Cu, Co, Fe, Pb,
Mn, Mo. Ni, Se, Ag.
Tl, Va, and Zn)
bHA 6010
EPA 7471A (Hg)
Polychlorinated
biphenyls (PCBs)
EPA 8032
"Note: In the event that water saturated sediments are to be analyzed for VOCs, the samples should
not be preserved with methanol.
4,5 Groundwater Sampling/Monitoring Approach
As a result of the release, there is concern that crude oil constituents may impair groundwater in the
vicinity of the Spill Release Area and affected water bodies, MDNRE and various county
departments of health (e.g.. Calhoun County. Kalamazoo County, etc.) are providing the FOSC with
a list and description of wells within the affected area. However, realizing that departmental lists
may not accurately reflect all private wells (Wells) within the affected area, the Company, or its
contractors, will be conducting a visual survey to identify private wells located within a 200-foot
buffer /one (in accordance with the direction of the Calhoun Count) Public Health Department) on
21
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either side of the affected water bodies (e.g., Talmadge Creek, Kalamazoo River, and Morrow Lake).
Hie survey is anticipated to be conducted house-to-house, from the shore where access allows, and
from boats, canoes, and/or other watereraft.
Other sources of information, including township tax records for property owner names and
addresses, electronic database searches, and mailings to all affected property owners asking for
information about their wells will be utilized to assist in locating wells. Information gathered from
the private well surveys will supplement information obtained from property queries and database
searches and is anticipated to include location, coordinates, depth to zone of extraction (if known),
and age. Wells identified during the visual survey and obtained from agency-provided lists will be
sampled as part of this SAP. pending approval from the well-owners within the 200-foot buffer zone.
In addition to sampling the wells identified in the visual survey, other wells may also be sampled to
address citizen calls to the Company Call Center in accordance with the "Environmental Procedure
Call Center Operations" protocol submitted to the FOSC for approval separately from this document.
4.5.1 Location and Frequency
The locations of the wells will be plotted on maps based on coordinates recorded during the survey.
All owners/operators of the identified wells will be contacted for permission to sample their
respective wells. The respective Count}' Health officials will be notified at least 48 hours in advance
of the well sampling ev ent to allow the count) time to observe and/or split the sampling event. The
results of the analyses will be pro\ ided to the landowner, resident and the FOSC. if requested.
Wells will initially be sampled once e\ery other week,
4.5.2 Groundwater Sample Analyses
Samples collected from the groundwater sampling events will be submitted to a Safe Drinking Water
Act (SDWA)-certified laboratory for laboratory analysis of VOCs, SVOC's. metals and Total
Petroleum Hydrocarbons (TPH) (TPI1/DRO. GRO. ORO). as shown on Table 4.4. The proposed
laboratory for this effort is Merit Laboratories. Inc. (Merit) located at 2680 East Lansing Drive. East
Lansing. Ml 48823. Representatives for Merit have indicated that the laboratory is a Michigan
SDWA-certified laboratory for VOC and metals analysis. At the request of the Company, Merit will
obtain Michigan SDWA certification for SVGCs, and until that time, will subcontract the SVOCs
analysis to a Michigan accredited laboratory. Merit has requested and is awaiting the necessary
state-performed audit of its facilities.
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Table 4.4 Groundwater parameters, methods, and container types
Parameter
Method
Container Number,
Size, and Type
Sample Preservatives
Volatile organic
compounds (VOC)
EPA 524.2
3 x 40 ml VOA vials
Hydrochloric acid
(HCI) to pH < 2; ice
Semi-volatile organic
compounds (SVOC)
EPA 525
2 x 1 L Amber glass
Ice
Total Petroleum
Hydrocarbons (TPH),
diesel range organics
TPH (DRO), oil range
organics TPH (ORO)
EPA 8015B
1 x 1 L Amber glass
Ice
Gas range organics
TPH (GRO)
EPA 8015B
2 x 40 mL VOA vials
HCI to pH < 2; ice
Metals: (Sb, As, 8a, Be,
Cd, Cr, Hg, Cu, Co, Fe,
Pb, Mn, Mo, Mi, Se, Ag,
Tl, Va, and Zn)
200.7(ICP), 200.8
(ICP-MS)
245.2
1 x 150 ml HDPE
bottle
Nitric Acid (HN03) to
pH < 2; ice
Polychlorinated
biphenyls (PCBs)
EPA 508
1 x 1 L Amber glass
Ice
Total Organic Carbon
(TOC)
EPA 415.3
1x11 Amber glass
Ice
Total Suspended Solids
2540D
Ice
Hardness
EPA 130.1
4.8 Soil Sampling
4,6,1 Overview and Rationale
Soil investigation and response activities, including excavation and source removal, for the purposes
of this plan, will continue in areas where there remains qualitative (i.e., visual evidence of oil) or
quantitative (i.e., confirmation sampling of representative sample from 0-6 inch depth interval
submitted for laboratory analysis in accordance with SOP-8 evidence of oil that poses a threat of
release of a visible oil or sheen discharge to navigable waterways, especially after significant
precipitation events. The Source Area Remediation (SAR.) Plan submitted separately to FOSC for
approval addresses some of the additional soil screening and sampling activities which will be
conducted; however, it is anticipated that longer term monitoring and soil sampling will be required.
23
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4.8.2 Location and Frequency
Soil removal from the Spill Release Area will continue until oil is no longer qualitatively (i.e.,
visually) identified; sample locations cannot be established definitively at this time. The area(s) of
investigation will be determined by the extent of initial response (e.g., excavation and source
removal) and/or the Shoreline Cleanup Assessment Technique (SCAT) Team activities. Soil
verification sampling locations will be established based on discussions with the MDNRE.
4.8.3 Soil Sample Analyses
It is anticipated that analytes. sample preservation and analytical methods will be as found in
Table 4.5,
Table 4.5 Soil parameters, methods, and container types
Parameter
Method
Container Number,
Size, and Type
Sample
Preservatives
Volatile organic
compounds (VOC)*
EPA 8260B
Methanol; ice
Method 5035A
Semi-volatile organic
compounds (SVOC)
EPA 8270A
Total Petroleum
Hydrocarbons (TPH),
diesel range organics
TPH (DRO), oil range
organics TPH (ORO)
EPA 8015B
3 x 4 oz wide-mouth
Gas range organics
TPH (GRO)
EPA 8015B
glass
Ice
Metals: (Sb, As, Ba.
Be, Cd, Cr, Hg, Cu,
Co, Fe, Pb, Mn, Mo,
Ni, Se, Ag, Tt, Va,
and Zn)
EPA 6010
EPA 7471A (Hg)
Polychlorinated
biphenyls (PCBs)
EPA 8082
4.7 Waste Characterization Sampling
4.7,1 Overview and Rationale
Response activities related to this release generate multiple waste streams requiring appropriate
characterization for proper disposal determination. Examples of anticipated waste generated from
the response activities may include, but are not limited to:
• crude oil:
24
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• impacted soil, water, sediments. Morrow Lake, Talmadge Creek, and the Kalamazoo River;
• vegetation;
• saturated absorbent materials;
• used disposable personal protection equipment (PPE);
• biological material associated with wildlife rescue operations; and,
• animal carcasses.
4.7.2 Location and Frequency
Waste is being generated and managed at various locations. Water and crude oil are being stored in
portable storage tanks (e.g.. frac tanks) at a centralized location north of the pumping station on
Division St. in Marshall. MI. Soiled absorbents and PPE are held in roll-off boxes at the major
centers of activity, such as the Spill Release Area, Kalamazoo River skimmer locations, and boom
maintenance sites. Vegetation, soil, and sediment samples will be generated in areas that will be
subject to restoration. Samples will be collected in accordance with the Waste Treatment,
Transportation, and Disposal Plan, approved with comments by FOSC August 3. 2010, on an as-
needed basis as activities and accumulated quantities dictate.
4.7.3 Soil Sample Analyses
Soil sampling of soils in the storage area will be performed as a preventive measure, so that
contaminants in the soil are known in the event that leakage of contaminants from the stockpile
occurs. Soils shall be analyzed for the same parameters as the other waste streams identified.
4.7.4 Waste Characterization Analysis
Collected samples will be transported to a NELAC certified fixed-base laboratory and analyzed by
medium as indicated in Table 4.6.
Table 4.6 Waste characterization parameters, methods, and container types
Parameter
Method
Container Number, Size,
and Type
Sample Preservatives
Volatile organic
compounds (VOC)
EPA 8260
Liquid
3 x 40 mi VOA
vials
Hydrochloric acid (HCI)
to pH < 2; ice
Solid
1 x 4 oz wide-
mouth glass
Ice
Semi-volatile organic
compounds (SVOC)
EPA 8270
Liquid
2x11 Amber
glass
Ice
Solid
1 x 4 oz wide-
mouth glass
25
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Parameter
Method
Container Number, Size,
and Type
Sample Preservatives
Toxicity Characteristic
Leaching Procedure
(TCLP) Metals
SW 8020
Liquid
1 x 150 ml HOPE
bottle
Ice
Solid
1 x 8 oz wide-
mouth glass
Flashpoint
(Closed cup)
D93
Liquid
From 1 L Amber
glass
Ice
Solid
From 8 oz wide-
mouth glass
pH
9040
Liquid
From 1 L Amber
glass
Ice
9045
Solid
From 8 oz wide-
mouth glass
Polychlorinated
biphenyls (PCBs)
EPA 8082
Liquid
1 x 1 L Amber
glass
Ice
Solid
1 x 4 oz wide-
mouth glass
Paint Filter
EPA 9056
Liquid
3 x 1 L Amber
glass
Ice
Solid
2 x 8 oz wide-
mouth glass
I'l'I l/DRO. GRO. ORO analysis will be added if required by disposal firms for waste coordination or
characterization purposes.
4.8 Product Sampling
Product samples will be collected, as necessary and prudent to support forensics investigations. On
July 27. 2010, an unweathered sample of the released crude oil was collected from the Spill Release
Area. The sample of the material was placed in an airtight container and refrigerated. Following
sample collection, an aliquot of this material was analyzed by an on-site, mobile laboratory for use as
a standard. Additional samples may be collected from the pipeline during repair operations to serve
as additional standards. The Company will collect representathe samples of sheen, oil/tar-like flecks
from downstream areas and submit them for comparathe fingerprint analysis if they meet one of the
following criteria: the oil/tar-like flecks appears in a new location or is observed for the first time in
a location: the oil/tar/like flecks that are observed currently are different in color, size, or form from
something previous!)' observed; or, the oil/tar-like Hecks are group in a large quantity or cover a
large surface area. See Table 4.7 below. The chromatograms of the additionally collected
representative sample and the sample used as the standard will be submitted to an independent
26
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laboratory for comparathe interpretation. Interpretation of the results will occur following receipt
anahses. Following a review of the interpretive results, additional samples may be warranted,
especially near heavily populated or industrial areas following precipitation events.
Table 4.7 Product Parameters/Forensic Fingerprinting (may change as needed)
Parameter
Method
Container Number,
Size, and Type
Sample
Preservatives
Volatile organic
compounds (VOC)
EPA 8206B
3 x 40 ml VOA vials
Hydrochloric acid
(HCI) to pH < 2; ice
Semi-volatile organic
compounds (SVOC)
EPA 8270A
2 x 1 L Amber glass
Ice
Diesel range organics
(DRO)/Oil range
organics (ORO)
EPA 8015B
1 x 1 L Amber glass
Ice
Gas range organics
(GRO)
EPA 8015B
2 x 40 ml VOA vials
HCI to pH < 2; ice
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5,0 Sample Management
Samples will be managed in accordance with the requirements set forth in the referenced analytical
method and/or laboratory SOPs,
Field samples will be contained and preserved in accordance with appropriate U.S. EPA
specifications. Sampling containers and preservatives will be provided by the laboratory. Samples
will be placed in individual pre-cleaned containers for shipment to the laboratory. Samples will be
collected and stored in accordance with U.S. EPA specifications, laboratory SOPs. and analytical
methods currently under development for this project, as specified in the Quality Assurance Project
Plan (QAPP. August 2010).
Sample container orders, when shipped by the laboratory, will include a packing list that details the
number and type of bottles shipped, the bottle lot numbers, chemical preservatives, and the packer's
signature. The C'OC Records will be completed by field sampling personnel and returned to the
laboratory with the samples.
Samples w ill be stored according to the applicable storage criteria from the time of collection until
the time of analysis by (he laboratory. Field personnel will keep samples cold by placing ice in the
coolers in which samples will be stored until delivery to the analytical laboratory personnel. After
receipt of the samples, it is the laboratory's responsibility to store the samples according to the
applicable preservation conditions until preparation and analysis has been initiated.
Samples have a finite holding time (the time between sample collection, sample digestion, and
sample analysis) to limit the potential for degradation of the analytes. The holding times for required
analyses are measured from the verified time of sample collection. When possible, samples will be
shipped by overnight carrier or hand delivered by same-day courier to minimize the time between
collection and laboratory receipt.
Samples will be preserved per the appropriate EPA method, immediately placed in a cooler following
sample collection, and maintained at 4 degrees €. Shipping or transporting of samples to the
laboratory will be done within a timeframe such that recommended holding times are met.
28
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5.1 Sample Labeling
Sample jars and vials will be clearly labeled with, at a minimum, the following information:
• Unique sample identification;
• Sample Type (discrete or composite area);
• Sampler name or initials;
• Date sample collected;
• Time sample collected; and
• Analysis to be performed.
The unique sample designation will include a matrix prefix, a numerical designation, and a unique
series of information including the month, day, time, sampler initials, and QA sample designation.
The following matrix prefixes will be used; "SO". "SE", "*\¥5". "WP"\ and "WG" which designate
soil, sediment, surface water, potable water, and groundwater, respective!)'. Agricultural wells will
be considered groundwater. A photograph will be taken at each sampling location. The photograph
will include the sample designation, date, and time showing the immediate surrounding area and any
distinctive feature that can be found in the future.
5.2 Chain of Custody Procedures
A primary consideration for environmental data is the ability to demonstrate that samples have been
obtained from specific locations and have reached the laboratory without alteration. Evidence of
collection, shipment, laboratory receipt, and laboratory custod) while samples are in the laboratory's
possession will be documented by maintaining a COC thai records each sample and the individuals
responsible for sample collection, shipment, and receipt at the project laboratory. Samples that are
collected will be accompanied by a COC Record. The following information will be recorded to
complete the COC Record;
• Project name and number.
• Name of sampler.
• Sample identifier/name, location, date and time collected, and sample type.
• Analyses requested.
• Special instructions and/or sample hazards, if applicable.
• Signature of sampler in the designated blocks, including date, time, and company.
29
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• Sample condition (including temperature) upon receipt as reported by the analytical
laboratory.
Copies of COC Records will be maintained under customary business practices and on-Spill Release
Area by the Sample Manager. Duplicates of all COC Records will be retained by the as part of the
Project File.
30
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6.0 Analytical Approach
Water and sediment samples, as well as confirmatory soil samples will be submitted to a full-service,
qualified, subcontracted commercial laboratory for the analyses as specified in the QAPP. During the
initial response period, sample turnaround times (TATs) be expedited to assist in making quantitative
driven decisions. After a review of the data, it may be agreed upon by the FOSC that expedited
TATs may be scaled back to a standard TAT.
Level II data packages will be required for validation for 90% of the samples analyzed. Level IV
data packages will be required for full data validation of the remaining 10% of the samples analyzed.
Lab contacts and shipping information are as follows:
Merit Laboratories. Inc.
2680 East Lansing Drive
East Lansing, MI 48823
Cell: 517-202-1340
Maya Murshak
TestAmeriea. Inc.
2417 Bond Street
University Park. 1L 60484
708-534-5200
Pace Analytical Services. Inc.
7726 Mo Her Road
Indianapolis, IN 46268
Phone:317-875-5894
Karl Anderson
ALS | Environmental
3352 128th Avenue
Holland, Ml 49424
Direct Phone 616-738-7346
Office Phone 616-399-6070 Ext. 525
Mobile 616-218-5574
FAX 616-399-6185
www.aIsglobal.com
New Age/Landmark, Inc.
160 Veterans Blvd.
South Haven. Michigan 49090
Phone: (888) 685-1628
Fax:(269) 637-5664
31
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7.0 Quality Assurance
Sampling will be carried out in conjunction with a defined quality assurance (QA) program. The
goal of the field QA program is to document that samples are collected without introducing a bias
(i.e.. the effects of accidental cross- or svstematie contamination are eliminated) and refers to the
sampling, analysis, and data validation procedures for generating \alid and defensible data. To
provide QA for the proposed sampling, the following sampling, analysis. and data validation
procedures will be performed in addition to the Quality Assurance Project Plan (QAPP) prepared for
this project and submitted to the FOSC under a separate cover letter for review-.
7.1 Initial Field Evaluation
7.1.1 Surface Water Samples
Surface water sample containers collected for VOC analysis will be evaluated for "acceptability" in
the field prior to submittal to the laboratory. VOA vials containing air bubbles will be judged
unacceptable. Containers containing air bubbles will be re-opened and an additional aliquot of
representative sample carefully decanted into the container to remove any air bubbles in the sample
without losing any of the preservative.
7.1.2 Sediment
The sediment sample will be retrieved aboard the boat and evaluated for "acceptability"". For
example, a sediment sample will be considered "'acceptable" if it meets all of the following
characteristics for ""representativeness"":
• Sediment surface is not against the top of the sampler (i.e.. not over-filled);
• Sediment surface is relatively flat indicating minima! sediment disturbance;
• Overlying water is present indicating minimal leakage;
• Overlying water has minimal turbidity indicating minimal sample disturbance: and.
• Desired penetration is achieved.
7.1.3 Groundwater
Groundwater sample containers collected for VOC analysis will be evaluated for "acceptability" in
the field prior to submittal to the laboratory. VOA vials containing air bubbles will be judged
unacceptable. Containers containing air bubbles will be re-opened and an additional aliquot of
representative sample carefully decanted into the container to remove any air bubbles in the sample
32
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without losing any of the preservative. Groundwater will be purged the appropriate volume (i.e.,
three volumes) prior to sample collection to achieve representativeness.
7.1,4 Soil
Soil samples collected for VOC analysis will be evaluated for "acceptability" in the field prior to
submittal to the laboratory. Ten milliliters of methanol will be combined with 10 grams of soil in the
appropriate soil sample container.
7.2 Field Duplicate Sample
Field duplicate samples are used to check for sampling and analytical error, reproducibility, and
homogeneity. For approximately even twenty (5%) samples collected in the field, one field
duplicate will be collected and submitted for laboratory analyses to verify the reproducibility of the
sampling methods. Field duplicates will be prepared by separately submitting an aliquot from the
same sample location to the laboratory for analysis consistent with the proscribed analyses. For
sediment samples, the duplicate will be obtained by collecting a sample from an area adjacent to the
routine sample or by collecting a separate aliquot of sediment from within the same core (i.e.. co-
located sample), whichever is more appropriate for the type of sample/sampling technique (i.e.,
surface or subsurface sediment sample). At least one field duplicate will be collected each day that
samples are collected.
7.3 Equipment Rinsate Sample
Collection and analysis of equipment rinsate blanks are performed to assess the efficiency of field
equipment decontamination procedures in preventing cross-contamination between samples. Each
day of sampling, one equipment rinsate sample will be collected and submitted for laboratory
analysis. The rinsate sample will be collected by decanting deionized water over the post-
decontaminated non-disposable sampling equipment (e.g., ponar sampling device, stainless steel
bowls and spoons used for sample collection) into laboratory-supplied sample containers. The
deionized water comprising the rinsate blank will make contact with each piece of decontaminated
sampling equipment used in the collection of the sample.
7.4 Trip Blanks
Trip blanks will be prepared by the lab and included in coolers containing water samples to be
analyzed for VOCs. The trip blanks will be used to assess the potential for contamination of the
containers during handling and transit.
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7.5 Field Split Samples
Field split samples refer to samples collected by the regulatory agency or its designee from the same
sampling location and independently submitted to a different laboratory for analysis. Field split
samples may be requested at the discretion of representatives of the regulatory agency or the FOSC.
7.8 Laboratory QA
Laboratory quality control procedures will be conducted in a manner consistent with relevant State
and federal regulatory guidance. Level II data packages will be required for validation for 90% of
the samples analyzed. Level IV data packages will be required for full data validation of the
remaining 10% of the samples analyzed. Internal laboratory quality control checks will include
method blanks, matrix spikes (and matrix spike duplicates), surrogate samples, calibration standards,
and laboratory control standards (LCSs). A Level IV data package will additionally be requested for
10% of samples submitted for laboratory analyses as a result of this sampling event.
7.7 Matrix Spike/Matrix Spike Duplicate Sample
Matrix Spike/Matrix Spike Duplicate (MS/MSD) samples refer lo field samples spiked with the
analvtes of interest prior to being analyzed at the laboratory to gauge the quality of analysis.
Approximately one in twenty samples will be anahzed as MS/MSD samples.
7.8 Data Validation
Validation of the data generated by the laboratory performing the analyses will include at a
minimum, sample holding times, accuracy, precision, contamination of field generated or laboratory
method blanks, and surrogate compound recovery. Accuracy will be determined by evaluating LCS
and MS recovery. Precision will be determined by evaluating laboratory and field duplicate samples.
Ten percent of the analytical samples with Level IV data packages from each matrix will be
submitted to a third party laboratory for data validation. Level II summary validation will occur on
the remaining 90% of samples, unless significant concerns are raised during the validation process.
Level II validation typically consists of an audit for compliance with analytical holding times, GCMS
calibration, (initial calibration, continuing calibration verification standards), and internal standard
and ICP interference check against accepted criteria in accordance with the EPA Functional
Guidelines. Data are reviewed for compliance with accuracy limits for surrogate recovery,
laboratory control samples, matrix spikes, matrix spike duplicate recoveries. Laboratory method
blank and field blank results will be reviewed for evidence of contamination and potential impacts on
34
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project data <.|ualit\ results. 1 he data validator w ill attach appropriate qualifier* to she data to reflect
data quality for future use in decision making.
35
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8.0 Sampling Equipment Decontamination
Procedures
Decontamination procedures refer to the steps undertaken to minimize the potential for offsite area
contamination and cross-contamination between individual sampling locations. Prior to collecting
any sample described in this SAP the following decontamination procedures will be undertaken:
non-disposable sampling equipment such as the ponar sampling device, stainless steel bowls and
spoons which come into contact with sampling media will be decontaminated using a bristled brush
and a solution comprised of a laboratory grade, non-phosphate detergent (e.g., Alconox or Liquinox)
and deionized water. The sampling equipment to be decontaminated will be placed in the first bucket
containing the detergent solution and thoroughly washed using a bristled brush. The items will then
be transferred to the second 5-galIon bucket containing deionized water for rinsing. Following the
initial rinsing, the item will be held over the third 5-gallon bucket while deionized water is carefully
decanted over each item. Decontaminated items will be wrapped in clean aluminum foil for transit to
the next sampling location.
All decontamination will be conducted according to SOP-5. appended to this Plan.
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9.0 Waste Disposal and Investigative Derived Waste
Excess sediment generated during sediment sampling shall be handled, characterised, and disposed
of as an Investigation Derived Waste (IDW) in accordance with the Waste Treatment,
Transportation, and Disposal Plan.
37
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10 J Data Management
Data obtained as part of this response will be managed in accordance with the Data Management
Plan. submitted for approval to the FOSC on August L 2010.
10.1 Sampling and Analytical Data
Sampling data is recorded on paper forms or captured using Motorola MC-S5 Enterprise Digital
Assistants (MC-55 HDAs). Analytical laboratory data sheets are provided from the laboratory as a
Portable Document File (PDF) and an Electronic Data Deliverable (EDD).
10.2 SIERA Data
Sample Instrument E\ent Receptor Awareness (SIERA) is a program developed to provide
situational awareness to a project. Field personnel utilize SIERA to geographically tag photographs,
establish sampling locations, and document important events that may influence, interfere, or
otherwise bias a particular sample. SIERA data points are collected on a MC-55 and synchronized to
the off-site data warehouse.
10.3 Data Flow
Sampling data, including but not limited to. hand-written field notes, photographs, real-time
monitoring parameters. SIERA data, will be entered into an off-site data warehouse, managed by the
Company's contractor, daily following the sampling event to the extent possible information will be
collected using a Motorola MC-55 Enterprise Digital Assistants (MC-55 EDAs). or equivalent, to
facilitate synchronized to the database. Data which has undergone Level II validation will be
published to the centralized Scribe.NET database being maintained by EPA's Environmental
Response Team (ERT).
10.4 Data Backup
Daily backups are performed on-site to a removable storage drive using off-the-shelf commercial
backup hardware and software. Every evening an off-site dump is performed to the Company's
Contractor's corporate file server over the network. Every night, this fileserver is backed up to tape
and stored off-site.
38
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11J Records Management
Records management refers to the procedures for generating, controlling, and archiving project-
specific records and records of field activities. Project records, particularly those that are anticipated
to be used as e\identiary data, directly support current or ongoing technical studies and activities,
and provide historical evidence needed for later reviews and analyses, will be legible, identifiable,
retrievable and protected against damage, deterioration, or loss on a centralized electronic database.
Handwritten records will be written in indelible ink. Records will likely include, but are not limited
to. the following: bound field notebooks on pre-numbered pages, sample collection forms, personnel
qualification and training forms, sample location maps, equipment maintenance and calibration
forms, chain-of custody forms, maps and drawings, transportation and disposal documents, reports
issued as a result of the work, procedures used, correspondences, and any deviations from the
procedural records. Documentation errors will be corrected by drawing a single line through the
error so it remains legible and will be initialed In the responsible individual, along with the date of
change, and die correction will be written adjacent to the error.
39
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Figures
-------
Lake Superior
Michigan
Lake;Huron
Wisconsin
Calhoun County
Minnesota
" 'S,
Lake Michigan
Kalamazoo County
Michigan
Enbridge Pipeline 6B
Kalamazoo River
Lake St. Claire
Illinois
Ohio
Indiana
Ontario
I Lake Ontario
New York
Pennsylvania
ENBRIDGE
Enbridge Energy, Limited Partnership
Enbridge Line 6B MP 608 - Marshall, Ml
Sampling and Analysis Plan
Figure 1: Site Location
Iowa
Miles
200
DATE REVISED:
SCALE: 1:1,500,000
DRAWN BY: NMS/JPM
SERIES: 1 of 10
DATE ISSUED: Aug 11, 2010
atural
giresources
ngineering Co.
715-3S5-5680
-------
Divis'ion.D
¦ugusta
Battle Creek
'Fort Custer Park
t.Galesburg DivisiomE
Division C
Marshall
Morrow Lake
' -- - ztjAgjat;
Division B
Division A
ENBRIDGE
Legend
Enbridge Pipeline 6B Water Access
River Centerline Lil J Division Boundary ^ Release Location
Major Road ) Containment Site (Boom) G Downstream Milepost
DATE ISSUED: Aug 12, 2010
DATE REVISED:
SCALE: 1:60,000
DRAWN BY: NMS/JPM
SERIES: 2 of 10
Enbridge Energy, Limited Partnership
Enbridge Line 6B MP 608 - Marshall, Ml
Sampling and Analysis Plan
Figure 2: Division Designation Map
-------
Division Boundary Legend
Enbridge Pipeline 6B ^ Release Location # Potable Well Sample
River Centerline $ Downstream Milepost O Sediment Sample
Major Road q Containment Site (Boom) O Soil Sample
Extent Of Pooled
Oil on Land
Surface Water Sample S Water Access
Enbridge Energy, Limited Partnership
Enbridge Line 6B MP 608 - Marshall, Ml
Sampling and Analysis Plan
Figure 3: Division A - Multiple Media Sampling Locations
DATE ISSUED: Aug 13, 2010
DATE REVISED:
SCALE: 1:700
DRAWN BY. NMS/JPM
SERIES: 3 of 10
resources
I™"
-------
-------
Easthill!
mm&i
Ptfeifflgjal
LG.oiu rh bja"!
[ig^i
n '¦
L'r-Fs*
^S?3?SSi
1 v
DivisrqnTG;
iDivisio'nJBJ
Legend B
~ Background Sediment Sample
~ Background Soil Sample
¦ Background Surface Water Sample
DRAWN BY: NMS/JPM
Division Boundary
Enbridge Pipeline 6B ^
River Centerline ®
Major Road q
Extent Of Pooled a
Oil on Land
Legend A
Release Location #
Downstream Milepost O
Containment Site (Boom) O
Surface Water Sample
Potable Well Sample
Sediment Sample
Soil Sample
Water Access
DATE REVISED:
SCALE: 1:25,000
resources
Enbridge Energy, Limited Partnership
Enbridge Line 6B MP 608 - Marshall, Ml
Sampling and Analysis Plan
Figure 5: Division C - Multiple Media Sampling Locations
DATE ISSUED: Aug 13,2010
SERIES: 5 of 10
-------
ENBRIDGE
Potable Well Sample
Division Boundary
— Enbridge Pipeline 6B -5^ Release Location
---- River Centerline « Downstream Milepost O Sediment Sample
Major Road q Containment Site (Boom) O Soil Sample
CD poded
-------
DiyisionjD.
SBiHl
u-,< - IrJtfjfy,
SOsCs'!
I HH
' ' SI
i
Division E
&5sgs4
Legend
DATE ISSUED: Aug 13,2010
Enbridge Energy, Limited Partnership
Enbridge Line 6B MP 608 - Marshall, Ml
Sampling and Analysis Plan
Figure 7: Division E - Multiple Media Sampling Locations
Potable Well Sample
Sediment Sample
Soil Sample
Water Access
DATE REVISED:
SCALE: 1:24,000
^sources
DRAWN BY: NMS/JPM
SERIES: 7 of 10
-------
1
Plainwell
'^[IteESC0©a!DDiQ7
• W
Kalamazoo
Morrow Lake
Legend
DATE ISSUED: Aug 13, 2010
Enbridge Energy, Limited Partnership
Enbridge Line 6B MP 608 - Marshall, Ml
Sampling and Analysis Plan
Figure 8: Downstream Surface Water Sampling Locations
Morrow Lake to MP 76
DATE REVISED:
Ppiatural
j^iesources
Engineering Co
M 5-395-5680
River Centerline
O Sediment Sample
• Downstream Milepost
O Containment Site (Boom)
# Surface Water Sample
ENBRIDGE
DRAWN BY: NMS/JPM
E3 Water Access
-------
'(
H Miles
ENBRIDGE
River Centerline
Major Road
Legend
Downstream Milepost
Surface Water Sample ~ Water Access
Enbridge Energy, Limited Partnership
Enbridge Line 6B MP 608 - Marshall, Ml
Sampling and Analysis Plan
Figure 9: Downstream Surface Water Sampling Locations
MP 74 to Lake Michigan
DATE ISSUED: Aug 13, 2010
DATE REVISED:
SCALE: 1:60,000
DRAWN BY: NMS/JPM
SERIES: 9 of 10
atural
rces
ngineering Co
715-395-5680
Lake Michigan
-------
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Figure 11
Enbridge Line 68, MP 808
Quality Assurance Project Plan
Organization Chart
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Appendix A
Air Sampling and Monitoring Plan
Dated July 31, 2010 (Air Sampling QAPP)
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Center for Toxicology and Environmental Health, L.L.C,
5120 N. Shore Drive, North Little Rock, AR 72118 Phone; 501,801.8500 www.cteh.com
Air Sampling and Monitoring Plan
Enbridge Energy Oil Spill
Marshall, Michigan
July31, 2010
Revised August 15, 2010
Prepared by:
Center for Toxicology and Environmental Health, L.L.C.
5120 North Shore Drive
North Little Rock, AR 72118
501-801-8500
WWW.CTEH.COM
University of Arkansas for Medical Sciences Bioventurcs Program Associate
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Table of Contents
1. Purpose....,,..,,,,...,,.,,.,,.,,,,.,....,,,,,,..,,..,,,,.,.,,....,..,,,.,,,,,.,,,.,,,,..,,.,.,,.,..,.,,.,...,,,..,,,,.,,.,,,,,.,,,,,,, 3
2. Air Monitoring....,...,,,,,,.,,..,,..,,.,...,..,......,..,..,,,..,.,,,.,,...,...,,.,...,,,..,,.,.....,..,,,.,.,..,,..,.,,.,.,,,., 3
2.1 Sampling Frequency and Coverage 5
3. Air Sampling 5
4. Odor Investigation,,..,,..,,..,.,,,,,.,.,,,,..,,..,,,,,.,,,,,.........,..,..,.,,,..,.....,.,,.,.,,,. 9
5. Decision Tree and Action Levels...,,.,.,,..,.....,,....,..,.,.,,,,,,.,.....,...,.,.,,...,.....,.,.......,..,..,.9
6. Sample Station Locations 9
7. Data Quality and Management 9
8. Project Organization 12
10, Calibration and Maintenance of Field Instruments 12
It, Chain of Custody (COC) 12
12. Sample Labels 12
14. Packaging and Shipping 12
Appendix A - GPS Coordinates
Appendix B - CTEH QAPP
Appendix C - CTEH DMP
Appendix D - Equipment SOPs
Table 3 ...,..,,...6
University of A r k a n s a s for Medical Sciences Bioventures Program Associate
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1. Purpose
Center for Toxicology and Environmental Health, LLC. (CTEH®) was requested to
respond in support of site operations for the Enbridge Energy crude oil release on
Monday, July 27, 2010, CTEH® is providing air monitoring, air sampling, and
toxicology support to address public health concerns resulting from the crude oil
spill CTEH® has been conducting community air monitoring and sampling in
communities to protect human health.
This work plan addresses air monitoring and sampling in communities potentially
affected by fumes from the crude oil spill The purpose of this sampling includes the
following:
• Air monitoring and sampling in the community potentially impacted by the
presence of crude oil vapors and/or fumes from the spill
• Air monitoring and sampling throughout the community during mitigation
activities to evaluate the potential for exposure.
• Perform air monitoring and sampling in response to reports of odors in the
community.
• Provide personnel monitoring for CTEH and EPA contractors performing air
sampling and monitoring to protect against overexposure to chemicals in
crude oil vapors and/or fumes,
CTEH® will conduct community air monitoring in support of Unified Command
actions. Data from air monitoring and sampling will be evaluated to make decisions
regarding the need for additional monitoring and sampling. Data will be reported to
Unified Command, Enbridge representatives and USEPA, as soon as available.
Two types of air monitoring will be conducted, analytical and real-time. These are
discussed at greater length in the following sections of this report.
University o 1 Arkansas for Medical Sciences Bio ventures Program Associate
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2. Air Monitoring
Air monitoring will be conducted using a number of real-time instruments including
the MultiRAE Plus, AreaRAE, Gastec colorimetric detector tubes, and/or UltraRAE/
UltraRAE 3000 throughout impacted communities. The major sampling routes are
show in Figure 1. Monitoring locations may be modified based on operational
requirements. The air monitoring equipment used is listed in Table 1.
Figure 1
Major Sampling Routes for Air Monitoring
Table 1
Real-Time Air Monitoring Equipment
Instrument
Chemical
Detection
Limit
AreaRAE
VOCs
0.1 ppm
AreaRAE
h2s
1.0 ppm
MultiRAE P1D
VOCs
0.1 ppm
MultiRAE H2S electrochemical sensor
h2s
1 ppm
MultiRAE SO2 electrochemical sensor
S02
0.1 ppm
UltraRAE/UltraRAE 3000 PID with
Benzene
0.05 - 0.1 ppm
benzene sep filters
Gastec detector tube with pump
Benzene
0.05 ppm*
* Gastec detection limits are based upon detector tubes used
University of Arkansas for Medical Sciences Bioventures Program Associate
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CTEH personnel will perform continuous air monitoring in the community using an
AreaRAE or MuitiRAE Plus, Real-time data using these instruments will be collected
for volatile organic compounds (VOCs), hydrogen sulfide (H2S), oxygen (O2) and
lower explosive limit (LBL), Benzene levels will be monitored using an UltraRAE,
UltraRAE 3000 and/or benzene specific colorimetric tubes.
2.1 Sampling Frequency and Coverage
Roaming vehicles in the community will operate 24 hours per day. Air monitoring
will be conducted throughout the communities near affected waterways. In
addition, real-time air monitoring will be conducted as needed to respond to
potential concerns raised on or off-site, and for air quality during operations
performed by Fish and Wildlife or first responders.
Two readings will be taken at locations along the length of the spill, returning
multiple times to monitor areas with detectable VOCs or benzene levels. Multiple
readings in the same location will be used as one method to determine if VOC
and/or benzene detects from instantaneous readings from real-time
instrumentation are due to transient elevations or spikes in air concentration or if
the elevated air concentrations are sustained. If sustained, further air monitoring
and/or sampling would be initiated. Benzene readings will also be taken in all areas
with detectable VOCs or where an odor is present.
AreaRAEs with data-logging capabilities may also be used at some fixed locations
and in roaming to supplement analytical data.
3. Air Sampling
Analytical air sampling will be conducted in community areas close to the
waterways impacted by the spill. Analytical samples will be taken in fixed locations
(Figure 2) in the community, at locations selected to represent background (Figure
3), at community receptors near oil collection points (Figure 4) and as needed due
to changing site conditions, odor complaints, wind direction, and evaluation of
benzene or oil-related other air concentrations for possible evacuation and re-entry.
Background stations may be eliminated after sufficient data are collected to
establish background VOC concentrations. The GPS coordinates of initial analytical
stations is included in Appendix A. Methods may include either NIOSH Method
1500/1501 and/or EPA TO-15,
Initial fixed community sampling and background locations were chosen with input
from Unified Command representatives and Enbridge industrial hygienist, Daniel
Lu, PhD, CIH, Air samples will be collected 2 -3 times per day at each location during
a 24-hour period (sorbent tubes or regulated evacuated canisters) or for a 24-hour
sampling interval (regulated evacuated canisters) each day. The criteria that will be
used to select sampling locations will include proximity to residences, areas of oil
University of Arkansas for Medical Sciences Bioventures Program Associate
5
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collection, and areas downwind of the oil release point. Air samples collected using
sorbent tubes will be analyzed for aromatic hydrocarbons using NIOSH method
1500/1501 (Table 2). Canister samples will be analyzed for VOCs using EPA Method
TO-1S (Table 3), Methods are summarized in Table 4,
Table 2
Aromatic Hydrocarbons Detected using NIOSH 1500/1501
Benzene
Cumene
Toluene
Styrene
Ethylbenzene
p-tert butyl toluene
Xylene
methyl styrene
Table 3
Predominant Crude Oil VOCs Detected by TO-15
Benzene
Heptane, n-
Butane, 2-methyl-*
Hexane, n-
Cyclohexane
Naphthalene
Cyclohexane, 1,3-dimethyl-*
Nonane*
Cyclohexane, 1,3-dimethyl-,
cis-*
Octane*
Cyclohexane, butyl-*
Octane, 4-methyl-*
Cyclohexane, ethyl-*
Pentane, 2-methyl-*
Cyclohexane, methyl-*
Toluene
Cyclohexane, propyl-*
Trimethylbenzene, 1,2,4-
Decane*
Triniethylbenzene, 1,3,5-
Dodecane*
Undecane*
Ethylbenzene
Xylene, rn&p-
Ethyltoluene, 4-
Xylene, o-
*- Tentatively identified compound (TIC)
Table 4
Summary of Integrated Air Sampling Method
;; . V. «>:¦
VOCs
§ssg|
Umm
EPA TO-15
Canisters
HJJflj j
MA
University of Arkansas for Medical Sciences Bioventures Program Associate
6
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Aromatic hydrocarbons
NIOSH 1500/1501
Coconut shell
charcoal
200
Figure 2
Location of Fixed Analytical Stations
Figure 3
Background Locations
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Figure 4
Location of Oil Collection Sites
Evacuated canisters may also be used to collect air samples to address community
concerns about odors. Canister samples will consist of either grab or regulated 12
or 24-hour collections. The collection time will be based on monitoring needs. For
instance, a grab sample will be collected for confirmatory purposes in response to
data from real-time instruments. Longer sampling times may be appropriate for
evaluation of air concentrations over time. A 12-hour sampling period would be
used for analysis of air concentrations during mitigation activities over a work shift,
while 24-hour sampling would be appropriate for evaluating the potential for
exposure at certain receptor sites like homes and daycare centers.
All collected air samples will be sent to Galson Laboratories, an American Industrial
Hygiene Association [AIHA] accredited laboratory in East Syracuse, New York.
Samples will be expedited for shipping and analysis. A 1 - 2 days turnaround is
anticipated for data is anticipated.
University of Arkansas for Medical Sciences Bioventures Program Associate
8
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A CTEH team will be designated as the Odor Response Team. The Odor Response
Team will be deployed as soon as possible after receiving odor complaints/concerns
referred by the hotline, Enbridge, and Unified Command staff. The response team
will additionally include representatives USEPA and the Calhoun County Public
Health Department, as available. Air monitoring equipment (e.g. MultiRAE Plus,
AreaRAE, Gastec colorimetric detector tubes, and/or Ultra RAE) will be used to
evaluate the levels of VOCs and specific oil-related chemicals in the air. The
evaluation of the results should follow the decision process described below.
5. Decision Tree and Action .t vels
A decision process has been developed for the evaluation of air monitoring results
for VOCs, NIOSH 1500/1501, and real-time detections for benzene. For VOC
detections, a trigger level of 1 ppm will be used to designate the need for chemical-
specific sampling. The decision process for the evaluation of benzene levels from
Ultra RAE, GASTEC, NIOSH 1500/1501, and HAP analysis (Tedlar bag collection) is
summarized in Figure 5. If benzene levels are detected above 200 ppb, then
confirmation with the HAP instrument should be employed. If benzene levels
exceed 60 ppb, then an 8-24 hr time-weighted sample should be collected. The
target for longer-term exposures to benzene has been set at 6 ppbv. Air sampling
will be performed as need to meet requirements established by the Public Health
Unit.
6, Sample Station J c.caisonn;
Real-time and integrated sampling locations will be selected based on the presence
of communities near impacted waterways (Figure 1) and in addressing specific
community concerns. Mobile AreaRAE data will be mapped using GPS coordinates.
Additional, manually logged real-time data will be collected and reported on CTEH®
electronic field and/or paper forms.
\ * i"?j f..Ki Management
Integrated air samples will be sent to Galson Laboratories located in Syracuse, N.Y.
Air sampling preliminary results will be provided to Enbridge Energy's designated
representative and the USEPA within 1-2 days of receipt by the laboratory. The
expedited turnaround time for Galson is one business day. All data will undergo a
University or Arkansas tor M o ih c a 1 Sciences BiovenUires Program Associate
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Level II data validation by eDATApro prior to release to the EPA SCRIBE data base.
The CTEH QAPP is included as Appendix B of this report
All air sampling and air monitoring data will be provided in a format compatible
with SCRIBE. The data management plan can be found in data management plan
(Appendix C),
University of Arkansas for Medical Sciences Bio ventures Program Associate
10
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Figure 5
Real-time monitoring for benzene (Ultra RAE, GASTFC, NIOSH 1500/1501, and BAP Analysis) (ppb)
University of Arkansas for Medical Sciences Bioventures Program Associate
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8 Project Organization
CTEH will be responsible for the following;
• Toxicologica! support
• Air data quality assurance/quality control
• Data evaluation and reporting
h* ( .'l;b>ation and Maintenance of field Instruments
The calibration and maintenance of field equipment and instrumentation will be in
accordance with each manufacturer's specifications or applicable test/method
specifications, and will be recorded in CTEII calibration logs. Standard operating
procedures for each type of instrument are in Appendix D.
Each sample will be identified on a chain of custody record. The integrated sample
numbering system will include site name, date, analyte, and identification code
unique to each sample.
Sample 1 ^bels
Sample labels will be securely affixed to the sample container. They will clearly
identify the particular sample and should include the following information;
¦ Sampling location
• Date and time the sample was collected,
¦ Analysis requested,
¦ Unique identifier
1 ^ kl?ekagi^ asiu SLipphj,.
Packaging and shipping of samples will vary depending upon sample media,
contaminant concentration, preservation technique, and sample container. The
person packaging the samples is responsible to ensure that the sample packaging is
in suitable condition for shipping.
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University of Arkansas for Medical Scu-nciss Biunnuures Program Associate
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Table 1
GPS Coordinates at Fixed Analytical Locations
station name
latitude
lonrjitudi.1
mmmm
Station 1
42.24643
-84.9762
analytical
Station 2
42.25891
•85.0074
analytical
Station 3
42.24675
-84.9809
analytical
Station 4
42.2547
-84.9855
analytical
Station 5
42.25024
-84.9885
analytical
Station 6
42.28166
-84.6543
background
Station 7
42.22631
-84.6379
background
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Table 2
rdinates at Oil Collection Sites
Sitp Name
Division
Boom
X
v
Approx Release Site
Division A
-84.97153654
42.24328227
608
Division A
-84.97595329
42,24275523
A1 Release Site
Division A
-84.97404082
42.24220305
B1 MP 0,0
Division B
-84.97420968
42.24318202
B2 MP 0,3
Division B
Y
-84.97747813
42.24652001
B3 MP 0.9
Division B
Y
-84.98531523
42.2513746
B4 MP 1.00
Division B
Y
-84.98831667
42.25165
B5 MP 1.7
Division B
Y
-84.99537766
42.25689902
CI MP 5.1 (Add Boom)
Division C
-85.05361235
42.26667246
C2 MP 7.0 (Add Boom)
Division C
-85.08484296
42.27576335
C3 MP 8.9
Division C
Y
-85.11479057
42.29010592
C4 MP 11.1 (Add Boom)
Division C
-85.14015217
42.30864478
C5 MP 13.1 (Add Boom)
Division C
-85.18711736
42.29720573
€6 MP 14.8 (Add Boom)
Division C
-85.18716213
42.3102401
C7 MP 16.4 (Add Boom)
Division C
-85.20406232
42.32651713
K 3.0 MP 33.8
Division C
-85.41261846
42.28422964
1 MP
Division E
-85.32282535
42.35359682
E2 MP 28.9
Division B
Y
-85.35818541
42.32421571
Sheen Limit (5:30pm EST 7/27)
Division E
-85.3856568
42.30063438
E2.5 MP 33.3
Division E
-85.40592243
42.28830782
River Oaks County Park Access
Division E
-85.44507052
42.28831395
E4 MP 36.4
Division E
-85.45037364
42.27698084
Sheen Location (9:30 am EST 7-28)
Division E
-85.44282317
42.27655843
E5 MP 38.5
Division E
-85.49021375
42.28348629
01 MP 17.4
Division D
Y
-85.21820616
42.33452887
D2MP 17.9
Division D
Y
-85.23023889
42.33697579
D3 MP 18.7
Division D
-85.24040801
42.34165021
1)4 MP 19.8 (Add Boom)
Division D
-85.26219413
42.34642123
5 MP 20.6
Division D
-85.27544835
42.35048898
El MP 25,5 Priority 3
Division E
-85.3228204
42.35358879
E2 MP 28.9 Custer Boat Launch (400' boom, 1
Vac Truck, 1 Skimmer)
Division E
-85.35818046
42.3242077
Sheen Limit (5:30 pm EST 7/27)
Division E
-85.38565184
42.30062637
E 2.5 MP 33.3
Division E
-85.40591746
42.28829981
River Oaks County Park Access
Division E
-85.44506554
42.28830594
E4 MP 36.4 Priority 1 Morrow Lake Boat Launch
(10500' available boom, 2 Vac Tankers)
Division E
-85.45036866
42.27697283
Sheen Location (9:30 am EST 7-28)
Division E
-85.44281819
42.27655042
E5 MP 38.5 Priority 1A
Division F.
-85.49020876
42.28347829
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Appendix 8
University of Arkansas for Medical Sci ences B i o vc nIu r os Prog) am Associate
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Center for Toxicology and Environmental Health, L.L.C.
5120 N. Shore Drive, North Little Rock, AR 72118 Phone: 501,801,8500 www,cteh,com
Quality Assurance Project Plan
Enbridge Pipeline Crude Release
July 29, 2010
Prepared For:
Incident Command
Prepared By:
Center for Toxicology and Environmental Health, L.L.C,
5120 North Shore Drive
North Little Rock, AR 72118
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Table of Contents
1. Purpose 3
2. SCOPE AND OBJECTIVES . 3
3. Project Organization and Responsibility 3
3.1. Project Organization...................................... ............................................................4
3.2. Responsibility for Quality Assurance and Quality Control .......................................4
3.3. Qualified Individual ....4
3.4. Project Manager............. 4
3.5. Laboratory Subcontractors 5
3.6. DATA QUALITY OBJECTIVES............................................................. 5
3.7. Intended Data Use and Objectives... 5
3.8. Data Quality/Measurement Objectives............................................................................ 5
3.9. Representativeness.......................................... .6
3.10. Precision and Accuracy.................................................... Error! Bookmark not defined,
3.11. Completeness 6
3.12. Comparability...,. ...........6
3.13. Analytical Methods and DQOs... 6
4. SAMPLING PROCEDURES AND FIELD MEASUREMENTS 7
5. SAMPLE HANDLING, DOCUMENTATION, AND CUSTODY 7
6. QUALITY ASSURANCE PROCEDURES FOR LABORATORY ACTIVITIES............ 7
7. QUALITY ASSURANCE PROCEDURES FOR FIELD ACTIVITIES............................ 8
7.1. Internal Quality Control 8
7.2. Equipment 8
7.3. Sampling Equipment Decontamination 9
7.4. Calibration, Operation and Maintenance 9
7.5. Supplies and Consumables Error! Bookmark not defined.
7.6. Field Documentation........ .......9
7.7. Procedures to Assess Precision, Accuracy, Completeness and Comparability..9
7.8. Corrective Action......................................................................................................................9
8. DATA REDUCTION, ASSESSMENT AND VALIDATION. ......................................9
8.1. Laboratory Data .9
8.2. Field Measurement Data 10
8.3. Data Management 10
8.4. Data Validations.......,......,,...,,,.......,,... 10
9. AUDITS............................................................................................................................... 10
9.1, Field Systems Audit 10
9.2. Laboratory Audit 11
10. CORRECTIVE ACTION 11
10.1. Immediate Corrective Action 11
10.2, Long-Term Corrective Action,..,,....,,.,,.,..,.,.,,.,..,.,....,.,.,,....,.......,.,.....,,.,.,.,,,...,,,..........,. 11
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1. Purpose
This Quality Assurance Project Plan ("QAPP") has been prepared to provide assurance
that community air monitoring and sampling activities conducted as part of the
response to the Enbridge Pipeline crude oil release meet performance goals. In
addition, the methods and procedures described herein were developed in general
accordance with conventionally-accepted Quality Assurance and Quality Control
(QA/QC) objectives.
2. M Oi'K OUJFC IVES
This QAPP represents the foundation of QA/QC that will be utilized to assess and
verify that sampling, testing, and analysis activities are executed in a manner
consistent with applicable guidance and conventional QA/QC objectives. The
procedures described in the QAPP are intended to assess the data generated in terms
of representativeness, precision, accuracy, completeness and comparability.
Details about the sampling methodologies can be found in the individual work plans
prepared for each activity type. Much of the field sampling QA/QC methodology and
rationale is described in the individual work plans and, for conciseness, is not
reproduced herein. Rather, this QAPP presents the following:
Project Organization and Responsibility
Data Quality Objectives
Sampling Procedures and Field Measurements
Sample Handling, Documentation and Custody
Quality Assurance Procedures for Laboratory Activities
Quality Assurance Procedures for Field Activities
Data Reduction, Assessment and Validation
- Audits
Corrective Action
This QAPP is applicable to the work plans approved as of the date of this document.
To the extent that other work plans are written and approved that this QAPP is
applicable to, those activities will be incorporated by reference to the scope of the
QAPP herein.
3. Project Organization Responsibility
This section describes the project organization and specifies personnel
responsibilities. The project organization presented in this section has been
developed to guide and assess the quality of sampling and testing procedures for
obtaining reliable data, and to facilitate effective communication and decision-making
during the project
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The principal entities relevant to this QAPP that are involved in activities related to
the -Enbridge Pipeline Crude Release, and their respective roles, include the
following;
Enbridge Energy - Responsible Party
Unified Command Health and Environmental Representatives - review and
approval for procedures and deliverables
Center for Toxicology and Environmental Health (CTEH) - complete all site
investigation work, including data validation.
- Sampling Manager - CTEH project manager responsible for sampling activities
3.2, Responsibility for Quality Assurance and Quality Control
The responsibilities of key members of the proj ct team are summarized in the
following subsections.
3.3,Qualified individual (Ql)
Enbridge Energy and their representatives will have full authority to direct, supervise,
and coordinate the project team, and to commit resources as deemed necessary. One
or more Enbridge Energy designates will be the focal point of communications for
contractual matters with the Project Managers and all subcontractors. The Ql will
oversee all project planning and will review and approve project specifications, plans,
and procedures. The Ql will have ultimate project responsibility for assuring that the
project is completed according to plan.
3.4, Project Manager
CTEH Sampling Managers will be responsible for the preparation of project plans,
specifications, and reports within their defined scope of work. The PMs will attend
meetings and conferences between Unified Command and any other project
participants. They will ensure that the necessary equipment, facilities, and staffing are
available to implement their portion of the project.
Sampling Managers are responsible for maintaining the schedule of the work and will
regularly advise the Ql of the progress of the project. Each PM will provide direction
to the field staff and subcontractors involved in field sampling activities within his
scope so that the project is completed in accordance with the Work Plans and QAPP.
The PM will consult with any subcontractors to discuss compliance with the relevant
Work Plans and QAPP, and to evaluate corrective measures if problems occur.
The PM will also be responsible for the development and execution of QA/QC
activities in all phases of the project, including plan design, execution, data reduction,
and reporting for the scope of work. Each PM will serve as an in-house consultant to
the Ql in the development of a project-specific internal QC system, as well as
providing an independent review of the project approach, methods and design.
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Integrated air samples will be sent to Galson Laboratories and, if resource limitations
require, Pace Analytical Services, Inc. and Air Toxics Ltd located in Syracuse. NY,
Minneapolis, MN, , and Folsorn, CA, respectively, Galson Laboratories is A1HA
Accredited, and Pace and Air Toxics are NELAP certified.
3.6. DATA QUALITY OBJECTIVES
This section on Data Quality Objectives (DQOs) presents the intended data usage and
QA objectives for the sampling and analysis that will be performed during the project.
The overarching DQO is to generate validated data that is suitable for its intended use.
The data collected during fietd activities will be used to characterize the chemical
properties of media collected during the response. The data collected during field
activities will be used to characterize potential exposures of members of the public to
constituents potentially related to the release of oil from the Enbridge Energy
pipeline, by reporting on chemical constituents found in the environment at the time
and location of sample collection. The data may also be used to inform decisions
related to appropriate protective actions necessary to ensure health and safety of
members of the community.
3.8. Data Quality/Measurement Objectives
The purpose of DQOs is to establish a target level that can be measured against
whether data that is collected [through the sampling and analysis program) are of
appropriate quality to produce documented, consistent, and technically defensible
results. These results ultimately will define the characteristics and chemical
constituent concentrations present at the Site.
The quality of measurements made and the data generated will be evaluated in terms
of the following characteristics;
1. Representativeness
2. Precision and Accuracy
3. Completeness
4. Comparability
Specific objectives for each characteristic are established to develop sampling
protocols and identify applicable documentation, sample handling procedures, and
measurement system procedures. These objectives are established based on Site
conditions, objectives of the project, and knowledge of available measurement
systems. In addition, the following criteria for chemical sample handling and analysis
will help attain the DQOs:
Standard chain-of-custody procedures
- Analytical testing will be performed according to approved laboratory
methods with data packages prepared that are consistent with Level 2 protocol
(a Level 3 and 4 CLP protocol may be required in some instances).
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3.9, fey! 'ess
Measurements will be made so that analytical results are as representative as
practical of the actual field conditions. Sampling protocols will be utilized to help
assure that samples collected are reasonably representative of the media present in
the field, Appropriate sample handling protocols, including such tasks as storage,
transportation, and preservation, will be used to protect the representativeness of the
samples gathered during the project. Proper documentation in the field and the
laboratory will verify whether protocols have been followed, and whether sample
identification arid integrity have been preserved.
Representativeness will be assessed also by comparing the results of co-located
samples to determine the spread in the analytical results. The results of QC blanks
will be examined for evidence of contamination unrelated to the Site on sampling
activities. Such contamination may be cause for invalidation or qualification of
affected samples. Sample analytical data classified as "questionable" or "qualitative"
by any of the above criteria may be invalidated.
It is also anticipated that CTEH sampling activities in some instances may be
conducted in cooperation with EPA or other agency personnel. If available, results of
co-located samples may be evaluated to address representativeness of samples.
3.10, Completeness
The characteristic of completeness is a measure of the amount of valid data (or
samples) obtained as compared with the amount that was specified to be obtained
under normal conditions. The objective for completeness is to provide enough valid
data to ensure the goals of the field investigation are met. Completeness will be
evaluated for each sampling event specified relative to each activity on an individual
basis.
3.11, Comparability
The characteristic of comparability expresses the confidence that one set of analytical
data may be compared with another. Data sets that can be used for comparison
include results of studies conducted previously in the area. Comparability is
maintained by use of standard analytical methods, and units consistent with those
used in previous studies. Also, the personnel involved in data acquisition and
reduction must operate measurement systems within the calibrated range of the
particular instrument as well as utilize analytical methodologies that produce
comparable results. The comparability of field investigation tasks will be maintained
by following the applicable EPA Technical Guidance documents, and/or the applicable
Work Plan.
Analytical testing will be performed according to the methods outlined in the
approved Work Plans.
University of A i k a n » a i f o r M e d l eI S c it; n c e s B i o v e otures Prog r a m Associate
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4. SAMPLING PROCEDURES OJD ! itLO H'iLA5Uirth(VlENTS
The objectives of air sampling procedures and field measurements are to obtain
samples and measurements that are representative of the environment being
investigated. Through the use of proper sampling tools, sampling techniques, and
equipment decontamination procedures, the potential for cross contamination due to
trace levels of chemicals will be reduced. These procedures are described further in
the individual Work Plans.
5. SAMPLE HANDLING A!! IN, AND CUSTODY
The purpose of specific procedures for sample handling, documentation and custody
is to maintain the integrity of samples during collection, transportation, analysis and
reporting. These procedures are necessary to validate the history of sample data,
from collection through reporting, by providing adequate documentation. The
sampling handling, documentation and custody procedures are provided in the
individual Work Plans. QA/QC checks will be performed during the field activities to
assess whether the procedures elaborated in the Work Plans are followed. An
appointed representative will perforin the QA/QC check prior to packaging the
samples and transportation to the designated laboratory.
Qualified laboratories will perform chemical sample analyses of samples collected
under the direction of CTEH. Each laboratory maintains an internal Quality Assurance
Plan, These plans include the respective laboratory's internal QA/QC procedures that
cover all aspects of QA/QC during implementation of laboratory procedures. The
technical quality systems that are described in the Quality Assurance Plans include the
following;
Personnel Qualifications and Training
Demonstration of Capability
Standard Operating Procedures
Documentation and Record-Keeping
- Analytical Test Methods and Procedures
Method Detection Limits
Method Quantitation Limits and Reporting Limits
- Traceability, Preparation of Standards, and Reference Materials
Measurement Process
QC Samples
Control Charting
Performance Evaluation
- Corrective Action
Preventative Maintenance
Sample Handling and Management
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In addition, the plan includes the following information that will be utilized for this
project;
Test Procedures and Standard Operating Procedures Performed
- Data Quality Acceptance Criteria
Calibration and QC Requirements
Containers, Preservation, and Holding Times
Instrumentation, Software, and Applications
Preventative Maintenance Schedule
- Training Certification Statements
The Galson Laboratories QAPP has been reviewed and are available from the lab upon
request.
v)i - r / PROCEED * JU fit! U U ' )V» •
This section describes the general QA/QC procedures related to field activities during
the collection, handling, labeling, packaging, preservation, and custody of samples for
chemical analysis, Specific procedures for field activities are described in the
individual Work Plans. Field QA/QC samples will be used to verify that the sample
collection and handling process has not affected the quality of samples that will be
subjected to chemical analyses. This section discusses the preparation and collection
frequency of field QA/QC samples constituting of blanks and duplicates. This section
also provides a general guidance on maintaining QA/QC on the subsequent activities
to ensure the goals of the field activities are met.
7.1. Internal Quality Control
Field QA/QC samples will follow the procedures set forth below and in accordance
with the individual Work Plans. The required analyses and the amount of sample
needed to complete the analyses will be evaluated prior to the initiation of the
sampling event. The required quantity of sample matrix to perform all the analyses
will be collected.
Co-located Samples - True duplicates of many media types are not typically possible
because chemical constituents are rarely distributed uniformly in the media, even
within small volumes. For this reason, duplicate samples collected during this project
will be referred to as co-located samples. They are samples that are collected at the
same time and place.
Co-located samples will be collected for each media type at a rate of approximately
10% of samples collected or at least 1 duplicate sample per day per media type,
whichever is greater. US EPA region 5 has been invited to shadow field operations and
will collect co-located samples at a rate that they determine necessary.
7.2. Equipment
Appropriate tools and equipment will be utilized for collecting samples during the
field investigations. Using the correct equipment for sampling is important in meeting
University of Arkansas for Medical Sciences Bioventurcs Program Associate
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the objectives of QA/QC. Laboratory supplied equipment such as sample containers
are generally imcontaminated. However, a simple visual QA/QC check of any
containers in cases that were opened may identify certain potential issues. Sample
labels will be clearly printed in waterproof, indelible ink and placed directly on the
sample container(s).
7.3. Sampling Equipment Decontamination
No sample equipment decontamination procedures are anticipated for this project.
7.4. Calibration, Operation and Maintenance
Instruments and equipment utilized for field measurements will be calibrated in
accordance with the frequency requirements and instrument manufacturer's
instructions. More frequent calibration may be performed if deemed appropriate.
Appropriate methods and calibration material (gases, etc.) will be used and the
procedures documented in the field records. The field measurement instruments will
be operated and maintained in accordance with the manufacturer's instructions and
industry standard specifications/procedures in order to maintain the consistency and
reliance of the measurement capacity of each instrument.
"" * zj. I" I 1 CI . j ?j1 C U}"i ii'k \ tl\.
Field logs, documentation forms, and calculation work sheets utilized during the field
investigations will be maintained accurately and in accordance with the requirements
of the individual Work Plans. Field logs and form may be collected in electronic
format, if deemed appropriate. Copies of paper field logs will be included in the
project reports as appropriate.
7.6. Procedures to Assess Precision, Accur3cy, Completeness siici
Comparability
No quantitative levels for precision and accuracy have been specified for field
measurements. However, proper maintenance and operation of instruments will be
followed to ensure instrument accuracy so that reliable results will be obtained.
Multiple readings and analysis of duplicate samples will be performed to measure the
precision of field measurements.
Vj 'sccive Aioo!!
If QA audits of data result in identification of unacceptable data, the field sampling
project manager will be responsible for developing and initiating corrective action.
Corrective action for sampling procedures may include evaluating and amending
sampling procedures or re-sampling.
Reduction of laboratory measurements and laboratory reporting of analytical
parameters will be in accordance with the procedures specified for each analytical
University of Arkansas for Medical Sciences Bioventures Program Associate
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method (i.e., perform laboratory calculations in accordance with the method-specified
procedure). Upon receipt of the laboratory data, the data will be processed according
to the Data Management Plan (DMP) included as Appendix B,
8.2, F 5 e i d iVi e a s u r e vn s? n I D « ia
Project data personnel will perform assessment of field measurement data. Data
assessment will be performed (as appropriate) by checking calibration procedures
utilized in the field, evaluating duplicate and control sample analyses, and by
comparing the data to previous measurements obtained at the specific location. Large
variations, depending on matrix type, will be examined in association with changes in
local conditions and general trends. In some instances, instrument drift or
malfunction may be detected. If this is apparent, the data may be disregarded, but a
record of the evaluation will be maintained in the project records. If variations in data
cannot be explained, the data will be qualified and will be used for appropriate
purposes.
^ < J j'J '!'' i Field Systems j%ti€irt
Field auditors will visit field sampling teams periodically to observe the designated
control procedures that are set forth in this document and in the individual Work
Plans. These audits will address whether field tools, analytical instruments, and
reporting processes are selected and used to meet the requirements specified by the
project objectives stated in this plan and other project Work Plans. Equipment and
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facilities provided for personnel health and safety will also be evaluated. Calibration
and documentation procedures for instruments used in the field will receive special
attention. Field documentation and sample custody records will be reviewed. During
the audit, the sampling manager will review data handling procedures with the
appropriate personnel. Accuracy, consistency, documentation, and appropriate
selection of methodologies will be discussed,
9.2. Laboratory Audit
Laboratory audit procedures are described in the DMP.
10. CORRECTIVE ACTION
Corrective or preventive action is required when potential or existing conditions are
identified that may have an adverse impact on data quality. Corrective action can be
immediate or long terra. In general, any member of the project staff who identifies a
condition adversely affecting quality can initiate corrective action by notifying in
writing their supervisor or the sampling manager. The written communication will
identify the condition and explain how it may affect data quality.
Corrective action in the field is the responsibility of the on-site staff. This includes
reviewing the procedures to be followed prior to sampling events and checking the
procedures taking place after the sampling event is completed. Corrective action with
regard to laboratory analyses are the responsibility of the selected laboratory.
10,1, Immediate Corrective Action
This type of corrective action is usually applied to spontaneous, nonrecurring
problems, such as instrument malfunction. The individual who detects or suspects
nonconformance to previously established criteria or protocol in equipment,
instruments, data, methods, etc., will immediately notify his/her supervisor. The
supervisor and the appropriate task leader will then investigate the extent of the
problem, if any, and take necessary corrective steps.
If a large quantity of data is affected, the sampling manager must prepare a
memorandum to the Ql. These individuals will collectively decide on a course of
action to correct the deficiencies while the project continues to proceed. If the
problem is limited in scope, the task leaders will decide on a corrective action
measure, document the solution, and notify the sampling manager,
i.O,{.;.cs /{-cLjye
Long-term corrective action procedures are devised and implemented to reduce the
potential for the recurrence of a potentially serious problem. The sampling manager
and the QI will be notified of the problem and will conduct an investigation to
determine the severity and extent of the problem. Corrective actions may be initiated
as a result of other activities such as audits.
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The sampling manager will be responsible for documenting all notification,
recommendations, final decisions, and notifying project staff and implementing the
agreed upon course of action. The development and implementation of preventive
and corrective actions will be timed, to the extent possible, to minimize any adverse
impact on project schedules and subsequent data generation/processing activities.
However, scheduling delays will not override the decision to correct the data
collection deficiencies before proceeding with additional data collection. The
sampling manager also will be responsible for developing and implementing routine
program controls to minimize the need for corrective action.
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Appendix C
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CTEH. LLC,
Data Management Plan
Enbridge Pipeline Release Environmental Sampling Data Management Plan
1
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CTEH, LLC,
Data Management Plan 1
1. Executive Summary 3
2. General Information 3
2.1 Background 3
2.2 Special Considerations 3
2.3 Data Management Plan (DMP) Revision History 3
3.1 Real-Time Monitoring Data 3
3.2 Sampling and Analytical Data 4
3.3 SIERA Data 4
3.4 EPA Data 4
3.5 Roles and Responsibilities 4
3.6 Backup 5
4. Data Collection 5
4.1 Field Data Collection Methodology and Data Deliverables 5
4.2 Data Collection SOP's and Checklists 6
5.1 Data Processing 6
5.2 Scribe Import Mappings 7
5.3 Data Element Dictionary 7
5.3 Entity Relationship Diagram 8
5.4 Database Inventory 8
7. Data Verification and Validation 10
7.1 Verification SOP's and Checklists 10
7.2 Data Verification 10
7.2.1 Level II Laboratory Data Report ID
8, Data Analysis and Reporting 11
8.1 Data deliverables 11
8.2 Reporting Requirements 11
8.3 Reporting SOP's and Procedures....... 11
8.4 SQL Reporting Queries: 11
8.5 GIS / Spatial Data Visualization Requirements 11
8.8 Site Specific Requirements 11
Appendix A 12
Appendix B 15
Appendix C 1
Table 1 Field Data Collection Methodology and Data Deliverables 5
Table 2 Data Processing.......................... .6
Table 3 Monitoring Data Elements.......................................... 7
Table 4 Air Sampling Data Elements 8
Table 5 Database Inventory 8
Table 6 Data Communication 9
Enbridge Pipeline Release Environmental Sampling Data Management Plan 2
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CTEH, L.L.C,
Enbridge Pipeline Release
Environmental Sampling Data Management Plan
1. Exeeyfi ; n mrrwy
This plan describes the initial data management needs and workflow for the air sampling
activities being conducted by CTEH for the Enbridge Pipeline Release in Marshall, Ml.
iae-nora' imeimcuam
< Baciuyound
Center for Toxicology and Environmental Health, L.L.C. (CTEH®) was requested to respond in
support of site operations for the Enbridge Energy crude oil release on Monday, July 27, 2010.
CTEH® is providing air monitoring, air sampling, and toxicology support to address public health
concerns resulting from the crude oil spill, CTEH® has been conducting community air
monitoring and sampling in communities to protect human health.
2.2 Special Considerations
CTEH is collecting approximately 1,000 data points per day, spanning a.geographic area along
the Kalamazoo River from Marshall, Ml to Greater Galesburg, ML There are over 10 teams
working around the clock collecting samples in this area. Managing data in this scenario
requires consistent communications to the project managers, field teams, and data
management team.
Currently EPA Region 5 is independently managing their data. CTEH will also operate in this
fashion, maintaining a local master Scribe database which is published to the merged
Scribe.NET.
2,3 Data Management Plan (DMP) Revision History
M
ion
on
¦
Date
evis
¦
Jlease
(1.0)
8/1/2010
Anton Avguchenko
NA
3,1 Real-Time Monitoring Data
CTEH field personnel retrieve readings from hand-held air monitoring devices and enter them
into their Motorola MC-55 Enterprise Digital Assistant (MC-55 EDA). After each monitoring data
point is entered they are synchronized to CTEH's off-site data warehouse.
Enbridge Pipeline Release Environmental Sampling Data Management Plan
3
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CTEH, LLC.
3,2 Sampling anil Analytical Data
Field analytical data is collected on paper forms and entered directly into Scribe. Meta
information about each sample is collected and synchronized using MC-55's (sample ID,
latitude, longitude, station name, sample date/time).
5.') Sit m i Mia
Sample Instrument Event Receptor Awareness (SIERA) is a program developed by CTEH to
provide situational awareness to a project. Field personnel utilize SIERA to geographically tag
photographs, establish sampling locations, and document important events. SIERA data points
are collected on a MC-55 and synchronized to CTEH's off-site data warehouse.
3.4 EPA Data
EPA Region V is individually maintaining on-site Scribe databases. Their data is published to
the centralized Scribe.NET database being maintained by EPA's Environmental Response
Team (ERT).
3,6 Roles .and Rc-sponsihiikws
Field Sampling Personnel.
• Operate and maintain the sampling and monitoring equipment
• Collect samples
• Input data into MC-55 EDA.
Sample Handling Personnel:
• Package and ship samples to laboratory
• Generate Chain of Custody (COC)
• Input field sample data into on-site Scribe database
Site Data Manager(s):
• Maintain on-site Scribe database by importing lab EDO's
• Monitoring and field sampling data from CTEH Data Warehouse and SIERA
data.
QAQC Team:
• Assist with data processing
• Perform quality control by checking for completeness and accuracy
• Interviewing field personnel to resolve data issues.
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CTEH, LLC.
3.8 Backup
Daily backups are performed on-site to a removable storage drive using off-the-shelf
commercial backup hardware and software. Every evening an off-site dump is performed to
CTEH's corporate file server over the network. Nightly, CTEH's fileserver is backed up to tape
and stored off-site.
Table I Field Data Collection Methodology and Data Deliverables
I M Bii
LfdLci UOHWOIIUII
¦¦¦¦¦
File Type Comments
Real-Time Air
Monitoring
-
MultiRAE
Input direct
read-out into
MC-5S EDA
Download from
CTEH Data Ware-
house, import into
Scribe
.CSV
Real-Time Air
Monitoring
Gastec Color
metric Tubes
Input direct
read-out into
MC-5S EDA
Download from
CTEH Data Ware-
house, import into
Scribe
.CSV
Real-Time Air
Monitoring
UltraRAE
Input direct
read-out into
MC-55 EDA
Download from
CTEH Data Ware-
house, import into
Scribe
.CSV
Air Sampling
Summa
Input field sam-
pling data into
MC-55 EDA, fill
out paper field
forms
Download from
CTEH Data Ware-
house, import into
Scribe
.CSV
Air Sampling
Passive Do-
simeter
Fill out paper
forms
Download from
CTEH Data Ware-
house, import into
Scribe
CSV
Air Sampling
Sorbenf Tube
Input field sam-
pling data into
MC-55 EDA, fill
out paper forms
Download from
CTEH Data Ware-
house, import into
Scribe
CSV
Photos
Digital Image
MC-55 EDA
Synchronized to
CTEH Data Ware-
house
•jpg
Available
through CTEH
Data Warehouse
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4.2 Data Collection SOP's and Checklists
See Table 1 for data collection SOP's. Additional data streams will be added to the table as they
are identified.
5. Data Management
5.1 Data Processing
Table 2 Data Processing
Monitoring,
Sampling, or
Analytical Type
Instrument or
Method
Data Collection
Tool
Data Processing
Instructions
File Type
Comments
Real-Time Air
Monitoring
MultiRAE
Input direct
read-out into
MC-55 EDA
Download daily CSV
in Scribe format,
import using custom
Scribe import for
Monitoring Data.
.CSV
Real-Time Air
Monitoring
Gastec Color
metric Tubes
Input direct
read-out into
MC-55 EDA
Download daily CSV
in Scribe format,
import using custom
Scribe import for
Monitoring Data.
.CSV
Real-Time Air
Monitoring
UltraRAE
Input direct
read-out into
MC-55 EDA
Download daily CSV
in Scribe format,
import using custom
Scribe import for
Monitoring Data.
.CSV
Air Sampling
Summa
Input field
sampling data
into MC-55
EDA, fill out
paper forms
Enter sample ID,
date/time and
location information
directly into Scribe
GUI.
.CSV
Handwritten field
forms are
faxed/emailed by
field personnel to
site data manager.
Air Sampling
Sorbent Tube
input field
sampling data
into MC-55
EDA, fill out
paper forms
Enter sample ID,
date/time and
location information
directly into Scribe
GUI.
.CSV
Handwritten field
forms are
faxed/emailed by
field personnel to
site data manager.
L
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Monitoring,
Sampling, or
Analytical Type
Instrument or
Method
Data Collection
Tool
Data Processing
Instructions
File Type
Comments !
Photos
Digital Image
MC-55 EDA
•jpg
Photos are
geographically
tagged as well as
associated with
specific samples
and instrument
locations
5.2 Scribe Import Mappings
Real-time air monitoring data is exported from the CTEH Data Warehouse using a custom
designed format with native Scribe field names. Analytical results from each laboratory are
imported after verification and/or validation using a custom import mapping. See appendix A for
mapping.
5.3 Data Element Dictionary
The tables below identify what should be considered the minimum data requirements for the
identified data source. These elements may increase or have their description changed as a
result of a change in operational requirements. A complete list of all data elements in Scribe can
be found at http://www.epaosc.org/scribe.
Table 3 Monitoring Data Elements
Scribe Fields
Description
Type
Length
Primary Key?
Req?
Mon_Time
Monitoring Time (hh:mm:ss)
Text
30
PK
Yes
Mon_Parameter
Pollutant
Text
30
PK
Yes
Mon_Date
Monitoring Date (Required)
DateTime
0
PK
Yes
Location
Monitoring Location Code (Required)
Text
30
PK
Yes
InstrumentID
Instrument ID (Required)
Text
50
PK
Yes
Mon_Operator
Organization That Collected the Sam-
pling
Text
50
No
No
Mon_Measurement
Monitoring Measurement
Numeric
0
No
No
Mon Meas Units
Monitoring Measurement Units
Text
40
No
No
EventID
Identifies the date of the reporting pe-
riod and the start/stop time a value is
associated with
Text
50
No
No
Latitude
Latitude
Numeric
0
No
No
Longitude
Longitude
Numeric
0
No
No
Coord_Sys_Desc
Coordinate System
Mon_Qualifier
Monitoring Criteria such as detection
limit; action limit or other criteria
Text
10
No
No
Mon_Remark
Monitoring Data Remark
Text
255
No
No
Mon_Source
Describes the averaging period of the
result (ie 1-hr avg)
Text
50
No
No
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Table 4 Air Sampling D«i(a Elements
Samp_No
Sample Number. Scribe requires
a unique sample number (Re-
quired)
Text
25
PK
Yes
Location
Sampling Location Code (Re-
quired)
Text
30
No
Yes
EventlD
EventlD. Use to group data by
sampling events. Defaults to
'Sampling' (i.e. EOC; Site As-
sessment)
Text
50
No
No
Latitude
Latitude
Numeric
0
No
No
Longitude
Longitude
Numeric
0
No
No
Matrix
Sample Matrix (i.e. Air; Vapor)
Text
40
No
No
SampleCoileetion
Sample Collection Method (i.e.
Grab; Composite; Discrete Inter-
val)
Text
30
No
No
SampleDate
Date Sample Taken
DateTime
_ 1
No
No
SampleMedia
Sampling Media (i.e. Summa
Canister)
Text
30
No
No
Sampler
Sampler Name
Text
30
No
No
SampleTime
Time Sample Taken (hh:mm)
Text
5
No
No
SampleType
Sample Type (i.e. Field Sample;
Field Duplicate; Lab QC; Spike;
Trip Blank)
Text
30
No
No
Total Time
Total Sampling time
Numeric
0
No
No
Volume
Air Sampling Volume. Wipe
Sampling Area.
Numeric
0
No
No
Volume Units
Volume Units
Text
20
No
No
£ I
.ongth
5.3 Entity Rslatieuslv^ s'S .grain
See Appendix B
5.4 DaUtlnse inventory
Table 5 Database Inventory
anagor
Eribridge_Oil_SpilI.MDB
Community/Area Air Monitoring, Air
Sampling Data
Anton Avguchertko
Enbridge_Oil_Spill_personnel.MDB
Scribe
Personnel Sampling
Anton Avguchenko
Enbridge_arearae.mdb
MS Access
Community AreaRAE sampling from
initial response phase
Anton Avguchenko
Enbridge_Oil_Spill_reporting.MDB
MS Access
Staging/Reporting for
Community/Area Air Monitoring, Air
Sampling Data
Anton Avguchenko
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6. Data Communication
Table 6 Data Communication
Data Source
Owner
Contains
Communication
Method
Data
Release
Frequency
Comments
Real-Time Air
Monitoring
MultiRAE
Input direct read-
out into MC-55
EDA
Download daily CSV in
Scribe format, import
using custom Scribe
import for Monitoring
Data.
.CSV
Real-Time Air
Monitoring
Gastec Color
metric Tubes
input field
sampling data into
MC-55 EDA
Download daily CSV in
Scribe format, import
using custom Scribe
import for Monitoring
Data.
.CSV
Real-Time Air
Monitoring
UltraRAE
Input direct read-
out into MC-55
EDA
Download daily CSV in
Scribe format, import
using custom Scribe
import for Monitoring
Data.
.CSV
Air Sampling
Summa
Input field
sampling data into
MC-55 EDA, fill
out field forms
Enter sample ID,
date/time and location
information directly into
Scribe GUI.
.CSV
Handwritten field
forms are hand
delivered by field
personnel to site
data manager.
Air Sampling
Sorbent Tube
Input field
sampling data into
MC-55 EDA, fill
out field forms
Enter sample ID,
date/time and location
information directly into
Scribe GUI.
.CSV
Handwritten field
forms are hand
delivered by field
personnel to site
data manager.
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CTEH, L.L.C.
Data Source
Owner
Contains
Communication
Method
Data
Release
Frequency
Comments
Photos
Digital Image
MC-55 EDA
•jpg
Photos are
geographically
tagged as well as
associated with
specific samples
and instrument
locations
7. Data Verification and Validation
7.1 Verification SOP's and Checklists
See Appendix C
7.2 Data Verification
Prior to import into Scribe, all analytical data will go through level II data verification by third
party. The following Quality Assurance/Quality Control (QA/QC) parameters are reviewed
during level II:
Chain-of custody: completeness and sample custody
Holding time: time of collection to time of sample preparation and analysis
Preservation: temperature and chemical
Blank Contamination: laboratory and field blanks
Matrix: precision and recovery of matrix spikes, laboratory control samples, duplicates and
system monitoring compounds (Organics)
7.2.1 Level II Laboratory Data Report
Level II data reports will also be delivered with the EDD's from the laboratories. The project
laboratory will provide reports as a deliverable suitable for data verification. Each data validation
package will include, but is not limited to, the following information for review:
Case Narrative,
Chain-of-Custody,
Method blank summary,
Matrix spike/matrix spike duplicate summary,
Laboratory control sample recovery summary,
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CTEH, LLC,
System monitoring compounds recovery (Orgariics)
A hard copy and an electronic disk deliverable of the analytical results, consistent with the
format specified by the data validator, will be issued by the laboratory. The samples to be
included in each SDG will be efficiently grouped such that holding times are not jeopardized for
any of the analyses.
8. Daia An .vh*»
3.' Data il^JverabSst*-.
Unified Command (UC), EPA ERT, Enbridge representatives
S,2 Reportinci Requsnwlems
Monitoring, sampling, and analytical data will be stored in a normal fashion. All report and map
products will identify exceedances of action levels setup in the CTEH's Air Sampling Plan.
a.-i KaporniKj Mjp s anci
Developing these will be the responsibility of the initial site data manager and remote support
personnel.
8,4 SQL Reporting Queries:
Developing these will be the responsibility of the initial site data manager
3 h Ok"* / >>H l ViolMiLOEjO1* t
X/lap products are produced using an Arc-Scribe OLE Database Connection to the On-Site
Scribe database.
Required Tools:
• Scribe (3.8.0)
• Computer/Laptop running Windows XP, Vista, Windows 7 OS
• Network connection to internet (for Scribe.NET subscriptions)
• ArcGIS
• Microsoft Access
• Microsoft Excel
• Web Browser (Chrome, Mozilia Firefox, Safari etc.)
Reference Files:
• CTEH Analytical Results to Scribe Import Data Map
• CTEH Real-Time Air Monitoring to Scribe Import Data Map
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Lab Result EDO to Scribe
Data Mappings
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CTEH, LLC,
Gicbai L
be Fields (Destinat
Analysis
Analyte
Result_Units
Samp_No
Analytica!_Method
Basis
CAS_NO
CLP_Sample_No
Comments
Date_Analyzed
Dare Collected
Date_Extracted
Date_Received
Detected
Dilution_Factor
Extraction_Method
Firial_Volume
Final_Volume_Unit
Lab_Batch_No
Lab_Coc_No
Lab_Location_ID
Lab_Name
Lab_Result_Qualifier
Lab_5amp_No
Matrix_ID
MDL
MDL_Units
Percent_Lipids
Percent_Moisture
Percent_Recovery
Percent_Solids
QA_Com merit
QA_Date
QA_UserName
QAFlag
QC_Type
Quantitation_Limit
Quantitation_Limit_Units
Reportable_Result
Reporting_Limit
Reporting_Limit_Units
Result
Result_Qualifier
mport Fields (Sou
Analytical_Fraction
Parameter_Name
Result_Units
Sample_Point_ID
Analytical_Method
CAS_Number_Equivalent
Project_ID
Field_Sample_Classificatiori
Analysis_Date_Time
Sampling_Date_Time
Extraction_Date_Time
Preparation_Date_Time
Dilution_Factor
Retention_Time
InstrumentJD
SDGJD
Site_SampleJD
Laboratory^ ID
Laboratory_Qualifier
Lab_Sample_ID
Matrix
Percent Moisture
Top_Depth
Middle_Depth
Bottom_Depth
Reporting_Limit
Laboratory_Result
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Ibe Fields (Destination) Import Fields (Source)
Result_Type_Code
Sample_Type_Code
SubSample_Amount
SubSample_Amount_Ursit
Test_Type
Total Or Disolved
Analyte_Type
Lab_Sample_Type
Filtration Method
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Appendix B
Entity Relationship Diagram
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CTEH, LLC.
ipendix C
Data Management SOP's and Checklists
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CTEH, LLC.
Data Quality Control for Real-Time Air Monitoring QA/QC SOP
• Log into Samples.cteh.com
• Click "Projects" on the left panel
• Click "40005" on the project list
• Click "Realtime Readings" on the left panel
• Click on QAQ.C Next (#### remaining)
This brings you to your first reading. Review all fields for accuracy. When
complete, click Mark QAQC Complete and Next
Primary fields that require information are;
• Project number
• Reading date (Date should make sense. If a reading has been taken in 2006, this
needs to be corrected.)
• Latitude, Longitude
• Region
• Location Category (description of type of monitoring/work being done)
• Indoor/Outdoor (should always be Outdoor)
• Matrix (should always be Air)
• Instrument - Barcode (make sure it is the instrument serial number, not CTEH
ID)
• Analyta (VOC, S02, H2S, PM2.5, Benzene)
• Concentration (only when positive detection) with Units
• Detection flag (always "<") & Limit - both of these fields should be populated
when there is no positive detection
• Initials
• Comments (will not always be filled, but this is where personnel should note vis-
ible oil or crude oil odor)
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MultiRAK Detection Limits
le
Del eel inn Limit
I n it
VOC
<0,1
PPIB
H2S
<1.0
PPM
S02
<0.1
J®™
UltraRAE Detection Limits
MitWTIfK 1
IVicelion I.imil
QQgH
Benzene
1 ppm 1
Gastec Tube Detection Limits
1 ube #
Dcleetinii l imit
Volume
t. nil
Benzene
121L
<0,05
500mL1
ppm
Benzene
12 ISP
<0.1
300m L
ppm
If a chemical does not have a positive detection, the concentration should never
be reported as "0.0." Instead, the detection limit for that chemical should be used
based on the sampling equipment used. Particulate matter should always have a
concentration.
Enbridge QA
This is a selection on the main page under each project number in Samples. It
will take you to a site that has been designed to display the readings for that day
that fit certain parameters, such as being VOC detections, incorrect detection
limits and missing barcodes. These readings should be the top priority for the
QA/QC for that day, although all readings should be GA/GC'd on a daily basis if
at all possible.
Changing/Adding information in records;
Information will sometimes need to be changed and/or added during the QA/QC
process. When this occurs please note what information was changed or added
in the QA/QA comments box. You should also add what prompted the change (ie
talked with personnel to correct information).
Quality Flag:
Sometimes a reading will be determined to be not of good quality due to
equipment problems, personnel error or some other issue. This drop down box
will add a qualifier that will make that reading not included in the reportable data.
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CTEH, L.L.C.
There are classifications, for not usable, drift, non-sustained, or sustained. These
will cover various scenarios.
Calling field personnel/supervisors;
We will often need to contact the field personnel and/or supervisors to obtain
more information or to clarify certain information. The phone numbers for
personnel can be found in the Dabble database or on the various organizational
charts. Please note in the QA/QC comments that the information was obtained
from an interview with field personnel and/or supervisors.
Load Failures:
Occasionally the readings will get hung up in the samples system due to an entry
that is not recognized by the system. These will be placed into the Load Failures
section on the main page. These readings will need to be opened, then scroll to
the bottom to see the reason for the load failure. This will need to be corrected
and then the reading will be processed along with the other samples from that
day. This should be checked several times a day.
Enbridge Pipeline Release Environmental Sampling Data Management Plan
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Appendix D
University of Arkansas for Medical Sciences Bioventures Program Associate
-------
CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C,
Toxicology Emergency Response Program (June 3, 2008)
STANDARD OPERATING PROCEDURE NO. (Version 1.1)
SUBJECT: SKC Universal Pump Model 224-PCXR8 (5 to 5,000 mL/min)
Description of the SOP: This procedure is intended to provide instruction on the
proper use of SKC Universal Sample Pump yodel #224-PCXRA for analytical air
sampling.
Calibration Instructions;
1, There are two settings for the pump, high flow (£500 ml per minute) and low flow
(<500 ml per minute). To adjust it to high flow or low flow un-screw the smaller
copper colored screw located on top of the pump (Figure 1 #18) and you will see a
slotted screw (set screw).
2. For high flow sampling:
a) Turn the set screw (Figure 1 # 18) in a clockwise position all the way
down and replace the copper colored screw to the top of the pump.
b) Attach an approximately 3 foot piece of plain Tygon tubing to the pump
intake (Figure 1 #13) on the right hand side of the pump.
c) Place air sampling media on the end of the tubing not attached to the
pump (insure proper directionality of sampling media), with the arrow on
the media pointing towards the tubing.
d) Use a Bios Drycal or DC- Lite to attach to the open end of the air
sampling media.
e) Turn on the SKC pump using the black toggle switch (Figure 1 #8) on the
front of the pump.
f) Adjust the flow rate using the small set screw on the front of the SKC
pump labeled "flow adjust" (Figure 1 #11) to the desired flow rate. To
increase the flow rate, turn the set screw clockwise. To decrease the flow
rate, turn the set screw counterclockwise. Continue to adjust flow rate
until calculated flow rate has been achieved. Write your pre-cal on the
analytical data sheet (see example).
-------
3. For low flow sampling:
a) Without any Tygon tubing attached to the pump, turn the set screw
(Figure 1 #18) in a clockwise position all the way down.
b) Using the set screw (Figure 1 #11) and the flow indicator on the front of
the SKC pump (Figure 1 #17); adjust the ball so that it is approximately at
1.5.
c) Turn the set screw on top of the pump (Figure 1 #18) counterclockwise 5
full turns and replace the copper colored screw.
d) Attach a piece of Tygon tubing to the pump intake (Figure 1 # 13) located
on the right hand side of the pump.
e) An "adjustable low flow holder," (Cat. No. 224-26-01, 224-26-02, 224-26-
03, 224-26-04 for single, dual, tri, and quad, respectively) should be
attached to the free end of the Tygon tubing.
I .
4 ii
1 f* IT *
Cat. No. 224-26-01 Cat. No. 224-26-02 Cat. No. 224-26-03
f) Place air sampling media on the end of the tubing not attached to the
pump (Insure proper directionality of sampling media).
g) Use a Bios Drycal or DC-Lite to attach to the open end of the air sampling
media.
h) Turn on the SKC pump using the black toggle switch on the front of the
pump (Figure 1 #8).
i) Adjust the air sampling flow rate using the set screw located on the
adjustable low flow holder to the desired flow rate. To increase the flow
rate, turn the set screw clockwise. To decrease the flow rate, turn the set
screw counterclockwise. Continue to adjust flow rate until calculated flow
rate has been achieved. Write your pre-cal on the analytical data sheet
(see example).
-------
Equipment Use Instructions (step by step)
This instrument has six keys on the front that perform a variety of functions. The
following is a review of each key function:
1. The top left hand key is labeled "START/HOLD." When the pump is turned on, push
the "START/HOLD" key to pause the pump, the screen will say hold (no air will be
pulled through the sampling media). To restart the pump, push the key again.
2. With the pump on hold, press the SET-UP key to enter the "Delayed Start" mode.
Enter the number of minutes delay before the sampling period begins by pressing
the DIGIT SELECT and DIGIT SET keys. The DIGIT SELECT key advances the
flashing digit and the DIGIT SET key increases the value of the flashing digit.
3. Press the MODE key to enter the "Sample Period" mode. Press the DIGIT SELECT
and DIGIT SET keys to enter the sampling time period in minutes.
NOTE: The sample period is the total time of the sampling evert.
4. Press the MODE key to enter the "Pump Period" mode. This is the actual running
time of the pump. Use the DIGIT SELECT and DIGIT SET keys to enter the pump
run time in minutes. If intermittent sampling is not desired, set the sampling period
equal to the pump period.
NOTE: The pump period is the time in which the pump is actually pulling air through the
media. Pump period is always equal to or less than the sample period.
5. Press the start button to begin sampling.
-------
Figure 1
Cassette Notes: When using cassettes, the calibration will require a hose with an
adaptor tip to insert into the cassette. The cassettes generally require holders, make
sure the side of the cassette the air comes in through says inlet.
Placement Notes:
-Pump should be set up so the media is at breathing level.
-Tubing should not be pinched or crimped by position.
-Media should be horizontal to maximize exposure.
-Media should be facing downwards to discourage moisture build up.
-Always cover the pumps if rain is likely. However, media should still be exposed
to the outside air. Be sure to tape the sample tag and use a tube cover if
applicable.
-If not at an AreaRAE station, make sure to GPS the location for later mapping.
Media Note:
-Some analytes require the use of a tube and a cassette.
-Example: PAH sampling. The air is first pulled through a cassette, which
is connected to a tube.
-------
-Some analytes are sensitive to UV rays, these must be handled a certain way
after sampling.
-Example: PAH. The tube must be wrapped in foil. The cassette must be
pried open using the crescent-ended tool in the media bag. The cassette
filter must be picked up with forceps (also in media bag) and placed into
an amber bottle. It helps to make double labels for the media. One set
on the media, and one set for the bottle and the wrapped tube.
Labeling Note; Especially if rain is expected, using clear tape over the labels will keep
the number from smearing. Always make the sample number is as easy to read as
possible, do not confuse the letter o from the number zero, etc...
Additional Media Needed for This Equipment:
Air sampling media appropriate for the analyte of concern.
Notification Procedures for Equipment Failure:
1. Tiffani Ray
2. Contact SKC Gulf Coast at 1-800-225-1309 and request a Return Authorization form.
Fill it out and ship the damaged equipment with the included form to:
SKC, Inc
Attn: Repair Department
863 Valley View Road
Eighty Four, PA 15330
1-800-752-8472
Specialized Training Required or Recommended:
Chemical specific sampling techniques
References and Further Assistance:
1. SKC Universal Sample Pump Operating Instructions for Cat. No. 224-PCXR8
2. SKC 2004 Comprehensive Catalog & Air Sampling Guide
3. http://www.skcqulfcoast.com/
4. Jack Shriver
9827 Whithorn Drive
Houston, TX 77095
1-800-225-1309
Review Date for this SOP
Emily Schmitz and Ben Gehring; June 3, 2008
CTEH
-------
ssa
-------
CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C.
Toxicology Emergency Response Program (6/17/08)
STANDARD OPERATING PROCEDURE NO. {Version 1.1)
SUBJECT: MuitiRAE Plus
Description of the SOP. This SOP describes the set-up and use of the MuitiRAE Pius.
Calibration Instructions: Calibration should be done at least once a shift.
To get to Calibration Screen
1) Turn on MuitiRAE by pressing and holding the MODE button. Wait for the instrument to
warm up.
2) To get to the calibration screen press the MODE and "No" buttons at the same time.
Hold until screen says "Calibrate Monitor", press Y/+.
3) When the message "Fresh Air Calibration?" appears, make sure before pressing Y/+ you
have either a fresh air environment or are using zero grade air. When calibrating sensors
for the first time, do not Fresh Air calibrate.
For Multiple Sensor Calibration
1) To calibrate multiple sensors at the same time in the MulitRAE, select Y/+ at the multiple
sensor calibration screen.
2) To accept these chemicals for multiple sensor calibration, press Y/+
3) To change the chemicals for the multiple sensor calibration, press HI- at the "OK?"
screen
4) The "Pick" screen will appear, To choose other sensors, press MODE scroll from one
sensor to the next and press Y/+ to select a sensor and N/- to deselect a sensor.
5) An asterisk (*) will appear by the sensors that are selected to be calibrated with the
multiple sensor calibration.
6) The instrument will recognize the Calibration gas and begin counting down from 59
seconds.
7) After 59 seconds, the instrument will show "Calibration Complete"
NOTE: Quad gas allows for the calibration of CO, HaS, 02, arid LEL.
1) To calibrate single sensors, select y/+ at the single sensor calibration screen.
2) Use the MODE button to navigate between sensors. Press Y/+ to select the sensor.
-------
3} After pressing Y/+ on the VOC sensor, the MultiRAE will ask you to Apply Gas =
Isobutylerie.
4) When you apply the calibration gas to MultiRae, it will begin a countdown from 59 sec.
5) At the end of the 59 sec., the instrument will show ''Calibration Complete, Turn off cal
gas"
NOTE: The MultiRae is set to calibrate to a specific concentration of calibration gas. For
each sensor, the calibration gas and concentration will be different.
Using a Different Calibration Gas: If you need to calibrate your instrument with a calibration
gas that is not sold to you by Rae Systems, you will need to check the span gas value which
should equal concentration of the calibration gas.
1) To modify span gas value, press Y/+ when the "Modify Span Gas Value" screen appears.
2) Use the MODE button to scroll from digit to digit and the Y/+ and N/- buttons to adjust
values.
3) Before calibration, the span gas values need to represent the calibration gas
concentrations.
Bump Calibration: This is done to check a sensor's function; this does not take the place of a
standard calibration.
1) Can be done in either diagnostic mode in the raw screen or in standard mode in the
readings screen.
2) Attach the calibration gas that coincides with that sensor to the MultiRAE
3) Expose the instrument to the gas (example: isobutylene to check VOCs)
4) Watch the readings and make sure they reach the correct value. (RAW values have an
acceptable range. The ranges for the most commonly used sensors will be provided at
the end of the SOP)
NOTE: Always record a calibration in the calibration log, there will be an example form at
the end of the SOP.
NOTE: Always calibrate the instrument in the environment it will be used in. If there is too
large a change in humidity arid temperature, the instrument will not react properly
NOTE: There are special case calibrations for some sensors.
Example: HCI and HF sensors. These sensors have a 4 minute calibration time.
NOTE: Some sensors need to be "burned in" for a period before fully operable.
Example: Cl2, HCL, HF, NO, NHS sensors: There "burn in" periods are recommended to
be between 12-24 hours.
-------
Equipment Use Instructions {step by step)
Battery Replacement and Monitor Start Up
1) Remove the water trap, if applicable, from the inlet, (replace water trap if there is visible
dirt or it has been in humid environment)
2) Remove the instrument from its casing.
3) Loosen the screws on the backside of the instrument and remove the front cover.
4) Replace the batteries, and screw the cover back on.
5) Press and hold the mode button until the monitor comes on.
6) Place the instrument back into its protective cover and put the water trap back on unless
you are using chemical sensors which call for the water trap to be left off (see MultiRAE
handbook for list of sensors).
7) Allow the MultiRAE to go through its startup procedures.
User Mode- Main Screen Menus
1) While the Instrument is showing readings, press MODE to scroll through the main
screens
2) Press MODE once to view the PEAK value.
3) Press MODE again to view the MINIMUM value.
4) Press MODE again for the STEL values. STEL values are only shown for TOX1, VOC,
and TOX2.
5) Press MODE again for TWA values. TWA values are also only shown for TOX1. VOC,
and TOX2.
8) Press MODE again to view the Battery Power screen.
7) Press Mode once again to view the Date, Time, Temperature, and Time the instrument
was turned on.
8) Pressing MODE again will take you to the "Start Datalog?" Screen. Press Y/+ to Start
Datalog then the screen will display Stop Datalog. When you stop the datalog, this will
complete one event.
9) Press mode once to view the LEL gas= screen. This tells you what calibration gas your
LEL is set.
10) Press MODE once more to view the calibration gas to which the PID is set.
11) Press MODE again for the "Print Reading?" Screen.
12) Press MODE again for the "Communicate with PC?" screen. To download information off
of the Multi Rae to your computer, press Y/+.
-------
Program Mode -_to go into Program Mode, PRESS and HOLD MODE and N/- for 5 seconds. (It
is sometimes easier to hold the N/- button first then hold MODE)
Change Alarm Limits
1) All sensors come from Rae Systems with a default alarm limit,
2) These limits can be found in the "Change Alarm Limits" screen on the Multi Rae.
3) Press mode and no at the same time. Use the mode button to scroll through the menu.
4) When the "Change Alarm Limits" screen appears, select Y/+.
5) You will have the option of changing the High alarm, Low alarm, STEL alarm, and the
Average alarm limits.
6) Press N/- to scroll to the Alarm limit that you would like to change.
7) Select Y/+ on the alarm limit that you intend to change.
8) Use the MODE button to scroll from digit to digit and the Y/+ and N/- buttons to select
digits.
9) To save your changes, hold down the MODE button.
Change Real Time Clock
1) Hit MODE when the command Monitor Setup? appears on the screen.
2) Select "Change Real Time Clock?" to adjust the date and time showing on the MultiRae,
then use Y/+ and N/- to adjust the time,
NOTE: ALWAYS do this, and double check it, before you start a datalog.
View or Change Dataloq
1) Press MODE and N+/ at the same time. Scroll through the menu by pressing the MODE
button,
2) To view or change the Datalog function, press Y/+ at the "View or Change Datalog?"
screen.
3) The first option will be to "Clear all Data?"
4) Select Y/+ to clear all of the data in the datalog memory.
5) The next option is to "Reset the Peak and Minimum?"
6) When you select Y/+ to "Reset the Peak and Minimum?" the Multi Rae wilt prompt "Are
you sure?"
7) Select Y/+ to reset your values that you see when scrolling the main menu.
8) The next option is to Enable/Disable datalog? If a * is displayed next to a sensor name,
data will be recorded. Use mode to move from sensor to sensor. An asterisk (*) means
-------
the sensor is enabled; no asterisk means the sensor is disabled. Press Y/+ to select, and
N/- to deselect. To save changes, press MODE until Save? appears. Then press Y/+ to
accept. Otherwise, hold MODE to escape and cancel changes.
NOTE: Do not datalog an instrument that is in diagnostic mode, it will record RAW values.
Always restart first then begin datalog.
Change Backlight
1) You can change the backlight mode by pressing Y/+ at the "Change Backlight Mode?"
screen.
2) To turn on the backlight, hold the N/- button down.
Change Pump Speed
1) To change Pump Speed continue until Change Pump Speed? appears on screen, Press
Y+/ or N+/ to change speed different than what it is previously set. Once you determine
which speed you prefer then hold the Y+/ to save.
2) Low pump speed- (default) used when operating conditions that are slow
to change, prolongs pump motor life, LEL sensor life and battery run time.
3) High pump speed- use for long lengths of tubing or when rapid changes in input
conditions are expected, such as HazMat response or when used for measuring heavy,
low vapor pressure compounds like jet fuel.
NOTE: Make sure to note it somewhere on an equipment tag when you have changed the
pump speed from a default setting, include your initials and date
NOTE: When using tubing as an extension, we must use Teflon tubing, Tygon tubing
readily absorbs volatiles, especially benzene.
Sensor Configuration
1) Hit MODE and N/+ at the same time.
2) Change LEL/VOC Gas Selection?
3) Enable/Disable Sensors?
4) Sensors have assigned sockets. These are identified on the RGB. High bias toxic in
socket 1/A.
5) Change RID Lamp Type? This only applies to PID monitors. The PID sensor can utilize
either a 10.6 eV or an 11.7 eV UV. Since each lamp type has a different correction factor
table, it is important to select the correct lamp type.
NOTE: 11.7 lamps have a much shorter lifespan, be aware of the expiration elate and leave
Tiffani a note when you mobilize with them.
-------
Using the MultiRAE
1) After recognizing your chemical of concern, look in the technical and application notes
and locate the correction factor for that chemical that corresponds with the lamp in your
MultiRAE
2) When two or more chemicals of concern need to be monitored, a general rule of thumb is
to use the highest correction factor and the chemical with the lowest PEL for action level
purposes.
NOTE: Correction factors are very important, for both the VOC and LEL sensors. Look
through both TN-106 {RID) and TN-156 (LEL).
NOTE: The new NHS sensors are un-biased. However the NO sensors are still high-bias.
How to clean a lamp
1) Acquire a lamp cleaning kit. Make sure it includes cotton swabs, methanol, tweezers.
Gloves can be found in the ER GO BAG if there are none in the kit.
2) Remove the front cover from the instrument.
3) Remove the metal casing from the PID using the tweezers and wearing gloves. Set it
aside
4) Using the tweezers carefully remove the top of the PID housing, it is usually fairly secure,
do not use too much force. Set it aside.
5) Carefully remove the lamp from the base, and securely hold it while you swab with cotton
soaked in the methanol. Be careful not to allow cotton fibers to stick to the lamp.
6) Give the lamp a few seconds to dry, then place back into base.
7) Carefully swab the metal screen in the top of the PID housing, and give it a few seconds
to dry before replacing,
8) Replace metal casing. If it appears dirty, swab with methanol also.
9) Replace cover on the instrument
NOTE: If replacing an expired or faulty lamp, please place the old lamp in box the new
lamp came out of. Mark the box with the serial number and date removed, and return to
Tiffani, It may riot have expired yet and be available for replacement
NOTE: Other than lamp cleaning/replacement or sensor changes, do not manipulate the
other components within the instrument. Red tag the unit and return to Tiffani.
sua
-------
Additional media needed for this equipment: (i.e. calibration gas or
chemcassettes)
MuttiRAE technical and application notes; MultiRAE users manual
Calibration gases appropriate to the sensors being used.
Lamp cleaning kit
Notification Procedures for Equipment Failure {i.e. Kae Systems tech support
number and CTEH contact)
RAE Systems 408.723.4800 CTEH- Tiffani Ray 801.501.8580
RED TAG inoperable equipment properly, example following SOP
References and Further Assistance
Review Date for this SOP
Emily Schmitz and Ben Gehring June 17, 2008
Attachments
Excerpt from TN-123
Calibration Log example
Red Equipment Tag example
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CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, LLC.
Toxicology Emergency Response Program April 14, 2009
STANDARD OPERATING PROCEDURE NO, (1)
SUBJECT: Mini Can or Mini-canister
Description of the SOP. The purpose of this SOP is to instruct the user about proper
methods and operation for collecting a Mini-Can air sample. Upon completion of this
manual the user should be able to collect both a grab sample and a time released air
sample using a Mini-Can air sampling instrument.
Calibration Instructions
1. All cleaning and calibration should be conducted at the laboratory by authorized
personnel.
Grab Sample Equipment Use Instructions (step by step)
1. Ensure that the sampler is not wearing any of perfume, cologne, or aerosol. These
products may affect the sample.
2. Remove protective cap from the Mini-Can sampler tip..
3. Using a grab sample regulator, slide the connection collar back,
4. Position the canister on its side in the direction of the area intended to sample.
5. Insert the sampler tip into the regulator and release the collar. NOTE; There should
not be a gap between the regulator and the canister.
6. Allow the canister ample time to fill (20-30 seconds)
7. Once the canister has been successfully filled with sample air puli back on the
connection collar to release the regulator.
8. Place protective cap on sampler tip.
9. Complete a Chain of Custody form and ship sample in accordance to laboratories
shipment instruction.
Additional media needed for this equipment:
-------
Quick Grab Sample Regulator
Time Released Equipment Use Instructions (step by step)
1. Ensure the sampler is not wearing any sort of perfume, cologne, or aerosol. These
products may affect the sample,
2. Remove protective cap from the Mini-Can sampler tip.
3. Using a time release regulator, slide the connection collar back.
4. Place canister in area intended for sampling and insert sampler tip into regulator.
NOTE: For stationary sampling the canister should be placed on its side. For
personnel sampling the canister should be fastened using a holster belt with a
sampling tube attached to the regulator and clipped to the collar of the individual
that is being sampled.
5. Release the connection collar. Note: There should not be any gap between the
regulator and the canister.
6. Allow the sample canister ample time to fill. NOTE: Progress can be monitored by
checking the vacuum gauge located on the regulator. The pressure should
decrease over time
7. Once sample time is complete and canister has been successfully filled with sample
air pull back the connection collar to release the regulator.
8. Place protective cap back on the Mini-Can sampler tip.
9. Complete a Chain of Custody form and ship sample in accordance to laboratories
shipment instruction.
Additional media needed for this equipment:
Time Released Grab Sample Regulator
Belt holster (depending on sample)
Sample tubing (depending on sample)
Notification Procedures for Equipment Failure
Galson Laboratories
6601 KirkviUe Road
East Syracuse, NY 13057
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Phone: 315-432-LABS (5227)
Toll Free: 888-432-LABS (5227)
aw. aalsonlabs. com
maiI@galsonlabs. com
Center for Toxicology and Environmental Health (CTEH)
5120 North Shore Drive
North Little Rock, AR 72118
Phone: 501-801-8500
Emergency: 1-866-TOX-CTEH (869-2834)
Fax: 501-801-8501
www.cteh.com
References and Further Assistance.
Centek Laboratories, LLC
143 Midler Park Drive
Syracuse, New York 13206
Phone: 315-431-9730
Fax: 315-431-9731
Review Date for this SOP
Chris Talley
04-14-09
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CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C.
Toxicology Emergency Response Program (June 3, 2008)
STANDARD OPERATING PROCEDURE NO. (Version 1.1)
SUBJECT: Gastec GV-100 and Colorimetric Detector Tubes
Description of the SOP: This procedure is intended to provide instruction on the proper
use of the Gastec piston pump (GV-100) with real-time colorimetric detector tubes for a
wide range of analytes.
Calibration Instructions:
Factory Calibrated.
Equipment Use Instructions (step by step):
1. Determine your analyte of concern,
2. Pick out a box of detector tubes and insure the following items (The following
instructions assume you have picked out a previously un-opened box):
a) The box of detector tubes is not expired (Expiration date is printed on the top of
the box).
b) The measuring range is appropriate for the sampling you are performing.
3. Determine if the analyte you are sampling for is a single tube method or a dual tube
method. To determine this, look on the front of the detector tube box and look at the
number of tests. If it says 10 tests, it is a single tube method, if it says 5 tests; it is a
dual tube method (example: Benzene 121L).
4. Assuming it is a single tube method:
a) Break off both ends of the glass detector tube in the tip breaker located on the
Gastec pump.
b) Insert the glass tube in the end of the Gastec pump with the arrow on the glass
detector tube pointing towards the pump.
5. Assuming it is a dual tube method:
a) There will be ten glass tubes in the box, 5 pre-treatment tubes and 5 detector
tubes.
b) Locate a pre-treatment tube (usually in the back row of the box and is identified
as a tube with no measuring scale printed on it), a detector tube (usually in the
-------
front row of the box and is identified as a glass tube with a measuring range
printed on it), and a pink piece of tubing located between the two rows of tubes.
c) Break off both ends of both tubes using the tip breaker on the side of the Gastec
pump,
d) The pretreatment tube should be placed in-line with the measuring tube using the
pink piece of tubing. The pretreatment tube should be in front of the detector
tube for sampling. The detector tube has the measuring range delineated on it,
and should be the one inserted into the pump while the other, pretreatment tube,
filters the air before it reaches it.
Note: The arrows on both glass tubes should be pointing towards the
Gastec pump.
e) Insert the measuring tube in the Gastec pump.
8. To determine the appropriate number of pump strokes, look at the instructions
located in the detector tube box. There are two types of pump strokes, a full stroke
(100 mL) and a half stroke (50 ml). To pull a full stroke or a half stroke line up the
arrow on the Gastec pump handle with the appropriate volume (either 100 ml or 50
mL). Every analyte has a different measuring range, but generally the more pump
strokes that are pulled, the lower the detection limits.
NOTE: Insure that you are pulling enough pump strokes to get below the
particular standard or guideline with which you are comparing your results.
Also, the "number of pump strokes" in the directions refers to full (100 mL)
pump strokes.
7. The pump stroke is complete when the "Flow Finish Indicator" is visible on the end of
the pump handle. The "Flow Finish Indicator" is a white disc that becomes visible
after pulling the pump stroke anywhere from 30 seconds to 5 minutes depending on
the analyte.
8. To read the airborne concentration of the analyte of concern, look at the measuring
scale on the detector tube. Consult the instructions for the appropriate reagent color
change that you should expect if the analyte is present in the air at detectable levels.
There is a statement on every detector tube such as "n=X", this indicates the number
of full pump strokes that you must pull to read the concentration directly from the
-------
detector tube. If you pull more or less than this number, you must apply a correction
factor that you will find in the instructions.
9. Note that all colorimetric detector tubes have chemical interferences as well as
corrections for humidity, pressure, and temperature. Consult the instructions for
details.
10. Do not re-use a detector tube or pretreatment tube if you have a color change in the
reagent (a detection).
Tips for detector tube reading
When the end of the color
change layer is flat,
simply read the value at
the end.
4 5 6
vQ-l I I I
In this case, the reading
would be 5%.
When the end of the color
change layer is slanted,
read the value in the
middle of the slant.
4 5 6
LLJ
CgH
bLL
In this exaggerated case,
the reading would be 5%.
When the demarcation of
the color change layer is
pale, the mean value
between the dark and the
pale layer ends is taken.
4 5 6
n this exaggerated case,
the reading would be 5%.
Tip for easier reading
When you mark the color change with a pen as soon as the sampling is complete, it is more
convenient to read.
Note: It is possible to have a positive detection that is not measurable. This
occurs when there is a positive color change, but it is not within the marked,
measurable part of the tube. To record this properly you would state that the
reading was above the detection limit, but below the measuring range. Example,
>1 ppm ,<5 ppm.
/
11. Dispose of the pretreatment and detector tube according to local governmental
standards.
Additional media needed for this equipment:
Detector tubes are available for a wide variety of analytes. We have at least one box of
most of the detector tubes that are manufactured by Gastec.
CTEH
-------
Notification Procedures for Equipment Failure:
Notify: Tiffani Ray
Specialized Training Required or Recommended:
None
References and Further Assistance:
1, Refer to the Gastec Handbook 2ncl Edition or later
2, Nextteq, LLC
8408 Benjamin Road, Suite J
Tampa, FL 33834
Phone: 877-312-2333
Fax: 877-312-2444
htto: //www, nextteq .com/
3, hitp'/.'Wav gastec co ;f»r.nqlis!Vim1ex prtp,
Review Date for this SOP:
Emily Schmitz and Ben Gehring 8/3/2008
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Appendix B
Crude USDS
-------
EnCana Corporation Material Safety Data Sheet
Heavy Crude Oil/Diluent Mix - Christina Lake/Foster Creek Page 1 of 2
SECTION 1 - MATERIAL IDENTIFICATION AND USE
Material Name: HEAVY CRUDE OIL/DILUENT MIX {CHRISTINA LAKE/FOSTER CREEK)
Use: Process stream, fuels and lubricants production
WHMIS Classification: Class B, Div. 2, Class D, Div. 2, Sub-Div, A and B
NFPA: Fire: 2 Reactivity: 0 Health: 3
TDG Shipping Name: Petroleum Crude Oil
TDG Class: 3 UN: 1267
TDG Packing Group: I! (boiling point 35 deg. C or above, and flash point less than 23 deg. C)
Manufacturer/Supplier: ENCANA CORPORATION
#1800, 855 - 2nd Street S.W., P.O. BOX 2850,
CALGARY, ALBERTA, T2P 2S5
Emergency Telephone: 403-645-3333
Chemical Family: Crude oil/condensate mix
SECTION 2 - HAZARDOUS INGREDIENTS OF MATERIAL
Hazardous Approximate C.A.S. LD50/LC50 Exposure
Ingredients Concentrations (%) Nos. Specify Species Limits
& Route
Crude oil 50 - 70 8002-05-9 LD5Q,rat, skin >2 g/kg 5 mg/m3 (OEL,TLV)
Hydrocarbon Diluent 30 - 50 N.Av. N.Av. 900 mg/m3 (OEL)*
Benzene 0.03 - 0.3 71-43-2 LD50,rat,oral,930 mg/kg 1 ppm (OEL),
LC50,rat,4 hr, 13200 ppm 0.5 ppm (TLV)
Hydrogen Sulphide <0.5 7783-06-04 LC50, rat, 4 hrs, 444 ppm 10 ppm (OEL,TLV)
OEL = 8 hr. Alberta Occupational Exposure Limit; TLV = Threshold Limit Value (8 hrs) *OEL for gasoline
SECTION 3 - PHYSICAL DATA FOR MATERIAL
Physical State: Liquid Vapour Pressure (kPa): 2.5 - 36.5 @ 20C
Specific Gravity: 0.65 - 0.75 Odour Threshold (ppm): N.Av.
Vapour Density (air=1): 2.5 -5.0 Evaporation Rate N.Av.
Percent Volatiles, by volume: 20 - 30 (estimated) Boiling PL (deg.C): 40-180
pH: N.Av. Freezing Pt. (deg.C): <0
Coefficient of Water/Oil Distribution: <0.1
Odour & Appearance; Brown/black liquid, hydrocarbon odour
(N.Av. = not available N.App. = not applicable)
SECTION 4 - FIRE AND EXPLOSION
Flammability Yes Conditions: Material will ignite at normal temperatures.
Means of Extinction: Foam. C02, dry chemical. Explosive accumulations can build up in areas of poor
ventilation.
Special Procedures: Use water spray to cool fire-exposed containers, and to disperse vapors if spill has not
ignited. Cut off fuel and allow flame to burn out.
Flash Point (deg.C) & Method: <-35 (PMCC)
Upper Explosive Limit (% by vol.): 8 (estimated) Sensitivity to Impact: No
Lower Explosive Limit (% by vol.): 0,8 (estimated) Sensitivity to Static Discharge: Yes, at normal
temperatures
Auto-Ignition Temp. (deg.C): 250 (estimated) TDG Flammability Classification: 3
Hazardous Combustion Products: Carbon monoxide, carbon dioxide, sulphur oxides
SECTION 5 - REACTIVITY DATA
Chemical Stability: Stable Conditions Heat
Incompatibility: Yes Substances Oxidizing agents (e.g. chlorine)
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Reactivity: Yes Conditions: Heat, strong sunlight
Hazardous Decomposition Products: Carbon monoxide, carbon dioxide, sulphur oxides
EnCana Corporation Material Safety Data Sheet
Heavy Crude Oil/Diluent Mix - Christina Lake/Foster Creek Page 2 of 2
SECTION 6 - TOXICOLOGICAL PROPERTIES OF PRODUCT
Routes of Entry:
Skin Absorption : Yes Skin Contact: Yes Eye Contact: Yes
Inhalation: Acute: Yes Chronic: Yes Ingestion: Yes
Effects of Acute Exposure: Vapour may cause irritation of eyes, nose and throat, dizziness and drowsiness.
Contact with
skin may cause irritation and possibly dermatitis. Contact of liquid with eyes may cause severe irritation/burns.
Effects of Chronic Exposure: Due to presence of benzene, long term exposure may increase the risk of
anaemia and
leukemia. Repeated skin contact may increase the risk of skin cancer.
Sensitization to Product: No,
Exposure Limits of Product: 1 ppm (Alberta 8 hr OEL for benzene)
Irritancy: Yes
Synergistic Materials: None reported
Carcinogenicity: Yes Reproductive Effects: Possibly Teratogenicity: Possibly Mutagenicity: Possibly
SECTION 7 - PREVENTIVE MEASURES
Personal Protective Equipment: Use positive pressure self-contained breathing apparatus, supplied air
breathing
apparatus or cartridge air purifying respirator approved for organic vapours where concentrations may exceed
exposure
limits (note: cartridge respirator not suitable for hydrogen sulphide, oxygen deficiency or IDLH situations) - see
also
Storage below).
Gloves: Viton (nitrite adequate for short exposure to liquid)
Eye: Chemical splash goggles. Footwear: As per safety policy Clothing: As per fire protection policy
Engineering Controls: Use only in well ventilated areas. Mechanical ventilation required in confined areas.
Equipment
must be explosion proof.
Leaks & Spills: Stop leak if safe to do so. Use personal protective equipment. Use water spray to cool
containers.
Remove all ignition sources. Provide explosion-proof clearing ventilation, if possible. Prevent from entering
confined
spaces. Dyke and pump into containers for recycling or disposal. Notify appropriate regulatory authorities.
Waste Disposal: Contact appropriate regulatory authorities for disposal requirements.
Handling Procedures & Equipment: Avoid contact with liquid. Avoid inhalation. Bond and ground all transfers.
Avoid sparking conditions.
Storage Requirements: Store in a cool, dry, well ventilated area away from heat, strong sunlight, and ignition
sources.
Caution: hydrogen sulphide may accumulate in headspaces of tanks and other equipment, even when
concentrations in the
liquid product are low. Overexposure to hydrogen sulphide may cause dizziness, headache, nausea and possibly
knockdown
and death. Factors increasing this risk include heating, agitation and contact of the liquid with acids or acid sals.
Assess the exposure risk by gas monitoring. Wear air supplying breathing apparatus if necessary.
Special Shipping Provisions: N.App.
SECTION 8 - FIRST AID MEASURES
Skin: Flush skin with water, removing contaminated clothing. Get medical attention if irritation persists or
large area of contact. Decontaminate clothing before re-use.
-------
Eye: Immediately flush with large amounts of luke warm water for 15 minutes, lifting upper and lower lids at
intervals. Seek medical attention if irritation persists.
Inhalation: Ensure own safety. Remove victim to fresh air. Give oxygen, artificial respiration, or CPR if needed.
Seek medical attention immediately.
Ingestion: Give 2-3 glasses of milk or water to drink. DO NOT INDUCE VOMITING. Keep warm and at rest.
Get immediate medical attention.
SECTION 9 - PREPARATION DATE OF MSDS
Prepared By: EnCana Environment, Health and Safety (EHS)
Phone Number; (403) 645-2000 Preparation Date: October 15, 2008 Expiry Date; October 15, 2011
-------
Appendix C
Sampling SOPs
-------
STANDARD OPERATING PROCEDURES 2010
SOP-1 - Multi-Media Sampling
SOP-2 - Sample Identification
SOP-3 - Field Documentation
SOP-4 - Water/Sediment Sampling
SOP-5 - Decontamination
SOP-6 - Equipment Calibration
SOP-7 - Potable Well Sampling
SOP-8 - Soil Sampling
Appendix A - Manta Operating Manual
-------
STANDARD OPERATING PROCEDURES 2010 -1
Multi-Media Sampling
Page 1 of 9
-------
Contents
1.0 Sampling Objectives 3
2.0 Equipment 3
3.0 Deployment Protocol 3
4.0 Sampling Methods 3
4.1 General 3
4.2 Sample Photographs 4
4.3 Complete Sample Collection Form 4
4.4 Sample Collection 4
4.5 Sample Preservation and Storage 5
4.8 Important Sampling Notes 5
5.0 References 5
Attachment 1 8
Attachment 2 7
Attachment 3 8
Page 2 of 9
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SOP-1 MULTI-MEDIA SAMPLING
1.0 Sampling Objectives
To collect representative samples of oil; oil derivatives; source oil; oily media and debris;
feathers; vegetation, contaminated PRE, contaminated booms and absorbent, etc. for analysis.
Call dispatches will originate with the Enbridge call center or Enbridge management individual.
2.0 Equipment
Clipboard, pencils
• Digital camera
• Field logbook (bound with numbered pages)
• Chain-of-custody (COC) forms
• 30 m waterproof measuring tape
Disposable spatulas
• Disposable plastic tongs
• 1 -qt heavy-duty freezer bags
1-gallon heavy-duty freezer bags
• 4-oz pre-cleaned glass jars
• 8-oz pre-cleaned glass jars
• VOA vials prepared for sheen sampling
• Ice chest & 10 lbs. of bagged ice
• Appropriate PRE, incl. disposable powder free nitrite gloves
Decontamination supplies
• Garbage bags (for investigation derived waste)
• GPS
• "Attachment 1" scale for sample photographs
• Hand-held data collectors
Pens with water-proof ink
• Custody seals
3.0 Deployment Protocol
The field manager will be notified of any reported media needing evaluation and sampling in the
area. The field manager will notify the team in the closest vicinity of the report. The field team
will deploy to the location of the media.
4.0 Sampling Methods
4.1 General
Field teams should consist of two technicians. One technician should be the note-taker. The
note-taker will record location and date and time of collection, and other appropriate data in their
field logbook. The note-taker should also note landmarks that will assist in relocating the
sampling site, if necessary. Refer to SOPS Field Documentation for procedures to ensure that
all notes are complete and detailed.
Page 3 of 9
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SOP-1 MULTI-MEDIA SAMPLING
Important notes:
• Data or other information that is entered incorrectly into the log book should have a
single line drawn through it, and be initialed, and dated.
• A vertical line should be drawn and initialed by the writer at the end of each day and at
the end of each incomplete page.
• Once project is complete the word "END" should be written below the last entry, dated,
and initialed.
• No pages shall be removed from the log book,
• Field notebooks will be relinquished to Field Operations Command once the notebook
has been filled or upon completion of the sampling event.
4.2 Sample Photographs
Photograph all sampled oil, reference, and potentially contaminated assemblages. Take
obliquely oriented photographs of habitat and structure from approximately 30 feet and nearly
normally oriented photos of sampled materials. Any photographs of samples should use the
scale included as "Attachment 1" for reference. For photographs taken with a digital camera,
keep a detailed photo log so that each photo can be labeled and located as to the oil zone it
represents. Label each photo with a unique code, such as team home base and sample
number. Photos taken with hand-held data collectors will automatically be linked to the
sampling file when data is uploaded. Other photos should be e-mailed to the team leader at the
end of the day.
4.3 Complete Sample Collection Form
(A copy of this form is included as "Attachment 3")
4.4 Sample Collection
• Put on gloves; at least one on each hand.
• Determine if a composite or grab sample is most appropriate for the sample.
• Collect sample.
o For solid materials;
¦ Collect sample using disposable sample spatulas/tongue depressors.
¦ If the sample cannot be easily collected with a sample spatula/tongue
depressor, collect sample utilizing disposable plastic tongs. Samples can
also be collected by gloved hand if the materials to be sampled are best
handled in that fashion.
¦ If the sample is a composite, place sample in plastic clean sample jar or
pyrex bowl, and using disposable sample spatula/tongue depressor,
homogenize.
¦ Dispense sample into appropriate containers.
¦ To split the sample for fingerprint analysis, use tongue depressor and
remove 2 to 10 grams (approximately the weight of two nickels) and place
into two sample containers.
Page 4 of 9
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SOP-1 MULTI-MEDIA SAMPLING
¦ Samples of boom, absorbent, or PRE may need to be cut in order to
place in sample jars. For safety purposes, care should be taken in cutting
the materials. Cutting tools will need to be decontaminated according to
accepted methods prior to use on other samples (see SOP-5
Decontamination).
o For liquids (product);
¦ Use a clean sample jar to collect free product.
¦ Dispense product into fresh sample container, taking care to avoid
contaminating the external surface of the sample jar.
¦ Properly Dispose of the jar used to collect and dispense product samples
per the waste management plan.
o For sheen
¦ Prepare sheen net apparatus.
¦ Slowly drag Teflon sheen net through the sheen. Several passes may be
necessary to collect .adequate sample, especially if the sheen is light.
¦ Deposit oiled net into 4-ounce jar.
• Three jars will need to be collected. For sheen sampling, three net samples should be
collected.
• Custody seal your sample jars.
• All sampling equipment will be disposable and should only be used once then properly
disposed per the waste management plan.
4.5 Sample Preservation and Storage
Bag ice in one-gallon freezer bags. Seal sample jars before placing in protective wrap. Seal ice
chest with custody seal on the ice chest opening. Cover custody seal with clear packaging tape
with two entire wraps around the cooler and transport samples and forms to the analytical lab.
Label each ice chest so any courier can easily identify which ice chest should go to which lab.
4.6 Important Sampling Notes
• If portable, Investigative Derived Waste will be disposed of at the Enbridge staging area
in the appropriate receptacles. If too large to move, it will be stored at the point of
generation awaiting proper disposal.
• All information contained in the field notebook, sample label, Sample Collection Form
and Chain of Custody should match, identically. Any deviations could invalidate the
sample.
5,0 References
USEPA Region 4, Environmental Investigations Standard Operating Procedures and Quality
Assurance Manual (EISOPQAM), November 2001
USEPA Region 4, Ecological Assessment Standard Operating Procedures and Quality
Assurance Manuel (EISOPQAM), January 2002
Page 5 of 9
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SOP-1 MULTI-MEDIA SAMPLING
Attachment
1
Photographic
Scale
Sf4TES O* *
August 2007
Carlos M. Gutierrez
Secretary, U.S. Department of Commerce
Vice Admiral Conrad C. Lautenbacher, Jr., USN (Ret.)
Under Secretary for Oceans and Atmosphere and NOAA Administrator
John H. Dunnigan
Assistant Administrator,
Ocean Services and Coastal Zone Management
NOAA Ocean Service
U.S. Department of Commerce • National Oceanic and Atmospheric Administration • NOAA Ocean Service
UD SI
Page 6 of 9
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SOP-1 MULTI-MEDIA SAMPLING
Attachment 2
USC6 RESPONSE FORM
(Located in front of binder)
Page 7 of 9
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SOP-1 MULTI-MEDIA SAMPLING
Attachment 3
SAMPLE COLLECTION FORM
(attached)
Page 8 of 9
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SOP-1 ¥ULTI-MCDIA SAMPLING
Project Name: Project Number:
Sample Collection Data Sheet
SAMPLE #
DATE
TIME
SAMPLE LOCATION (State, Latitude, Longitude)
COMMENTS
Name
Notes;
Page 9 of §
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STANDARD OPERATING PROCEDURES 2010 - 2
Sample Identification and Nomenclature
-------
Sample Identification/Nomenclature
Enbridoe Divisions
A Release Site to 1s Talmadge Flume
B Flume Site to Confluence of Talmadge Creek
and Kalamazoo River
C Confluence of Talmadge Creek and Kalamazoo
River to Angell Road
D Angell Road to County Line
E County Line to Morrow Dam
F Downstream of Morrow Dam
0 Upstream of Release
Nomenclature:
For ALL samples:
-First two letters will be Matrix Code (see above)
-Third letter will be Division Code (see above)
-Four numbers denoting the date (i.e. 0727 for July 27, 2010)
-Four digit time (i.e. 1300 for 1:00 PM)
-Sampler's initials (i.e. PDS)
-Lastly-the sample type: 1 - Sample; 2 - Duplicate; 3 - MS/MSD; 4 - Rinsate; 5 - Trip blank; 6
- Duplicate
EXAMPLE: Surface water sample collected from Division B on August 12, 2010 at 1:00 PM by
PDS - WSB08121300PDS1
Matrix Code
AB
Absorbent or Boom
PD
Product
SE
Sediment
SO
Soil
wc
Waste Characterization
WG
Groundwater
WP
Potable Water
WS
Surface Water
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STANDARD OPERATING PROCEDURES 2010 - 3
Field Documentation
Page t of 6
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1.0 PURPOSE
This standard operating procedure (SOP) describes requirements associated with the
documentation of field investigation (sampling) activities conducted during response
activities. Procedures described in this SOP include documentation of field logbooks,
sample labels, and chain-of-custody forms.
2.0 GENERAL CONSIDERATIONS
Field documentation is important for both technical and legal reasons. Proper
documentation of field activities is a critical aspect of the field investigation (sampling)
process. Documentation must be thorough and maintained at all times to track the
possession and handling of samples from time of collection through delivery to the
laboratory. This documentation is mandatory to locate the sampling site in the future; record
sampling methodology and equipment used, and identify personnel responsibilities. In
addition, this document also describes the actions and protocols for field data entry into the
field logbooks, labeling of samples, and chains-of-custody.
3.0 PROCEDURES
The following sections describe the procedures for proper documentation of sampling
events. In the event where these procedures cannot be followed as outlined in the SOP,
field technicians must contact their team leader, or supervisor, to get approval for any
deviations to the SOP prior to conducting field activities.
4,0 FIELD LOGBOOKS
Field documentation is a critical element of field activities; therefore, field technicians shall
strictly adhere to the logbook protocol. During sampling events, a field log book to document
sampling activities will be maintained by the field team leader. Information in this log book
must be written legibly, and in a clear and concise manner. The following information must
be included in the logbook for each sampling event: (first three bullets must appear on the
top of every page)
•Your name
•Project Name
• Date of sample collection
•Name of Field team leader, partner in field, and/or auditor or other sampling personnel
(USEPA, MDNRE, etc.)
• Name and location of sampling site
•Date of sample collection
•Time of sample/data collection
•Sample identification for each sample. This does not apply to field chemistry
Page 2 of S
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•GPS coordinates (latitude and longitude in decimal degrees) collected from either a MC-55
(handheld) or other approved GPS device
•Daily Sampling Plan (brief description of task and purpose for the day)
•Time of arrival on site
•Time of safety briefing
•Name of on-site coordinator
•Weather conditions
•Pertinent field observations
•Summary of equipment used
•Description of physical characteristics of sample acquired: color, texture, odor, appearance,
etc,
•Specific sample characteristics, such as depth, temperature, turbidity, specific conductivity,
pH, dissolved oxygen, etc. (if applicable)
•Record of contact with individuals at the site (site safety personnel, federal or state agency
personnel, etc. (and company affiliation if known)
~Management and disposal procedures of investigation-derived wastes (IDW) if generated
Logbooks will be provided. Key procedures of field documentation are described below:
•Logbooks must be bound
•Logbooks include consecutively numbered pages.
•Entries into the logbook should be chronological, so that each time notation introduces a
new entry.
•Use only indelible ink for logbook entries.
•Record all entries directly and legibly in the log book for each event.
•Strike out any errors with a single line, initial and date the correction.
•Do not leave spaces between entries into the logbook.
•Strike a diagonal line through any spaces at the bottom of each page of documentation in
the logbook. On the diagonal line sign and date each page of the logbook.
Page 3 of 6
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Logbooks carried into the field shall have the completed pages copied and placed into the
appropriate project binders in the office locations. The copies shall be made weekly at a
minimum. However, copying daily is preferred to reduce the possibility of loss or accidental
destruction of data within the field logbooks. Upon completion of all pages in a field logbook,
the logbook becomes part of the project file and will be retained by the water sampling office
for future reference.
5.0 SAMPLE LABELS
Sample label must include the following information:
•Preservative
•Parameter
•Sample ID {unique nomenclature for each sample)
•Date
•Time sample was acquired
•Sampler's (technician's) initials
•Type of sample (composite or grab)
Sample labels should be completed with as much of this information as possible prior to
departing to the field and will be placed on laboratory glassware only immediately prior to
each sampling event. Information such as time must be filled out immediately prior to taking
the sample at each location. When completing the sample labels, field technicians should
employ the same documentation techniques as previously described in the field logbook
section of this document.
6.0 CHAIN-OF-CUSTODY
The Chain-of-Custody (COC) form is a legal record of possession of samples from the time
the sample was collected to completion of laboratory analysis. Therefore, strict adherence to
the COC protocol must be performed at all times. The COC wilt be provided to the sampling
technician prior to being deployed to the field for each days sampling events, and must
accompany the samples at all times. The COC should be completed by the field team
leader, or technician, at the time of sample collection and thus should indicate the personnel
responsible for collecting, handling and securing the samples. The field team leader will
maintain the COC during the sampling event. The following information must be included on
each COC (some information may already be completed):
•Client name
•Client Number
Page 4 of 6
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•Name of laboratory and address
•Reporting information for results
•Project Name/Number
•Sampler's name and company name
•Matrix
•Date sample was collected
•Time (2400) sample was collected
•Sample type (composite or grab)
•Sample Identification
•Number of containers for the sample
•Preservative
•Parameters (analysis being performed)
•Number of containers for each parameter
When completing the COC's, the field technician will employ the applicable field
documentation techniques as previously described in the field logbook section of this
document. Blank spaces will be addressed in the same manner as field logbooks, and should
be lined through unless it is obvious from the nature of the COG section that information will
be added to those sections at a later time, e g. spaces marked "for lab use only". Strike a
diagonal line through any spaces at the bottom of the sample field box on the COC. On the
diagonal line, sign and date the COC.
Upon completion of the quality assurance /quality control (GA/QC) inspection the original
COC and the samples will be relinquished by the technician to the Field Sampling Manager
or other qualified supervisor. A working copy of the COC will be retained in the working files
within the mobile office for reference. The receiving laboratory will provide a completed copy
of the COC as part of the data deliverables and will become part of the Project Files.
Page 5 of 6
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7.0 REFERENCES
• U.S. EPA, A Compendium of Superfund Field Operations Methods. Office of Solid Waste and
Emergency Response. Directive 9355.0-14,1987,
http://www.hanford.gov/dqo/proiect/level5/Sfcompnd.pdf.
•U.S. EPA. Compliance-Focused Environmental Management System-Enforcement Agreement
Guidance. National Enforcement Investigations Center. EPA-330/9-97-002R.2005.
http://www.epa.gov/ocearth/resources/policies/neic/cfem5 05.pdf.
• U.S. EPA, Contract Laboratory Program Guidance for Field Samplers. Office of Superfund
Remediation and Technology Innovation. OSWER 9240.0-44, EPA 540-R-17-06, July 2007:
http://www.epa.gov/superfund/programs/clp/download/saiTipler/clp sampler guidance,pdf.
• U.S. EPA. Guidance for Conducting Remedial Investigations and Feasibility Studies Under CERCLA.
Office of Solid Waste and Emergency Response. Directive 9355,3-01,1988.
http://www.epa.gov/superfund/policy/remedv/odfs/540g-89004-s.pdf.
•U.S. EPA. Guidance for Performing Preliminary Assessments Under CERCLA. Office of Solid Waste
and Emergency Response. Directive 9345.0-01A, 1991,
http://www.epa.gOv/superfund/sites/npl/hrsres#PA%20Guidance.
• U.S. EPA. Guidance for Performing Site Inspections Under CERCLA. Office of Solid Waste and
Emergency Response. Directive 9345.1-05.1991.
http://www.epa.gOv/superfund/sifes/npl/hrsres#PA%206uidance,
• U.S. EPA, Region 4, Logbook Operating Procedure. Document #SESDPROC-Q10-R3. November 2007.
End of Document
Page 6 of 6
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STANDARD OPERATING PROCEDURES 2010 - 4
Surface Water and Sediment Sampling
i
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Table of Contents
1.0 PURPOSE 1
2,0 GENERAL CONSIDERATIONS 1
2.1 SAFETY 1
2.2 SAFETY BRIEFING 1
2.3 PERSONAL PROTECTIVE EQUIPMENT 1
2.4 SAMPLING SAFETY 2
2.5 SAMPLE SITES 2
2.6 LABELING 2
2.7 NOTE TAKING 2
2.8 DAILY DOCUMENT SUBMISSION 2
2.9 PREVENTING CONTAMINATION/SOLVENT LEAKAGE 3
3.0 WATER CHEMISTRY 3
3.1 PARAMETERS 3
3.2 TURBIDITY 4
3.3 OTHER OBSERVATIONS 4
4.0 WATER QUALITY SAMPLING 4
4.1 SAMPLE KITS 4
4.2 KEMMERER BOTTLE PROCEDURE 4
4.3 SPLIT SAMPLES 5
4.4 DUPLICATE SAMPLES 5
4.5 RINSEATE SAMPLES 5
4.6 TRIP BLANKS 6
5.0 SEDIMENT SAMPLING 6
5.1 SAMPLE SITE LOCATIONS 8
5.2 GENERAL CONSIDERATIONS 8
5.3 SEDIMENT SAMPLING PROCEDURE 8
5.4 SPLIT SAMPLES 8
5.5 DUPLICATE SAMPLES 8
5.6 RINSEATE BLANKS 8
5.7 TRIP BLANKS 9
5.8 TEMPERATURE BLANKS 9
2
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Surface Water and Sediment Sampling SOP
1.0 Purpose
The purpose of this standard operating procedure (SOP) document is to describe methods for
sampling water and sediment.
Water sampling will consist of recording water chemistry data as well as collecting water
samples for further water quality laboratory analysis, while sediment sampling will consist of
solely collecting samples for further laboratory analysis. Water samples will be collected from
the middle of the main channel. Sediment samples will be collected from the middle of the main
channel, with the exception of the locations where transects are specified in the SAP. The list of
analytes will continue to be updated based on results and may be reduced based on repeated
evidence of non-detection. Any changes to the analyte schedule will be made in consultation
with Unified Command.
The data obtained from these samples, along with any significant field observations taken at
collection points (e.g., sheen, odor, etc), wilt be recorded in the sampling record..
2.0 General Considerations
2.1 Safety
A copy of the health and safety plan should be easily accessible on the vessel, in the vehicle, or
on the sampler's person.
2.2 Safety briefing
Before sampling each day, a site safety briefing must be conducted. The briefing will be
recorded on the Safety Briefing Form and should address potential safety hazards and describe
courses of action in the event of an emergency or in climate weather. All team members and
samplers from other agencies should be included in the daily safety briefing (as needed).
Additional site-specific safety considerations should be addressed by the team as they arise.
2.3 Personal Protective Equipment (PPE)
Samplers must wear proper PPE at all times that is specific to the work they are doing and the
hazards they may encounter. This may include but is not limited to long pants, close-toed, steel-
toed shoes/boots, hard hats, Tyvek suit (if needed), and proper sun protection such as hat and
safety glasses, and fire retardant clothing as directed by the Company, A PFD (Personal
Flotation Device) must be worn when within 10 feet of a water body or when on a boat, dock, or
bridge. If a question arises concerning what is appropriate site specific PPE that determination
will be made by the Site Safety Officer, Field Team Leader, supervisor, or water sampling
manager. During water sampling, powder-free nitrile gloves must be worn at all times with the
exception being to collect or record water chemistry data with field instruments. However, while
calibrating the instrument, gloves must be worn. In all cases, nitrile gloves will be changed
before and after the decontamination process and between each sampling event; also when
clean gloves are contaminated by touching contaminated equipment or surfaces.
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SOP-4 Surface Water and Sediment Sampling
2.4 Sampling Safety and Access
For all water quality and sediment sampling from a vessel, the boat will be anchored and all the
motors and gas powered generators powered off before sampling begins. The sampling location
should be approached from downstream, and the sample shall be obtained from the upstream
side of the boat. If a safety issue arises such that it becomes a danger to either anchor or power
off the motor(s) water quality/sediment samples will not be collected. If only water chemistry
data are to be recorded, the boat need not be anchored nor motor powered off to collect data.
This is not recommended and should only be conducted if a safety issue arises, and after
consultation with the Field Team Leader. In any case, sampling should be conducted away from
the boat motor or bilge pump if located on the vessel. In all cases, the sample should be taken
from the upstream side of the boat.
Appropriate on-land safety protocols will be followed as outlined in the site specific Health and
Safety Plan.
2.5 Sample Sites
The sample sites are predetermined sites based on the operations analysis for the project.
These sites are subject to change as sampling goals and directives change, and are available in
the Project Work Plan.
2.6 Labeling
Labels for samples will be written in a clear and concise manner which is legible. Sample labels
are written in permanent marker and include sampler, analysis, date, time, sample ID and
preservative. Additionally, those samples must be taped completely around each piece of
laboratory glassware with a clear packing tape, it is also acceptable to write the sample
Identification Number on each lid of laboratory glassware; however, if those sample labels are
taped it is not required to write on the lid. A detailed description of relevant Standard Operating
Procedures (SOPs) for field note documentation and labeling can be found in as a
corresponding attachment to this SOP.
2.7 Note Taking
Daily field notes will be written in field books in a clear and concise manner which is legible.
Each page of field notes must have three main pieces of information: your name (and affiliation),
the project name and number, and the date.
Below that, you will note each sample taken in the following format (for example purposes only):
10:14 30.59623, -88.151809. Tar ball collected. No odor, brown in color, about the size
of a nickel with a thickness of one half inch. Noticed a high abundance of green
algae washed up on shore covering about 75% of the beach at the shoreline.
Skies are clear, -85 °F, with calm winds.
2
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SOP-4 Surface Water and Sediment Sampling
Notes, as shown above, will include time, GPS coordinates, Sample ID (if a sample is
collected), and any factual observation
At each location, observations of aquatic vegetation, water depth and/or water velocity shall be
made.
• Aquatic Vegetation: visually describe quantity and types of aquatic vegetation observed.
• Water Depth: using a marked staff, weighted line, or similar device, record the water depth
at the sampling location.
• Water Velocity: using a Watermark Model 6200 "USGS type" current flow meter, record
the water velocity at the sampling location.
2.8 Daily document submission
Daily field notes, safety briefing, and chain of custody forms must be copied and inserted into
the specific binder after completion of each sampling day. These documents are to be kept in
chronological order by geographical river division rather than by individual sampler.
2.9 Preventing Contamination
Samples will be collected with a variety of sampling equipment. All equipment will be used
according to manufacturer recommendations and instructions. Decontaminated equipment and
new expendable sampling gear will be used for each successive sample to prevent sample
contamination.
1) Nitrile powder-free gloves must be changed between calibration and sampling events,
between sampling sites, and whenever clean gloves come into contact with a surface
that has not been decontaminated.
2) The sampler nozzle (if used) cannot come into contact with any potentially contaminated
surface, including boat surfaces, clothes, ungloved hands, etc. Be especially sure when
filling laboratory glassware the lip of the vial/bottle does not touch the sampler nozzle.
3) Do not let the lip of the clean bottles/vials come into contact with any potentially
contaminated surface, including but not limited to: pant legs, boats, ungloved hands,
weights (for bottles), rinseate solution, sun screen, diesel fumes, etc.
4) Use a clean decontaminated surface to set unfilled and filled sample bottles before they
are placed on ice and only open the sample vial immediately before collecting sample.
5) Fill preserved vials without overflow as the preservatives will exit the bottle and not
effectively preserve the sample; also, this overflow may damage clothing or working
surfaces as well as labels.
3.0 Field Water Quality Measurements
3.1 Water Chemistry
Water depth will be measured at each sampling location. Sample depths will be based on the
water depth at the chosen location. Three samples will be collected from the water column.
3
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SOP-4 Surface Water and Sediment Sampling
One sample will be collected from the surface, one sample at the approximate mid point of the
column and one sample from within 6"-1' of the sediment layer or bottom.
Water chemistry parameters include those collected from a field instrument (YS! or equivalent)
and turbidimeter (or equivalent) (Water Temperature (°C), pH, Specific Conductivity (mS/cm), and
Dissolved Oxygen (ms4)) and have a minimal recommended holding time. Dissolved oxygen,
pH, specific conductivity, and water temperature data are collected using a YSl Multi-probe
Professional Plus, YSl 556MPS, or equivalent. Both YSl (or equivalent) units and turbidimeters
will be calibrated once at the beginning of each sampling day, unless abnormal readings,
damage, or malfunction of the YSl occurs throughout sampling. If any of these events occur, the
sampler should calibrate the instrument again before taking the next sample. The dissolved
oxygen parameter must be calibrated in the field while those other parameters can be calibrated
in another prior location. Each day's calibration must be documented on the Calibration Log
(Appendix B).
3.2 Turbidity (NTU)
If requested by the state or USEPA, a turbidity reading will be taken at each sampling site as
well. Turbidity is calculated using a HACH 2100Q turbidimeter (or equivalent), which should be
calibrated at the beginning of each sampling day.
4 J Water Quality Sampling
A. Surface Water Samples
1) In the event that free phase oil is observed on the surface, no samples will be
attempted.
2) The surface samples will be taken by dipping the bottles into the surface of the
water, being careful to not lose any of the preservative.
3) In the event a sheen is noted on the surface, a sheen sample will be taken as
described in Section 4.4 of SOP-1 Multi-media Sampling
B. Potential sampling methods for deeper samples are Kemmerer bottle or peristaltic pump.
1) Peristaltic Pump
i. The peristaltic pump will use disposable poly tubing that will be changed
between sampling locations. The tubing will be attached (avoid the use of
any tape within 1' of the end of the tube) to a marked staff or marked
weighted line and lowered to the desired depth. The pump will be turned
on and purged for a period of one minute.
ii. In the event a sheen is noted on the surface, the tubing shall be
connected to the peristaltic pump as described in B(1)i above, and air
pumped down the tubing to create positive pressure and prevent the entry
of sheen into the tubing . The tubing will then be attached (avoid the use
of any tape within 1' of the end of the tube) to a marked staff or marked
weighted line and lowered to the desired depth. The pump will then be
turned on and purged for a period of one minute.
4
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SOP-4 Surface Water and Sediment Sampling
Hi. After the bottles are filled for that depth, the tubing will be lowered to the
next depth and the process repeated,
2) Kemmerer Bottle
i. Obtain the sampler and check the knot at the bottom of the sampler for
tightness and size. The knot should be sufficiently large so that it will not
pull through the central tube of the sampler.
ii. To prepare the sampler for making a cast, cock the sampler by pulling the
trip head into the trip plate. Holding the top and bottom stoppers and
giving a short, hard pull to the bottom stopper does this.
iii. Tie the free end of the line to the railing of the vessel. This is done to
prevent accidental dropping of the sampler should the person operating
the sampler let go of the line.
iv. Lower the sampler to the desired depth. When the sampler is at the
desired depth, attach a messenger to the line. This is best done with the
messenger held over the deck until it is securely attached to the line.
v. Release the messenger. It will slide down the line to the sampler where it
will trigger the stoppers and they will close the ends of the tube. The
stoppers seal by their own weight.
vi. Retrieve the sampler. Untie the tine from the railing and carry the
sampler to the sample prep area where the water sample can be
transferred to clean sample glassware for storage and transport to the
laboratory.
vii. In the event additional sample is required, repeat steps 1 - vi as
necessary
4.1 Sample Kits
Bring appropriate bottles as outlined in the sampling plan.
4.2 Bottle Procedures
1) Nitrile powder-free gloves must be worn when decontaminating and sampling.
a. Used gloves will be changed for clean before and after both decontamination and
sampling events.
2) Decontaminate the sampler following the Decontamination procedure described in the
Decontamination SOP.
3) Record the time, depth range, GPS coordinates, any factual observations/ descriptions,
and sample identification number in the field notebook.
4) Allow some sample water to purge from the nozzle or sampling equipment into the
decontamination bucket below before beginning sample collection.
5) Fill all 11 pre-labeled sample bottles.
5
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SQP-4 Surface Water arid Sediment Sampling
a. The 3 40-mL Volatile Organic Analysis (VOA) vials are filled first. To fill VOA vial,
allow sample water to form a meniscus while preventing overflow of the vial.
Keep vial perpendicular to ground and screw lid on, making certain there are no
air bubbles in the vial. To check for air bubbles, invert the vial and hit against
palm of hand. If an air bubble is observed the vial must be refilled until no air
bubbles are detected. However, make sure not to pour sample over vial to avoid
contamination and loss of preservative.
6) Place all sampling bottles back into bubble wrap, into their respective zip lock bags
(which are also labeled with the sample ID and hold an entire sampling kit), and then in
cooler of ice (4±2°C)
7) A Chain of Custody (COC) form is filled out before a Quality Analysis/Quality Control
check of samples is complete. Samples are then sent out to the appropriate laboratory.
See Standard Operating Procedures for Field Documentation (Appendix D).
8) Those samples will be relinquished after all bubble-wrap and zip lock bags have been
sealed and coolers have been taped shut over their respective custody seals.
4.3 Split Samples
In the event that split samples are collected by state or federal representatives for submission to
independent, third party laboratories, sample containers will be provided by those agencies or
their designates if requested in advance.
Split samples are taken from the same grab sample. Often two grabs are needed to obtain
enough source water for all 20 bottles of the split sample. The VOA vials are filled first. All
amber bottles are filled halfway first and then filled completely with the second grab sample.
Split samples are documented in the field notebook along with the time they were taken.
4.4 Duplicate Samples
For water quality sampling, a duplicate sample will be collected on a 5% interval basis; at a
minimum, one per day.. A duplicate is a second sample at a certain site that will be submitted to
the same laboratory under a different sample ID. This duplicate is to verify consistency in
sample collection and decontamination techniques. The duplicate sample is taken in the same
manner as a split sample; each of two grabs taken will fill half of all sample glassware to
homogenize the sample. Field notes must document from which sample a duplicate was taken,
along with all other pertinent information that should be included in sample documentation.
4.5 Rmseate Samples
Equipment rinseate blanks will be collected after completion of each day's sampling events and
used to monitor the effectiveness of each team's decontamination process. The rinseate sample
is taken after the final decontamination. Rinseate blanks will be prepared by passing deionized
water through and over the surface of decontaminated water sampling equipment (although
deionized water is always preferred, distilled water is acceptable but must be documented in
field log book and in the comments section of MC-5S or MC-35 handheld or equivalent). The
rinse water will be collected in appropriate sample bottles, preserved, and handled in the same
manner as other samples collected that day. One rinseate blank will be collected for each day of
6
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SOP-4 Surface Water and Sediment Sampling
sampling for initial sampling events. If impacted surface water is identified in sampling events
the frequency of rinseate blanks will be evaluated for modification.
4.8 Trip Blanks
A set of trip blanks is to be present in each cooler that will hold a VOA vial during the sample
day. A trip blank set consists of three pre-filled VOA bottles, which will need to be labeled at the
start of each sampling day. The trip blanks are to be kept on ice (4±2°C) in the cooler and sent
through the quality assurance/quality control process at the conclusion of the sampling day (for
proper labeling procedures see Appendix D). These trip blanks are also sent to the appropriate
lab with samples collected.
5.0 Sediment Sampling
Sediment sampling will be performed in two types of locations;
1. Programmatic sediment sampling will consist of a single sample collected from the
middle of the main channel using a dredge sampler.
2. Transect sediment samples will be taken at selected locations and deeper samples will
be taken using a coring device or bucket auger.
5.1 Sample Site Locations
Sediment sampling sites are determined by the project team in conjunction with other
stakeholders and are subject to change. Those locations will be available in the figures in the
concurrent SAP. All sampling should be performed in depositional areas; the exact location to
be decided based on field conditions evaluated by the sampling team. Once the location is
determined, it shall be surveyed and marked on the bank so that subsequent sampling events
can easily and with confidence be performed at the same location.
5.2 General Considerations
For all water quality and sediment sampling from a vessel, the boat will be anchored and all the
motors and gas powered generators powered off before sampling begins. The sampling location
should be approached from downstream, and the sample shall be obtained from the upstream
side of the boat. If a safety issue arises such that it becomes a danger to either anchor or power
off the motor(s) water quality/sediment samples will not be collected. If only water chemistry
data are to be recorded, the boat need not be anchored nor motor powered off to collect data.
This is not recommended and should only be conducted if a safety issue arises, and after
consultation with the Field Team Leader. In any case, sampling should be conducted away from
the boat motor or bilge pump if located on the vessel. In all cases, the sample should be taken
from the upstream side of the boat.
Also, if dense product is observed on the surface, no sampling will occur at that sampling site
for that day. However, if only a light sheen or pockets of floating product is present, the ultimate
decision of whether or not to sample belongs to either the Field Team Leader or his/her
supervisor.
?
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SOP-4 Surface Water and Sediment Sampling
5,3 Sediment Sampling Procedure
Sediment samples from sampling locations 2 inches or less from the surface may be collected
with a stainless steel trowel or stainless steel Ponar or Ekman dredge to obtain a sample from
the upper 2" of sediment. Samples collected from the transects will be obtained using a bucket
auger or a Wildco core sampler to obtain samples from the upper 6" of sediment. The sample
will be mixed in a Pyrex baking dish or on a new piece of aluminum foil. The sediment samples
are placed in either four 4-oz sediment jars or one 8-oz and two 4-oz sediment jars that are pre-
labeled.
Protocol for collecting sediment samples in deep water:
1) Place tarp or protective covering on flat surface of vessel (boat) -
• Decontaminate all sampling equipment (Ponar/Ekman dredge, Wildco® Hand
Corer. Pyrex dish, and stainless steel sampling spoon, etc.) prior to sample
collection.
2) Sample Collection
a. When only the top two inches of bottom sediment sample is required for
laboratory analysis, the Ponar/Ekman dredge will be used.
• Determine Ponar/Ekman dredge is locked in open position by the safety
pin, and lower into water.
• Make sure to keep Ponar/Ekman rope taught while lowering as to not let
safety pin disengage.
• Also, industrial work gloves should be worn while lowering and lifting
Ponar/Ekman (clean nitrite powder-free gloves must be worn before any
sample may be handled).
• After equipment has reached sediment, either send messenger down
rope to trigger the device closed (Ekman), or slowly pull rope toward
surface to close equipment with sediment inside (Ponar).
• Raise Ponar/Ekman carefully onto boat avoiding sample contamination
and vessel damage.
b. When deeper bottom sediment samples are required (such as in the transect
locations), the Wildco® Hand Corer will be used.
• Insert CAB liner into tool
• Attach line to clevis pin in head of tool. Attach additional weights if
necessary
• Drop tool to bottom and push to a depth sufficient to recover a 6-inch
sample.
• After corer penetrates bottom, twist and pull free to retrieve sample.
8
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SQP-4 Surface Water and Sediment Sampling
3) Sediment sample will be collected into Pyrex mixing bowl'
a. Ekman - the upper two inches of sample may be accessed by opening flap
on top of instrument. Those two inches will be used to fill VOA 4-oz laboratory
glassware first.
b. Ponar - All collected sample will be emptied into Pyrex mixing bowl
• The top two inches will be used to fill 4-oz VOA laboratory glassware
first.
• The resulting sediment may be homogenized (stainless steel spoon)
and collected into remaining laboratory glassware.
c. Wildco® Hand Corer
• Empty the top 6" of the sediment from the sampling device into the bowl
or onto the clean foil.
4) If necessary, lower the sampling tool back into the water and repeat steps 2) and 3)
until enough sediment is obtained to fill all laboratory glassware (This will be done
before homogenization).
• If sampling events are within 15 minutes of each other, this may still be
classified a grab sample.
5) Collect sample for laboratory analysis as specified in SAP
6) All sample glassware will then be placed in bubble wrap and preserved on ice at 4+2
°C
7) A COC form will be completed for all sediment samples before returning to the office
for QA/QC protocols. Wastes generated during these sampling operations will be
segregated, containerized and disposed of properly.
Protocol for Wadeable Samples
If sediment samples are to be collected in shallow water that is accessible on foot or is
wadeable, the following procedures will be followed:
1. Approach sample location from downstream direction.
2. The Wildco® Hand Corer, bucket auger or shovel may be used to obtain samples
a. Wildco® Hand Corer
• Insert CAB liner into tool
• Attach line to clevis pin in head of tool. Attach additional weights if necessary
• Drop tool to bottom and push to a depth sufficient to recover a 6-inch sample.
• After corer penetrates bottom, twist and pull free to retrieve sample
9
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SOP-4 Surface Water and Sediment Sampling
b, Bucket Auger
• Utilize 4-inch to 6-inch conductor pipe, wrapped (capped) with plastic cling
wrap, or similar film.
• Place capped conductor pipe on the sediment bed and utilize a
decontaminated tool (hand auger, probe, coring tool, etc.) to breach the film
and access the sediment.
• Using bucket auger, obtain 6-inch sediment sample.
c. Shovel
• A shovel may be used where the depth and/or velocity of the water will not
cause the sample quality to deteriorate due to washing.
• The analytical sample will be collected from the center of the sample mass
3. All sample remnants will be containerized and disposed of per the Waste Management
Plan. Sediment sample will be collected into Pyrex mixing bowl.
4. If necessary, repeat steps 2) and 3) until enough sediment is obtained to fill all laboratory
glassware (This will be done before homogenization).
5. Collect sample for laboratory analysis as specified in SAP
6. All sample glassware will then be placed in bubble wrap and preserved on ice at 4-2 °C
7. A COC form will be completed for all sediment samples before returning to the office for
QA/GC protocols. Wastes generated during these sampling operations will be
segregated, containerized and disposed of properly.
5.4 Split Samples
In the event that split samples are collected by state or federal representatives for submittal to
independent third party laboratories, sample containers will be provided by those agencies or
the Company's designates if requested in advance. If split sampling is requested, VOA
glassware for each team will be filled first, followed by remaining glassware. All remaining
sediment sample glassware will be filled once enough sediment has been collected and
homogenized; these two sets of glassware will be filled in alternating order. Sediment sampling
is conducted according to above steps.
5.5 Duplicate Samples
One duplicate field sample will be collected for every 20 field samples. A duplicate is a second
sample at a certain site that will be submitted to the same laboratory under a different sample ID
(Appendix E). This duplicate is to verify consistency in sample collection and decontamination
techniques. The duplicate sample is taken in the same manner as a split sample; sediment
samples for all analyses, following VOA jars, will be homogenized then distributed to each
laboratory sample jar. Field notes must document from which sample a duplicate was taken,
along with all other pertinent information that should be included in sample documentation.
10
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SOP-4 Surface Water arid Sediment Sampling
5.6 Rinseate Blanks
Equipment rinseate blanks will be collected after completion of each day's sampling events and
used to monitor the effectiveness of each team's decontamination process. The rinseate sample
is taken after the final decontamination of the sampling equipment. Rinseate blanks will be
prepared by passing deionized water through and over the surface of decontaminated sediment
sampling equipment. The rinse water will be collected in (11) sample bottles, preserved, and
handled in the same manner as other samples collected that day. One rinseate blank will be
collected after decontamination following each day's final sampling event. If impacted surface
water is identified in sampling events the frequency of rinseate blanks will be evaluated for
modification.
5.7 Trip Blanks
Throughout the entire sampling day a set of trip blanks is to be present in each cooler that will
hold a sample for volatile organic compounds analysis. A trip blank set consists of three pre-
filled VOA bottles which will need labeled at the start of each sampling day. The trip blanks are
to be kept on ice (4±2 °C) in the cooler and sent through the QA/QC process at the conclusion
of the sampling day. These trip blanks are also sent to the appropriate laboratory with samples
collected.
5.3 Temperature Blanks
Temperature blanks will monitor the temperature at which each day's samples are kept during
transportation. These temperature blanks will be received from the laboratory at the start of
each day, not be opened only labeled, and kept in the same cooler as those samples collected
throughout the day. These, as well as all samples collected, must be kept on ice (4±2 °C).
11
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STANDARD OPERATING PROCEDURES 2010 - 5
Decontamination
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Purpose:
The purpose of this Standard Operating Procedure (SOP) is to provide a description of the
methods used for preventing, minimizing, or limiting cross-contamination of samples due to
inappropriate or inadequate equipment decontamination and to provide general guidelines for
developing decontamination procedures for sampling equipment to be used during hazardous
waste operations as per 29 Code of Federal Regulations (CFR) 1910.120.
These are standard operating procedures which may be varied or changed as required,
dependent upon site conditions, equipment limitation, or limitations imposed by the procedure.
In all instances, the ultimate procedures employed should be documented and associated with
the final report.
METHOD SUMMARY
Removing or neutralizing contaminants from equipment minimizes the likelihood of sample
cross contamination, reduces or eliminates transfer of contaminants to clean areas, and
prevents the mixing of incompatible substances. Gross contamination can be removed by
physical decontamination procedures.
These decontamination methods will be used for sampling tools, equipment, containers, etc.
Step One, a soap (Alconox or equivalent) and water wash, removes all visible particulate matter
and residual oils and grease. This may be preceded by a steam or high pressure water wash to
facilitate residuals removal.
Step Two, involves a triple rinse with tap water and/or a distilled/deionized water rinse to
remove the detergent. Rinsate blanks can be collected at this time if desired.
The decontamination procedure described above may be summarized as follows:
1. Physical removal by scrubbing or pressure washing or steam cleaning
2. Non-phosphate detergent wash
3. Tap water rinse
4. Distilled/deionized water rinse
5. Air dry
EQUIPMENT/APPARATUS
Decontamination equipment, materials, and supplies are generally selected based on
availability. Other considerations include the ease of decontaminating or disposing of the
equipment. For example, softwash and rinse solutions. Children's wading pools can also be
used. Large plastic garbage cans 5-gallon buckets or other similar containers lined with plastic
bags can help segregate contaminated equipment. Contaminated liquid can be stored
temporarily in metal or plastic cans or drums. Most equipment and supplies will be provided by
Enbridge.
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The following standard materials and equipment are recommended for decontamination
activities:
Decontamination Solutions
• Non-phosphate detergent
• Tap water
• Distilled or deionized water
Useful Decontamination Tools/Supplies
• Long and short handled brushes
• Bottle brushes
• Drop cloth/plastic sheeting
• Paper towels
• Plastic or galvanized tubs or buckets
• Pressurized sprayers (H O) 2
• Aluminum foil
Post Decontamination Procedures
Please refer to the Waste Handling and Disposal Plan for details concerning the handling of
solid and liquid waste,
• Empty all soap and water waste liquids from basins and buckets into drums or other
appropriate containers. Refer to the DOT requirements for appropriate containers based
on the contaminant of concern. Dispose of residual liquids properly.
• Place all solid waste materials generated from the decontamination area {i.e., gloves
and plastic sheeting, etc.) in an approved DOT drum. Refer to the DOT requirements for
appropriate containers based on the contaminant of concern. Dispose of discarded
materials properly.
• Write appropriate labels for waste and make arrangements for disposal. Consult DOT
regulations for the appropriate label for each drum generated from the decontamination
process
Adapted from: USEPA Publication, SAMPLING EQUIPMENT DECONTAMINATION SOP#:
2006 DATE: 08/11/94 REV. #: 0.0
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STANDARD OPERATING PROCEDURES 2010 - 8
Equipment Calibration
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Purpose: The purpose of this SOP is to ensure accurate arid consistent field chemistry, water
level, and organic vapor measurements using measurement equipment such as pH meter,
conductivity meter, dissolved oxygen meter and probe, water-level indicator, photoionization
detector, etc.
Field personnel are responsible for the calibration, calibration verification and
maintenance of the equipment in accordance with this procedure and manufacturer
maintenance/
calibration instructions. Calibration is essential for field equipment whose measuring accuracy
is critical to monitoring for safe work conditions and in gaining accurate reading of environment
indicators.
Calibration Records
Each piece of monitoring equipment must have its own calibration/maintenance logbook. The
following information should be documented in the calibration/maintenance logbook;
A. Date of entry and initials of the individual recording the entry,
B. Results of the calibration or calibration verification.
C. information on the standards and method used for calibration or
verification, including standard preparation details.
D. Maintenance performed.
E. Operator comments.
F. The calibration or verification status (i.e., "calibrated" or "not calibrated").
Equipment Calibration/Maintenance
Calibration of all field instruments will be conducted according to the equipment manufacturer's
recommendations. Field equipment maintenance shall be conducted according to the
manufacturers recommended schedule.
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STANDARD OPERATING PROCEDURES 2010-7
Private Well Sampling
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Private Water Well Monitoring Plan
PURPOSE
This Private Water Well Monitoring Procedure has been developed to direct a potable water well
monitoring program for private wells located within the area of concern.
A. Objective
The objective of this SOP is to describe the proper sampling techniques to be used as part of
the private well monitoring plan.
SAMPLING
A. Sample Identification
Unique sample numbers will be assigned to identify and describe each potable well sample
according to procedures described in SOP-2 - Sample Identification and Nomenclature.
Blank and duplicate samples will be identified by false or dummy numbers selected by the staff
conducting the sampling, followed by the date the sample was collected (for blanks, the date the
sampling event occurred).
B. Sample Labeling
Each sample container will be clearly labeled, following procedures described in Section 5,0 of
SOPS - Field Documentation, using an indelible ink pen on adhesive labels.
C. Sample Collection and Handling
All water samples will be collected using the following procedures;
1. Select a sampling location that is upstream or ahead of any water softening or filtering
devices.
2. Select a sample tap that best represents the water in the system between the pump and
any softening or filtration devices. Avoid poor sample sites such as swivel faucets, hot
and cold mixing faucets (with a single lever), leaky or spraying faucets, drinking
fountains, janitorial sinks, frost-free hose bibs, and faucets below or near ground level.
3. Remove any attachments from the faucet, including aerators, screens, washers, and
hoses.
4. Turn on the cold water only and let it run in a steady stream for at least fifteen minutes.
Before collecting the sample, don latex, nitrite or similar disposable gloves and turn the
water down to a thin %" stream, then let the water continue to run for one minute.
5. Physical parameters will be allowed to stabilize prior to a sample being collected.
6. To avoid contamination while taking the sample, hold the bottle near the bottom with one
hand, hold the top of the cap with the other, and then unscrew the cap. DO NOT set the
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cap face down, touch any part of the cap that touches the bottle, or let anything touch
the rim or inside of the cap. Hold the bottle under the stream of water, being careful not
to let the bottle touch the sample tap. Fill the bottle to the neck or indicated fill line, but
do not allow it to overflow. Remove the bottle from the water flow and replace the cap.
7. Complete the sample label and chain of custody form.
8. Place the sample in the chilled cooler (approximately 4°C or ~39°F).
D, Sample Storage and Preservation
Sample bottles will be supplied by the mobile laboratory for all sampling events and will include
the appropriate preservatives. Sample containers will be kept closed until each is to be filled.
Sample containers will be filled as outlined above and capped immediately. Immediately
following the sample collection, samples will be labeled, as described above, and placed into a
chilled cooler awaiting transportation to the laboratory. Samples will be delivered to the
laboratory at the end of that sampling day.
E, Documentation
The sample location and number will be recorded in the field log book. Sample conditions and
observations will be recorded in the log as well. After data is received, all potable sample
addresses will be located on a site map for the whole area. Documentation will include the
chain-of-custody and any field notes that are generated.
F, Chain-of-Custody Form
A chain-of-custody form will be completed by the staff for every day's sampling event. Samples
will be transferred to subsequent custodians (the mobile laboratory), the chain-of-custody form
will be signed by each person relinquishing and accepting custody of the samples. The chain-of-
custody forms will be included in the Superior project file and will also be maintained by the
laboratory. The chain-of-custody form will contain the sample location and number as outlined
above.
SAFETY
Site Safety
All staff must have attended the contractor orientation safety seminars and have received the
appropriate certifications prior to entering any field operation. Staff shall adhere to safety
policies and will also adhere to the Project and/or Corporate Safety Manual and site specific
HASP for all field activities. All staff members will have received 40-Hr OSHA HAZWOPER
training and annual refresher. Numerous staff will be qualified as Site Supervisors under
OSHA. Each will also have attended first aid and CPR training classes.
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STANDARD OPERATING PROCEDURES 2010 - 8
Soil Sampling
1
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Table of Contents
1.0 - Soil Classification and Logging ..... ...1
2.0 - Soil Sampling for VOCs 2
3.0 - Near Surface Soil Sampling .3
4.0 - Soil Sampling - Manual Soil Boring 4
5.0 - Drilling and Sampling Using Direct Push Techniques 5
8.0 - Drilling and Sampling Using Hollow Stem Auger (HSA) Techniques 6
7.0 - Soil Sampling - Test Pit Sampling 7
1
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SOP-8 SOIL SAMPLING
1.0 - Soil Classification and Logging
Purpose
The purpose of this technical practice is to provide a general guideline for the classification and
logging of soil,
Equipment/Materials
Unified Soil Classification System (USCS) Field Chart
Procedures
Soil descriptions shall be precise and comprehensive with enough detail to allow interpretation
by the project geologist. Field loggers shall minimize interpretation beyond soil type. The field
logger shall strive to capture sufficient detail.
The following format and order for soil descriptions shall be recorded on the log:
• Soil name (USCS Group name and symbol) or fill
• Color
• Mottles, if present
• Estimate of particle size percentages
• Plasticity
• Moisture
• Consistency
• Sedimentary structure, if present
• Bedding, if present
• Organic material, if present
• Lithologic contact
• Special features such as chemical staining, nodules, and caliche
• Potential hydrocarbon or other impacts
1
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SOP-8 SOIL SAMPLING
2.0 - Soil Sampling for VOCs
Purpose
The purpose of this technical practice is to provide a general guideline for collecting and
handling soil and sediment volatile organic compound (VOC) samples.
Equipment/Materials
• 4 oz jar for dry weight sample
• Methanol preserved 40 ml vial
• Nitrile gloves
Procedures
1. VOC sample should be collected first, before any other aliquot.
2. Collect undisturbed soil sampling in 10 ml syringe.
3. Inject soil filled syringe into pre-weighted, methanol preserved 40ml vial.
4. Replace cap and invert as many times as necessary to ensure that soil is saturated with
methanol.
5. Collect 4oz jar of undisturbed soil for dry weight analysis.
NOTE;
A. In the event that low level soil VOC testing is determined to be necessary, the methods
and procedures outlined Michigan Department of Natural Resources and Environment,
Remediation and Redevelopment Division (MDEQ/RRD) Operational Memorandum No.
2, Attachment 6, page 3: Method 5035A, Low Concentration Method shall be followed.
B. All soil testing results shall be reported on a dry weight basis.
References
MDNRE/RRD Operational Memorandum 2, Attachment 4
MDNRE/RRD Operational Memorandum 2, Attachment 6
2
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SOP-8 SOIL SAMPLING
3.0 - Near Surface Soli Sampling
Purpose
The purpose of this technical practice is to provide a general guideline for collecting and
handling soil samples obtained from the surface to 8 inches below the surface.
Equipment/Materials
• Appropriate level of personal protective equipment (PRE)
• Shovel or hand trowel
• Photo-ionization detector (PID)
• Appropriate sample containers provided by the analytical laboratory
• Alconox
• Scrub brush
• Distilled water
• 5 gallon pail
Procedures
1. Clear ground surface of vegetation, debris, and loose material to expose undisturbed
soil.
2. Use tools to gently obtain the appropriate sample volume.
3. Decontaminate the tools between each sample location.
4. Each sample will be screened with a PID for the presence of volatile constituents. A
boring log will be constructed based on observations from the soil samples. USCS
information, including soil type, grain-size, color, moisture content, and PID reading, will
be recorded on a field boring log.
5. Collect soil sample (see Section 2.0 of this document and/or Section 4.5 of the SAP for
recommended parameters and preservation, storage and analytical methods and
procedures)
6. Following completion of sampling, the location will be backfilled with any remaining
cuttings.
3
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SOP-8 SOIL SAMPLING
4.0 - Soil Sampling - Manual Soil Boring
Purpose
The purpose of this technical practice is to provide a general guideline for the manual collection
and handling of subsurface soil samples,
Equipment/Materials
• Appropriate level of PPE
• Hand auger
• P1D
• Appropriate sample containers provided by the analytical laboratory
• Alconox
• Scrub brush
• Distilled water
• 5 gallon pail
Procedures
1. The hand auger shall be decontaminated prior to the first, and between each soil boring.
2. Using the hand auger, manually advance the soil boring to obtain the requisite samples.
Soil samples will be obtained from the lower half of the auger bucket at six inch intervals.
3. Each sample will be field screened with a PID for the presence of volatile constituents.
4. A field boring log will be constructed based on observations from the soil samples. The
following information will be recorded:
• USCS information, including soil type, grain-size, color, moisture content
• PID reading
• Collect soil sample (see Section 2.0 of this document and/or Section 4.5 of the SAP for
recommended parameters and preservation, storage and analytical methods and
procedures)
5. Following completion of the boring, the borehole will be backfilled with any remaining
cuttings. At a minimum, the upper 2 feet of the borehole will be backfilled with bentonite
pellets. Surface features, such as pavement, asphalt, soil, etc., will be utilized to restore
the site to its original status.
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SOP-8 SOIL SAMPLING
5 J - Drilling and Sampling Using Direct Push Techniques
Purpose
The purpose of this technical practice is to provide a genera! guideline for the collection of soil
samples using direct push techniques.
Equipment/Materials
• Appropriate level of PRE
• Geoprobe®, or equivalent hydraulically-actuated direct-push drill rig
• Plastic sampling sleeves
• Razor knife
• PID
• Appropriate sample containers provided by the analytical laboratory
• Alconox
• Scrub brush
• Distilled water
• 5 gallon pail
Procedures
1. The stainless steel coring sleeve and drill rod shall be decontaminated prior to the first,
and between each boring.
2. When drilling with a direct-push drill rig, the drilling contractor will follow methods and
procedures outlined in American Society for Testing and Materials (ASTM) D6282-
93(2005). The drilling contractor will use hydraulic drive core/direct-push sampling
techniques. Continuous soil samples will be collected from the soil borings at
appropriate (generally 5-foot, 4-foot and/or 2-foot) intervals, according to ASTM. A
clean, plastic sampling sleeve will be used for each sample interval,
3. Every 2-foot section of the sample core will be field screened with a PID for the presence
of volatile constituents.
4. A field boring log will be constructed based on observations from the soil samples. The
following information will be recorded:
• USCS information, including soil type, grain-size, color, moisture content
• PID reading
• Collect soil sample (see Section 2.0 of this document and/or Section 4.5 of the SAP for
recommended parameters and preservation, storage and analytical methods and
procedures)
5. Following completion of boring, the borehole will be backfilled with any remaining
cuttings. At a minimum, the upper 2 feet of the borehole will be backfilled with bentonite
pellets. Surface features, such as pavement, asphalt, soil, etc., will be utilized to restore
the site to its original status.
5
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SOP-8 SOIL SAMPLING
6.0 - Drilling and Sampling Using Hollow Stem Auger (HSA) Techniques
Purpose
The purpose of this technical practice is to provide a general guideline for the collection of soil
samples using hollow-stem auger (HSA) techniques.
Equipment/Materials
• Appropriate level of PRE
• Drill Rig
• Hollow-stem augers
• Appropriate sample containers provided by the analytical laboratory
• PID
• Alconox
• Scrub brush
• Distilled water
• 5 gallon pail
Procedures
1. The hollow-stem augers shall be decontaminated prior to the first, and between each
boring,
2. When drilling with hollow stem augers, the drilling contractor will follow methods and
procedures outlined in ASTM 06151-97(2003). While drilling with hollow-stem augers,
soil samples will be collected at 5.0-foot-intervals using a 2-foot-long, 2-inch-diameter
clean stainless steel split-spoon sampler. The stainless steel split-spoon sampler will be
decontaminated between each sample.
3. Each sample will be screened with a PID for the presence of volatile constituents.
4. A field boring log will be constructed based on observations from the soil samples. The
following information will be recorded:
• IJSCS information, including soil type, grain-size, color, moisture content
• PID reading
• Collect soil sample (see Section 2.0 of this document and/or Section 4.5 of the SAP for
recommended parameters and preservation, storage and analytical methods and
procedures)
5. Following completion of boring, the borehole will be backfilled with a cement/bentonite
slurry (90/10 mixture). Soil cuttings will be handled in accordance with appropriate
investigative-derived waste practices. Surface features, such as pavement, asphalt, soil,
etc., will be utilized to restore the site to its original status.
8
-------
SOP-8 SOIL SAMPLING
7.® - Soil Sampling - Test Pit Sampling
Purpose
The purpose of this technical practice is to provide a general guideline for investigating
subsurface soils using test pit techniques to collect soil samples for visual and chemical
characterization.
Equipment/Materials
• Appropriate level of PRE
• Backhoe or other powered excavating equipment
• Appropriate sample containers provided by the analytical laboratory
• PID
• Alconox
• Scrub brush
• Distilled water
• 5 gallon pail
Procedures
1. Brush the backhoe bucket clean of loose dirt before beginning excavation of the test pit.
2. Begin excavation away from the target feature, and work towards the feature.
3. Dig pits in 2-foot increments with a backhoe. Excavate pits perpendicular to the long axis
of the target features, if possible and appropriate for the work plan.
4. A field logger is to record all activities, soil characteristics, and other observations in the
field. The field logger will record the appearance of the excavated soil and the
appearance of the sidewalls.
5. Use clean gloves and collect a full set of soil samples at each depth increment specified
in the field sampling plan. The backhoe will scoop the samples from the appropriate
sample layer. Collect the sample directly from the backhoe bucket. At no time is the field
logger to enter the excavation if it is greater than 3 feet deep.
6. See Section 2.0 of this document and/or Section 4.5 of the SAP for recommended
parameters and preservation, storage and analytical methods and procedures.
7. Continue excavating until the test pit extends to one of the following:
• The local water table
• Depth specified in the field sampling plan
8. At termination of excavation, backfilt test-pit with spoils of excavation. Compact the
material from time to time during backfilling with pressure from the backhoe bucket.
7
-------
SOP 8-SOIL SAMPLING
Appendix 1
MDEQ/RRD Op Memo 2, Attachment 4
'Sample Preservation, Sample Handling, and Holding Time Specifications*
1
-------
Remediation and
Redevelopment Division
Michiqan Department of Environmental Qualit
October 22, 2004
RRD OPERATIONAL MEMORANDUM NO. 2
SUBJECT: SAMPLING AND ANALYSIS - ATTACHMENT 4
SAMPLE PRESERVATION, SAMPLE HANDLING, AND HOLDING TIME
SPECIFICATIONS
Key definitions for terms used in this document:
NREPA:
Part 201:
Part 211:
Part 213:
MDEQ:
RRD:
U.S. EPA:
Criteria or criterion:
Facility:
PURPOSE
The Natural Resources and Environmental Protection Act, 1994 PA 451,
as amended
Part 201. Environmental Remediation, of NREPA
Part 211. Underground Storage Tank Regulations, of NREPA
Part 213, Leaking Underground Storage Tanks, of NREPA
Michigan Department of Environmental Quality
Remediation and Redevelopment Division
United States Environmental Protection Agency
Includes the cleanup criteria for Part 201 and the Risk-based Screening
Levels as defined in Part 213 and R 299.5706a(4)
Includes "facility" as defined by Part 201 and "site" as defined by Part 213
This attachment to RRD Operational Memorandum No. 2 provides sampling handling,
preservation, and holding time specifications. This attachment applies to site assessments, site
investigation and response activities under Part 201» Part 211, and Part 213.
SAMPLE CONTAINERS AND PRESERVATIVES
Containers and preservatives should be obtained from the laboratory performing the analysis
whenever possible. When this is not possible, arrangements must be made with the selected
laboratory to ensure the sample containers and preservatives to be used are appropriate.
Preservatives must be provided with appropriate identification marks, safety information,
instructions for use if necessary, and with expiration dates. The preservatives and expiration
dates must be recorded into field logbooks as samples are collected so that each preserved
sample is cross referenced with the added preservative(s).
The specific size, types of containers, and associated container codes used by the MDEQ
laboratory are identified in Table 1. Preservatives normally used are listed in Table 2.
Appropriate containers for each contaminant are specified with their respective bottle codes in
Table 3.
Chemical preservatives should be used in their recommended dosages. If a little preservative is
good, more is not necessarily better. Preservatives must be replaced at intervals specified by
the manufacturer or laboratory and whenever contamination is suspected. Chemical
preservatives should not be added to soil samples, except when specified in a sampling
protocol, e.g., methanol preservation of soils analyzed for volatile organic compounds.
Chemical preservatives should never be added to unknown or untreated liquid wastes and to
samples of unknown matrix or source. Violent reactions can occur as acids are added to basic
waste or conversely when bases are added to acidic waste. Adding acids to samples
-------
Remediation arid
Redevelopment Division
Michigan Department of Environmental Quality
containing high cyanide or sulfide levels could result in generation of dangerous quantities of
cyanide or sulfide gas.
Sample preservation should be performed immediately upon sample collection or arrangements
made with the laboratory to preserve samples within the specified time. For composite
samples, when possible, each aliquot used to make the composite should be preserved at the
time of collection. When use of an automated sampler prevents preservation of each aliquot,
the aliquots should be maintained at about four degrees centigrade (4° C) until composite
samples can be preserved.
If a sample reacts vigorously when preservatives are added, discard the sample and obtain a
new sample without preservation. Label the sample appropriately to advise the laboratory that it
is not preserved; record the behavior of the sample in the field logbook and on chain of custody
or sample receipt forms so that it is appropriately communicated to the laboratory.
CONTAMINATION FROM SAMPLE CONTAINERS OR PRESERVATIVES
Documentation must be maintained by the laboratory to uniquely identify the source of the
material used to make each preservative. The results of methanol blanks, trip, and field blank
samples should be routinely reviewed for evidence of contamination from preservatives or
sample containers. In the event preservative and sample containers cannot be ruled out as
contamination sources, relevant information must immediately be provided to the laboratory,
and suspect supplies not used until their suitability can be established. If the laboratory
determines that preservative or sample containers are possible sources of contamination, the
laboratory should then inform their clients as appropriate.
HOLDING TIMES
Samples should be processed and/or analyzed as soon as possible after collection. Table 3
specifies the maximum amount of time the sample and any sub-sample generated from the
sample can be held. Samples not meeting these specifications must receive a holding time
code or other data qualifier. Where more than one holding time is specified, all applicable
holding times should be used to validate results. Samples may be held for longer periods only if
the laboratory has data on file to show that the specific types of samples under study are stable
for longer periods.
Sample collection and delivery to the laboratory must ensure holding times will not be
exceeded. Laboratory sample schedules are contingent upon priorities of other samples and
unforeseen events such as instrument malfunction. Schedules can change after samples have
been delivered to the laboratory. To minimize the impact of schedule changes, it is important to
provide instructions to the laboratory, before or during sample receipt at the laboratory,
concerning actions to take when a schedule change affects the ability to meet holding times.
Results from samples analyzed past the holding times are not necessarily unusable. When
holding times are exceeded, the usability of the data will depend on such factors as the
relationship between sample levels and cleanup criteria, the type of decisions to be based on
the data, the presence of other data from other samples, and other factors relative to whether
the data establishes a reliable representative concentration of the hazardous substance. When
holding times are exceeded, results should be interpreted as a minimum concentration.
VOLATILE CONTAMINANTS
Specifications for collecting soil samples using methanol preservation are provided in RRD
Operational Memorandum No. 2, Attachment 6. The preservation of samples to be analyzed for
volatile contaminants is dependent upon the requirements provided in SW-846, Method 5035A.
D£€i
RRD Operational Memorandum No. 2 - Attachment 4
Page 2 of 20
October 22, 2004
-------
DIG
This method should be consulted for guidance. Table 3 below has the requirements taken from
Method 5035A. Future revisions of Method 5035A may alter these requirements.
DE-CHLORINATION
Water samples existing naturally in the environment should not need de-chlorination. De-
chlorination procedures may be required for some samples taken from water sources where
chlorination is used. De-chlorination is accomplished using the instructions provided in Table 3,
footnote number 4, under De-chlorinate. Specific procedures for methods and contaminants
may apply and should be used when possible. Applicable contaminants for which de-
chlorination procedures may be required are provided below.
Acetonitrile
Acrolein
Acrylonitrile
Acrytamide
Benzidines
Chlorinated Acids/Herbicides
Chlorinated Pesticides
1,2-Dibromo-3-Chioropropane
1,2-Dibromoethane (EDB)
Nitrosamines
Organophosphorus Pesticides
Phenolics
Polychlorinated biphenyls
1,2,3-Trichloropropane
Semivolatiles
Volatiles
ANALYSIS OF GASOLINE OXYGENATES
High temperature purging during analysis of acid preserved samples can cause ethers to
degrade which may result in underreporting of some ethers. When a sample is collected and
preserved with acid for the analysis of volatiles that include gasoline oxygenate compounds,
methyl(tert)butylether, t-Butyl alcohol, Di-isopropyl ether, Ethyl(tert)butylether, Ethyl alcohol,
Methyl alcohol, and Tertiaryamylmethylether, the acid-preserved samples should be neutralized
prior to analysis. Trisodium phosphate dodecahydrate (TSP) has been determined by the U.S.
EPA to be effective and safe for this purpose. Separate samples may be collected specifically
for the analysis of oxygenates, and preserved using TSP to adjust the pH to > 11 rather than
preserving them with acid.
SAFETY
Be aware of dangers associated with chemical preservatives and their handling. Obtain
Material Safety Data Sheets (MSDSs) from the laboratory providing the preservative prior to the
sampling event to determine appropriate safety precautions and first aid. MSDSs should
accompany personnel in the field. Preservatives must be stored in sealed containers away from
other preservatives, and away from environmental and quality control samples. Use safety
glasses and appropriate gloves to handle chemicals and properly place them into a closed
chamber at the site until proper disposal can be arranged.
APPLICABILITY
Many published methods include specifications for sample containers, preservation, and holding
times that may be specific for certain contaminants analyzed using the specific method. Those
specifications may be more detailed than the specifications provided in Table 3 or in similar
generic tables. When samples are collected for analysis by a method not specifically listed in
Table 3, the method-specific requirements for sample containers, preservation, and holding
times must be followed.
RRD Operational Memorandum No. 2 - Attachment 4 Page 3 of 20 October 22,2004
-------
Remediation and
Redevelopment Division
Michigan Department of Environmental Quality
There are additional sources of holding time and preservation guidance, including the Clean
Water Act, the Resource Conservation Recovery Act, the Safe Drinking Water Act, and the U.S.
EPA CLP. The guidelines and specifications in this document are applicable to water and soil
matrices and for contaminants regulated under Parts 201, 211, and 213. These guidelines and
specifications may not be applicable to other matrices or to cleanups conducted under other
regulatory programs. When samples are required to meet the criteria of another regulatory
agency, the requirements for sample preservation, sample containers, and holding time of that
agency should be applied.
Questions concerning this memorandum should be directed to Mr. A. Ralph Curtis, RRD, at
517-373-8389; or email to curtisar@michiaan.gov.
The following documents are rescinded with the issuance of this attachment:
• Environmental Response Division Operational Memorandum 16, Sample Preservation,
Sample Handling, and Holding Time Guidelines for the Act 307 Program, dated
January 4,1995.
• Storage Tank Division Operational Memorandum 14, Analytical Parameters and
Methods, Sample Handling, and Preservation for Petroleum Releases, Table 4,
Container, Preservation, and Holding Time Requirements for Common Petroleum
Product Sampling and Analysis, dated June 12, 1998.
APPENDED TABLES;
Table 1. Sample Containers and Container Codes
Table 2. Preservatives
Table 3. Specifications for Sample Containers, Preservation, and Holding Times
This memorandum and its attachments are intended to provide direction and guidance to foster
consistent application of Part 201, Part 211, and Part 213 and the associated administrative
rules. This document is not intended to convey any rights to any parties or create any duties or
responsibilities under the law. This document and matters addressed herein are subject to
revision.
RRD Operational Memorandum No. 2 - Attachment 4
Page 4 of 20
October 22, 2004
-------
DG&
Remediation and
Redevelopment Division
Michigan Department of Environmental Quality
Table 1, Sample Containers and Container Codes
Container
Size
Container
Size
Code
ml
Bottle Type
Code
ml
Bottle Type
DO
250
Glass, glass stopper
BNA
1000
Glass, ambi
GN
500
Plastic
MS
250
Glass, wide mouth
GA
500
Plastic
GS
250
Glass, wide mouth
GG
250
Glass, screw cap
OS/BNA
250
Glass, wide mouth
GB
500
250
Plastic
Plastic
VOA
40
Glass, septum vial
(soils require MeOH kit)
S
250
Plas
SCD
NA
S^rcot^"d^'ice T,J"
MA
500
Plas
MO
250
Glass, wide mo
MAD
500
Plas
OL
250
Glass, wide mouth
MD
500
Plas
HW
250
Glass, wide mo
MN
500
Plas
MX
250
Glass, wide mo
OG
250
Glass, wide mouth
OX
250
Glass septum j«
VOA
40
Glass Septum \
L
500
Fluoropolymer"
ON
1000
Glass, amber
M
250
"Glassor HDP7"
Sealed Vial
Varies
Laboratory Specific
HDP
125
High Density Polyethyt
1. SCD, L, M and HDP are not MDEQ Lab bottle codes.
2. The syringe type coring device, SCD, refers to the samplers listed in Method 5035A, or other
validated samplers,
3. Contact the lab regarding availability and cleaning instructions.
Table 2. Preservatives
The following tabie represents the preservatives normally used for sampling and the approximate
amounts to meet a targeted preservation.
Preservative
Concentration
Preservation
Approximate Amount
Sulfuric Acid (H2S04)
Cone.
pH <2
5 drops per 250 ml.
Nitric Acid (HN03)
1:1
pH <2
5 ml per 250 ml.
Hydrochloric Acid (HCl)
1:1
pH < 2
5 drops per 40 ml.
Sodium Hydroxide (NaOH)
10 N
pH > 9
2 drops per 250 ml.
pH > 12
10 drops per 250 ml.
Chloroacetic Acid
0.1 N
pH 4-5
Varies with sample
Trisodium phosphate
dodecahydrate (TSP)
Powder
pH> 10
Varies with sample
MeOH
Lab Grade
1:1
10 ml per 10 gr soil.
Ascorbic Acid
Powder
Oxidizing Agents
About 0.6 gr per L,
Sodium Arsenite
0.1 N
Oxidizing Agents
5 ml per L.
Zinc Acetate (ZnAc)
2 N
interferences
10 drops per 250 ml.
Disodium EDTA
2.5 %
Interferences
1 ml per 100 ml.
Ethylenediamine
Powder
Interferences
50 mg per L
RRD Operational Memorandum No. 2 - Attachment 4
Page 5 of 20
October 22, 2004
-------
DCa
Michigan Department of Environmental Qualit
Tab
Contaminants 2
Methods r
Container Codes 1
Preservation 4
Holding Time 5
Soil
Water
Specific Contaminants I
Collection to Analysis
Acidity
305.1
MN
4° C
14
D;
Alkalinity
; ¦
MN
4° C
14
Days
Anions by Ion Chromatography
9056 30
MN
Contaminant Specific6
Acetate
MN
4° C
2
Days
Formate
MN
4° C
2
Dt
Bromide
MN
None Required
28
Di
Chloride
MN
None Required
28
Days
Fluoride
MN
None Required
28
Days
Nitrate or Nitrite-N
MN
4° C
48
Hours
Nitrate and Nitrite-N
MN
pH < 2 H2S04, 4° C
28
Days
Ortho-Phosphate-P
MN
4° C
48
He
Sulfate
MN
4° C
28
Di
Bromate
MN
None Required
28
Days
Chlorate
MN
None Required
28
Days
Chlorite
BNA
50 mg Ethylenediamine per L. 4° C
14
Days
Asbestos
100.1
GN
4° C
48
Hours
Biochemical Oxygen Demand
405.
GN
4° C
48
Hours7
Bromide
320.1
GS
MN
None Required
28
Days
Chemical Oxygen Demand
410
GA
pH < 2 H2S04, 4° C
28
Dc
Chloride
325
GS
MN
None Required
28
Days
Chlorine, Total Residual
330
GN
None Required
Immediately
Color
110
GN
4° C
48
Hours
Conductance, Specific
9050A
—.
MN
4° C
28
Days
Fluoride
!
MN
None Required
28
Days
Hardness
'
MA
pH <2 1:1 HN03/H2S04, 4° C
8
Months
Hydrogen Ion, pH
904C. 90-:
GS
MN
None Requ
24
Hours
RRD Operational Memorandum No. 2 - Attachment 4 Page 6 of 20 October 22, 2004
-------
iH
Remediation and
Redevelopment Division
Michigan Department of Environmental Qualii
Table 3, Specifications for Sample Containers, Preservation, and Holding Times
Contaminants
Methods
Containers
Preservation
Holding Time
Soil
Water
Specific Contaminants
Collection to Analysis
Iodide
345.1
....
MN
4° C
28
Days
Odor
SM 2150B
—
GN
4° C
24
Hours
Total Organic Carbon (TOC)
415.1
GA
pH < 2 H2S04 / HGI/NaHS04, 4° C
28
Days
Fraction of Organic Carbon
Walkley-
Black
GS
GN
4° C
28
Days
Fraction of Organic Matter
D2974
GS
GN
4° C
28
Days
Oxygen, Dissolved, Probe
360.1
—
DO
None Required
Immediately
Oxygen, Dissolved, Winkler
360.2
—
DO
"Fix "on"site with DO Kit ffi,"awid"aeratio^"
8
Hours
store at 10-20° C in dark.
Perehlorate
340.1 9058
GS
MN
None Required
28
Days
Petroleum Hydrocarbon Materia?
1684
9071B
2xOG
2xOG
pH < 2 HCL, 4° C. For dry soils cool to
4° C. For pourable sediments and soils
add 2 ml 1:1 HCI periOOg, 4° C
ASAP5
nolics
420.2
GG/GP
pH < 2 H2S04, 4° C
28
Days
Phosphorus, Ortho, Dissol i
365
—
GN(D)
Filter on site immediately, 4° C
48
Hours
Phosphorus, Element?1
—
GA
4° C
48
Hours
Phosphorus, T<
385.4
—
GA
pH < 2 H2S04, 4° C
28
Days
Residue, Total
160.3
GN
4° C
7
Days
Residue, Filterabl
160.1
GN
4° C
7
Days
sidue, Non-Filterable (TSS)
160.2
GN
4° C
7
Days
Residue, Settleabio
160.5
—
GN
4° C
48
Hours
Residue, Volatile
160.4
—
GN
4° C
7
Days
Silica
370.1
—
GN
4° C
28
Days
Sulfate
375.1
—
MN
4° C
28
Days
RRD Operational Memorandum No, 2 - Attachment 4 Page 7 of 20 October 22, 2004
-------
Remediation and
Redevelopment Division
Michigan Department of Environmental Qualit
Table 3. Specifications for Sample Containers, Preservation, arid Holding Times
Contaminants
Methods
Containers
Preservation
Holding Time
I
Water
Specific Contaminants
Collection to Analysis
Sulfide
9030 376.1
GS
See Footnote 11
7 Day:
S
Cover surface of collected soil with 2 M
ZnAc until moistened. No headspace.
Sulfite
377.1
—
HDP
Avoid contact with air, cool < 50" C and
add 1 ml EDTA 12 per 100 ml., < 50° C
Immediately
Temperature
170.1
Not Applicable
On site
Total Recoverable Petroleum
Hydrocarbons (TRPH)
8440 13
GS
4° C
ASAP s
Turbidity
180.1
—
GN
4° C
48 Hours
Biological Tests
Coliform, Fecal and Total
9131 9132
—
M
4° C
8 Hours14
Fecal Streptococci
SM 9230
M
4° C
i" I lO'.lio
Cyanides
Cyanide, Total
9010B
GS
—
See Footnote 15
14 bay;-
Unpreserved
24 Hours
Cyanide, Available
OIA1677
/% £**
bo
GB
See Footnote 15
14 Days
Unpreserved
24 Hours
Cyanide, Amenable (Free;
D4298-02
GB
pH a 12 NaOH, store in dark, 4° C
24 Hours to diffusion
Nitrogen Forms
Ammonia - N
350.1
GS
GA
pH < 2 H2S04, 4° C
28 Days
Kjeldahl - N
351.1
GS
GA
pH < 2 H2S04, 4° C
28 Da v.-
(Nitrate + Nitrite) - N
353.2
GS
GA
pH < 2 H2S04, 4° C
28 Dc
(Nitrate + Nitrite) - N
Nitrate - N or Nitrite - N
353.2
353.2
GS
GS
GA
GN
4° C
4° C
24 Hours
48 Hours
RRD Operational Memorandum No. 2 - Attachment 4 Page 8 of 20 October 22, 2004
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Dca
Remediation and
Redevelopment Division
Michigan Department of Environmental Qualit
Table 3, Specifications for Sarot itainers, Preservation, and Holding Times
Contaminants
Methods
Containers
Preservation
Holding Time
Soil
Water
Mercury
Collection to Analysis
Mercury, Total
7470 7471
MS
MA
pH < 2 1:1 HM03 , 4° C
28 Days
Mercury, Low Level
1669/1631
MS
L
10 ml 1:1 Hg-free HN03 per L, 4° C
28 Days
Hexavaient Chromium
Chromium VI (waters)
7199
HDP
Ose buffer solution 16 to adjust pH 9-
9.5 (check with pH paper or pH meter)
4° C
24 Hours
7196
—
MM
4° C
24 Hours |
Collection
To
Preparation
Preparation I
To Analysis
Chromium VI (soils)
3060A 17
MS
4° C, Store field-moist
Dry Soils:
High moisture soils and sediments:
2 Days
7
Day:
30 Days
7
Days |
Low Molecular Weight Acids
5560 C
GS
GN
None Required
NA
~NA
Glycols
8015C
GS
GN
None Required
NA
~NA I
Phosphorus, White 18
7580
OX
VOA
Limit contact with air. No headspace,
4° C, store in dark. Tightly seal extracts
and refrigerate.
5 Days
Extracts:
Ether Extract
—
8 Hours
Iso-Octane Extract
^
30 Days
RRD Operational Memorandum No. 2 - Attachment 4 Page 9 of 20 October 22, 2004
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D6-1
Michigan Department of Environmental Qualit.
Table 3. Specifications for Sample Containers, Preservation, and Holding Times
Contaminants
Methods
Containers
Preservation
Holding Time
Soil
Water
Metals
Collection To Analysis
Metals, Totals
6010/6020
MS 19
MA
pH < 2 1:1 HN03, 4" C
6
Months
Metals, Dissolved
6010/6020
—
MD
MA(D)
Filter and preserve < 24 Hours of
sampling. pH < 2 1:1 HN03 , 4° C
6
Months
Specific Organic Compounds
Acetonitrile
8033
—
2 x VOA
pH < 2 H2S04, 4° C
14
Days
Acrolein
603 8316
2 x VOA
pH 4-5 HCI, 4° C
14
Days
Acrolein
603
2 x VOA
4° C
3
Days
Acryionitrile
603
2 x VOA
4° C
14
Days
Acrolein and Acryionitrile
603
2 x VOA
pH 4-5 HCI, 4° C
14
Days
Acrolein and Acryionitrile
603
—
2 x VOA
4° C
3
Days
Acrylarr
8032
—
2 x VOA
pH < 2 HCL/H2S04, 4° C
14
Days
Specific Organic Compounds
Collection to
Preparation
Preparation
to Analysis
Benzidines
605 8270C
OS
BNA
BNA
Adjust pH 2-7 using H2S04 and
10 N NaOH. If 1,2-
dephenylhydrazine is expected to be
present, adjust pH to 3.8-4.2 H2S04
and 10 N NaOH 4° C, store extracts
in inert atmosphere in dark
W:
7 days
7 days
Carbamates
8318
OS
BNA
BNA
Cool, pH 4-5 using 0.1 N Chloroacetic
Acid, 4° C, store sample and extracts
in dark
W:
S:
7 days
7 days
40 days
40 days
Carbonyls
8315A
OS
BNA
BNA
4° C
W:
S:
3 days
3 days
3 days
3 days
RRD Operational Memorandum No. 2 - Attachment 4 Page 10 of 20 October 22, 2004
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DGa
Remediation and
Redevelopment Division
Michigan Department of Environmental Qualit
Table 3. Specifications for Sample Containers, Preservation, and Holding Times
I
Containers
I Contaminants
Methods
Soil
Water
Preservation
Holding Time
Specific Organic Compounds
Collection
To
Preparation
Preparation
To
Analysis
Chlorinated Acids/Herbicides
8151A
OS/B
NA
BNA
4° C, store samples and extracts in
dark
W: 7 Days
S: 14 Days
40 Days
40 Days
Dioxins and Furans
8290 1613
OS/B
NA
ON
4° C, store in the dark
30 Days
45 Days
1,2-Dibromoethane (EDB)
1,2-Dibromo-3~ChIoropropane,
1,2,3-T richloropropane
8011 504.1
VOA
4° C
W: 14 Days
Immediately
Nitrosamines
8270C
OS/B
NA
BNA
pH 7-10 with H2S04 and 10 N NaOH,
store extracts in sealed vials, in dark at
-10° C
W: 7 Days
S: 14 Days
40 Days
40 Days
Chlorinated Pesticides 20
8081A
OS/B
NA
2 x ON
See 23 23
pH 5-9 with H2S04 and 10 N NaOH
within 72 hours, 4°C, store extracts in
dark.
W: 7 Days
S: 14 Days
40 Days
40 Days
Organophosphorus Pesticides 21
8141A
OS/B
NA
ON
4° C Store samples and extracts in dark
W; 7 Days
S: 14 Days
40 Days
40 Days
Polychlorinated biphenyls
8082
OS/B
NA
2 x ON
See 23 23
4° C Store extracts in dark
W: 7 Days
S: 14 Days
40 Days
40 Days
Semivolatiles22 — •— -
8270C
OS/B
NA
2 x BNA
See 23
Store extracts in sealed vials, in dark at
-10° C
W: 7 Days
S: 14 Days
40 Days
40 Days
RRD Operational Memorandum No. 2 - Attachment 4 Page 11 of 20 October 22, 2004
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oca
Remediation and
Redevelopment Division
Michigan Department of Environmental Qualit
Table 3, Specifications for Sample Containers, Preservation, and Holding Tiroes
Contaminants
Methods
Containers
Preservation
Iding Time
Volatiles (waters)
Collection To Analysis
Fuel Oxygenates
8260B
2 x VOA
no headspace, TSP to pH > 11, 4° C
180 Days
Reactive compounds24
8260B
2 x VOA
no headspace, 4° C
ASAP®
Other Compounds
8260B
2 x VOA
pH < 2 using 1:1 HCI or solid NaHS04, no
headspace, 4° C
14 Days
Volatiles (soils)25
Reactive Compounds
Examples include styrene,
2-Chloroethylvinylether
Low
Concentration
Sealed Vial
Use reagent water (no acid preservative),
freeze > -20° C , < -7° C on site
ASAP 5
SCD
4° C or freeze > -20° C , < -7° C on site,
extruded into sealed vial without acid
preservative within 48 hours
ASAP"5
Volatile Compounds
Methanol
2 x VOA
Preserve on site using ratio 1:1 methanol to
soil, 4° C
14 Days
Volatile Compounds
Methanol
SCD 1 4° C or freeze > -20° C , < -7° C on site and
extruded into sealed vial with methanol within
I 48 hours
14 Days
RRD Operational Memorandum No. 2 - Attachment 4 Page 12 of 20 October 22, 2004
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Michigan De.
1
JSl
Table 3. Specifications for Sample Containers, Preservation, and Holding Times
Hazardous Waste Characterization Using Method 1312
Field Collection
TCLP Extraction
Preparative Extraction
To
To
To
Total Elapsed
Contaminants
Containers
TCLP Extraction
Preparative Extraction
Determinative Analysis
Time
Volatiles
OX
14 Days
Not Applicable
14 Days
28 Day:
Semivolatiles
MX
14 Days
7 Days
40 Day:
61 Day
Mercury
MX"
28 Days
Not Applicable
28 Day;
56 Day
Metals
MX
130 Days
Not Applicable
180 Days
380 Da>
Radiochemistry Contaminants
Containers
I
Holding Time
Radiochemistry Contaminant
Method
Water
I Preservation
Collection To Analysis
Gross Alpha, and Gross Beta
9310
1 L HDP or Glass
JPTtoTTirHNOS
6 Month--
Alpha Emitting Radium Isotop
9315
1 L HDP or Glass
llWtoYTTTMoa
6 Months
Radium 228
9320
1 L HDP or Glass
1 pH to 2 1 N HN03
6 Months
Unpreserved samples for analysis of radiochemistry contaminants must be received at the laboratory within five days of collection.
RRD Operational Memorandum No, 2 - Attachment 4 Page 13 of 20 October 22, 2004
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DE©,
Remediation and
Redevelopment Division
Michigan Department of Environmental Qualit
Table 3, Specifications for Sample Containers, Preservation, and Holding Times
Wisconsin GRO/DRO Guidelines
Contaminants
Organic Compounds
Methods
Containers
Preservation 26
Holding Times
Soil
Water
Collection To
Preparation
Preparation
To Analysis
Gasoline Range Organics
Waters:
Carbonate aquifer waters:
Carbonate aquifer waters:
Soils:
8015-Wis
3 x VOA
0.5 ml 1:1 HCI to sample bottie first, no
headspace, avoid agitation, 4° C
14 Days
14 Days
3 x VOA
P re"^ rveTwl t iT S od i unT Az id e ~~
14 Days
14 Days
3 x VOA
Without Sodum Azide i7
2 Days
14 Days
VOA
Preserve in field with MeOH, 4° C
21 Days
21 Days
SCD
4° C, preserve with MeOH < 48 Hours
21 Days
21 Days
Diesel Range Organics
Waters:
Carbonate aquifer waters:
Carbonate aquifer waters:
Soils:
8015-Wis
BNA 28
5 ml 1:1 HCL to sample bottle first, no
headspace, 4° C
7 Days
47 Days
BNA 28
Preserved with Sodium Azide27
7 Days
47 Days
BHA
Without Sodium Azide77
2 Days
47 Days
VOA
SCD
4° C, preserve with MeOH 1:1 <72 hours
47 Days
47 Days
RRD Operational Memorandum No, 2 - Attachment 4 Page 14 of 20 October 22, 2004
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Remediation and
Redevelopment Division
Michigan Department of Environmental Quality
Table 3. Specifications for Sample Containers, Preservation, and Holding Times
For soils requiring leach tests to evaluate the mobility of non-volatile contaminants in soils 29
Contaminants31
Methods
Containers
Preservations (sample and
leachate)
Iding Ti.v:n- "
Sample
Leachate 32
Collection
To
Leaching
Leaching
To
Preparation
Leaching
To
Analysis
paration
To
Analysis
Mercury
7470
MX
4° C
pH <2 1:1 HNOS, 4° C
28 Days
28 Days
Metals
6010B/6020
MX
4° C
pH < 2 1:1 HN03, 4° C
180 Days
180 Days
Semivolatiles
8270C
MX
4° C
4° C, Store extracts from
the leachates in dark at
-10 0 C
14 Days
7 Days
40 Days
Pesticides
8081A
MX
r C
pH 5-9 10 N NaOH arid
H2S04, 4° C
14 Days
7 Days
40 Days
PCBs
8082 || MX
4° C
4° C, Store extracts from
the leachate in dark
14 Days
7 Days
40 Days
For soils requiring leach tests to evaluate the mobility of volatile contaminants in soils
Contaminants
Methods
Containers
Preservations (sample and
leachate)
Holding Times
Sample
Leachates
Collection To Leaching
Leaching To Analysis
"V^tatiies"53"" ~T
8260B 1 2 x SCD
<4° C
pH < 2 1:1 HCl, 4° C
48 Hrs
14 Days
D6&
RRD Operational Memorandum No. 2 - Attachment 4
Page 15 of 20
October 22, 2004
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Table 3 Footnotes
1. The container sizes and types specific for the MDEQ Environmental Laboratory (MDEQ Lab) are
listed in this table when applicable. Other laboratories may specify other sizes and types. Letters
in parentheses () indicate that the included letter must be added to the prefix code on the bottle
from the MDEQ Lab to indicate to the laboratory what process was used, if any, for preservation.
2. "Contaminants" refers to elements, individual compounds, groups of compounds, chemical or
physical properties. Contaminant groups in Table 3 are underlined and are simply identified for
convenience. These group names do not reflect any official or standardized groups used by other
agencies. Italicized contaminant names indicates that the MDEQ Lab does not perform analysis for
the contaminant.
3. Methods in the table are listed primarily to clarify the type of method routinely used for
environmental samples and preservation used for associated contaminants. The methods listed
are not the only methods acceptable. RRD Operational Memorandum No. 2, Attachment 1, TDLs
and Available Methods lists the available analytical methods the MDEQ has determined capable of
achieving theTDLs. When available methods are used, applicable sample preservation techniques
within those methods must be used.
4. Abbreviations and terms used for preservation are as follows:
Abbreviation Meaning Abbreviation Meaning
< - > Less than - Greater than HN03 Nitric acid
M Molar concentration NaOH Sodium hydroxide
N Normal concentration ZnAc Zinc acetate
HCI Hydrochloric acid ° C Degrees centigrade
H2S04 Sulfuric acid In Situ Measure in matrix
EDTA Ethylenediamine.tetra,acetic acid
ASAP - Make arrangements to deliver samples overnight and have laboratory analyze samples
upon receipt.
immediately - Transport samples to laboratory within 24 hours or overnight. Plans must be made
in advance to have the laboratory analyze the samples upon receipt.
4° C - Store samples at about four degrees centigrade. Just above freezing up to six degrees C is
acceptable. Ice is preferred to cool samples. If commercial ice packs are used, the bottom, waits,
and top inside cover of the cooler must be lined with the packs so as to completely encapsulate the
samples as much as possible. A temperature control sample should be included when blue ice
packs are used.
De-chlorinate - Means that a portion of the sample should be separated and tested for residual
chlorine. Diethyl-p-phenylenediamine (DPD) kits are commercially available to test for residual
chlorine in the field. About 25 mg ascorbic acid powder per 40 ml sample, for each 5 mg/L of
residual chlorine determined from the DPD kit, should be added to sample bottles testing positive
that are to be used to analyze for volatile contaminants, prior to sampling. For non-volatile
contaminants use 80 mg/L sodium thiosulfate per liter of sample for each 5 mg/L of residual
chlorine found. If pH adjustment is necessary, perform pH adjustment after dechlorination. Do not
mix dechlorination reagents with the preservatives used to adjust the pH. Treat the samples only if
they contain free or combined chlorine. Most environmental samples are not chlorinated while tap
water samples originating from a municipal water source usually are chlorinated.
PH - Indicates an estimated hydrogen ton measurement. Use only the specified chemicals to
adjust pH. Do not add more than is needed to obtain the desired pH. If preservation using
hydrochloric or sulfuric acids (HCI or H2S04 ) is needed, two drops of 1:1 HCI, or H2S04 for every
40 ml of sample, will lower the pH to less than two for most waters.
RRD Operational Memorandum No. 2 - Attachment 4 Page 16 of 20 October 22, 2004
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Remediation and
Redevelopment Division
Michigan Department of Environmental Quality
Table 3 Footnotes
5. "Holding Time" refers to the maximum time that a sample or sub-sample can be held before the
next step in the analysis is performed. Samples may be held for other specified times if the
laboratory has supporting data to demonstrate stability. Exceptions to times specified in the
heading of this column are explained within the table for each applicable contaminant.
6. The method of preservation and the holding time for samples analyzed by this method are
determined by the anions of interest. In a given sample, the anion that requires the most
preservation treatment and the shortest holding time will determine the preservation treatment.
Note: The addition of EDA has no effect on bromate or chlorate, so they can also be determined in
a sample preserved with EDA. Residual chlorine dioxide should be removed from the sample. Any
residual chlorine dioxide present in the sample will result in the formation of additional chlorite prior
to analysis. If any concentration of chlorine dioxide is suspected in the sample, the sample must be
purged with an inert gas (helium, argon, or nitrogen) for approximately five minutes or until no
chlorine dioxide remains. This sparging must be conducted prior to ethylenediamine preservation
and at time of sample collection.
7. Limit compositing to less than 24 hours and then follow grab sample guideline of 24 hours after
collection.
8. Several methods are available to measure TPH. Results are method dependent.
9. No hold time has been established. Samples should be analyzed as soon as possible.
10. The MDEQ Lab DO kit uses solutions designated as DO-1 (Manganese Sulfate ) and DO-2
(alkaline lodide-Azide).
11. Prior to collection, add to sample bottle 8 drops 1 M ZnAc per 100 ml sample to be collected and
enough 10 N NaOH expected to make pH > 9. Collect sample with minimum of aeration, add more
NaOH as needed to increase pH > 9. Fill bottle without headspace. If the sulfide concentration is
expected to exceed 64 mg/L, increase the amount of ZnAc proportionally.
12. Disodium EDTA. Prepare using 2.5 g per 100 ml distilled water,
13. Applicable to mineral oils. Not appropriate for analysis of soils for gasoline and other light
petroleum fractions.
14. Under the Federal Safe Drinking Water Act guidance, a 30-hour holding time for coliform samples
mailed from water treatment systems is acceptable. Water samples for coliform analysis should
have 1-2 inches of headspace in the sample container.
15. Aqueous samples should be tested for sulfides, oxidizing agents, and soluble aldehydes within 15
minutes of sampling to determine and preserve as appropriate. Alternatively, all samples may be
preserved with NaOH to a pH>12 and sent to the lab for analysis within 24 hours.
A. Test for Oxidizing Agents
Test a drop of the sample with potassium iodide-starch test paper. A blue color indicates the
need for treatment.
To samples testing positive add 0.1N Sodium Arsenite solution a few ml at a time until a drop of
sample produces no color on the indicator paper. Add an additional 5 ml of Sodium Arsenite
solution for each liter of sample.
Ascorbic Acid can be used as an alternative although it is not as effective as Sodium Arsenite.
Add a few crystals of Ascorbic Acid at a time until a drop of sample produces no color on the
indicator paper. Then add an additional 0.6 g of Ascorbic Acid for each liter of sample volume.
D£€L
RRD Operational Memorandum No. 2 - Attachment 4 Page 17 of 20
October 22, 2004
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Remediation and
Redevelopment Division
a
Table 3 Footnotes
B. Test for Sulfides (Note that samples are always treated with Lead Carbonate or Cadmium
Nitrate.)
Samples with visible particulates must be filtered.
Keep this filter (#1).
Treat samples with solid Lead Carbonate or Cadmium Nitrate powder and immediately filter.
Discard this filter.
Test filtrate for sulfides using Lead Acetate paper and further treat samples showing positive
results with Lead Carbonate or Cadmium Nitrate powder and filter.
Discard this filter.
Continue testing until samples show a negative result for sulfides using Lead Acetate paper,
C. Soluble Aldehydes Test
Use a separate solution of the sample to test for aldehydes.
Treat samples showing a positive result with 20 ml of 3.5% Ethylenediamine solution per liter of
sample.
D. Preservation
Reconstitute the sample by adding the sediment collected on filter #1 back into the filtrate.
Add NaOH until the sample pH > 12 and cool to 4°C.
Maximum holding time is now 14 days. Equipment blanks must be handled the same as real
samples.
16. Buffer Solution. Dissolve 33 g of ammonium sulfate in 75 ml of reagent water and add 6.5 ml of
ammonium hydroxide. Dilute to 100 ml with reagent water. Degas the solution with helium gas for
5-10 minutes prior to use. Add the buffer solution, drop wise, to the sample and check after
addition with pH paper, or continuously with a pH meter.
17. Method 3060A must be used for preparation of soils. Barium chromate is only partially soluble
using Method 3060A. This method may not be appropriate for investigations involving this
contaminant when high levels of barium are found at sites.
18. White phosphorus from munitions is released into the environment in the form of small, discrete
particles. These particles persist in soils, sediments, and may occur as suspended or colloidal
particles in anoxic waters. Therefore, some samples or sample aliquots from a given location may
contain P4 particles while others do not. The nature and distribution of P4 contamination from other,
non-military, sources has not been studied, but sample collection procedures should address the
likelihood that P4 is present in discrete particles, and must be designed to ensure that multiple
representative samples of the matrix of interest are collected. In addition, soil and sediment
samples must be carefully homogenized and sub-sampled.
Aqueous samples should be poured gently into the sample container to minimize agitation which
might drive off the volatile P4. If bubbling does occur while transferring the sample to the container,
the sample should be discarded and another sample collected. Each container should be filled with
sample until it overflows. Each container should be tightly sealed with a PTFE-Iined cap. The
container should then be inverted to check for air bubbles. If any air bubbles are present, a new
sample must be collected.
19. If boron is a chemical of concern at a site, use a wide mouth plastic container for collection of soil
samples.
RRD Operational Memorandum No. 2 - Attachment 4 Page 18 of 20
October 22, 2004
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Table 3 Footnotes
20. If analysis includes BHCs, cis, trans-Permethrin, or Trifluralin, samples should be extracted as soon
as is practical. See requirements for specific pesticides, published under the Safe Drinking Water
Act and applicable to drinking water samples.
21. If analysis includes Disulfoton Sulfoxide, Diazinon, Pronamide, or Terbufos, samples must be
extracted as soon as is practical.
22. Includes groups referred to in other guidance as:
Total Petroleum Hydrocarbons (TPH), Acid Extractables (Phenols), Chlorinated Hydrocarbons,
Nitroaromatics and Isophorone, Nitrosoamines except Diphenylnitrosamine. Polynuciear Aromatics,
Phthalate Esters, Haloethers, and Phenolics.
23. If samples are to be analyzed for semivolatiles and pesticides/PCBs, collect a total of three
containers. For quality control purposes, collect an additional container for each contaminant
group, for every 20 samples.
24. Reactive contaminants with cleanup criteria include 2-chloroethylvinyl ether and styrene. Contact
the laboratory regarding other contaminants.
25. Preservation as provided in RRD Operational Memorandum No. 2, Attachment 6 is required for the
collection of soils. The MDEQ Lab provides a sampling kit to collect soil samples using this
procedure. Soils collected to determine volatiles leached from soils should be sampled with 25 gr
syringe-type coring devices.
The sonication time used to extract the volatile compounds from the soil is important and must be
standardized for analysis of volatile organic compounds in soil and comparison of results with the
cleanup criteria. Soils should be sonicated as soon as possible after receipt, and a 20-minute
sonication time must be used as specified in the MDEQ Lab SOP #501, Volatile Organic
Compounds by Gas Chromatography/Mass Spectrometry (GC/MS).
26. Specifications must be followed from Modified DRO, Method for Determining Diesel Range
Organics, Wisconsin DNR, September 1995 for DRO and Modified GRO, Method for Determining
Gasoline Range Organics, Wisconsin DNR, September 1995, for GRO.
27. The pH of all water samples must be determined by the laboratory unless sample vials containing
acid for field preservation were supplied by the lab. The pH measurement may be performed on
left-over sample. If the pH is greater than two, the sample results must be flagged. Flagging is not
required of samples collected from carbonate aquifers if preserved with sodium azide or extracted
within 48 hours of collection.
28. The Wisconsin procedure requires a Teflon™ lined cap. The Teflon™ must be touching the
sample.
29. The data in this table applies to soils to determine potential leaching of contaminants. See RRD
Operational Memorandum No.2, Attachment 2. Soil Leaching Methods for applicable leaching tests.
Each soil type tested should have associated quality control as provided in the leaching procedures.
This requires spiking the leaching solution with the contaminants of concern at levels above the
TDLs listed in RRD Operational Memorandum No.2. Attachment 1. When relevant pathways have
been evaluated for response activity under Part 201 or Part 213, spiking the leaching solution may
be appropriate at approximately one-half of the cleanup criteria for the appropriate pathway
whenever possible. Duplicate samples should be collected to facilitate the spiking of samples.
RRD Operational Memorandum No. 2 - Attachment 4 Page 19 of 20 October 22, 2004
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om
Table 3 Footnotes
Remediation and
Redevelopment Division
Michigan Department of Environmental Quality
The crushing, cutting, grinding, sieving, and filtering, or other procedures used in leaching
procedures may alter the physical characteristics of soils. As the physical characteristics of soils
may affect the mobility of contaminants, such procedures are not appropriate for soils for the
purposes of this test. Such procedures may be appropriate for other types of material such as brick
and concrete.
Samples collected and stored using a syringe-type coring device (SCD), as specified in
Method 5035 of SW-846, should be extruded directly into the leaching solution by the laboratory to
minimize exposure to the atmosphere.
After completion of the leaching procedure for soils, aliquots taken for analysis of specific
contaminants must be immediately collected and preserved as specified in Table 3 for aqueous
solutions of the respective contaminants,
30. Other holding times, specific for compounds within the contaminant groups, may be more
appropriate. If the compounds of concern at a site have been established, use specifications in this
table specific for these compounds, or specifications as may be provided in the analytical method
itself.
31. Contact the MDEQ Lab concerning the use of leaching procedures for other contaminants.
32. Extracts from leaching tests should be preserved immediately after leaching, according to the
guidance given in the individual analysis methods for the contaminants being measured.
33. Sample collection procedures using a syringe-type coring device, as provided in Method 5035, are
appropriate when leaching is used to evaluate the mobility of volatile components leached from
soils. Extrusion of the soil sample into the leaching solution by the laboratory is required within 48
hours. After completion of the leaching procedure, an aliquot of leaching solution must be
immediately collected and preserved as specified in Table 3 for associated contaminants in
aqueous solutions. If larger sample sizes are required, multiple devices must be used.
RRD Operational Memorandum No. 2 - Attachment 4 Page 20 of 20 October 22, 2004
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SOP 8 - SOIL SAMPLING
Appendix 2
MDEQ/RRD Op Memo 2, Attachment 6
'Sampling Methods for Volatile Organic Compounds'
2
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Remediation and
Redevelopment Division
SUBJECT:
October 22, 2004
RRD OPERATIONAL MEMORANDUM NO. 2
SAMPLING AND ANALYSIS - ATTACHMENT 6
SAMPLING METHODS FOR VOLATILE ORGANIC COMPOUNDS
Key definitions for terms used in this document;
NREPA:
Part 201:
Part 211:
Part 213:
MDEQ:
RRD:
U.S. EPA:
Contact time:
Criteria or criterion:
Facility:
Method 5035A:
Method 5021A:
Response Actions:
Sonication:
The Natural Resources and Environmental Protection Act, 1994 PA
451, as amended
Part 201, Environmental Remediation, of NREPA
Part 211, Underground Storage Tank Regulations, of NREPA
Part 213, Leaking Underground Storage Tanks, of NREPA
Michigan Department of Environmental Quality
Remediation and Redevelopment Division
United States Environmental Protection Agency
The time from when the sample was preserved with methanol to the
time the aliquot was taken for analysis, or the time the sample was in
contact with the methanol prior to analysis.
Includes the cleanup criteria for Part 201 and the Risk-based Screening
Levels as defined in Part 213 and R 299.5706a(4)
Includes "facility" as defined by Part 201 and "site" as defined by
Part 213
U.S.EPA Method 5035, "Closed-System Purge-and-Trap and Extraction
for Volatiles Organics in Soil and Waste Samples," Test Method for
Evaluating Solid Waste, Physical/Chemical Methods,
SW-846, USEPA, Office of Solid Waste and Emergency Response,
Dec 1996, Third Edition.
U.S.EPA Method 5021A, "Volatile Organic Compounds in Various
Sample Matrices Using Equilibrium Headspace Analysis", Test Method
for Evaluating Solid Waste, Physical/Chemical Methods, SW-846,
U.S.EPA, Office of Solid Waste and Emergency Response, Dec 1996,
Third Edition.
Includes "response activities" as defined by Part 201 and "corrective
action" as defined by Part 213
The procedure for mixing the soil with methanol using sound waves.
PURPOSE
This attachment to RRD Operational Memorandum No. 2 provides direction for the collection
and preservation of soil samples using the procedures in U.S.EPA Methods 5035A and 5021A
for analysis to determine concentrations volatile organic compounds (VOCs). This attachment
is applicable for site assessments, site investigations, and response activities under Part 201,
Part 211, and Part 213,
To produce reliable representative analytical results, the MDEQ implemented the use of the
methanol preservation procedures for the preservation of soil samples collected for analysis to
determine concentrations of VOCs on April 30, 1998.
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DG&
Remediation and
Redevelopment Division
Michigan Department of Environmental Quality
INTRODUCTION
The requirements for collection and preservation of samples are based on the latest revisions of
U.S. EPA Methods 5035A and 5021A. The applicable contaminants that can be measured are
listed within the methods. Other contaminants may be included if method performance data
exists for the contaminant that demonstrates the accuracy, precision and detection that can be
measured.
Guidance on applicable target detection limits (TDLs) and available analytical methods are
included in RRD Operational Memorandum No. 2, Attachment 1.
USE OF PROCEDURES WITHIN METHODS 5035A and 5021A
Method 5035A includes several procedures for the collection and preparation of soils for VOCs
analysis. These include high concentration methods (methanol preservation), sealed samplers
using soil coring devices, and the low concentration soil method using sealed containers for
direct attachment to the analytical instrument. Method 5021A provides for the sample
preparation of both waters and soils using sealed containers.
Method 5035A. High Concentration Method - Option 1. Methanol Preservation
The MDEQ accepts results generated using the high concentration soil method of Method
5035A for site assessment, site investigations, and response activities, provided the
requirements listed below are followed and documented;
• Samples are preserved with methanol in the field using a procedure consistent with that
provided in this document.
• At least ten grams of soil are collected,
• The ratio of methanol volume to soil weight is equal to or greater than one.
• Samples are sonicated for at least 20 minutes as soon as possible upon receipt at the lab.
• An aliquot of methanol is taken immediately after sonication, and stored for analysis,
• The sample with methanol is not used for analysis of volatiles once the aliquot of methanol
is taken.
• The laboratory standard operating procedures provide the information listed within this
document's section entitled Laboratory Related Procedures and Documentation.
• Operational Memorandum No. 2, Attachment 1, Target Detection Limits and Available
Methods direction has been followed.
Method 5035A. High Concentration Method - Option 2. Bulk Sampling
The bulk sampling procedure in Method 5035A does not produce a reliable representative
sample because it is susceptible to volatilization and biodegradation. Therefore, the MDEQ
does not accept results generated using bulk sampling procedures, unless acceptable
justification is provided that documents the nature of the sample prevents sampling by the
procedures described as acceptable in this document.
RRD Operational Memorandum No. 2- Attachment 6
2 of 12
October 22, 2004
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D€G
Remediation and
Redevelopment Division
Michigan Department of Environmental Quality
Method 5035A. Low Concentration Method
The MDEQ accepts results generated using the low concentration soil method of Method
5035A, for site assessment, site investigations, and response activities, provided the
requirements listed below are followed and documented:
• The sealed containers are attached directly to the instrumentation,
• The preservation is applied correctly to the various soil types.
• Information that validates the use of the method with the appropriate type of soil is provided,
• Information that demonstrates the effectiveness of the sealed containers ability to prevent
the exposure of the sample to environmental conditions is provided.
The low concentration preservation procedure may not be appropriate for all soil types. For
example, calcareous soils cannot be sampled by the low concentration method when sodium
bisulfate is used because a chemical reaction occurs that adversely affects the results. Soil
samples must be tested in the field prior to collecting the samples for analyses, as discussed in
Method 5035A, to determine if the acidic preservation for the low concentration procedure can
be used. If the acidic preservation cannot be used, alternate procedures for preservation in
Method 5035A should be used. The preferable alternate procedure is to extrude the samples
into empty sealed vials and freeze on site to < -7 C°. Care must be taken to not freeze the vials
below -20 C° to avoid potential problems with vial seals.
Method 5021 A. Headspace Analysis using Sealed Containers
The MDEQ accepts results generated using the sample collection and preservation methods of
Method 5021A for site assessment, site investigations, and response activities, provided the
same requirements for Method 5035A, Low Concentration Method are documented. The
preferred analytical method is Method 8260B (see RRD Operational Memorandum No. 2,
Attachment 1). This sample and collection procedure is highly recommended for the analyses
of contaminants that are very soluble in water.
Method 5Q35A. Soil Coring Devices (used to transfer samples to the laboratory)
The MDEQ requires the use of soil coring devices to evaluate the leaching of volatiles from
soils, as provided in Operational Memorandum No. 2, Attachment 2, Soil Leaching Methods.
The requirements in Attachment 2 must be met.
The MDEQ does not recommend the use of soil coring devices for initial site characterization
where the objectives include establishing the contaminants of concern; or for response activities
where the objectives are to demonstrate final compliance with cleanup criteria. The MDEQ may
accept results using the soil coring devices, providing the following requirements are
documented;
• Scientific studies exist that demonstrate the device to be effective for the use intended. The
manufacturer of the device should be contacted regarding studies that prove them effective.
• The party proposing the use of the soil coring devices must demonstrate the effectiveness of
the devices to retain volatile chemicals, for the specific chemicals of concern at the facility.
Demonstration of the effectiveness of the devices proposed to be used can be
accomplished using duplicate sampling. The demonstration must include duplicate samples
RRD Operational Memorandum No. 2- Attachment 8
3 of 12
October 22, 2004
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Remediation and
Redevelopment Division
Michigan Department of Environmental Quality
collected using methanol preservation in the field. Duplicate samples must be collected for
a minimum of one sample, or for at least one of every five samples collected.
• Written protocols must be established regarding the use of the devices to collect samples,
and to preserve samples at the laboratory. These protocols must be provided to the MDEQ.
• Confirmation samples must be collected using methanol preservation in the field, equivalent
to the standard operating procedure of this document. Confirmation samples must be
collected for a minimum of two samples, or for at least two from every ten samples
collected,
• All requirements of Method 5035A regarding the use of the samplers must have been met.
OXYGENATES
Oxygenates refer to methyl(tert)butylether (MTBE), t-Butyl alcohol (TBA), Di-isopropyl ether
(DIPE), Ethyl(tert)butylether (ETBE), Ethyl alcohol, Methyl alcohol, and Tertiaryamylmethylether
(TAME), and the oxygenated ethers refer to MTBE, DIPE, ETBE and TAME. When any of the
oxygenated ethers are required for analysis, and high temperature purging is used in the
analysis, samples collected must have the pH adjusted to > 10 in the field using Trisodium
phosphate dodecahydrate (TSP), or two samples can be collected and the laboratory instructed
to neutralize one prior to the analysis for oxygenated ethers. The laboratory should be
contacted regarding its procedure for the analysis of oxygenated ethers to determine if high
temperature purging is used. Methods 5035A and 5021A can be used for sampling for
oxygenates, provided the requirements in this document are met. Method 5021A is highly
recommended.
Questions concerning this document should be directed to Mr. A, Ralph Curtis, Toxicology Unit,
RRD, at 517-373-8389. or email to curtisar@michigan.gov.
The following documents are rescinded with the issuance of this attachment:
• Environmental Response Division procedure for the Collection and Methanol
Preservation of Soils for Volatile Organics, dated May 1, 2000.
• Storage Tank Division procedure for the Collection and Preservation of Soil Samples for
Volatile Organic Analysis, dated May 18, 2000.
• Storage Tank Division Informational Memo No. 13 "Implementation of Environmental
Protection Agency (EPA) SW-846 Method 5035 Closed-System Purge and Trap and
Extraction for Volatile Organics in Soils and Waste Samples", dated September 4,1998.
APPENDAGE:
Standard Operating Procedure for Methanol Preservation in the Field
RRD Operational Memorandum No. 2- Attachment 6
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This memorandum arid its attachments are intended to provide direction and guidance to foster
consistent application of Part 201, Part 211, and Part 213 and the associated administrative
rules. This document is not intended to convey any rights to any parties or create any duties or
responsibilities under the law. This document and matters addressed herein are subject to
revision.
RRD Operational Memorandum No. 2- Attachment 6 5 of 12 October 22,2004
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D6€a
Remediation and
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t of Environmental Quality
STANDARD OPERATING PROCEDURE for METHANOL PRESERVATION IN THE FIELD
SUMMARY
Soil samples are collected using conventional procedures, including auger and split spoon
techniques. Sub-samples are then taken using syringe-type coring devices and immediately
transferred into pre-weighed VOC vials containing reagent grade methanol sufficient to obtain
an estimated ratio of 1:1 with the soil. The samples are transferred to the laboratory. Upon
receipt at the laboratory, the following steps are taken as soon as is practical:
An accurate sample weight is determined.
The sample container is swirled gently to break up soil clumps.
The sample is sonicated for 20 minutes.
An aliquot taken and stored for analyses using Method 8280B.
Method 5035A uses a 2:1 ratio of methanol volume to soil weight. This ratio is acceptable
contingent that the requirements in Operational Memorandum No. 2, Attachment 1, Target
Detection Limits and Available Methods, are met.
LABORATORY RELATED PROCEDURES AND DOCUMENTATION
Procedures - The laboratory selected should have written standard operating procedures that
address the provision of sampling supplies intended for methanol preservation of samples,
sample receipt checks, sample preparation steps and documentation, sample collection
requirements, and analyses. The laboratory should first be contacted regarding specific
requirements. The laboratory's standard operating procedure governing the sample preparation
should specify the contact time routinely applied, and when this time period is not met, this must
be narrated with the results. The following documentation must be included:
Copies of the certifications of the methanol used.
Percent moisture in the samples (determined using separate vial/container with just soil).
Dates samples were collected, and preserved if not immediately performed upon collection.
Dates samples were received at the laboratory.
Sample weights.
Sample moisture (soils and sediments).
Actual ratios of methanol to soil.
Sonication dates/times.
Minutes of sonications if different from 20 minutes.
Dates/times aliquots were taken for analysis, if not taken immediately after sonification.
The dates of the analysis.
MDEQ LABORATORY SPECIFICATIONS FOR SAMPLE COLLECTION
The following specifications apply for sample collection kit provided by the MDEQ laboratory.
Other laboratories may have similar kits with specifications. Contact the laboratory selected.
RRD Operational Memorandum No. 2- Attachment 6
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Target Soil Weight = 10 grams Methanol Volume (provided in tubes) = 10 ml
Allowed Weight = 9 to11 grams Soil Coring Device (Syringe Sampler) Size = 10 ml
Size of VOC Sampling Vials = 40 ml Green Sticker to Warn of Hazardous Waste
Wide Mouth Jars (4 oz, and 8 oz.)
HEALTH AND SAFETY
Material Safety and Data Sheets (MSDSs) providing health and safety data, and emergency
procedures should accompany staff in the field. Methanol ampoules, tubes, and vials must be
provided to field staff inside protective containers to hold any spillage. Methanol is a toxic and
flammable liquid. Handle with proper safety precautions. Wear safety glasses and protective
gloves. Nitrile Rubber or Viton gloves are recommended. Avoid inhalation. Store and handle in
a ventilated area, away from sources of ignition and extreme heat. Store methanol in a cool
place, preferably in sample coolers on ice. This is especially important for methanol in tubes,
where pressure buildup due to extreme heat may result in rupture. Vials should be opened and
closed quickly during collection. In the event of eye contact, immediately flush with large
amounts of water for at least 15 minutes, occasionally lifting upper and lower lids. Seek medical
attention immediately.
SHIPPING
The shipping of methanol is regulated by the U.S. Department of Transportation (DOT), Title 49
of the Code of Federal Regulations. The DOT number is UN 1230. The amount of methanol
used for sample preservation falls under the exemption for small quantities. Requirements for
shipment of samples by common carrier are as follows;
Maximum volume of methanol in a sample container cannot exceed 30 ml.
The sample container cannot be full of methanol.
Sufficient absorbent material must be used in the container to completely absorb sample
content.
Each cooler must have less than 500 ml of methanol.
The cooler or package weight must not exceed 64 pounds.
Each cooler must be identified as containing less than 500 ml methanol.
APPARATUS AND MATERIALS NEEDED FOR SAMPLE COLLECTION
Absorbent Material - If the samples are to be shipped by common carrier, vermiculite or similar
material, sufficient to completely absorb the methanol for each sample.
Calibration Weight - Near or equal to the target sample weight.
Certified Methanol - Methanol certified for purge and trap gas chromatography is analytically
verified prior to sampling (by lot). In this procedure the methanol is provided in sealed
ampoules. Some labs may provide methanol in the sampling vial.
Field Balance - Capable of holding sampling vial and syringe on the wide mouth jar used to
prevent balance contamination, and measurement within + 0.2 grams.
Hazardous Waste Warning Label - Suitable via! labels to warn personnel of the presence of
methanol as a preservative.
Methanol Sampling Kit/Method 5035A Sampling Kit;
RRD Operational Memorandum No. 2- Attachment 6
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Protective Wear - Nitrile rubber or Viton gloves. Splash proof safety goggles.
Plastic Bags - Air tight seals, capable of holding three sample VOC vials, and sub-coring device.
Protocol to be used for the collection of samples.
Sub-Coring Device - A syringe type device, whose material has been tested and found free of
contaminants,. This device is used to sub-sample the targeted amount of soil, for transfer into
methanol in the field.
Wide Mouth Jar (for holding methanol tubes) - Of suitable size to allow temporary storage and
shipment of the methanol tubes.
Wide Mouth Jar (for preventing balance contamination) - Of suitable size to allow temporary
storage of the syringe type sampler and VOC sample vial on the field balance.
Volatile Organic Compound (VOC) Syringe Labels - Methanol resistant labels.
VOC Vials - Vials with Teflon™ lined septa, pre-weighed, with methanol resistant labels.
SAMPLE CONTAINERS, PRESERVATION AND HOLDING TIMES
Containers - Sample containers are VOC Vials with Teflon™ lined septa of suitable size to hold
the soil plus methanol, supplied with methanol resistant labels.
Preservation - Samples are preserved in the field approximately one to one ratio of soil weight
to methanol volume, using pre-weighed vials and a field balance. The exact sample weights
and ratios are determined at the laboratory. More methanol is added to make the ratio one to
one when possible. When weights are less than the specified minimum, the reporting limit is
increased. The maximum and minimum limits for the weights of soils specified by the MDEQ
laboratory are provided in the section of this document entitled "Specifications for the Collection
of Samples Using Methanol Preservation."
Holding Times - The maximum allowable holding time is 14 days from sample collection to
analysis. If the maximum allowable holding time is exceeded, interpret the results as minimum
concentrations of the measured compounds.
QUALITY CONTROL
Field Blanks
Use - Field blanks are used to determine sample contamination that may occur during the
storage, transportation, sampling, and analysis of samples. A field blank is a sample vial
containing a pre-measured quantity of VOC-free methanol, obtained from the laboratory or
prepared in a contaminant free environment.
Frequency - The number of field blanks depends upon project objectives and the field activities
being performed at specific locations. It is recommended that a field blank be created at each
location where activities may result in significant VOCs released into the environment, or for
every 20 samples, whichever is more.
Interpretation - Positive results may indicate contamination from the methanol, the sample
container, from the air at the site, from diffusion of air containing volatiles into the blank during
transport to the laboratory, or from the laboratory environment. Compare field blank results with
RRD Operational Memorandum No. 2-Attachment 6 8 of 12 October 22,2004
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Remediation and
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Michigan Department of Environmental Qu
trip blank results and laboratory method blanks to isolate the cause. Sample results that
approach the field blank results may be unusable.
Trio Blanks
Use - Methanol trip blanks are used to determine if contamination is occurring from the
methanol, storage, transportation, or the field.
Frequency - One trip blank should be used per cooler.
interpretation - Positive trip blanks can be attributed to the methanol, sample vial material, and
the environment in the cooler or sample transport container. Trip blanks should be prepared at,
and provided by, the laboratory in order to make this interpretation. If consistent positive results
are obtained, contact the laboratory and have a trip blank prepared at the laboratory and
immediately analyzed to attempt isolation of the cause.
Methanol
Only purge and trap grade methanol verified to be suitable for methanol preservation should be
used. Field staff should maintain documentation of the methanol lot numbers for all associated
samples. If consistently high levels of compounds are measured in methanol field blanks
associated with a specific lot number, request the laboratory to verify the quality of the methanol
lot used to preserve the samples.
Contamination
Contamination by airborne VOCs in the air is possible by diffusion through the vial septum
during shipment, storage, collection, and analysis. To control such contamination:
Use appropriate VOC sample vials.
Avoid sources that generate VOCs such as petroleum products, especially auto exhaust fumes.
Keep sample containers in coolers as much as possible.
Collect samples quickly.
Use methanol provided in sealed ampoules, tubes, or VOC vials.
Attempt to isolate the source of contamination and incorporate appropriate procedures to avoid
similar circumstances.
FIELD BALANCE CALIBRATION CHECK
The field balance calibration should be checked prior to each sampling event, and whenever
necessary because of handling in the field. Record this check in the field notebook.
CORRECTIONS FOR SAMPLES WITH HIGH WATER CONTENT
Concentrations of volatile compounds in soils must be reported on a dry weight basis, using the
moisture content of the soil to adjust results. Routine procedures by the laboratories include
this correction. Laboratories may not routinely correct results because of the effects due to the
miscibility of the methanol with the water in the sample. The effects are to bias the results low,
and if the moistures in the samples are high, these biases may be significant. The effects of
RRD Operational Memorandum No. 2- Attachment 6 9 of 12
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Michigan Department of Environmental Quality
this biases upon results should be considered when soils are sampled, and if necessary the
laboratory instructed to correct results accordingly.
ELEVATED REPORTING LIMITS DUE TO HIGH MOISTURE
For samples with excess moisture, reporting limits may need to be elevated higher than levels
routinely reported by the laboratory. Elevated reporting limits may be acceptable if they do not
exceed applicable criteria. Historical site information and published information can be used to
ascertain the range of moisture levels that can be expected. This can be used to determine if
the biases are significant. Additional guidance regarding elevated reporting limits is available in
RRD Operational Memorandum No. 2, Attachment 1.
OTHER METHANOL PRESERVATION PROCEDURES
Variations to the field procedure in this method may be used if approved in advance by the
MDEQ. Important considerations are:
• Samples must be preserved in the field, a target ratio of 1:1 for the weight of the soil to
the volume of methanol should be used.
• Samples must be sonicated for 20 minutes at the laboratory.
• A methanol aliquot must be taken and stored for analysis immediately after sonication
that is sufficient for initial analysis, and analysis of any subsequent dilutions.
• Sufficient documentation to validate the data must be provided to the MDEQ.
(
RRD Operational Memorandum No. 2- Attachment 6
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apartment of Environmental Quality
FIELD SAMPLING PROCEDURE
1. Make arrangements with the laboratory to obtain appropriate Methanol Preservation
Sampling Kits.
2. Record the tracking or lot number(s) for the methanol in the field notebook. If more than one
lot is used, each lot must be associated with the samples for which it was used.
3. Prior to collection, check the calibration of the balance. See "Field Balance Calibration
Check" on page 10 of this document.
4. Prior to collection prepare a temperature blank sample using tap water and a VOC vial.
5. Prior to collection prepare a sufficient quantity of methanol field blanks, i.e., at least one per
cooler and one per methanol lot as follows;
a) Select an area free of VOC sources,
b) Remove a methanol tube from the wide mouth jar.
c) Use scissors to cut off the top, and place the methanol into one of the pre-weighed
sample vials.
d) Place the cap on the vial and tighten it. Avoid over-tightening.
e) Place a green sticker on the top of the cap.
f) Record the identification of the vial as "Methanol Field Blank" on both the vial label and
in the field notebook.
8. Calibrate the syringe to estimate the amount of soil needed to meet the target weight, and
use that syringe as a comparison for how much sample is needed.
Calibration is performed using steps 10-17 below, using the syringe only, and part of the
soil that is to be collected. The soil used for calibration cannot be used as the sample. It
must be extruded from the sampler and discarded at the site before collecting the sample.
The sampler does not have to be cleaned between calibration using this step, and collection
of the sample.
7. Place the wide mouth glass jar, used to prevent balance contamination, on the balance.
8. Record the location, date, and time of sampling in the field log book. Do not place any
labels, stickers, tape, etc. on the pre-weighed sample vials.
9. For methanol field blanks, remove the cap from a methanol field blank which was prepared
in Step 5 above, place the opened vial in the collection area for the approximate time it
takes to collect a sample, and then cap the methanol field blank for storage and transport to
the laboratory.
10. Place a pre-weighed VOC vial and syringe in the wide mouth jar on the balance.
11. Record the weight in the field log book. If the balance features re-zeroing, zero the balance.
12. Remove the syringe. If a cap is provided, remove the cap and place it in the jar.
13. insert the open end of the syringe into a fresh face of undisturbed soil, and fill it as
appropriate according to the calibration of the syringe (Step 6).
14. If necessary, use your gloved finger (decontaminate before next sample), or other
appropriate instrument, and push the soil deeper into the syringe sampler.
15. If a cap was provided, immediately cap the end of the syringe.
RRD Operational Memorandum No. 2- Attachment 8
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opment Division
? mMBBSM
16. Place the syringe in the jar on the balance. Read the weight, and if necessary, subtract the
weight of the syringe, vial, and jar, as appropriate, to determine the weight of the soil.
17. If the weight of the sample is determined to be more than the maximum amount allowed,
extrude enough soil to obtain the target amount within the specified tolerance, and re-weigh.
See the table in this document, "Specifications for the Collection of Samples Using
Methanol Preservation" for the applicable target sample size and tolerance,
18. If the weight of the sample is less than the minimum amount allowed, re-sample and repeat
steps starting with Step 7.
19. Record the soil weight in the field notebook. DO NOT RECORD the weight on the sample
vial label.
20. Remove the cap from the sample vial, and place it in the jar on the balance, with the septum
upwards.
21. If the required amount of methanol is not included with the pre-weighed vial, immediately
remove a methanol tube from the wide mouth glass storage jar, holding the tube upright use
scissors to cut (plastic) off one end, and pour the methanol into the sample vial, taking care
to avoid spillage.
22. Insert the open end of the syringe sampler into the mouth of the vial, and carefully extrude
the soil, taking care to avoid spillage. Loss of several drops will not make a significant
difference in the results. If a significant amount is spilled, a new sample must be collected,
or the sample must be appropriately flagged to indicate estimated results.
23. Using a clean brush, paper towel, or other suitable material, thoroughly wipe excess soil
particles from the threads and vial body. Particles left on the threads will prevent a good
seal.
24. Place the VOC cap on the sample vial. The cap must be tight; however, over-tightening
should be avoided.
25. Gently swirl the sample and methanol for about 10 seconds to break up the soil. DO NOT
SHAKE.
26. Place the sample in a plastic bag on ice in a cooler.
27. Attach a green sticker on the plastic bag to indicate a hazardous waste.
28. Using the syringe sampler, take another sample from the soil.
29. Cap and label the syringe with the sample identification.
30. Place the syringe with the sample in the plastic bag. This sample is for dry weight
determination.
31. Decontaminate the jar/balance using decontamination procedures appropriate for the type
and level of contamination.
32. Unused methanol must be returned to the laboratory for disposal.
RRD Operational Memorandum No. 2- Attachment 8 12 of 12 October 22,2004
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STANDARD OPERATING PROCEDURES 2010
Appendix A
Manta Operating Manual
1
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Center for Toxicology and Environmental Health, LLC.
5120 N. Shore Drive, North Little Rock, AR 72118 Phone: 501.801,8500 www cteh.com
STANDARD OPERATING PROCEDURES FOR:
MANIA 2 MULTIPROBE - OPERATING MANUAL
Prepared By
Center for Toxicology and Environmental Health, L.L.C.
For;
Internal Use Only
In Reference to:
Enbridge-Marshall Release
Sector Mobile
Valid until replaced by a global CTEH plan
August 14, 2010
This document, in part or in whole, is the property of Center for Toxicology and Environmental Health, LLC (CTEH) for the sole use of CTEH
employees or CTEH contractors or as otherwise consented to in writing by CTEH.
-------
sm
Center for Toxicology and Environmental Health, LLC.
5120 N. Shore Drive, North Little Rock, AR 72118 Phone: 501,801,8500 www etefitcm
Manta 2 Multiprobe - Operating Manual
1.0 Introduction
1.1 Applications
1.1.1 Manual Method
1.1.2 Unattended Sampling
1.1.3 Telemetry System
2.0 Manta 2 Multiprobe
2.1 Sensors arid Parameters
2.1.1 Temperature
2.1.2 pH
2.1.3 Dissolved Oxygen (DO)
2.1.4 Conductivity / IDS /
Salinity
2.1.5 Turbidity
2.1.6 Fluorometer CDOM
2.2 Amphibian Data Display
2.3 Underwater Cable
2.4 Storage / Calibration Cup
2.5 Weighted Sensor Guard
2.6 Battery Pack
2.7 LED Lights
2.8 Software
2.8.1 Eureka Manta2 Control
Software - ver.
0.1.8.34
2.8.2 Microsoft Mobile
Device Manager - ver.
6.1
3.0 Calibration
3.1 Basics
3.2 Barometric Pressure
3.3 Date & Time
3.4 General Calibration Procedure
3.5 Sensor Specific Calibrations
3.5.1 pH
3.5.2 Conductivity
3.5.3 Turbidity
3.5.4 Dissolved Oxygen (DO)
3.5.5 Fluorometer CDOM
3.6 Fluorometer CDOM Instrument
Check Procedure (Pre & Post
Sampling)
4.0 Data Management
4.1 Calibration Log
4.2 Logging vs. Snapshot
4.3 Snapshot & Automatic Snapshot
4.3.1 Snapshot
4.3.2 Automatic Snapshot
4.3.3 SS & Annotate
4.4 Scrolling Interval
4.5 Logging & Managing Data via
Amphibian or PC
4.5.1 Managing Logged Data
4.5.2 Logging Interval
4.5.3 Log on or Log Off
4.5.4 Accessing Logged Data
File
4.5.5 GPS Coordinates
4.5.6 Telemetry Unit
5.0 Summary
This document. In part or in whole, is the property of Center for Toxicology and Environmental Health, LLC (CTEH) for the sole use of CTEH
employees or CTEH contractors or as otherwise consented to in writing by CTEH.
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Center for Toxicology and Environmental Health, LLC.
5120 N. Shore Drive, North Little Rock, AR 721 !8 Phone: 501,801.8500 www.cteh.com
Manta 2 Multiprobe - Operating Manual
1.0 Introduction
The Manta 2 is a multi-parameter water sampling probe, composed of a transparent housing,
communication circuitry, and multiple sensors such as; temperature, pH, dissolved oxygen, etc.
Using the Manta 2 Control Software, the multiprobe interfaces with either the Amphibian Data
Display (Microsoft Mobile Device) or a laptop computer.
1.2 Application
The Manta 2 is used in one of three different applications:
1.2.1 Manual Method
The Manta 2 connects to either the Amphibian (Field PC) or a laptop with the
underwater cable. The user can then interface with the multiprobe and gather data over
a short time period.
1.2.2 Unattended Sampling
The Manta 2 can be anchored and left unattended to gather data over an extended
period. Data is downloaded from the multiprobe at the end of the sampling period.
1-2.3 Telemetry System
A modem, battery pack and data logger makes up the data telemetry system. This
system transmits data gathered by the Manta to a secure website via a cellular or
satellite system. The telemetry unit is a great application for unattended sampling.
2.0 Manta 2 Multiprobe
2,1 Sensors and Parameters
A sensor is composed of a sensing element and the necessary circuitry to communicate with the
multiprobe. A parameter is a unit in which data is displayed. For example, the Optical DO Sensor
provides data in one or more parameters such as, percent saturation or mg/L. You have the
option of selecting which sensors (if equipped) and parameters are displayed. The program will
only collect data from what you select. Following is a list of sensors and parameters.
This document, in part or in whole, is the property of Center for Toxicology and Environmental Health, LLC (CTEH) for the sole use of CTEH
employees or CTEH contractors or as otherwise consented to in writing by CTEH.
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Center for Toxicology and Environmental Health, LLC.
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2.1.1 Temperature
The temperature sensor is an electrical resistor (thermistor) that measures a change in
resistance predictably with temperature. The thermistor does not require calibration.
Parameters: °C and °F
2.1.2 f)H
The pH of water is measured by using a glass electrode and a reference electrode filled
with a standard electrolyte (KC!) solution. The specially formulated glass on the pH
electrode absorbs water, specifically the H+ and OH" ions. When these ions attract to the
glass, they offset the ionic constituency of the KCI electrolyte. This offset results in a
charge separation across the glass and the voltage is measured. The displayed pH
measurement is compensated for temperature (corrected to 25°C).
Parameter: 0 -14 pH Units
2.1.3 Dissolved Oxygen (DO)
The DO sensor is an optical sensor comprised of a blue-light source, a sensing surface,
and a red-light receiver. The sensing surface is an 02 -active compound stabilized in an
02 permeable polymer, typically silicone. The 02 - active compound fluoresces, or
absorbs energy in the form of blue light, then emits energy as red light. The red-light
receiver measures the amount of emitted red light resulting from the blue-light's
energy. The optical sensor has very little calibration drift and is not flow dependent
(typical DO sensors consume oxygen requiring the use of a circulator).
Oxygen quenches fluorescence, meaning the amount of red light is reduced if 02
molecules are present to interfere with the 02 - active compound. An increase in
oxygen results in a decrease of red light directly relatable to the amount of oxygen
present. Sensor output is corrected for the temperature characteristics of the
membrane, and for the temperature characteristics of the oxygen-saturated water.
Parameters: 0 -25 mg/L
0-200% Saturation
2.1.4 Conductivity / TPS / Salinity
The multiprobe uses a four electrode (two pairs situated in a stable geometry) method
for determining water conductivity. Each electrode pair receives a constant voltage.
Conductivity is measured as the current required to maintain that voltage. Therefore, an
increase in water conductivity results in an increase in voltage.
This document, in part or in whole, is the property of Center for Toxicology and Environmental Health, LLC (CTEH) for the sole use of CTEH
employees or CTEH contractors or as otherwise consented to in writing by CTEH.
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Center for Toxicology and Environmental Health, LLC,
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The voltage is reported as specific conductance (conductivity corrected to 25°C). The
multiprobe also reports Total Dissolved Solids (TDS) and Salinity. These two parameters
are calculated from conductivity, not calibrated.
Parameters: Conductivity 0 - 100 pS/cm
Salinity 0-70 PSU (PPT)
TDS 0-85 g/L
The optical turbidity sensor measures suspended solids in water using a beam of
infrared light. The beam is scattered by particles in the water and measured as the
fraction of light scattered 90° to that beam. An increase in particles equals an increase in
turbidity. Although the sensor requires little maintenance, it should be checked
periodically to ensure the optical window is free of accumulation. The sensor installed
on the multiprobe has a small wiper that cleans the optical window. Occasionally
inspect to ensure proper working order.
Parameter: 0 - 3000 NTU (Nephelometric Turbidity Units)
2.1.6 Fluorometer CDQM
The Manta 2 is equipped with a CDOM Fluorometer configured and scaled for the
analysis of crude oil. CDOM stands for colored dissolved organic matter. The sensor
measures the fluorescence of dissolved organic matter present in the water and delivers
an output voltage proportional to the concentration. Fluorescence is temperature
sensitive, meaning an increase in sample temperature will result in a decrease in
fluorescence.
Parameter: ppm (range to follow)
2.2 Amphibian Data Display
The Amphibian Data Display (Archer Field PC) is a Microsoft based PDA. Calibration, data
acquisition, and other various controls are performed using the Manta 2 Control Software. With
the onboard GPS locator, the user can pair GPS coordinates with each sample point. Data
collected and stored within the Amphibian can be transferred to a laptop computer.
2.3 Underwater Cable
The Underwater Cable is capable of deploying the multiprobe to a max depth of 200 ft. The
cable connects the multiprobe to the Amphibian, a laptop computer or telemetry device.
This document, in part or in whole, is the property of Center for Toxicology and Environmental Health, LLC (CTEH) for the sole use of CTEH
employees or CTEH contractors or as otherwise consented to in writing by CTEH.
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Center for Toxicology and Environmental Health, LLC.
5120 N Shore Drive, North Little Rock, AR 72118 Phone 501.801,8500 www cteh.com
2.4 Storage / Calibration Cup
The storage / calibration cup covers and protects the sensors when the probe is not in use. The
cup should always contain a few ounces of tap water to keep the sensors moist. During
calibration, hold the probe with the sensors pointing up. Remove the black lid from the
calibration cup and pour in the solution standard. The lid is then replaced and the probe turned
upright. This should fully immerse the sensors in the calibration standard, add solution if
necessary.
2.5 Weighted Sensor Guard
The weighted sensor guard replaces the storage / calibration cup when sampling with the Manta
2. The sensor guard is vented allowing water to flow over the sensors.
2.6 Battery Pack
The battery pack provides power to the multiprobe. The underwater cable connects to the
batteries 9-pin connector and the second cable (attached to batteries 9-pin connector) connects
to the Amphibian (If using a laptop computer, use the 9-pin to USB converter cable).
2.7 LED Lights
The circuitry installed inside the Multiprobe is equipped with three LED lights. These lights are
visible through the Manta's housing.
Green: Blinks once every two (2) seconds to indicate the Manta 2 has adequate
operating voltage.
Yellow: Blinks briefly, when the Manta 2 receives RS-232 communication.
Red: Blinks every two (2) seconds for ten (10) seconds upon each power up if
logging is enabled.
2.8 Software
2.8.1 Eureka Manta2 Control Software - ver. 0.1.8.34
This software is loaded onto both the Amphibian and can be loaded on a laptop
computer. The software interfaces with the communication circuitry inside the Manta 2,
allowing the user to set-up, program, log data and calibrate the sensors.
2.8.2 Microsoft Mobile Device Manager - ver. 6.1
Installation of the Mobile Device Manager software is necessary in order to transfer files
saved in the Amphibian to a computer. The software can be downloaded for free on
Microsoft's website.
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3.0 Calibration
3.1 Basics
Use the Amphibian hand held device (or PC) and start the Eureka Amphibian Software. Select
Manta2 at the bottom of the screen to open the Menu {top of page if using a PC). A pop-up
screen will appear listing parameters to calibrate. Next, click on the sensor / parameter you wish
to calibrate. Another screen will appear with instructions for the specific parameter, current
reading and a box for you to enter the value of the calibration standard. For most parameters,
you enter the value of the standard and hit "enter". The Current Box will show the sensors
reading. Hit "enter" to accept the value once the reading has stabilized. The value is accepted if
the calibration returns an acceptable sensor response factor (SRF) value between 60% and
140%. However, if the SRF is not acceptable (outside the 60% -140% range), you are given the
option to accept the calibration despite the deviant SRF, or you can return to the calibration
steps and review instructions, calibration value, etc.
3.2 Barometric Pressure
You must enter the local Barometric Pressure (BP) before each calibration,
1. Open the Manta2 Menu and select Calibrate.
2. Select BP from the pop-up menu of calibration parameters.
There are four options for entering BP. For the preferred method, Option 1, enter
the BP value in mm Hg. If you are unable to look up the local BP, Option?, allows you
enter the elevation. Elevation must be taken from an altimeter or GPS unit. Option 3
cannot be used since the multiprobe is not equipped with a depth sensor. Option 4
can be used (not preferred) if you are unable to look up the local BP or elevation.
3. Enter the value in the box and select "OK". You will be immediately returned to the
main screen.
3.3 Date & Time
The date and time are currently set in the device, but if you need to make changes, open the
calibration menu. Then select Date & Time from the pop-up screen, and follow the instructions.
3.4 General Calibration Procedure
1. Clean the sensor and perform any necessary sensor-specific maintenance.
2. Select a calibration standard with a value similar to the values you expect to see.
3. Rinse sensors thoroughly with de-ionized water by filling the calibration cup and shaking
vigorously to remove traces of old calibration solutions. Repeat if necessary.
4. Rinse the sensors twice with a small amount of the calibration solution.
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5. Fill the calibration cup with the solution and immerse the sensor. Most parameters are
temperature compensated. The thermistor is the shortest sensor so be sure to immerse it in
the solution. Typically, you need to fill the calibration cup entirely in order to immerse all
the sensors during calibration.
6. Select the parameter to be calibrated from the menu describe above.
a. Enter the calibration value and press enter to accept.
b. Press enter again once the reading has stabilized to calibrate. The Manta 2 will
report the resulting SRF, Press Y to accept, N to back up one step, or Exit to leave
the sensor un-calibrated.
3.5 Sensor Specific Calibrations
3.5.1 pH
Use a (2)-point calibration using 2 buffers, 7.00 and 10.0.
1. Rinse the sensors in Dl water, discarding rinse into the decon bucket.
2. Rinse the sensors with the first buffer (7.00).
3. Fill cup with the number 7.00 buffer and upright the probe to immerse the sensors.
4. Follow the calibration instructions and discard the used solution into the decon
bucket
5. Rinse the sensors with Dl water. Discard rinse into decon bucket.
6. Rinse sensors with the second buffer (10.0).
7. Fill calibration cup with the number 10.0 buffer and upright probe to immerse the
sensors.
8. Follow the calibration instructions and discard the used solution into the decon
bucket.
3.5.2 Conductivity
Use a (l)-point calibration.
1. Rinse the sensors with Dl water, discarding rinse into decon bucket.
2. Fill the calibration cup with the standard (appropriate to the sampled waters). Use
the 12,586 uS/cm solution to calibrate for seawater.
3. Follow the calibration instructions and discard the used solution into the decon
bucket.
3.5.3 Turbidity
Use a (2)-point calibration, a zero and an approximate standard dependent upon
water(s) to be tested. For our purposes, we will use a standard solution of 400 NTU.
To Zero;
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1. Rinse sensors twice with deionized water. Partially fill the calibrations cup with DI
water, close and shake vigorously. Discard rinse into decon bucket.
2. Fill the calibration cup with the zero turbidity standard, replace lid and upright the
multiprobe to immerse the sensor in the solution.
3. Follow the calibration instructions in the control software.
To set the second point, repeat the steps above using a 400 NTU standard solution.
Discard used solutions into your decon bucket.
3.5.4 Dissolved Oxygen (DO)
Calibrate by setting the sensor's saturation point Be sure to set the local Barometric
Pressure before calibrating DO.
1. Take a 1-liter jar and fill halfway with distilled water, screw on cap, and shake
vigorously for one minute.
2. Remove cap and let jar stand for one minute. This lets the tiny air bubbles float out
of the top.
3. Completely immerse the sensor in the aerated water, cap and upright.
4. Wait a few minutes for the temperature and reading to equilibrate.
5. Follow the calibration instructions in the control software.
3.5.5 Fluorometer CDOM
Use a two-point calibration.
1. Rinse sensors twice with deionized water. Partially fill the calibrations cup with DI
water, close and shake vigorously. Discard rinse into decon bucket.
2. Fill the calibration cup with the zero standard and upright the multiprobe to
immerse the sensor in the solution.
3. Follow the calibration instructions in the control software.
To set the second point, repeat the steps above using a relative standard solution.
Discard used solutions into your decon bucket.
3.6 Fluorometer CDOM Instrument Check Procedure fPre and Post Sampling)
This procedure checks for instrument drift and is not a method of calibration. The check should
determine if the instrument's response to a known quantity of fluorescing material is changing
overtime. Anyone monitoring for a subsurface plume of oil resulting from MC 252 incident are
requested to conduct this type of procedure before and after each sampling event.
To Zero;
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1. Use a Glass Beaker for your water samples. (Avoid plastic beakers. Plastic fluoresces
and will interfere with the sample fluorescence)
2. Place the glass beaker on a Non-Reflective Surface, preferably black.
3. Ensure that the sensor is more than 3 inches above the bottom of the glass beaker.
4. Ensure that the sensor is in the center of the glass beaker, and has more than 2
inches clearance between the circumference of the sensor and the inside surface of
the beaker. Turner Designs recommends using a 1L Glass Beaker for measurements.
5. Check that the optical surface of the sensor is free of air bubbles.
6. Be sure your sensor is calibrated.
7. To maximize consistency between measurements, place sensor at exactly the same
height for each sample. This is most easily done using a Lab Stand.
4.0 Data Management
4.1 Calibration Log
All calibrations are stored within the Manta 2 multiprobe in the cal.Log file. When performing
calibrations, regardless of whether the Amphibian or PC is used, the calibrations are always
appended to end of the cal.Log. You can choose to view this log with either the Amphibian or
PC. You will need to use the PC to export, save and/or print a copy of the cal.Log file.
4.2 Logging vs. Snapshot
There are two methods in which to log and store data. Logging and Snapshot.
Logging: Unattended data capture and storage into the Manta 2.
Snapshot: Manual capture and storage of data in the PC or Amphibian.
4.3 Snapshot & Automatic Snapshot
Snapshot is a manual method of data collection but can be automated. There are two
options to store data using Snapshot; first, a previously set snapshot location can be
appended, or a new location can be created. Snapshot can be accessed by selecting
"PDA" at the bottom of the Amphibian screen, or by selecting PC if using a laptop. From
the pop-up menu, select Snapshot Locations. This will open the snapshot location menu
where you can "Select to Use" a previously set-up location, or "Create New" to create a
new location.
4.3.1 Snapshot
By clicking Snapshot at the top of the main screen, you record a single point of data for
each parameter each time you click it.
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4.3.2 Automatic Snapshot
This option sets the snapshot (manual) function into automatic and records a set of
points according to the scrolling interval setting. This will continue for as long as data
display is on. Automatic snapshot ends if you exit out of the program. To turn on
Automatic Snapshot, click on the PDA or PC depending on what you are using to display
the information. Select Automatic Snapshot to open up the next menu. From this menu,
select "On" or "Off to record data at the scrolling interval previously set.
43.3 SS & Annotate
This option is to the right of the Snapshot button and allows the user to add a note to
the Snapshot. Not an option when Automatic Snapshot is on.
4.4 Scrolling Interval
Once the file you wish to use has been selected or created, you will need to set-up your scrolling
interval. Click on PDA on the Amphibian or PC on the computer. From here, you can select from
the list of intervals or enter a custom value, hit "OK". The program will always use this interval
until changed.
4.5 logging and Managing Data via the Amphibian or PC
4.5.1 Managing Logged Data
Logging is intended for gathering unattended data, as the data is stored within the
Manta 2. This method could provide a backup data file to the snapshot method. Open
up the Manta 2 Menu at the bottom of the data display and select "Manage Manta 2
Files". This will open another menu listing previously created .LOG files including the
file's last modified date. From here, you can create a new .LOG file specific to a sampling
event, or append data to an existing file. Once you are finished, click on the OK button in
the upper right-hand corner of the display.
4.5.2 Logging Interval
To set the Logging Interval, open the Manta 2 Menu and select the "Logging Interval"
option. This will open a menu listing intervals from one to 360 minutes. There is also an
option to enter a custom interval. Select your interval and click "OK" to return to the
main menu,
4.5.3 Log On or Log Off
To ensure you are logging and storing data in the Manta 2 multiprobe, make sure you
read "Log On" at the bottom of the main data display screen for the Amphibian, or the
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logging button on the PC screen reads Manta 2 is Logging. If "Log Off or "Not Logging"
is displayed, then click the button on the Amphibian or PC to activate data logging.
4.5.4 Accessing Logged Data File
In order to access the logged data, you will need to set-up the equipment and access via
a laptop. Remember the .LOG file is stored in the Manta 2 multiprobe and not the
Amphibian. To access the logged data file you must first connect the multiprobe to the
battery, and then connect the USB to 9-pin serial connector to your PC. Make sure the
Green LED light is blinking letting you know the Probe has sufficient power. Once the
multiprobe is set-up and connected to the PC, you may open up the Manta2 Control
Software. It is important to open the Manta 2 Control Software AFTER the multiprobe is
connected and turned on. The menus in the Manta 2 Control Software are set up the
same as the Amphibian.
1. Open the Manta2 Menu
2. Select the Manage Manta 2 Files option
3. Select the .LOG file you wish to transfer
4. Select Export Data to upload data and save onto your PC
If the PC and Control Software was being used to Log Data then several options are
available. You can periodically export and save the log file during sampling, or export
one time when the sampling event is over (recommended).
4.5.5 GPS Coordinates
The Amphibian Data Display is equipped with a GPS locating device. Enable GPS in order
to log coordinates for each data point. To enable, click on the PDA menu and select
Enable GPS from the pop-up menu.
4.5.6 Telemetry Unit
A Telemetry Unit is the best choice for acquiring unattended data. The unit collects data
automatically (at set intervals) and transmits the data via cellular or satellite
communication systems. The data is uploaded to a secure website where it can be
managed and displayed. A modem, battery pack and data logger makes up the data
telemetry system.
5.0 Summary
The Manta 2 multiprobe and software are easy to use and maintain. Calibration is
straightforward, and accurate 5RF values can be acquired if the calibration instructions are
followed. People using the multiprobe for the first time should take the necessary time to
familiarize themselves with the unit before conducting any field sampling.
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Enbridge Line 6B MP 608
Marshall, Ml Pipeline Release
2011 Air Monitoring and Sampling Addendum to the Sampling and
Analysis Plan
Prepared for United States Environmental Protection Agency
Enbridge Energy, Limited Partnership
Submitted: June 15, 2011
Approved: June 21, 2011
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I.0 INTRODUCTION AND PURPOSE 1
2.0 AIR SAMPLING METHODS 1
3.0 METEOROLOGICAL DATA 2
4.0 COMMUNITY EVALUATIONS 3
5.0 WORK AREA PERIMETER EVALUATIONS 4
5.1 Work Zone Perimeter Sampling 4
5.2 Work Zone Real-time Monitoring 5
6.0 WORKER EXPOSURE MONITORING 5
7.0 ODOR INVESTIGATIONS 8
8.0 TAR PATTY STUDY 9
9.0 DATA QUALITY AND MANAGEMENT 9
10.0 AIR SAMPLING AND MONITORING REPORTING 10
II.0 PROJECT ORGANIZATION 11
12.0 CALIBRATION AND MAINTENANCE OF FIELD INSTRUMENTS 12
13.0 CHAIN OF CUSTODY (COC) 12
14.0 SAMPLE LABELS 12
15.0 PACKAGING AND SHIPPING 12
ATTACHMENTS
Attachment A Predominant Crude Oil VOCs Detected by TO-15 Analysis
Attachment B Enbridge Oil Spill Human Health Screening Levels
Attachment C Meteorological Station Specifications
Attachment D Field Standard Operating Procedures
Attachment E Galson Laboratories SOP for VOCs by OSHA PV-2120 & EPA TO-15
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LIST OF ACRONYMS
ACGIH
American Conference of Governmental Industrial Hygienists
AIHA
American Industrial Hygiene Association
COC
Chain of Custody
COPC
Contaminate of Potential Concern
Enbridge
Enbridge Energy, Limited Partnership
D/T
dilution-to-threshold
GPS
global positioning system
Line 6B
The pipeline owned by Enbridge Energy, Limited Partnership that runs
just south of Marshall, Michigan
MIOSHA
Michigan Occupational Safety and Health Administration
NIOSH
National Institute of Occupational Safety and Health
NIST
National Institute of Standards and Technology
OSHA
Occupational Safety and Health Administration
OVM
Organic Vapor Monitoring
PEL
Permissible Exposure Limit
PPm
parts per million
ppmv
Parts per million by volume
QAPP
Quality Assurance Project Plan
SEG
Similar Exposure Group
STEL
Short Term Exposure Limit
Supplemental Order
Supplement to Order for Compliance Under Section 311 (c) of the Clean
Water Act, issued by U.S. EPA Region 5 on September 23, 2010 to
Enbridge Energy Partners, L.P. etai, Respondents, Docket No: CWA
1321-5-10-001
U.S. EPA
United States Environmental Protection Agency
U.S. EPA Order
U.S. EPA Removal Administrative Order Under Section 311(c) of the
Clean Water Act, issued on July 27, 2010 to Enbridge Energy
Partners, L.P., Docket Number: CWA 1321-5-10-001
TICs
Tentatively Identified Compounds
TWA
Time Weighted Average
VOCs
Volatile Organic Compounds
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1.0 INTRODUCTION AND PURPOSE
Enbridge will conduct air sampling and air monitoring to protect worker safety and public
health during assessment and recovery operations. Enbridge has been directed to conduct
real-time air monitoring and air sampling in the following areas:
• Surrounding communities including Baker Estates and Ceresco;
• Work areas where impacted soil and/or sediment is being disturbed from removal
activities,
• Work areas where submerged oil is being removed,
• Other areas in response to odor concerns, and
• Real-time monitoring in Communities along impacted shorelines.
The air monitoring will include volatile organic compounds (VOCs), hydrogen sulfide (H2S),
sulfur dioxide (S02), and benzene. Air sampling will only be conducted for VOCs.
Data gathered in the above mentioned areas will be used to assess the potential for
community and worker exposures. All field work and data collection will be conducted in
accordance with approved work plans and standard operating procedures (SOPs). More
detailed discussions of air sampling and real-time air monitoring can be found in the
following sections.
2.0 AIR SAMPLING METHODS
Air samples for VOCs will be collected by subatmospheric sampling using evacuated
canisters. The collected whole-air samples will be analyzed according to modified U.S. EPA
Method TO-15 and OSHA PV-2120. Attachment E presents the laboratory SOP for this
sampling. The list of target compounds (with detection limits) is presented in Attachment A .
The laboratory will also provide a report of all Tentatively Identified Compounds (TICs)
detected in each canister sample.
Canister samples will consist of either grab (instantaneous), 8-hour, or 24-hour collections.
The collection time will be based on monitoring objectives. For instance, a grab sample will
be collected in response to odor reports, 8-hour collection for work shift related monitoring,
and 24-hour sampling for evaluating the potential for long-term exposure at community
and/or residential sites. All extended duration samples will be collected using critical flow
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orifices calibrated by the laboratory to collect a specified target volume into the canister over
the desired period. Details of the flow rate settings and pressure limits of the flow controllers
are contained in the applicable SOP.
All air samples will be sent to Galson Laboratories, an American Industrial Hygiene
Association (AIHA) accredited laboratory, in Syracuse, NY. Samples will be expedited for
shipping and analysis. Initial samples will be on a one-day turnaround time for sample
results. If approved by U.S. EPA, the turnaround time may be extended to a three to 10 day
period.
3.0 METEOROLOGICAL DATA
Meteorological data is an important consideration for deploying canisters and for interpreting
air sampling results. A combination of portable meteorological stations and National
Weather Service (NWS) data will be used to support air sampling and monitoring.
Two portable meteorological stations will be deployed to provide more time-resolved
meteorological data than the once-hourly NWS observations. The stations will include
sensors for wind speed, wind direction, air temperature, relative humidity, barometric
pressure, and precipitation (precipitation gauge). The meteorological station clocks (or
SAFER computer, if it assigns the 5-minute data timestamp) should be maintained in
reference to a National Institute of Standards and Technology (NIST) clock source. The
stations will be mounted on tripod-based masts. The stations will operate on battery power.
Specifications for the meteorological stations are presented in Attachment C.
Specific station locations will be determined to the extent possible based on U.S. EPA
guidance for instrument exposure. Primary consideration will be placing the stations in open
areas with unobstructed wind flow. The wind direction sensors will be aligned to within 5
degrees of true north, and have a measurement accuracy of 5 degrees or better. Data will
be recorded, and downloaded from the stations on a daily basis. The station clocks will be
set to Eastern Standard Time. Station locations will be documented with global positioning
system (GPS) devices.
One meteorological station will be set up near Ceresco Dam, and the other will be placed
near Baker Estates (MP 12.1). Data from these two sources will be used to create daily
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wind roses for the areas of concern, and identify samples collected as being upwind or
downwind of the contaminated areas.
In other areas potentially impacted by the removal, NWS data from Battle Creek (call sign
KBTL) or Kalamazoo (call sign KAZO) will be used to produce wind roses and classify
upwind/downwind samples. The observations will be downloaded from the internet daily,
and placed into a database. In the event portable weather station data are not available for
a period, representative NWS data will be used in its place.
Forecasts issued by the NWS, accessed via the NWS web site, will be used to plan sampler
deployment. Samplers will be placed in patterns so as to capture (as best possible)
conditions both upwind and downwind of a contaminated area based on these forecasts.
Predicted shifts in winds due to frontal passages will be taken into consideration in sample
placement.
4.0 COMMUNITY EVALUATIONS
Community evaluations will initially be conducted in the Baker Estates and Village of
Ceresco communities. U.S. EPA may request evaluation of these or other communities in
the future, if changing removal conditions warrant. The evaluations will be performed using
both sampling and real-time monitoring.
Real-time air monitors will collect data for total VOCs, H2S, S02, and benzene using the
equipment listed in Table 1.
Table 1 Summary of Real-Time Air Monitoring Equipment
Instrument
Analyte
Detection Limit
MultiRAE PID
Total VOCs
0.1 ppm
MultiRAE H2S electrochemical sensor
H2S
1 ppm
MultiRAE S02 electrochemical sensor
so2
0.1 ppm
UltraRAE PID with benzene sep filters
Benzene
0.05 ppm
Gastec Pump w/Benzene Colorimetric Tubes
Benzene
0.05 ppm
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One MultiRAE (5 gas instrument) and one UltraRAE benzene monitor will be utilized to take
snapshot readings of air quality in the vicinity of the community, during work activity periods
each day. The instruments will be used in a mobile mode, covering areas between the
contaminated areas and the community (or within the community), based on forecasted
prevailing wind directions. Each monitoring location will be documented with GPS
equipment, along with the time of the reading.
In addition to real-time air monitoring, analytical air samples will also be collected in or
adjacent to select community areas. Three canister samples will be collected
simultaneously over contiguous 24-hour periods in the vicinity of the communities being
evaluated. The target compound list for community sampling is the same as the list
presented in Attachment A. Multiple canisters in each community area allow for better
evaluation of the presence or absence of crude oil related chemicals and can capture vapors
as changes in wind direction occur. The samplers will be deployed based on forecast wind
directions, so as to capture a representative sample of air flowing from contaminated areas
into the community. All sampling locations will be documented with GPS devices.
Air monitoring and sampling will be conducted for a minimum period of 14 24-hour periods.
Based on the review of the data collected during the initial period, sampling and/or
monitoring may be reduced in frequency or discontinued at the discretion of U.S. EPA.
Results from the initial 14-day period will be compared to the screening concentrations found
in Attachment B. Enbridge and U.S. EPA will evaluate this comparison to determine the
need for ongoing sampling and/or monitoring. If results from the initial 14-day time period
yield no detections above applicable screening values, then sampling operations may be
reduced or discontinued. In the event that results should exceed a screening level,
additional sampling, monitoring, or protective measures may be required.
5.0 WORK AREA PERIMETER EVALUATIONS
5.1 Work Zone Perimeter Sampling
Perimeter samples will be collected at all work sites involving the submerged oil, dredged
sediment, and overbank excavation. Three canister samples will be collected
simultaneously over an 8-hour period along the perimeter work areas, coinciding with work
activity. Sample locations will be selected based on anticipated activities and forecast wind
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directions. The purpose is to select locations with the greatest opportunity to detect volatile
organic compounds, if any, that are released during recovery activities. Work area samples
will be positioned to ensure both upwind (1 sample) and downwind (2 samples) capture
zones from work operations to evaluate VOC vapors on-site and as background. Sample
canisters will be placed as close as practical to the actual removal activities, without
compromising site safety or work efforts. All sample locations will be documented using
GPS devices.
Perimeter sampling will be conducted at all work locations for a minimum period of 14 days,
or until results can be evaluated for that time period. Enbridge and U.S. EPA will review all
sampling results from the initial 14-day period, and determine the perimeter sampling
frequency and strategy needed for ongoing operations.
5.2 Work Zone Real-time Monitoring
Real-time air monitoring for VOCs, H2S, S02, and benzene, will be conducted using a
MultiRAE and UltraRAE/Gastec Pump with benzene colorimetric tubes (Table 1) by Health
and Safety (H&S) personnel within and along the perimeter of all the work zones, including
the tar patty recovery work zones. If the H&S monitoring indicates a VOC alarm above
applicable action levels, benzene checks will be initiated with a real-time benzene monitor
along with appropriate protective action as described in the HASP. The benzene checks will
be recorded in air monitoring log books or by entry into a handheld data collection device.
6.0 WORKER EXPOSURE MONITORING
Enbridge will evaluate worker exposure to benzene, toluene, ethylbenzene, xylenes, and n-
haxane(COPCs) by collecting breathing zone samples representative of each worker
population associated with the oil recovery operations. Each oil recovery workgroup consist
of two to four workers conducting similar tasks within close proximity to one another and at
similar distances to potentially contaminated sediment for the duration of their respective
work shifts. Each workgroup will be evaluated to identify the "maximum risk employee"
based on the work task and their proximity to contaminated material. The maximum risk
employee(s) from each work group, collectively, will represent the sample population from
which exposure samples should be collected.
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Worker exposure monitoring for the COPCs will be conducted using both real-time and
analytical methods. Worker exposure real-time data for VOCs will be collected using a data-
logging MultiRAE PID equipped with a Teflon tubing inlet positioned in the worker's
breathing zone. Prior to each work shift, the MultiRAE plus PID will be calibrated using 100
ppm isobutylene calibration gas. The real-time data collected form the data-logging
MultiRAE will be downloaded at the conclusion of the work shift. The data will be
downloaded via ProRAE Suite software and incorporated into the air monitoring database.
The worker's TWA concentration for VOCs will be calculated for each sampled worker.
In addition to the MultiRAE plus PID personal monitor, Enbridge may elect to co-locate an
organic vapor monitor (OVM) badge in the worker's breathing zone. These analytical
samples will be collected on the 3M 3500/3520 organic vapor monitor (OVM) badge and
analyzed for benzene, ethyl benzene, n-hexane, toluene, and xylene using gas
chromatography flame ionizing detection (GC/FID) in accordance with the National Institute
for Occupational Safety and Health (NIOSH) air sampling method 1500/1501. The OVM
badge is a passive dosimeter, composed of a permeation membrane and activated charcoal
which collects air samples at a flow rate controlled by the physical process of diffusion.
Collected samples will be properly logged and shipped to an AIHA accredited laboratory for
subsequent analysis. Table 2 summarizes the analytical detection levels for the OVM
badges.
Table 2 OVM badge limit of detection (LOD) for COPCs.
COPCs
Collection
Media
Flow Rate
(cc/min)
Sample
Duration*
(min)
Laboratory
LOQ (ug)
Limit of
Detection (ppm)
Benzene
3M 3520
35.5
600
2.0
0.029
Ethyl benzene
3M 3520
27.3
600
5.0
0.070
n-Hexane
3M 3520
32.0
600
5.0
0.074
Toluene
3M 3520
31.4
600
5.0
0.070
Xylene
3M 3520
27.3
600
15.0
0.211
*Sample duration may vary
6
-------
Approved
Once analyzed, a time-weighted average (TWA) concentration will be calculated to
determine if the worker's exposure meets or exceeds the COPC's site action levels
referenced in the Enbridge Health and Safety Plan and/or applicable occupational exposure
limits (OELs). Table 3 displays the applicable OELs including standards established by
OSHA. The Michigan Department of Labor and Economic Growth Director's Office
Occupational Health Standards for benzene are also referenced in Table 3.
Table 3 Occupational Exposure Limits
COPCs
OSHA
PEL-
TWA(a)
OSHA
PEL-
STEL©
OSHA
PEL-
Ceiling^)
ACGIH
TLV-
TWA(d)
ACGIH
TLV-
STEL(e)
MIOSHA
PEL-
TWA©
MIOSHA
PEL-
STEL(g)
Benzene
1
5
NE(h)
0.5
2.5
1
5
Ethyl
Benzene
100
NE
NE
20
125
NE
NE
n-Hexane
500
NE
NE
50
NE
NE
NE
Toluene
200
NE
300
20
NE
NE
NE
Xylene
100
NE
NE
100
NE
NE
NE
a. OSHA PEL-TWA = The permissible concentration in air of a substance that shall not be
exceeded in an 8-hour work shift or a 40-hour work week (OSHA, 1989).
b. OSHA PEL-STEL = The time-weighted average exposure that should not be exceeded
for any 15-minute period (OSHA, 1989).
c. OSHA PEL-Ceiling = The exposure limit that shall at no time be exceeded. If
instantaneous monitoring is not feasible, then the ceiling shall be assessed as a 15-minute
timw-weighted average exposure, which shall not be exceeded at any time during the work
day (OSHA, 1989).
d. ACGIH TLV-TWA = The Threshold Limit Value-TWA is the concentration for a normal 8-
hour workday and a 40-hour work week, to which nearly all workers may be repeatedly
exposed, day after day, without adverse effect (ACGIH, 2011).
7
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Approved
e. ACGIH TLV-STEL = The time-weighted average exposure that should not be exceeded
for any 15-minute period (ACGIH, 2011).
f. MIOSHA PEL-TWA = The permissible concentration in air of a substance that shall not be
exceeded in an 8-hour work shift or a 40-hour work week (R 325.77103 Rule 3 (1) MIOSHA
Reference of OSHA Permissible Exposure Limits).
g. MIOSHA PEL-STEL = The time-weighted average exposure that should not be exceeded
for any 15-minute period (R 325.77103 Rule 3 (2) MIOSHA Reference of OSHA Permissible
Exposure Limits).
h. NE = Not Established.
If sample results indicate an exceedance of the site action level and/or OELs for the COPCs,
additional measures will be taken to protect worker health. If the monitoring required by
paragraph (e)(2)(i) of the OSHA benzene standard 1910.1028 and R 325.77102 (B) of the
MIOSHA benzene standard R 325.77102 section reveals employee exposure at or above
the action level of 0.5 ppm but at or below the TWA, the employer shall repeat such
monitoring for each such employee at least every year. Specifically, if OVM sample results
indicate a benzene exceedance in excess of the OSHA Permissible Exposure Limit (PEL-
TWA), a regulated area will be established wherever the airborne concentration of benzene
exceeds or can reasonably be expected to exceed the permissible exposure limits
(1910.1028(d)(1)) (MIOSHA R 325.77104 Rule 4). If a regulated area is established based
on detections of elevated benzene , access will be limited to authorized persons with
appropriate personal protective equipment (PPE) (1910.1028(d)(2).
7.0 ODOR INVESTIGATIONS
Enbridge will provide an Odor Response Team. The Odor Response Team will be deployed
within 30 minutes (maximum) after receiving odor complaints/concerns. Responses will be
conducted 24 hours a day, 7 days a week. Enbridge will immediately relay all initial odor
reports to U.S. EPA Air Monitoring Operations Section and MDEQ. The MDEQ will notify
Michigan Department of Public Health staff of the odor complaints.
Personnel responding to the odor event will travel to the location where the report originated.
Real-time air monitoring data and analytical "grab" canister sample data will be collected at
the reported location. Short-term real-time readings will be taken for VOCs, H2S, and S02
8
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Approved
using a MultiRAE monitor and benzene using an UltraRAE monitor or Gastec pump with
benzene specific colorimetric tubes. These readings will be reported to the complainant
immediately, and recorded in log books. At least one canister sample will be obtained, with
additional canisters possible depending on the situation encountered. The canister samples
will be analyzed using the same analytical approach and target compound list as routine
samples (Attachment A). In addition, at the time of sampling, the Odor Response Team will
document the presence or absence of odors and the subjective quality of the odors. The
odor event location will also be documented using GPS.
After completion of the field visit, the Odor Response Team will relay the collected
information to Enbridge. Enbridge will provide U.S. EPA with daily summaries of all Odor
Response Team activities. Upon receipt of canister sampling results, Enbridge contractor
will prepare a follow-up letter report, to be transmitted to Enbridge Safety, the complainant,
and U.S. EPA.
8.0 TAR PATTY STUDY
The potential for fugitive VOCs from tar patties will be evaluated using a bagging technique.
Several tar patties will be enclosed in a mylar or equivalent bag, and allow to warm in direct
sunlight. The air inside the bag (headspace) will then be sampled and analyzed.
At 10% of the tar patty removal sites, headspace samples will be collected. At all of the
selected sites, one bag of material will be sampled by directly pulling headspace air into a
MultiRAE instrument and an UltraRAE benzene-specific monitor. At half of the selected
sites, an additional bag of material will be collected and the headspace air sampled by
extracting to a Tedlar bag for TO-15 analysis (Attachment A).
The results of these results will be obtained on rapid turnaround from the laboratory, and
submitted by Enbridge to U.S.EPA. Enbridge and U.S. EPA will determine the need for
monitoring and/or sampling during tar patty removals based on the results.
9.0 DATA QUALITY AND MANAGEMENT
Air samples will be sent to Galson Laboratories located in Syracuse, N.Y or other approved
laboratory. Preliminary results will be provided to Enbridge Energy's designated
representative and to any other designated representative or organization within one to two
9
-------
Approved
days of receipt by the laboratory. Analytical results will be flagged in instances where the
contaminant is also detected in the laboratory blanks. The expedited turnaround time for
Galson can be as little as one business day, upon laboratory receipt. All data will be
submitted to the U.S. EPA Scribe database through Enbridge data management system. In
addition, Enbridge will provide daily monitoring summary reports to U.S. EPA (by end of
following day).
Collocated duplicate samples will be collected at a frequency of 1 per 10 (10%). Trip blank
analysis will be conducted once per week as directed by U.S. EPA.
10.0 AIR SAMPLING AND MONITORING REPORTING
Enbridge will provide on a daily basis the following deliverables:
An overview of air sampling and monitoring activities conducted the previous day. The
overview will consist of a map of the area between the spill site and Morrow Lake, or the
geographical extent of air sampling and monitoring activities, whichever is smaller. The map
will include the following layers:
• Locations of discrete analytical samples collected the previous day. Labels will
include a common name (e.g. Ceresco) or project marker name (e.g. MP 24.75),
count of discrete sampling locations, and count of samples collected.
• Locations of instantaneous readings collected the previous day. The symbols will be
color-coded by analyte. Benzene readings will be colored differently from the other
analytes.
• Summary table of instantaneous readings collected the previous day. The table will
list counts of readings collected by location category (e.g. Work Area, Community),
as well as counts of any detections.
• Windrose(s) generated from meteorological data collected the previous day.
An overview of the latest full day of air sampling laboratory analysis results received. The
overview will consist of one or more maps of the area(s) encompassing all locations where
any compounds were detected. The map(s) will include the following layers:
• Locations of all discrete analytical samples. Labels will include a unique location
code for each symbol, as well as common name or project marker name.
10
-------
Approved
• Chart listing concentrations and applicable screening levels of all analytes detected
in the locations included in the extent of the map.
• Windrose(s) generated from meteorological data collected the day of sampling.
• The daily report package will also contain tabular summaries of hourly meteorological
data. This shall be a set of tables that show air monitoring parameters for each day
(by hour), as recorded from each portable weather and NWS station. The
summaries shall also include a daily average for each parameter.
These deliverables are provided following an internal QA/QC process. The analytical data is
received and reviewed by a qualified individual (project manager/industrial hygienist and/or
toxicologist). The data will be reviewed on a daily basis to ensure that necessary actions are
implemented if required (such as additional canister placement and/or real-time monitoring).
Data is then uploaded to the Sharefile site for dissemination. An email notice will be sent
informing participating regulatory agencies that the information for that day is available for
viewing or download.
The final report will be produced upon completion of air monitoring/sampling activities
detailed in this plan. The final report will consist of a compilation of real-time and analytical
data, physical parameters such as wind direction, and geographical area. An evaluation of
the results will be conducted to determine if COPCs were present during the oil recovery
operations and if those COPC concentrations exceeded applicable human health air
screening levels.
11.0 PROJECT ORGANIZATION
Enbridge Consultants will be responsible for the following:
• Toxicological support;
• Air monitoring;
• Air sampling;
• Air data quality assurance/quality control, and
• Data evaluation and reporting
Mr. Chase Selby, Environmental Scientist Project Manager, will serve as the Project
Manager and Dr. Phillip T. Goad (Principal Toxicologist) will serve as the Project Director
11
-------
Approved
and Mr. Brett Yokom, Project Engineer, will serve as Enbridge's Task Manager for this
scope of work.
12.0 CALIBRATION AND MAINTENANCE OF FIELD INSTRUMENTS
The calibration and maintenance of field equipment and instrumentation will be in
accordance with each manufacturer's specifications or applicable test/method specifications,
and will be recorded in Enbridge's Consultant calibration logs.
13.0 CHAIN OF CUSTODY (COC)
Each sample will be identified on a chain of custody record. The air sample numbering
system will include site name, date, analyte, and identification code unique to each sample.
14.0 SAMPLE LABELS
Sample labels will be securely affixed to the sample container. They will clearly identify the
particular sample and should include the following information:
• Sampling location;
• Date the sample was collected, and
• Unique identifier.
15.0 PACKAGING AND SHIPPING
Packaging and shipping of air samples will be conducted following method
recommendations. Canisters will be shipped in a box via carrier service (ex. FedEx). Air
samples do not require sample preservation in the field. However, caps will be placed on
canisters and regulators or critical orifices will be detached during shipment. The person
packaging the samples is responsible to ensure that the sample packaging is in suitable
condition for shipping.
12
-------
Attachment A
Compounds Detected by TO-15 Analysis
-------
Attachment A
Table 1 Predominant Crude Oil VOCs Detect by TO-15 Analysis1
Analyte
Laboratory
LOQ
Analyte
Laboratory
LOQ
Benzene
5.0
Heptane, n-
5.0
Butane, 2-methyl-*
Hexane, n-
5.0
Cyclohexane
5.0
Naphthalene
5.0
Cyclohexane, 1,3-
dimethyl-*
Nonane*
Cyclopentane, methyl-*
Hexane, 2-methyl*
Cyclohexane, 1,3-
dimethyl-, cis-*
Octane*
Cyclohexane, butyl-*
Octane, 3-methyl-*
Cyclohexane, ethyl-*
Pentane, 2-methyl-*
Cyclohexane, methyl-*
Toluene
5.0
Cyclohexane, propyl-*
Benzene, 1,2,4-
trimethyl
5.0
Cyclopentane, 1,1-
dimethyl*
Hexane, 3-methyl*
Cyclopentane, 1,3-
dimethyl-, trans *
Hexane, 3-methyl*
Cyclopentane, 1,2-
dimethyl-, trans *
Heptane, 2-methyl-*
Heptane, 3-methyl-*
Cyclohexane-1,1,3-
trimethyl*
2-Octene, 2,6-dimethyl-*
Benzene, 1,3,5-
trimethyl
5.0
Decane*
Undecane*
Dodecane*
Xylene, m&p-
10
Ethyl benzene
5.0
Xylene, o-
5.0
Ethyltoluene, 4-
5.0
1 - The laboratory will also be asked to report on all analytes included in their TO-15 method
standard analyte list.
*- Tentatively identified compound (TIC)
-------
Attachment B
Enbridge Oil Spill Human Health Screening Levels
-------
Attachment B
Enbridge Oil Spill
Human Health Air Screening Levels
August 13, 2010
Chemical
Screening
Level in
Chemical Name
Abstract
Service
Number
parts per
billion by
volume
(ppbv)
Source of
Screening Level
1,1,1-trichloroethane
71-55-6
700
ATSDR Int. MRL
1,1,2,2-T etrachloroethane
79-34-5
0.006
EPA RSL
1,1,2-T richloro-1,2,2-trifluoroethane
76-13-1
4,000
EPA RSL
1,1,2-T richloroethane
79-00-5
100
Chronic MRL or RfC
1,1-Dichloroethane
75-34-3
100
Chronic MRL or RfC
1,1-Dichloroethene
75-35-4
20
ATSDR Int. MRL
1,2,4-T richlorobenzene
120-82-1
30
Chronic MRL or RfC
1,2,4-T rimethylbenzene
95-63-6
1.5
EPA RSL
1,2-Dibromoethane
106-93-4
1
Chronic MRL or RfC
1,2-Dichloro-1,1,2,2-T etrafluoroethane
76-14-2
9,900
EPA RSL
1,2-Dichlorobenzene
95-50-1
30
Chronic MRL or RfC
1,2-Dichloroethane
107-06-2
1,000
Chronic MRL or RfC
1,2-Dichloropropane
78-87-5
7
ATSDR Int. MRL
1,3-Butadiene
106-99-0
1
Chronic MRL or RfC
1,3,5-T rimethylbenzene
108-67-8
45
MDNRE
1,3-Dichlorobenzene
541-73-1
0.5
MDNRE
1,4-Dichlorobenzene
106-46-7
200
ATSDR Int. MRL
1,4-Dioxane
123-91-1
1,000
ATSDR Int. MRL
2,2,4-T rimethylpentane
540-84-1
750
MDNRE
2-Chloro-1,3-butadiene
126-99-8
2.1
EPA RSL
2-Propanol
67-63-0
3,000
EPA RSL
3-Chloropropene
107-05-1
0.3
Chronic MRL or RfC
Acetone
67-64-1
13,000
ATSDR Int. MRL
Acetonitrile
75-05-8
38
EPA RSL
Acrylonitrile
107-13-1
1
Chronic MRL or RfC
Benzene
71-43-2
6
ATSDR Int. MRL
Benzyl chloride
100-44-7
0.01
EPA RSL
Bromodichloromethane
75-27-4
0.01
EPA RSL
Bromoform
75-25-2
0.21
EPA RSL
Bromomethane
74-83-9
50
ATSDR Int. MRL
Butane
106-97-8
10,000
MDNRE
Carbon disulfide
75-15-0
200
Chronic MRL or RfC
Carbon tetrachloride
56-23-5
30
ATSDR Int. MRL
Chlorobenzene
108-90-7
200
Chronic MRL or RfC
Chloroethane
75-00-3
4,000
Chronic MRL or RfC
Chloroform
67-66-3
50
ATSDR Int. MRL
Chloromethane
74-87-3
200
ATSDR Int. MRL
cis-1,2-dichloroethene
156-59-2
8.6
MDNRE
cis-1,3-Dichloropropene*
10061-02-6
4.4
MDNRE
Cumene
98-82-8
100
Chronic MRL or RfC
Cyclohexane
110-82-7
2,000
Chronic MRL or RfC
-------
Cyclohexane, methyl
108-87-2
4,000
MDNRE
Chemical
Screening
Level in
Chemical Name
Abstract
Service
Number
parts per
billion by
volume
(ppbv)
Source of
Screening Level
Cyclopentane
287-92-3
6,000
MDNRE
Dibromochloromethane
124-48-1
0.01
EPA RSL
Dichlorodifluoromethane
75-71-8
42
EPA RSL
Ethyl Acetate
141-78-6
890
MDNRE
Ethyl benzene
100-41-4
700
ATSDR Int. MRL
Heptane
142-82-5
850
MDNRE
Hexachlorobutadiene
87-68-3
10
Chronic MRL or RfC
Hexane
110-54-3
200
Chronic MRL or RfC
Isobutane
75-28-5
10,000
MDNRE
Methyl butyl ketone
591-78-6
10
Chronic MRL or RfC
Methyl ethyl ketone
78-93-3
2,000
Chronic MRL or RfC
Methyl isobutyl ketone
108-10-1
700
Chronic MRL or RfC
Methyl tert-butyl ether
1634-04-4
700
ATSDR Int. MRL
Methylene chloride
75-09-2
300
ATSDR Int. MRL
Napthalene
91-20-3
1
Chronic MRL or RfC
Nonane
111-84-2
100
MDNRE
Pentane
109-66-0
6,000
MDNRE
Propene
115-07-1
2,000
Chronic MRL or RfC
Styrene
100-42-5
200
Chronic MRL or RfC
Tetrachloroethene
127-18-4
40
Chronic MRL or RfC
Tetrahydrofuran
109-99-9
6.1
MDNRE
Toluene
108-88-3
1,000
Chronic MRL or RfC
trans-1,2-Dichloroethene
156-60-5
200
ATSDR Int. MRL
trans-1,3-Dichloropropene*
10061-01-5
0.5
MDNRE
Trichloroethene
79-01-6
100
ATSDR Int. MRL
T richlorofluoromethane
75-69-4
130
EPA RSL
Vinyl acetate
108-05-4
10
ATSDR Int. MRL
Vinyl bromide
593-60-2
1
Chronic MRL or RfC
Vinyl chloride
75-01-4
30
ATSDR Int. MRL
Xylenes
1330-20-7
2,000
ATSDR Int. MRL
* MDNRE provisional screening value for Dichloropropene based on a 1 in 100,000 cancer risk
ATSDR Int. MRL - The Agency for Toxic Substances and Disease Registry Intermediate
Minimal Risk Level (MRL) is the preferred screening level. The MRL is protective of daily human
inhalation exposure for up to a year, including sensitive individuals such as children, the elderly,
and those with pre-existing illnesses.
ATSDR Chronic MRL or EPA RfC - If no Intermediate MRL is available, the screening level is
the ATSDR Chronic MRL or the EPA Reference Concentration (RfC). The chronic MRL and the
RfC are protective of daily human inhalation exposure over a lifetime, including sensitive
individuals.
EPA RSL - If none of the above are available, the EPA Regional Screening Level (RSL) is the
screening level. The RSLs are protective of daily human inhalation exposure over a lifetime,
including sensitive individuals.
MDNRE - If none of the above are available, the Michigan DNRE Air Quality Division, Air Toxics
Screening Level is the screening level. The MDNRE screening levels are protective of daily
human inhalation exposure over a lifetime, including sensitive individuals.
-------
Attachment C
Meteorological Station Specifications
-------
a chemical emergency'.
Datalogging Specs:
The Coastal WeatherPak outputs data every 30 seconds. SAFER reads this stream as the data comes in
and compiles 5 five minute average of the data for use with its model. The data is logged internally to
the computer in the SAFER STAR file structure and can be accessed through dbf format by opening the
file in Excel. It can also be accessed for further analysis by using the Meteorological analysis application
that is a part of the SAFER STAR program suite. Because the data is stored on the hard drive, it is never
deleted (no FIFO buffer) and the only way the data can be erased is by manually deleting the files or a
hard drive crash.
Technical specs of the instruments:
Wind Speed:
Range: 0 to 60 m/s (130 mph)
Survival: 100 m/s (220 mph)
Threshold: 1.0 m/s (2.2 mph)
Wind Direction
Range: 360° mechanical, 355° electrical
Survival: 100 m/s (220 mph)
Threshold: 0.9 m/s (2.0 mph)
Temperature
Operational Range: -40°Cto 50°C (-40°F to 122°F)
Accuracy: ±0.2°C overfull range (0.36°F)
Resolution: 0.5°C (1.0°F)
Humidity
Operating Temperature Range: -40°Cto +80°C
Measuring Range: 0 to 100% RH
Accuracy at +20°C: +/- 2% RH (0 to 90% RH)
+/- 3% RH (90 to 100% RH)
Temperature Dependence: +/- 0.05% RH/°C
Compass
Accuracy: ±1.0°
Resolution: 1°
Tilt Limit: ±45°
Mechanical Specs
Size: 4" x 22.5" (10.3 cm x 57.2 cm) (base unit without wind monitor)
Weight: 8 lbs (3.6 kg) (base unit without wind monitor)
Carry Weight: ABS Carry Case w/WEATHERPAK® 24 lbs. (10.9 Kg)
Canvas Tripod Bag 30 lbs. (13.6 Kg)
Material: 6061-T6 aluminum, 316SS hardware, O-Ring sealed Mil-Spec connector,thermoplastic resin coated
Set-up Time: 60 seconds, from carry case to full operation
Operating Specs
Temperature: Operation from -40°C to 70°C (-40°F to 160°F)
Pressure: Operation from 800 to 1100 mBar
Humidity: 10 day exposure with 100% RH
Rain: 20 in/hr
Shock/Vibration: Survival of 6 ft drop
-------
Tipping Bucket / Rain Gauge
S1068W I S1068Z
• Rugged aluminum housing
• Completely automatic
• 0.01" Accuracy
This sensor consists of a gold anodized aluminum
collector funnel with a knife edge that diverts the
water to a tipping bucket mechanism. The
mechanism is so designed that one alternate tip of
the bucket occurs for each 0.01 inch of rainfall.
Connecting the sensor to the ZENO® 3200 data
logger, or to the WEATHERPAK® will allow
record keeping of accumulated rainfall.
The spent water drains out of the bottom of the
housing, so the sensor requires no attention or
servicing of any kind. The aluminum housing is
covered with a white baked enamel surface to
withstand years of exposure to the environment.
This sensor is factory calibrated, and due to the
nature of its operation, should not require field
calibration. Occasional cleaning of debris from
the filter screen may be required.
6?
15.4cm
Bf,
25 fn in
Coastal Environmental Systems, Inc. 820 First Avenue South, Seattle, WA 98134
(800) 488-8291 I (206) 682-6048 I Fax: (206) 682-5658 www.CoastalEnvironmental.com
Rev 06/24/09
-------
Technical Specifications
Resolution:
Accuracy:
Average Switch Closure Time:
Maximum Bounce Settling Time:
Maximum Bounce Closure Time:
Maximum Switch Rating:
Temperature Limits:
Humidity Limits:
PHYSICAL
Height:
Weight:
Receiving Orifice Diameter:
Cable:
S1068W / S1068Z
0.01" (0.25 mm)
1.0% at 2"/hr. or less
135 ms
0.75 ms
0.25 ms
30 VDC a) 2 A. I 15 VAC fg| 1 A
0°C to +52°C (+32°F to +125°F)
0 to 100%
10" (25.6 cm)
2.5 lbs (1.13 kg)
6" (15.4 cm)
15 ft, 2-conductor
Coastal Environmental Systems, Inc. 820 First Avenue South, Seattle, WA 98134
(800) 488-8291 / (206) 682-6048 / Fax: (206) 682-5658 www.CoastalEnvironmental.com
-------
Attachment D
Field Standard Operating Procedures
-------
CTEH QA/QC and Data Validation Procedures for Real-Time Air
Monitoring and Air Sampling
Quality Assurance and Quality Control
Quality assurance and quality control (QA/QC) measures are conducted following the
collection of real-time air monitoring and analytical sampling to ensure that air monitoring
and sampling results are defensible. Analytical sampling can be performed to verify
real-time air monitoring results or to provide quantifiable data. The following sections
describe QA/QC actions taken to ensure completeness and correctness of data.
1.0 Real-Time Air Monitoring
The term "real-time" refers to data collected using direct reading instruments that allow
nearly instantaneous determinations of airborne chemical concentrations. Real-time
measurements provide immediate information for worker and community exposure
scenarios and, with the use of appropriate site safety measures, help prevent
overexposures. Real-time air monitoring follows methods and procedures that are
similar to analytical sampling. The following sections describes these actions.
1.1 Field Calibration
All field real-time air monitoring instruments or equipment will be calibrated prior to use
in the field. Real-time instruments will be calibrated daily or as needed, according to
manufacturer recommendations. Specifically, photo ionization detectors (PIDs) will be
calibrated with a known concentration of isobutylene gas or zeroed using zero-grade air
or at background site locations. Particulate matter monitors will be zeroed using
manufacturer supplied zero filters. Gastec chemical specific colorimetric detector tubes
are hermetically sealed and are calibrated by the manufacturer, and therefore, do not
require field calibration.
1.2 Field Documentation
During the sampling events, all applicable notes, calibrations, sample locations, and
sampling periods will be maintained in either various field books, portable handheld
devices, or site logs. All instrument calibrations are to be documented on the field
calibration log. The serial number of the instrument, gas applied, concentration, lot
number of the gas, and expiration date of the gas are all documented.
All real-time readings will be documented either in bound notebooks, on CTEH field
forms, in portable handheld devices, or by using radio telemetry systems combined with
computer databasing capabilities. Each real-time record will have a description of the
1
-------
location, global positioning system (GPS) data, sampling date and time, sampler's
initials, concentration, analyte, and proper unit of measurement.
1.3 Verification of Real-Time Readings
Direct reading instruments perform sampling and analyses within the instrument and
concentration readings can usually be obtained immediately. These instruments have
fast response times and can follow rapid changes in concentration. Many are capable of
storing continuous readings and displaying averages for selected time intervals.
However, the presence of humidity, temperature extremes, and other atmospheric
conditions may produce a phenomenon known as instrument drift. A second real-time
instrument is often used to verify readings when drift is suspected or to confirm
detections.
1.4 Data Management
All real-time data will be entered manually into a database or downloaded from the
instrument source and imported into a database. This includes air data that were
collected utilizing RAE System's Inc.'s instruments (AreaRAE, MultiRAE, ppbRAE,
UltraRAE, MiniRAE), Lumex mercury monitor, Gastec colorimetric tubes, and TSI's
aerosol monitors. All real-time manually-logged readings will undergo 100 percent
QA/QC by field personnel. Data entered into databases will be reviewed electronically
and manually by personnel.
2.0 Analytical Sampling
Steps are performed to ensure analytical samples are identified and handled properly in
the field. The following sections describe these steps.
2.1 Sample Media Inspection
Analytical sampling media is shipped by a vendor and are prepared by the manufacturer.
Upon receipt by CTEH, sampling media are inspected prior to use in the field and during
time of preparation by field personnel. If sampling media appear to be damaged,
broken, or incorrectly labeled, the media is discarded. Field personnel inspect to ensure
media has not expired. Furthermore, field personnel inspect media to ensure that
sample integrity will not be compromised prior to the sampling event. When samples are
collected after a sampling event, they are inspected again before shipment to the
analytical laboratory.
2
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2.2 Integrated Sample Flow Rate Calibration
Integrated air sampling will be conducted utilizing a sample collection device that that
pulls air across a medium and stabilizes chemicals for subsequent laboratory analysis.
Sampling devices will be calibrated with a DryCal primary flow meter before and after
each use. Pre-calibration and post-calibration of devices are recorded on CTEH field
forms.
2.3 Sample Documentation
During the sampling events, all applicable notes, calibrations, sample locations, and
sampling periods will be maintained in either field books, handheld devices, or site logs.
All analytical sample documentation for samples collected in the field will be in
compliance with the procedures outlined in this section, regardless of the sample media.
2.4 Sample Identification and Labels
Each analytical sample prepared and collected will be allocated a unique CTEH identifier
(sample ID). This sample ID will be labeled on its assigned sample. All sample labels
used on sample containers will include, at a minimum, a sample identification code, the
date of the sample, site name, and an indication of the chemical sampled. The label will
adhere to the media and the writing on it will be in indelible ink. The label will be
secondarily affixed to the media with clear adhesive tape completely covering the label.
2.5 Field Blanks
Field blanks are designed to determine whether samples have been contaminated prior
to or during the sampling event. The blank media are submitted to the laboratory without
having air pulled through them. At least one field blank will be collected, for each
different method, for each set of samples. The number of field blanks collected will be
dependent upon method recommendations. If field blanks are not sent with analytical
samples, the laboratory will prepare a method blank per QC batch and analyzed with
samples. All samples analyzed at the laboratory will have a method blank prepared and
analyzed with samples.
2.6 Field QA/QC Samples
Field blank samples will be collected as field QC checks for the samples. There are no
known sources of QC samples for industrial hygiene sampling. Therefore, duplicates
and matrix spike samples cannot be collected and sent to the laboratory for analysis.
Laboratory QC samples will be analyzed concurrently with the analytical batch to which
they are assigned.
3
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2.7 Packaging and Shipping
Packaging and shipping of samples will vary depending upon sample media,
contaminant concentration, preservation technique, and sample container. Packing and
shipping samples should follow recommendations or requirements of analytical method.
The person packaging the samples is responsible to ensure that the sample packaging
is in suitable condition for shipping.
2.8 Chain of Custody
Chain of Custody (COC) is a legal term (a concept in jurisprudence) that refers to the
ability to guarantee the identity and integrity of the sample and provides a chronological
history of the sample from the time of collection through to reporting of the test results for
the production of legally defensible data. Each sample will be identified on a COC
record. Information recorded will include, at a minimum, sample collection date, time,
sampler's initials, identification of sample matrix, sample volume, number of containers,
analyses requested, preservation method, and signature blocks for each individual who
has custody for the sample(s).
2.9 Custody Seals
Custody seals are placed on either the sample container or the sample or both. Custody
seals are signed by the sampler with date and time. This is done to ensure that samples
are not tampered with until received by the laboratory.
3.0 Laboratory Analytical Procedures
The most current versions of NIOSH, OSHA, or EPA methods will be used by the
contract laboratory for the analyses of chemicals sampled for. Each contract laboratory
is selected to comply with local, state, or federal regulations. Laboratories are either
dictated by governing agency, by accreditation, or due to limitations on who can perform
prescribed analysis. When options are available, CTEH chooses AIHA accredited
laboratories who are also certified locally for analytical method. The following sections
describe procedures to ensure data quality and usability.
3.1 Sample Containers, Preservation, and Holding Times
All sample media will be provided by the analytical laboratories or media manufacturers.
Sample preservation and temperature, if necessary, shall be checked immediately upon
receipt of samples at the laboratory. The results of these checks will be recorded on the
4
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chain-of-custody form submitted with the sample. This is performed to ensure sample
integrity.
3.2 Sample Handling in the Laboratory
Upon receipt, all samples will proceed through an orderly processing sequence (as
defined in the laboratory QA/QC Plan) specifically designed to ensure continuous
integrity of both the sample and other pertinent information to the analysis. All samples
will be carefully checked and verified for proper chain-of-custody (COC) records, proper
label identification, and any associated discrepancies. These items will be documented
by use of a laboratory receipt form.
If no discrepancies are identified, the sample COC record will be signed, and the
samples will subsequently be assigned a unique laboratory identification number by the
laboratory for tracking and filing. The laboratory QA system and the use of an internal
COC procedure will ensure that the samples are appropriately tracked from storage
through the laboratory until the analytical process is complete.
Analytical and procedural information and activities will be documented with the use of
Standard Operating Procedures (SOPs), a laboratory data management system,
laboratory bench sheets, laboratory notebooks, and orderly project files containing any
information pertinent to the analysis or integrity of the results.
The contracted laboratory will provide a written QA/QC program that discusses rules and
guidelines to ensure the reliability and validity of all analytical work conducted in their
laboratory. Compliance with the QA/QC program is coordinated and monitored by
designated laboratory quality assurance personnel.
The laboratory will document, in each data package provided, that both initial and
ongoing instrument and analytical QC functions have been met. Corrective action will be
initiated on any samples analyzed in non-conformance with the QC criteria.
3.3 QA/QC Samples Prepared at the Laboratory
Method quality control checks will be analyzed as outlined in the individual method for
each analysis performed. Furthermore, laboratories will prepare at minimum, one
method blank per analytical batch. The method blank is carried through each step of the
analytical method to examine the potential for cross-contamination. In addition or at the
request of clients, laboratories will prepare a laboratory control sample (LCS). The
primary purpose of the LCS is to demonstrate that the laboratory can perform the overall
analytical approach in a matrix free of interferences (e.g, in reagent water, clean sand, or
5
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another suitable reference matrix). The LCS is a blank sample that is spiked with a
known concentration of analyte. The LCS is prepared and analyzed with samples.
Since there are no known sources for duplicate or matrix spike samples, a laboratory
control sample duplicate (LCSD) is often prepared and analyzed. This should be
accomplished at a frequency of 1 in every 20 samples analyzed or as necessary,
whichever is more frequent.
3.4 Data Reduction
The laboratory will perform in-house analytical data reduction and review of chemical
analyses under the direction of the laboratory's technical staff, QA Officer, and Project
Manager for this project. These individuals are responsible for evaluating the quality of
the data and indicating which, if any, data may be listed as "unacceptable" and/or which
should be considered potentially unreliable. A report by the personnel assessing data
quality will be submitted to the Laboratory Project Manager or designee with every data
package prior to transmittal to the client.
Data reduction, review, and reporting by the laboratory will be conducted as detailed as
necessary in the laboratory Quality Assurance Project Plan (QAPP).
3.5 Data Reporting
The specific data items in each analytical data set submitted to CTEH will include, but
will not be limited to, the following items:
• Cover sheet listing the samples included in the report and narrative comments
describing problems encountered during analysis;
• Copies of signed COC records;
• Tabulated results of the compounds identified and quantified;
• Analytical results for QC field blanks;
• Calculations of detection (reporting) limits;
• Raw electronic data files
3.6 Preventive Maintenance and Calibration
The approved laboratory will be responsible for the maintenance of laboratory
instruments and equipment. Instruments and measurements made as part of the
analytical methodology will be as specified in the method, without modification. The
laboratory's QA program ensures that only trained personnel perform routine
maintenance on all major instruments and that repairs are performed by trained
laboratory personnel or service technicians employed by the instrument manufacturer or
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representative. Instrument maintenance will be appropriately documented through the
use of instrument logs that will be included in the laboratory project file.
3.7 Corrective Measures
When errors, deficiencies, or out-of-control situations exist, the laboratory QA program
provides systematic procedures, called corrective actions, to resolve problems and
restore proper functioning to the analytical system.
3.8 Laboratory Data Report
Laboratory data reports will be issued for each work order generated by the laboratory. A
work order is generated for a single client's samples, received by the laboratory on the
same day. The deliverable components of the data report are listed below:
• Data Report (analyte, method, detection limit, date and time of analysis and results
for each sample)
• Field and Laboratory Blank Summaries
• Dilution Factors
• Chain-of-Custody Records
• Cooler Receipt Forms
• Laboratory Sample Preparation Data Sheets
• Extraction/Digestion Logs
As appropriate, each of these deliverable components is given for each of the types of
analyses that are conducted.
4.0 Data Validation/Verification
Prior to reporting and submittal to client, CTEH conducts data verification or data
validation procedures on analytical data. A CTEH Environmental Chemist will conduct
data verification on the analytical data at the request of the client. Frequency and
methods are chosen to best represent the intended use of the data. Data verification is
the process of evaluating the completeness, correctness, and conformance/compliance
of a specific data set against the method, procedural, or contractual requirements. The
analytical data will be evaluated to determine whether the reported laboratory results are
compliant with the requirements of the sampling and analysis methods and procedures
used to generate results.
The following parameters will be evaluated:
• Data Completeness
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• Holding Times
• Sample Preservation
• Sample Receipt
• Sample Analysis
At the completion of the data verification process, the reviewer will prepare a summary
of the results and note data usability.
Furthermore, data validation is a systematic procedure of reviewing a body of data
against a set of established criteria to provide a specified level of assurance of its validity
prior to use. The validation process will include checks for internal consistency, checks
for transmittal errors, and checks for verification of laboratory capability. Evaluation of
these criteria will involve review of parameters listed above and:
• Evaluation of Holding Times
• Review of Surrogate Recoveries
• A review of all QA/QC samples
• Detection limit records
• Instrument calibration records
• Continuing calibration records
• Internal standard records
• Target compound results
• Sample results
At the completion of the data validation process, the reviewer will prepare a summary of
the results, validate sampling results, and specify the uses for which the data are
suitable.
8
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CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C.
Toxicology Emergency Response Program (6/3/2008)
STANDARD OPERATING PROCEDURE NO. (Version 1.1)
SUBJECT: Gastec GV-100 and Colorimetric Detector Tubes
Description of the SOP: This procedure is intended to provide instruction on the
proper use of the Gastec piston pump (GV-100) with real-time colorimetric detector
tubes for a wide range of analytes.
Calibration Instructions: Factory Calibrated.
Equipment Use Instructions (step by step)
1) Determine your analyte of concern.
2) Pick out a box of detector tubes and insure the following items (The following
instructions assume you have picked out a previously un-opened box)
a) The box of detector tubes are not expired (Expiration date is printed on the
top of the box).
b) The measuring range is appropriate for the sampling you are performing.
3) Determine if the analyte you are sampling for is a single tube method or a dual
tube method. To determine this, look on the front of the detector tube box and
look at the number of tests. If it says 10 tests, it is a single tube method, if it says
5 tests; it is a dual tube method (example: Benzene 121L).
4) Assuming it is a single tube method:
a) Break off both ends of the glass detector tube in the tip breaker located on
the Gastec pump.
b) Insert the glass tube in the end of the Gastec pump with the arrow on the
glass detector tube pointing towards the pump.
5) Assuming it is a dual tube method:
a) There will be ten glass tubes in the box, 5 pre-treatment tubes and 5 detector
tubes.
b) Locate a pre-treatment tube (usually in the back row of the box and is
identified as a tube with no measuring scale printed on it), a detector tube
(usually in the front row of the box and is identified as a glass tube with a
measuring range printed on it), and a pink piece of tubing located between
the two rows of tubes.
I
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c) Break off both ends of both tubes using the tip breaker on the side of the
Gastec pump.
d) The pretreatment tube should be placed in-line with the measuring tube using
the pink piece of tubing. The pretreatment tube should be in front of the
detector tube for sampling. The detector tube has the measuring range
delineated on it, and should be the one inserted into the pump while the
other, pretreatment tube, filters the air before it reaches it.
NOTE: The arrows on both glass tubes should be pointing towards the Gastec
pump.
I I I I I H
o o
to I— ^ n. II
I i I I I 4 1
a c
e) Insert the measuring tube in the Gastec pump.
6) To determine the appropriate number of pump strokes, look at the instructions
located in the detector tube box. There are two types of pump strokes, a full
stroke (100 ml_) and a half stroke (50 ml_). To pull a full stroke or a half stroke
line up the arrow on the Gastec pump handle with the appropriate volume (either
100 ml_ or 50 ml_). Every analyte has a different measuring range, but generally
the more pump strokes that are pulled, the lower the detection limits.
NOTE: Insure that you are pulling enough pump strokes to get below the
particular standard or guideline with which you are comparing your results. Also,
the "number of pump strokes" in the directions refers to full (100 ml_) pump
strokes.
7) The pump stroke is complete when the "Flow Finish Indicator" is visible on the
end of the pump handle. The "Flow Finish Indicator" is a white disc that becomes
visible after pulling the pump stroke anywhere from 30 seconds to 5 minutes
depending on the analyte.
8) To read the airborne concentration of the analyte of concern, look at the
measuring scale on the detector tube. Consult the instructions for the
appropriate reagent color change that you should expect if the analyte is present
in the air at detectable levels. There is a statement on every detector tube such
as "n=X", this indicates the number of full pump strokes that you must pull to read
the concentration directly from the detector tube. If you pull more or less than
CTEH
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this number, you must apply a correction factor that you will find in the
instructions.
9) Note that all colorimetric detector tubes have chemical interferences as well as
corrections for humidity, pressure, and temperature. Consult the instructions for
details.
10) Do not re-use a detector tube or pretreatment tube if you have a color change in
the reagent (a detection).
Tips for detector tube reading
When the end of the color
change layer is flat,
simply read the value at
the end.
When the end of the color
change layer is slanted,
read the value in the
middle of the slant.
When the demarcation of
the color change layer is
pale, the mean value
between the dark and the
pale layer ends is taken.
4 5 6
CGH I
n this case, the reading
would be 5%.
n this exaggerated case,
the reading would be 5%.
;g-
i
"p i
n this exaggerated case,
the reading would be 5%.
Tip for easier reading
When you mark the color change with a pen as soon as the sampling is complete, it is
more convenient to read.
NOTE: It is possible to have a positive detection that is not measurable. This
occurs when there is a positive color change, but it is not within the marked,
measurable part of the tube. To record this properly you would state that the
reading was above the detection limit, but below the measuring range. Example,
>1 ppm ,<5 ppm.
11) Dispose of the pretreatment and detector tube according to local governmental
standards.
Additional media needed for this equipment.
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Detector tubes are available for a wide variety of analytes. We have at least one box of
most of the detector tubes that are manufactured by Gastec.
Notification Procedures for Equipment Failure:
Notify: Equipment Room Manager
Specialized Training Required or Recommended:
None
References and Further Assistance:
1) Refer to the Gastec Handbook 2nd Edition or later
2) Nextteq, LLC
8406 Benjamin Road, Suite J
Tampa, FL 33634
Phone: 877-312-2333
Fax: 877-312-2444
http://www.nextteq.com/
3) http://www.qastec.co.ip/enqlish/index.php
Review Date for this SOP:
Nathan Williams 4 12 2011
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CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C.
Toxicology Emergency Response Program 04-19-2011
STANDARD OPERATING PROCEDURE NO. (Version 1.0)
SUBJECT: Motorola MC-55 Handheld
Description of the SOP. The purpose of this document is to provide the reader with a
thorough understanding of the general capabilities, proper usage and maintenance, and
field data collection procedures with the Motorola MC-55.
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Motorola MC 55 EPA (PDA/Handheld)
General notes
The Motorola MC 55 is an Enterprise Personal Assistant (EPA) device that runs
Windows Mobile 6 operating system. The models that CTEH owns have the following
amenities:
Touch screen
Blue Tooth
Mobile Broadband
Barcode Scanner
Barcode Scanner
Camera
Key pad
Phone/Text
**Note: as of this writing we do not have a means to have the barcode scanner and the
camera enabled at the same time.
Proper usage
• The elastic strap on the back is there for you to put your off hand through while
using the device. It makes holding the device easier.
• The stylus on the right side of the device is for use with the touch screen. While
not required to use the touch screen, the stylus provides greater control and
precision.
• If you take good care of your unit it will be more reliable than one that is
mishandled or used improperly. Taking the battery out is the only way to turn the
unit off. Even if the red power button is pressed and the screen goes black the
unit is still on.
Section 1 Battery
The charge of one battery on a MC 55 will last 100 hours in standby mode and 6
hours of talk time (most units won't have phone feature on). For data entry purposes this
translates to a couple of days. In the case of
a failing or worn out battery it may not last a
whole day of regular data entry. As is the
case with any rechargeable battery, life and
function will be optimized if the following is
done:
• The battery is charged only if it is very
low and not left charging after the battery
has been fully charged.
• Extreme heat and cold temperatures are
avoided. Battery is kept in a dry
environment and not submerged in water.
If the battery or the unit manages to get
wet remove the battery immediately and
allow the unit and the battery to dry
separately. If the battery gets wet and the
small white rectangle (on the right) turns
pink or red, discontinue use of battery and dispose of it at a facility that recycles
batteries.
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• Note: The battery will not work as well if the battery gets excessively hot; which can
happen if the unit is charged and used non-stop, is used intensely or is left in the sun.
If the performance has degraded significantly due to overheating it might be
beneficial to take the battery out and let the battery cool off.
• Removing or replacing battery: Figures 1.1 and 1.2 demonstrate the proper
procedures for removing and replacing the unit's battery.
Figure 1.1: Procedure for removing battery from unit.
STEP 1 STEP 2
Flip the unit over so that the screen is Pull up on the strap to let the strap down,
facing down.
STEP 3 STEP 4
On the gray metal piece there is a black Pull the battery off of the unit.
battery lock. Slide the lock to the Right
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Figure 1.2: Procedure for replacing battery in unit.
STEP 1
(If the elastic band has already been taken down
then continue to step one otherwise do step three
from Figure 1.1 first)
Slide the bottom of the battery into the back of
the unit.
STEPS 2 & 3
Hold the unit with both hands so your
fingers are on the battery and your
palms are on the sides of the screen.
STEP 4
Reattach the elastic band by sliding the metal clip on the end of the band onto the top of the
unit. The unit should come on as soon as the battery is installed. If not you may need to press
the red power button once to turn it on.
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Section 2 General Hand Held Unit IFractices and Guidelines
Following is a list of best practices and guidelines which should ensure optimal usage of
the MC 55 unit.
• Do not drop or subject unit to sudden impacts.
• Avoid getting the unit wet. If the unit does get wet remove the battery
immediately.
• For general transport, make sure that the unit is secured in a closeable pouch or
container when not in use. Failure to secure the unit in a closable pouch or
container may result in the unit getting dropped or left behind.
• This MC 55 has not been certified for usage in volatile or flammable
environments. Make sure the unit is off if before entering a flammable or volatile
environment.
• Do not use a writing pen or sharp objects on the touchscreen.
Section 3 Windows Mobile 6 OS Basics
3.1 Resetting the device:
A lot of the problems that you might encounter with your device can be solved by
resetting the device. This is done by pressing and holding the red power button until the
screen goes white or about 5 seconds.
3.2 Volume
The rocker arm on the left of the unit is the volume control
3.3 Keyboards
Some units have a full QWERTY keyboard below the screen while some have a
numerical keypad that is similar to a cell phone. The shift, orange and blue button have
two modes: single and lock. Pressing the shift key t) once will only capitalize the very
next letter pressed, while pressing shift D twice will essentially turn caps lock on.
Inputting text with the numerical pad is similar to texting with a phone. With the orange
button enabled press the number that has the letter you want until the letter you want
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appears. For the letter C this means pressing the 2 button three times. After a brief pause
pressing 2 again (with orange locked) will result in an 'a' (or 'A').
3.3.1 On Screen Keyboard
Of course all devices have an onscreen keyboard that is fairly easy to use.
When you are at a point that you can input text on the device, press the keyboard button
to bring up the onscreen keyboard.
The stylus will be very helpful in typing the
correct keys. However, the screen can
occasionally get out of line making using the
onscreen keyboard very difficult. In the case of
bad screen alignment follow the Screen
Alignment section.
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3
4
5
6
7
8
9
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3.3.2 Other input modes
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Options...
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Block Recognizer
• Keyboard
Letter Recc
Transcriber
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There are other ways to input characters into the
device, which you can see if you press the up
arrow next to the keyboard. You might find that
your keyboard is gone in place of something
else, in which case use the up arrow and select
Keyboard.
3.4 GPS:
Figure 3.1 shows the steps for setting up the GPS on the MC-55.
• You should only manipulate the settings of the GPS after you have tried
troubleshooting the problem. Your handheld shouldbe set up for GPS by the time
you get it. However, in some rare cases it seems that the device loses the saved
values for the GPS settings. There is also a different setup that works that your
unit might be set up with, where the Pocket PC GPS settings uses COM:8 instead
of COM:3.
• The GPS locator works off of satellites, which means that a clear line of sight
with the sky is critical. Being indoors or under large structures will block the
GPS signal.
• The first satellite synch can take 10-20 minutes or longer on occasion. Staying in
one place will help your device find its location during this period. After the first
synch the GPS location should be more responsive.
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Figure 3.1: Steps for setting up GPS on the MC-55
STEP 1
£ 1 Start j
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In my personal experience (Matt Reed) I have seen very few GPS radios fail in the
MC55. However, if after thoroughly troubleshooting your GPS issues without success
call your equipment or IT tech for help.
1. Press jlffi Start]-> (Settings)
2. Click the jSystem) tab on the bottom and select External GPS
3. In the Programs tab the GPS program port should be COM3
4. In the Hardware tab the GPS Hardware Port should be COM8 and the baud rate
set to 57600
5. In the Access tab Check the box Manage GPS Automatically
6. When you are getting your latitude and longitude for a data point in a Pocket PC
Creations app (like S.I.E R.A. 2, Personnel Sampling, Real Time 2.2 etc.) and you
choose automatic, a window should pop up saying "Connecting to GPS..from
there click "Setup". The Port Name should be COM3 (the same as the GPS
program port) and the Baud Rate should be 57600.
Section 4 Screen Alignment
The MC55 touch screen translates where you press the screen with your finger or stylus
into coordinates in the operating system. Sometimes the translation is off. Pressing on
top of the item that you want to press translate to
a different spot in the OS.
For example: If you press the 'g' on the onscreen
keyboard and the 'x' is what gets highlighted
then the translation is off and you have a screen
alignment problem.
123
L 2
3
4
5
6
7 8 9 0 -
-
*
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1
4.
t
Project \ Options
Then follow the
onscreen directions.
There has been one
instance (out of 200 +)
that I am aware of
where the screen would
not stay aligned after
doing a software screen
alignment. In these
cases report the problem
and get a replacement.
You can fix this by
rl. Pressing the blue button followed by
2. Pressing the backspace button.
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Section 5 Pocket PC Creations (PPCC)
Each application in Pocket PC Creations is project specific. If you have questions
regarding how to use it or what to put into a certain app ask your supervisor or site lead.
If you don't have the Pocket PC Apps that you need to do your function you will need to
call your site lead or IT tech to get it.
The settings for Pocket PC Creations can be found under the "Options"
Proiert
Options
menu.
I
5.1 Wireless Options
First let's go over the Wireless Options.
Wireless synchronisation
0 Connect to a PPCC server:
Address;
samples, cteh, com;4001
Password:
Internet
0 Automatically connect to:
0 Maintain a continuous connection
1 | Require and use AES-256 encryption
I I Auto submit sessions:
0 Receive new sessions upon connect
0 Allow remote assistance
] (checked) Receive new sessions upon connect.
] (checked) Allow remote assistance
\/] (checked)
Connect to a
PPCC server:
The top check
box often gets
unchecked if a
recent connection attempt was unsuccessful (more on
this later)
The Address: is (samples.cteh.com:4001|
note the colon between "com" and "4001"
There isn't a password.
[S] (checked) Automatically connect to: (Internet).
[S] (checked) Maintain a continuous connection,
[ ] (unchecked) Require and use AES-256 encryption.
[ ] (unchecked) Auto submit sessions:
If your unit is having trouble connecting contact Matt Reed, Brady Davis, or Anton
Avguchenko at 501-801-8500.
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Section 6 Real-time Readings
Basic:
Use the stylus to enter data for each required field. Navigate through the pages by using
"Next" at the bottom and the scroll bar on the right side of the screen.
A good rule-of-thumb is to think about what information would be helpful to someone
looking at this data several months/years from now if they were trying to get a good idea
of what happened and where you were.
You can navigate between different Pocket PC Creations using the "Back" button inside
each program.
Detailed:
1)
2)
3)
4)
5)
6)
Turn on the hand held unit by pushing the small red
button at the bottom front of the handheld.
Handhelds are notoriously hard to actually turn off,
so you may also be able to just tap the screen.
After a couple of minutes it will come to a green -
screen with start at the top left corner of the screen.
Press Start.
The next screen will be a green screen. Go to Pocket
PC Creations.
The next screen will be white with several files. Pick
RealTime 2.2. (or the most recent version of
RealTime)
Your next screen will be a white screen, |~T
go to the bottom and pick new. —
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7)
8)
9)
You can enter text and numbers using
the physical keys on the handheld or by tapping the small keyboard icon in the
bottom right of the screen with the stylus. This will bring a keyboard up on the
screen that you can type with using the stylus.
Fill in the correct date (this should be automatically filled in when you start a new
reading), project number, and region
Next enter your name, choose indoor or outdoor sampling, and select the
appropriate "Location Category".
Hit "Next" to move on to the next page when you've completed the current one.
-------
(Tap to Update GP5 Coordinates)
Lon
(Tap to Update GP5 Coordinates)
Comments (multiple select)
10) Make sure you enter coordinates whenever
possible. If outside, you should be able to choose
'Automatic" and just tap the box(es) for
Latitude/Longitude. It can take several minutes to
acquire satellites and provide a reading the first
time you do this after powering on the MC55, but
after that it should be fairly instantaneous. If the
GPS isn't working, you can often get coordinates
from your cellphone or Google Earth, Google Maps, etc. and enter them by
choosing "Manual".
11) Enter the address if known and be concise, specific, but also detailed in the
"Location Description" and later "Additional Comments".
12) Next enter the matrix (what you measured for: air, water surface, soil), the
instrument used, its barcode number, the analyte that you measured for (H2S,
LEL, 02, S02, VOC, etc), result flag either non-detect or detect, reading that
your instrument gave you, detection limit of the analyte, units measured (%,
ppm), instrument details (was there fog, rain, elevated humidity, moisture
interferer, drift of areaRAE, battery low, 100ml, 200ml, 300ml).
a. *NOTE If entering a Gastec reading,
indicate how many pump strokes here
by choosing the volume of air pumped.
Be sure to enter the Gastec Tube
Number in the "Additional Comments"
field.
13) On the next two screens, choose any comments
that apply, and concisely provide any other
details that might be useful in "Additional
Comments"
14) Then hit "Finish".
15) To synchronize and send data to main
computer on site, tap "Sessions" at the bottom
of the screen, touch "Mark All for Send",
touch "Synchronize".
16) You should synchronize your data regularly.
Don't use the "duplicate" feature unless
expressly told you can do so. This often leads
to errors that invalidate the data you are
collecting and costs CTEH more time than you
will save.
No Visble Oil
Vac Trucks Present
Exhaust furnes odor
Exhaust funnes present
Crude oil odor
Visible Oil
boom present
Area evacuated
I
Previous Next Finish
RealTime 2.2
-------
Section 7 SIERA Points
Basics:
SIERA Points are used to record samples, monitoring stations, and events. The
SIERA2 program works a lot like RealTime described above. Navigate through
the pages using "Next" and the scroll bar on the right of the screen.
$ Today
Office Mobile
m Calendar
a Contacts
£ Internet Explorer
a Messaging
* , Phone
Q Pocket PC Creations
Details:
Turn on the hand held unit by pushing the small red
button at the bottom front of the handheld.
N
After a couple of minutes it will come to a green
screen with start at the top left corner of the screen.
Press "Start". —
The next screen will be a green screen. Go to
"Pocket PC Creations" and press it.
The next screen will be white with several files.
Pick "SIERA 2".
Your next screen will be a white screen, go to the
bottom and pick "New".
Fill in the Project, DateTime (should be
automatic), GPS method (pick automatic
if outside), region or state that you are
in, Location Description, your initials, SIERA
Type (sample, survey, tar ball, safety, source,
instrument, event, receptor), SIERA subtype,
Primary identifier (the Sample ID), Other
identifier (Station Name), comments, touch "tap
to attach image", push !v5TnB button on front of
handheld (or tap the screen) to take picture, back
out of screen by pushing "Back" at bottom of
screen, touch "Finish".
To synchronize and send data to main computer
on site, tap sessions at the bottom of the screen,
touch "Mark all for send", hit "Sessions" again,
touch "Synchronize".
New Sessions -Back
RealTime 2.2
9 +:X X
Date
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-------
Additional media needed for this equipment:
A/C adapter (necessary for charging battery)
Car charger (necessary for charging battery in the field)
Docking station (for both charging and synchronizing directly to computer)
SIM Card
Notification Procedures for Equipment Failure:
CTEH-Matthias "Papa Lemur Finkelstein" Reed - (501) 801-8652
References and Further Assistance
Motorola MC-55 User's Guide
Call Anton Avguchenko, Matt Reed, or Brady Davis if you need help.
CTEH Main Number: 501-801-8500
Created by
Matthias Reed April 19, 2011
David Quibell April 25, 2011
Johnnie Chamberlin April 27, 2011
Attachments:
none
-------
CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C.
Toxicology Emergency Response Program April 14, 2009
STANDARD OPERATING PROCEDURE NO. (1)
SUBJECT: MiniCan or Mini-canister
Description of the SOP: The purpose of this SOP is to instruct the user about proper
methods and operation for collecting a Mini-Can air sample. Upon completion of this
manual the user should be able to collect both a grab sample and a time released air
sample using a Mini-Can air sampling instrument.
Calibration Instructions
1. All cleaning and calibration should be conducted at the laboratory by authorized
personnel.
Grab Sample Equipment Use Instructions (step by step)
1. Ensure that the sampler is not wearing any of perfume, cologne, or aerosol. These
products may affect the sample.
2. Remove protective cap from the Mini-Can sampler tip..
3. Using a grab sample regulator, slide the connection collar back.
4. Position the canister on its side in the direction of the area intended to sample.
5. Insert the sampler tip into the regulator and release the collar.
NOTE: There should not be a gap between the regulator and the canister.
6. Allow the canister ample time to fill (20-30 seconds)
7. Once the canister has been successfully filled with sample air pull back on the
connection collar to release the regulator.
8. Place protective cap on sampler tip.
9. Complete a Chain of Custody form and ship sample in accordance to laboratories
shipment instruction.
-------
Additional media needed for this equipment:
Quick Grab Sample Regulator
Time Released Equipment Use Instructions (step by step)
1. Ensure the sampler is not wearing any sort of perfume, cologne, or aerosol. These
products may affect the sample.
2. Remove protective cap from the Mini-Can sampler tip.
3. Using a time release regulator, slide the connection collar back.
4. Place canister in area intended for sampling and insert sampler tip into regulator.
NOTE: For stationary sampling the canister should be placed on its side. For
personnel sampling the canister should be fastened using a holster belt with a
sampling tube attached to the regulator and clipped to the collar of the individual
that is being sampled.
5. Release the connection collar.
Note: There should not be any gap between the regulator and the canister.
6. Allow the sample canister ample time to fill.
NOTE: Progress can be monitored by checking the vacuum gauge located on the
regulator. The pressure should decrease overtime.
7. Once sample time is complete and canister has been successfully filled with sample
air pull back the connection collar to release the regulator.
8. Place protective cap back on the Mini-Can sampler tip.
9. Complete a Chain of Custody form and ship sample in accordance to laboratories
shipment instruction.
Additional media needed for this equipment:
Time Released Grab Sample Regulator
Belt holster (depending on sample)
Sample tubing (depending on sample)
-------
Notification Procedures for Equipment Failure
Galson Laboratories
6601 Kirkville Road
East Syracuse, NY 13057
Phone: 315-432-LABS (5227)
Toll Free: 888-432-LABS (5227)
www.galsonlabs.com
mail@galsonlabs.com
Center for Toxicology and Environmental Health (CTEH)
5120 North Shore Drive
North Little Rock, AR 72118
Phone: 501-801-8500
Emergency: 1-866-TOX-CTEH (869-2834)
Fax: 501-801-8501
www.cteh.com
References and Further Assistance.
Centek Laboratories, LLC
143 Midler Park Drive
Syracuse, New York 13206
Phone: 315-431-9730
Fax: 315-431-9731
Review Date for this SOP
Nathan Williams 4 12 2011
-------
UltraRAE 3000
User's Guide
f
©RAE
i v s r e m s
Rev. A
May 2008
P/N 059-4023-000
-------
FCC Information
Contains FCC ID: S22BTMODULE-CL2
The enclosed device complies with part 15 of the FCC rules.
Operation is subject to the following conditions: (1) This device may
not cause harmful interference, and (2) This device must accept any
interference received, including interference that may cause undesired
operation.
© Copyright 2008 RAE Systems, Inc.
-------
UltraRAE 3000 User's Guide
Contents
1 Standard Contents 9
2 General Information 9
3 Physical Description 11
4 Specifications 11
5 Replacing Alkaline Batteries 14
6 Charging A Lithium-Ion Battery 16
6.1 Charging A Spare Battery 18
6.2 Low Voltage Warning 18
6.3 Clock Battery 19
6.4 Data Protection While Power Is Off 19
7 User Interface 20
7.1 Display 22
8 Operating The Instrument 23
8.1 Turning The Instrument On (Simple) 23
8.2 Turning The Instrument On (Power On Zero) 24
8.3 Turning The Instrument Off 24
8.4 Operating The Built-in Flashlight 24
8.5 Pump Status 25
8.6 Calibration Status 26
9 Operating Modes 27
10 Compound-Specific Operation 31
10.1 Compound-Specific Measurement 31
10.2 Measurement Phases 31
10.3 Performing A Measurement 31
10.4 Separation Tube Preparation 32
10.5 Inserting The Separation Tube 34
10.6 Measuring 35
11 VOC Operation 38
11.1 Basic User Level/Hygiene Mode (Default Settings).... 3 8
12 Alarm Signals 41
12.1 Alarm Signal Summary 42
12.2 Preset Alarm Limits & Calibration 43
12.3 Testing The Alarm 43
13 Integrated Sampling Pump 43
14 Backlight 44
15 Datalogging 44
15.1 Datalogging Event 44
1
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UltraRAE 3000 User's Guide
15.2 Datalogging Sample 44
15.3 Auto/Manual/Snapshot Datalogging 45
16 Accessories 45
17 Standard Kit & Accessories 46
17.1 AC Adapter (Battery Charger) 46
17.2 External Filter 47
18 Optional Accessories 48
18.1 Calibration Adapter 48
18.2 Calibration Regulator 48
18.3 Organic Vapor Zeroing Kit 48
19 Standard Two-Point Calibration (Zero & Span) 49
19.1 Entering Calibration 50
19.2 Zero (Fresh Air) Calibration 51
19.3 Span Calibration 52
19.4 Exiting Two-Point Calibration In Basic User Level ....55
20 Three-Point Calibration 56
20.1 Span 2 Calibration 58
20.2 Exiting Three-Point Calibration 59
21 Programming Mode 60
21.1 Entering Programming Mode 60
22 Programming Mode Menus 61
22.1 Exiting Programming Mode 63
22.2 Navigating Programming Mode Menus 63
22.3 Calibration 64
22.3.1 Zero Calibration 64
22.3.2 Span Calibration 64
22.4 Measurement 65
22.4.1 Meas. Gas 65
22.4.2 Meas. Unit 66
22.4.3 Tube Selection 67
22.5 Alarm Setting 68
22.5.1 High Alarm 69
22.5.2 Low Alarm 69
22.5.3 STEL Alarm 70
22.5.4 TWA Alarm 71
22.5.5 Alarm Mode 72
22.5.6 Buzzer & Light 73
22.6 Datalog 73
22.6.1 Clear Datalog 74
2
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UltraRAE 3000 User's Guide
22.6.2 Interval 74
22.6.3 Data Selection 75
22.6.4 Datalog Type 76
22.6.5 Manual Datalog 76
77
22.6.6 Snapshot Datalog 78
22.7 Monitor Setup 78
22.7.1 Radio Power 78
22.7.2 Op Mode 79
22.7.3 Site ID 79
22.7.4 User ID 80
22.7.5 User Mode 81
22.7.6 Date 81
22.7.7 Time 82
22.7.8 Duty Cycle 82
22.7.9 Temperature Unit 83
22.7.10 Pump Speed 83
22.7.11 Language 84
22.7.12 Real Time Protocol 84
22.7.13 Power On Zero 85
22.7.14 Unit ID 85
22.7.15 LCD Contrast 86
22.7.16 Lamp ID 86
23 Humidity Compensation 87
24 Hygiene Mode 87
24.1 Basic User Level & Hygiene Mode 88
24.2 Entering Search Mode From Hygiene Mode 90
24.3 Optional Graphic Screen In Search Mode 91
25 Advanced User Level (Hygiene Mode Or Search Mode) 92
25.1 Advanced User Level & Hygiene Mode 92
25.2 Basic User Level & Search Mode 94
25.3 Advanced User Level & Search Mode 96
25.4 Diagnostic Mode 97
25.4.1 Entering Diagnostic Mode 97
25.4.2 Adjusting The Pump Stall Threshold 98
25.4.3 Pump High 98
25.4.4 Pump Low 98
25.4.5 Testing The Humidity Sensor 99
25.4.6 Exiting Diagnostic Mode 100
3
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UltraRAE 3000 User's Guide
26 Transferring Data To & From A Computer 102
26.1 Downloading The Datalog To A PC 102
26.2 Uploading Firmware To The instrument From A PC 103
27 Maintenance 104
27.1 Battery Charging & Replacement 104
27.1.1 Replacing The Li-ion Battery 105
27.1.2 Replacing The Alkaline Battery Adapter 105
27.2 PID Sensor & Lamp Cleaning/Replacement 107
27.3 Cleaning The PID Sensor 108
27.3.1 Cleaning The Lamp Housing Or Changing The Lamp . 108
27.3.2 Determining The Lamp Type 109
27.3.3 Sampling Pump 110
27.3.4 Testing The T.H.P. Sensor 110
27.3.5 Cleaning The Instrument 110
27.3.6 Ordering Replacement Parts 110
27.4 Special Servicing Note Ill
28 Troubleshooting 112
29 Technical Support 113
30 RAE Systems Contacts 114
31 Regulatory Information 117
32 Basic Operation 117
32.1 Turning The Instrument On 117
32.2 Turning The Instrument Off 117
33 Alarm Signals 118
33.1 Alarm Signal Summary 118
34 Preset Alarm Limits & Calibration 119
35 Charging The Battery 120
35.1 Low Voltage Warning 121
35.2 Clock Battery 121
35.3 Replacing The Rechargeable Li-Ion Battery 122
35.4 Alkaline Battery Adapter 122
36 Troubleshooting 123
4
-------
UltraRAE 3000 User's Guide
Read Before Operating
This manual must be carefully read by all individuals who have or
will have the responsibility of using, maintaining, or servicing this
product. The product will perform as designed only if it is used,
maintained, and serviced in accordance with the manufacturer's
instructions. The user should understand how to set the correct
parameters and interpret the obtained results.
CAUTION!
To reduce the risk of electric shock, turn the power off before
removing the instrument cover. Disconnect the battery before
removing sensor module for service. Never operate the instrument
when the cover is removed. Remove instrument cover and sensor
module only in an area known to be non-hazardous.
ATEX WARNING!
To reduce the risk of electrostatic ignition, do not use the instrument
without the rubber boot in place.
The instrument is classified as to intrinsic safety for use in Class I,
Division 1, groups A, B, C, D, and ATEX II 2G EEx ia IIC T4, or
non-hazardous locations.
5
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UltraRAE 3000 User's Guide
Special Notes
When the instrument is taken out of the transport case and
turned on for the first time, there may be some residual organic
or inorganic vapor trapped inside the detector chamber. The
initial PID sensor reading may indicate a few ppm. Enter an
area known to be free of any organic vapor and turn on the
instrument. After running for several minutes, the residual
vapor in the detector chamber will be cleared and the reading
should return to zero.
The battery of the instrument discharges slowly even if it is
turned off. If the instrument has not been charged for 5 to 7
days, the battery voltage will be low. Therefore, it is a good
practice to always charge the instrument before using it. It is
also recommended to fully charge the instrument for at least
10 hours before first use. Refer to this User Guide's section on
battery charging for more information on battery charging and
replacement.
6
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UltraRAE 3000 User's Guide
WARNINGS
STATIC HAZARD: Clean only with damp cloth.
For safety reasons, this equipment must be operated and serviced by
qualified personnel only. Read and understand the instruction manual
completely before operating or servicing. Use only RAE Systems
battery packs, part numbers 059-3051-000 and 059-3052-000. This
instrument has not been tested in an explosive gas/air atmosphere
having an oxygen concentration greater than 21%. Substitution of
components may impair intrinsic safety. Recharge batteries only in
non-hazardous locations.
Do not mix old and new batteries or batteries from different
manufacturers.
The calibration of all newly purchased RAE Systems instruments
should be tested by exposing the sensor(s) to known concentration
calibration gas before the instrument is put into service.
For maximum safety, the accuracy of the instrument should be
checked by exposing it to a known concentration calibration gas
before each day's use.
Do not use USB/PC communication in hazardous locations.
7
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UltraRAE 3000 User's Guide
AVERTISSEMENT
DANGER
RISQUE D'ORIGINE ELECTROSTATIQUE: Nettoyer
uniquement avec un chiffon humide.
Pour des raisons de securite, cet equipement doit etre utilise,
entretenu et repare uniquement par un personnel qualifie. Etudier le
manuel d'instructions en entier avant d'utiliser, d'entretenir ou de
reparer 1'equipement.
Utiliser seulement l'ensemble de batterie RAE Systems, reference
059-3051-000 ou 059-3052-000. Cet instrument n'a pas ete teste dans
une atmosphere de gaz/air explosive ayant une concentration
d'oxygene plus elevee que 21%. La substitution de composants peut
compromettre la securite intrinseque. Ne charger les batteries que
dans des emplacements designes non-dangereux.
Ne pas melanger les anciennes et les nouvelles batteries, ou bien
encore les batteries de differents fabricants.
L'etalonnage de tout instrument de RAE Systems doit etre teste en
exposant l'instrument a une concentration de gaz connue avant de
mettre en service l'instrument pour la premiere fois.
Pour une securite maximale, la sensibilite de l'instrument doit etre
verifiee en exposant l'instrument a une concentration de gaz connue
avant chaque utilisation journaliere.
Ne pas utiliser de connexion USB/PC en zone dangereuse.
8
-------
UltraRAE 3000 User's Guide
1 Standard Contents
Instrument
Calibration Kit
Charging Cradle
AC/DC Adapter
Alkaline Battery Adapter
Data Cable
CD-ROM With User's Guide, Quick Start Guide, and related materials
2 General Information
The UltraRAE 3000 is a hand-held, programmable compound specific
PID monitor designed to provide instantaneous exposure monitoring
of a specific organic gas. It monitors a specific gas by utilizing a gas
separation tube and the photoionization detector (PID) with a 9.8 eV
gas discharge lamp. It also can be used to measure total volatile
organic compound (VOC) as a broadband monitor by utilizing the
PID with a 9.8 eV, 10.6 eV, or 11.7 eV lamp.
Features include:
Lightweight and Compact
• Compact, lightweight, rugged design
• Built-in sample draw pump
Dependable and Accurate
• Up to 16 hours of continuous monitoring with rechargeable
battery pack
• Designed to continuously monitor VOC vapor at parts-per-
million (ppm) levels
User-friendly
• Preset alarm thresholds for STEL, TWA, low- and high-level
peak values.
• Audio buzzer and flashing LED display are activated when the
limits are exceeded.
Datalogging Capabilities
• 260,000-point datalogging storage capacity for data download to PC
9
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UltraRAE 3000 User's Guide
The UltraRAE 3000 consists of a PID with associated microcomputer
and electronic circuit. The unit is housed in a rugged case with a
backlit LCD and 3 keys to provide easy user interface. It also has a
built-in flashlight for operational ease in dark locations.
10
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UltraRAE 3000 User's Guide
3 Physical Description
The main components of the portable compound-specific and
VOC monitoring instrument include:
• Three operation/programming keys for normal operation or
programming
• LCD display with back light for direct readout and calculated
measurements
• Built-in flashlight for illuminating testing points in dark
environments
• Buzzer and red LEDs for alarm signaling whenever exposures
exceed preset limits
• Charge contacts for plugging directly to its charging station
• Easy-to-use separation tube holder
• USB communication port for PC interface
• Protective rubber cover
4 Specifications
Size:
10" L x 3" W x 2.5" H
(25.5 cm x 7.6 cm x 6.4 cm)
26 oz (738 g) with battery pack
Photoionization sensor with 9.8, 10.6, or
11.7 eV UV lamp
A 4.2V/3300mAH rechargeable Lithium-Ion
battery pack (snap in, field replaceable, at
non-hazardous location only)
Alkaline battery holder (for 4 AA batteries)
Less than 8 hours to full charge
Up to 16 hours continuous operation
Large dot matrix screen with backlight
Weight:
Detector:
Battery:
Battery Charging:
Operating Hours:
Display:
11
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UltraRAE 3000 User's Guide
Measurement range & resolution
Lamp
Range
Resolution
10.6 eV
50 ppb to 10,000 ppm
(VOC mode)
50 ppb
9.8 eV
50 ppb to 200 ppm, for
benzene and butadiene;
50 ppb to 5,000 ppm
(VOC mode)
50 ppb
11.7 eV
50 ppb to 2,000 ppm
(VOC mode)
50 ppb
Response time (T90):
Accuracy
(Isobutylene):
PID Detector:
Correction Factors:
Calibration:
Calibration Reference:
Inlet Probe:
Radio module:
Keypad:
Direct Readout:
2 seconds
3% at calibration point
Easy access to lamp and sensor for cleaning
and replacement
Over 200 VOC gases built in (based on RAE
Systems Technical Note TN-106)
Two-point field calibration of zero and
standard reference gases
Store up to 8 sets of calibration data, alarm
limits and span values
Flexible 5" tubing (a short tube is also
available)
Separation tube housing with permanent
VOC tube
Bluetooth (2.4GHz)
1 operation key and 2 programming keys; 1
flashlight switch
Instantaneous, average, STEL, TWA and
peak value, and battery voltage
12
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UltraRAE 3000 User's Guide
Intrinsic Safety:
EM Interference:
Alarm Setting:
Operating Mode:
Alarm:
Alarm Type:
Real-time Clock:
Datalogging:
Communication:
Sampling Pump:
Temperature:
Humidity:
Housing (including
rubber boot):
US and Canada: Class I, Division 1, Group
A, B, C, D
Europe: ATEX (II 2G EEx ia IIC T4)
Highly resistant to EMI/RFI. Compliant
with EMC R&TTE (RF Modules)
Separate alarm limit settings for Low, High,
STEL and TWA alarm
Hygiene or Search mode
Buzzer 95dB at 12" (30cm) and flashing red
LEDs to indicate exceeded preset limits, low
battery voltage, or sensor failure
Latching or automatic reset
Automatic date and time stamps on
datalogged information
260,000 points with time stamp, serial
number, user ID, site ID, etc.
Upload data to PC and download instrument
setup from PC via USB on charging station.
Internally integrated. Flow rate: 450 to 550
cc/min.
-20° C to 50° C (-4° to 122° F)
0% to 95% relative humidity (non-
condensing)
Polycarbonate, splashproof and dustproof
Battery can be changed without removing
rubber boot.
13
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UltraRAE 3000 User's Guide
5 Replacing Alkaline Batteries
An alkaline battery adapter is supplied with each instalment. The
adapter (part number 059-3052-000) accepts four AA alkaline
batteries (use only Duracell MN1500 or Energizer E91) and provides
approximately 12 hours of operation. (An optional rechargeable
lithium-ion battery pack, part number 059-3051-000, is also
available.)
To install the adapter in the instrument:
1. Remove the alkaline battery adapter from the instrument by
sliding the tab and tilting out the adapter.
3. Tilt the alkaline batten adapter and put it into the instrument.
4. Slide the tab back into place to secure the battery adapter.
To insert batteries into the adapter:
1. Remove the three hex-socket screws to open the compartment
in the adapter.
14
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UltraRAE 3000 User's Guide
2. Insert four fresh AA batteries as indicated by the polarity (+/-)
markings.
3. Replace the cover. Replace the three screws.
IMPORTANT!
Alkaline batteries cannot be recharged. The instalment's internal
circuit detects alkaline batteries and will not allow recharging. If you
place the instrument in its Travel Charger or Charger Stand, the
alkaline battery will not be recharged. The internal charging circuit is
designed to prevent damage to alkaline batteries and the charging
circuit when alkaline batteries are installed inside the instrument. If
you try to charge an alkaline batteries installed in the instrument, the
Charging Cradle or Travel Charger's charging LED does not glow,
indicating that it will not charge the alkaline batteries.
Note: When replacing alkaline batteries, dispose of old ones properly.
15
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UltraRAE 3000 User's Guide
6 Charging A Lithium-Ion Battery
Always fully charge the battery before using the instrument. The
instrument's Li-ion battery is charged by attaching the instrument to
the Travel Charger (or by placing the instrument in the optional
Charger Stand). Contacts on the bottom of the instrument meet the
Travel Charger's (or Charger Stand's) contacts, transferring power
without other connections.
Charger Stand
Note: Before connecting the charger to the instrument, visually
inspect the contacts to make sure they are clean. If they are not, wipe
them with a soft cloth. Do not use solvents or cleaners.
Follow this procedure to charge the instrument:
1. Plug the AC/DC adapter's barrel connector into the
instrument's Charger Stand or Travel Charger.
In. j
Travel
Charger
DC 12V W
2. Plug the AC/DC adapter into the wall outlet.
3. Connect the AC/DC adapter to the Travel Charger (or
Charger Stand).
16
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UltraRAE 3000 User's Guide
4. Place the instrument into the Travel Charger or Charger Stand.
The LED in the Travel Charger (or Charger Stand) should
glow.
The instrument begins charging automatically. (If the optional
Charger Stand is used, the "Primary" LED blinks green to
indicate charging.) During charging, the diagonal lines in the
battery icon on the instrument's display are animated and you see
message "Charging..."
Note: If the Li-ion battery has been discharged below a certain
threshold, the "Charging..." message does not display immediately.
The charging LED blinks to indicate that it is charging, and after it
has been charging for a while, the "Charging..." message appears.
When the instrument's battery is fully charged, the battery icon is no
longer animated and shows a full battery. The message "Fully
charged!" is shown. (If the Charger Stand or Travel Charger is used,
its LED glows continuously green.)
Note: If you see the "Battery Charging Error" icon (a battery
outline with an exclamation mark inside), check that the
instrument or rechargeable battery has been properly set into
the Travel Charger (or Charger Stand). If you still receive the
message, check the Troubleshooting section of this guide.
Note: If the instrument or battery has been charging for more than 10
hours and you see the "Battery Charging Error" icon and a message
that says, "Charging Too Long," this indicates that the battery is not
reaching a full charge. Try changing the battery and make sure the
contacts on the instrument are meeting the Travel Charger's (or
Charger Stand's) contacts. If the message is still shown, consult your
distributor or RAE Systems Technical Services.
17
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UltraRAE 3000 User's Guide
6.1 Charging A Spare Rechargeable Battery
(Optional Charger Stand Only)
A rechargeable Li-ion battery can be charged when it is not inside the
monitor. The Charger Stand is designed to accommodate both types
of charging. Contacts on the bottom of the battery meet the contacts
on the Charger Stand, transferring power without other connections,
and a spring-loaded capture holds the battery in place during
charging.
1. Plug the AC/DC adapter into the Charger Stand.
2. Place the battery into the Charger Stand, with the gold-plated
contacts on top of the six matching charging pins.
3. Plug the AC/DC adapter into the wall outlet.
The battery begins charging automatically. During charging, the
Secondary LED in the Charger Stand blinks green. When charging is
complete, it glows steady green.
Release the battery from the Charger Stand by pulling it back toward
the rear of the Charger Stand and tilting it out of its slot.
Note: If you need to replace the Li-ion battery pack, replacements are
available from RAE Systems. The part number is 059-3051-000.
WARNING!
To reduce the risk of ignition of hazardous atmospheres, recharge
and replace batteries only in areas known to be non-hazardous.
6.2 Low Voltage Warning
When the battery's charge falls below a preset voltage, the
instrument warns you by beeping once and flashing once every
minute, and the "empty battery" icon blinks on and off once
per second. You should turn off the instrument within 10
minutes and either recharge the battery by placing the
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UltraRAE 3000 User's Guide
instrument in its cradle, or replace the battery with a fresh one with a
full charge.
6.3 Clock Battery
An internal clock battery is mounted on one of the instrument's
printed circuit boards. This long-life battery keeps settings in memory
from being lost whenever the Li-ion battery or alkaline batteries are
removed. This backup battery should last approximately five years,
and must be replaced by an authorized RAE Systems service
technician. It is not user-replaceable.
6.4 Data Protection While Power Is Off
When the instrument is turned off, all the current real-time data
including last measured values are erased. However, the datalog data
is preserved in non-volatile memory. Even if the battery is
disconnected, the datalog data will not be lost.
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UltraRAE 3000 User's Guide
7 User Interface
The instrument's user interface consists of the display, LEDs, an
alarm transducer, and four keys. The keys are:
Y/+
MODE
N/-
Flashlight on/off
The LCD display provides visual feedback that includes the reading,
time, battery condition, and other functions.
Flashlight
on/off key
In addition to their labeled functions, the keys labeled Y/+, MODE,
and N/- act as "soft keys" that control different parameters and make
different selections within the instrument's menus. From menu to
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UltraRAE 3000 User's Guide
menu, each key controls a different parameter or makes a different
selection.
Three panes along the bottom of the display are "mapped" to the
keys. These change as menus change, but at all times the left pane
corresponds to the [Y/+] key, the center pane corresponds to the
[MODE] key, and the right pane corresponds to the [N/-] key. Here
are three examples of different menus with the relationships of the
keys clearly shown:
RELATIONSHIP OF BUTTONS TO CONTROL FUNCTIONS
0.00'$
1 «i 5:1
Yes |~© I 1 (Setectfiack | > J
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UltraRAE 3000 User's Guide
7.1 Display
The display shows the following information:
Calibration needed
Reading.
Gas info-
-Radio power
-Radio signal
Oft ft fT.llI ®f—Battery
.WW1 PPm |— Measurement
CF=1.00 Isobuten ^Unit
w
'Datalog
/
\ \ Pump
Y/+ key
Mode key N/- key
Gas info
Tells the Correction Factor and type: of
calibration gas
Reading
Concentration of gas as measured by the
instrument
Calibration needed
Indicates that calibration should be
performed
Radio power
Indicates whether radio connection is on or
off
Radio signal
Indicates signal strength in 5-bar bargraph
Battery
Indicates battery level in 3 bars
Pump
Indicates that pump is working
Datalog
Indicates whether datalog is on or off
Y/+
Y/+ key's function for this screen
MODE
MODE key's function for this screen
N/-
N/- key's function for this screen
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UltraRAE 3000 User's Guide
8 Operating The Instrument
The instrument is designed as a broadband VOC gas monitor and
datalogger for work in hazardous environments. It gives real-time
measurements and activates alarm signals whenever the exposure
exceeds preset limits. Prior to factory shipment, the instrument is
preset with default alarm limits and the sensor is pre-calibrated with
standard calibration gas. However, you should test the instrument and
verify the calibration before the first use. After the instrument is fully
charged and calibrated, it is ready for immediate operation.
8.1 Turning The Instrument On (Simple)
1. With the instrument turned off, press and hold [MODE].
2. When the display turns on, release the [MODE] key.
The RAE Systems logo should appear first. (If the logo does not
appear, there is likely a problem and you should contact your
distributor or RAE Systems Technical Support.) The instrument is
now operating and performs self tests. If any tests (including sensor
and memory tests) fail, refer to the Troubleshooting section of this
guide.
Once the startup procedure is complete, the instrument shows a
numerical reading screen with icons. This indicates that the
instrument is fully functional and ready to use.
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UltraRAE 3000 User's Guide
8.2 Turning The Instrument On
(Power On Zero)
If your UltraRAE 3000 has been configured to perform a zero (fresh
air) calibration upon startup, called Power On Zero, then the startup
routine is interrupted so that you can perform a fresh air calibration.
(See page 85 for details on turning this feature on or off.)
-T 0.00! ^
If you do not want to perform a zero calibration, press [MODE] to
bypass it. If you start a zero calibration and want to abort it, press
[N/-], and the calibration stops and the main display is shown.
8.3 Turning The Instrument Off
1. Press and hold the Mode key for 3 seconds. A 5-second
countdown to shutoff begins.
2. When you see "Unit off..." release your finger from the
[MODE] key. The instrument is now off.
Note: You must hold your finger on the key for the entire shutoff
process. If you remove your finger from the key during the
countdown, the shutoff operation is canceled and the instrument
continues normal operation.
8.4 Operating The Built-in Flashlight
The instrument has a built-in flashlight that helps you point the probe
in dark places. Press the flashlight key to turn it on. Press it again to
turn it off.
Note: Using the flashlight for extended periods shortens the battery's
operating time before it needs recharging.
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UltraRAE 3000 User's Guide
8.5 Pump Status
IMPORTANT!
During operation, make sure the probe inlet and the gas outlet are free
of obstructions. Obstructions can cause premature wear on the pump,
false readings, or pump stalling. During normal operation, the pump
icon alternately shows inflow and outflow as shown here:
During duty cycling (PID lamp cleaning), the display shows these
icons in alternation:
If there is a pump failure or obstruction that disrupts the pump, the
alarm sounds and you see this icon blinking on and off:
If you see this blinking icon, consult the Troubleshooting section of
this guide.
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UltraRAE 3000 User's Guide
8.6 Calibration Status
The instrument displays this icon if it requires calibration:
I
Calibration is required (and indicated by this icon) if:
• The lamp type has been changed (for example, from 10.6 eV
to 9.8 eV).
• The sensor module has been replaced.
• It has been 30 days or more since the instrument was last
calibrated.
• If you have changed the calibration gas type without
recalibrating the instrument.
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UltraRAE 3000 User's Guide
9 Operating Modes
The UltraRAE is actually two monitors in one:
Compound-specific monitor
• VOC monitor
As a compound-specific monitor, it takes timed measurements and
uses a separation tube in conjunction with software that enables the
UltraRAE 3000 to give specific readings on one particular type of
compound, such as benzene or butadiene.
As a VOC monitor, the UltraRAE 3000 operates in different modes.
In some cases, you can change modes using a password and using the
instrument's navigation. In other cases, you must use ProRAE Studio
software.
The following two sections cover operation in the two modes.
Compound Specific, 31.
VOC, page 38.
The diagram on the next page shows the basic flow of the UltraRAE
3000's functions. The area with the gray field is the compound-
specific (tube) mode, while the rest shows VOC mode. Navigate
through the steps by using the [Y/+] and [N/-] keys as shown in the
diagram.
Note: If you use a password to access Programming Mode (see page
60), then the navigation changes slightly, entering part of Advanced
Hygiene Mode's settings, as shown on page 29.
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UltraRAE 3000 User's Guide
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UltraRAE 3000 User's Guide
'5
Main
Display
(Shows CF)
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UltraRAE 3000 User's Guide
The default setting for your instrument is:
User Mode: Basic
Operation Mode: Hygiene
This is outlined in detail on page 88.
The other options, covered later in this guide, are:
User Mode: Advanced (page 92)
Operation Mode: Hygiene
User Mode: Advanced (page 96)
Operation Mode: Search
Using ProRAE Studio allows access to other options. In addition,
Diagnostic Mode (page 97) is available for service technicians.
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UltraRAE 3000 User's Guide
10 Compound-Specific Operation
10.1 Compound-Specific Measurement
The UltraRAE 3000 can perform compound-specific measurement in
addition to general VOC measurement. This requires using a RAE-
Sep separation tube (butadiene or benzene) and having the UltraRAE
3000 in Tube Mode, operating with a 9.8eV lamp.
10.2 Measurement Phases
To perform a compound-specific measurement, follow this order:
1. UltraRAE 3000 is ready for sampling
2. Prepare the separation tube
3. Insert the separation tube
4. Start measurement
5. UltraRAE 3000 displays and logs measurement
6. Remove the separation tube
10.3 Performing A Measurement
Before performing a compound-specific measurement for Benzene or
Butadiene using a RAE-Sep separation tube, make sure the UltraRAE
3000 is in Tube Mode and that the appropriate tube type is selected.
The UltraRAE 3000 only acts as a compound-specific measurement
device when it is equipped with a 9.8eV lamp. The UltraRAE 3000 is
designed to auto-sense the lamp type. It can also be manually set to
default to a 9.8eV lamp type.
Make sure the UltraRAE 3000 is set to operate with your selected tube:
1. Enter Programming Mode.
2. Select Measurement.
3. Select Tube Selection.
4. Make a choice of Benzene or Butadiene.
5. Save your choice.
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UltraRAE 3000 User's Guide
To begin measuring, turn on the UltraRAE 3000. This screen is
shown, which includes the CF (correction factor) and measurement
gas type for calibration reference:
o.ooC®
CF=1.00 Isobutene"^ O
** I 0
Press [N/-] to advance. You will see this screen:
Tube : Benzene
Start sampling?
Yes
Do not begin sampling yet!
Before you start sampling, you must insert a RAE-Sep separation tube
into the inlet/holder. Follow the Separation Tube Preparation and Placing
A Tube Into The UltraRAE 3000 instructions before pressing any
buttons on the UltraRAE 3000. Once the tube is in place, then proceed to
measuring.
IMPORTANT!
Once a tube's ends are broken off, the material inside is exposed.
Therefore, use the tube for sampling as soon as possible.
10.4 Separation Tube Preparation
CAUTION!
Wear hand and eye protection when breaking tube tips. Use caution
in handling tubes with broken ends. Keep away from children. RAE-
Sep tubes should be disposed of according to local regulations. See
footnotes of data sheets for disposal information.
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UltraRAE 3000 User's Guide
1. Open a package of RAE-Sep separation tubes and remove one.
2. Place the tip in the package's tube tip breaker (the small hole on
the front) and snap off the tip.
3. Turn the tube around and snap off the other end.
o
©
)
©
X
©
©
©
)
©
X
CAUTION!
Handle tubes with care. Tube ends are sharp after ends are broken off.
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UltraRAE 3000 User's Guide
10.5 Inserting The Separation Tube
1. Unscrew the front of the sampling probe from the base.
2. Slip the tube into the rubber holder in the front portion. Make
sure the arrow on the side of the tube points toward the
instrument.
3. Insert the other end of the tube into the middle of the base while
turning the front portion to tighten it onto the base's threads.
I I |
I ~ A
1
;
to
p
IMPORTANT!
Do not overtighten any portion of the sampling assembly.
Note: When the UltraRAE 3000 is used for VOC monitoring, no tube
is inserted.
IMPORTANT!
To ensure that there are no leaks, periodically test the seals:
With the UltraRAE 3000 running, place your finger over the end of
the inlet probe. The alarm should sound and the pump-stall icon
should flash on the display. This indicates that all seals are good. Stop
the alarm by pressing | Y/+1. If the pump does not alarm or show the
stalled-pump icon, then check that all inlet parts are tight and inspect
the O-ring for damage (replace it if necessary).
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UltraRAE 3000 User's Guide
10.6 Measuring
Once the tube is in place, begin measuring by pressing [Y/+],
The display shows a countdown (60 seconds is shown here, but sampling
time depends on the type of separation tube selected and the temperature):
Wait..
60
Abort
Note: You can abort the sampling by pressing [N/-] at any time.
Once the countdown is complete, the reading is shown:
Benzene= 0.00 ppm
Continue and
establish STEL?
Yes
No
Press [Y/+] to continue sampling with the tube for 15 minutes to
establish a STEL reading, or press [N/-] to return to the main menu.
WARNING!
At least 1/4 of the tube should still be yellow-orange at the bottom. If
not, the STEL value is not valid. Abort the measurement and change
the tube. Then do a snapshot test instead of a STEL test. Note: If the
STEL is exceeded, the UltraRAE 3000 goes into alarm.
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UltraRAE 3000 User's Guide
If you press [N/-] to return to the main menu, which shows the tube
type instead of the CF (correction factor):
Press [N/-] to advance to this screen:
TWA:
- - - - -ppm
STEL:
PPm
Peak:
0.00 ppm
Clear
©
->
If you press [Y/+], you are asked, "Clear peak value! Are You Sure?"
to confirm:
Clear peak value!
Are you sure?
Yes
No
Press [Y/+] to clear the Peak value and exit to VOC operation.
If you press [N/-], this display is shown:
Remove tube and
return to VOC mode!
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UltraRAE 3000 User's Guide
Remove the tube and put the inlet back together. Then press [N/-].
This display is shown:
Resetting
TWA, STEL, and Peak!
After a few seconds, the UltraRAE 3000 enters VOC mode and
shows this display:
Date
11/21/2007
Time
06:30:55
Temp
71° F
®
->
You can step through the rest of the steps by pressing [N/-] repeatedly
until you reach the main menu again.
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UltraRAE 3000 User's Guide
11 VOC Operation
11.1 Basic User Level/Hygiene Mode
(Default Settings)
The instrument is programmed to operate in Basic User Level/Hygiene Mode
as its default. This gives you the most commonly needed features while
requiring the fewest parameter adjustments.
Pressing [N/-] steps you from one screen to the next, and eventually return to
the main display. If you do not press a key within 60 seconds after entering a
display, the instrument reverts to its main display.
Note: While viewing any of these screens, you can shut off your instrument by
pressing [MODE],
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UltraRAE 3000 User's Guide
E
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UltraRAE 3000 User's Guide
After the instrument is turned on, it runs through the start-up menu. If
the UltraRAE 3000 is set for "Power On Zero," then the message
"Apply zero gas..." is displayed.
At this point, you can perform a zero air (fresh air) calibration. If the
ambient air is clean, you can use that. Otherwise, use a cylinder of
zero air. Refer to Zero Calibration on page 51 for a more detailed
description of zero calibration.
Start zero calibration by pressing Start [Y/+], You see the message
"Zeroing..." followed by a 30-second countdown.
Note: You can press [MODE] to quit, bypassing the zero air
calibration.
When zero calibration is complete, you see the message:
Zeroing is done!
Reading = 0.0 ppm
The instrument is now sampling and collecting data.
Note: At the Average & Peak, Date & Time & Temperature, Calibration
Gas & Measurement Gas & Correction Factor, and PC Communications
screens, the instrument automatically goes to the main display after 60
seconds if you do not push a key to make a selection.
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UltraRAE 3000 User's Guide
12 Alarm Signals
During each measurement period, the gas concentration is compared
with the programmed alarm limits (gas concentration alarm limit
settings). If the concentration exceeds any of the preset limits, the
loud buzzer and red flashing LED are activated immediately to warn
you of the alarm condition.
In addition, the instrument alarms if one of the following conditions
occurs: battery voltage falls below a preset voltage level, failure of
the UV lamp, or pump stall.
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UltraRAE 3000 User's Guide
12.1 Alarm Signal Summary
Message
Condition
Alarm Signal
HIGH
Gas exceeds "High
Alarm" limit
3 beeps/flashes per second*
OVR
Gas exceeds
measurement range
3 beeps/flashes per second*
MAX
Gas exceeds electronics'
maximum range
3 beeps/flashes per second*
LOW
Gas exceeds "Low
Alarm" limit
2 beeps/flashes per second*
TWA
Gas exceeds "TWA"
limit
1 Beep/flash per second*
STEL
Gas exceeds "STEL"
limit
1 Beep/flash per second*
Pump
icon
flashes
Pump failure
3 beeps/flashes per second
Lamp
PID lamp failure
3 beeps/flashes per second
plus "Lamp" message on
display
Battery
icon
flashes
Low battery
1 flash, 1 beep per minute
plus battery icon flashes on
display
CAL
Calibration failed, or
needs calibration
1 beep/flash per second
NEG
Gas reading measures
less than number stored in
calibration
1 beep/flash per second
* Hygiene mode only. In Search mode, the number of beeps per
second (1 to 7) depends upon the concentration of the sampled gas.
Faster rates indicate higher concentrations.
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UltraRAE 3000 User's Guide
12.2 Preset Alarm Limits & Calibration
The instrument is factory calibrated with standard calibration gas, and
is programmed with default alarm limits.
Cal Gas
Cal
Span
unit
Low
High
TWA
STEL
Isobutylene
100
ppm
50
100
10
25
Benzene
5
ppm
2
5
0.5
2.5
Butadiene
10
ppm
10
5
2
5
12.3 Testing The Alarm
You can test the alarm whenever the main (Reading) display is
shown. Press [Y/+], and the audible and visible alarms are tested.
13 Integrated Sampling Pump
The instrument includes an integrated sampling pump. This
diaphragm-type pump that provides a 450 to 550 cc per minute flow
rate. Connecting a Teflon or metal tubing with 1/8" inside diameter to
the gas inlet port of the instrument, this pump can pull in air samples
from 200' (61 m) away horizontally, or 90' (27.5 m) vertically, at
about 3' (0.9 m) per second flow speed.
Note: In Search Mode, the pump turns on when a sample
measurement is started, and turns off when the sample is manually
stopped.
If liquid or other objects are pulled into the inlet port filter, the
instrument detects the obstruction and immediately shuts down the
pump. The alarm is activated and a flashing pump icon is displayed.
You should acknowledge the pump shutoff condition by clearing the
obstruction and pressing the [Y/+] key while in the main reading
display to restart the pump.
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UltraRAE 3000 User's Guide
14 Backlight
The LCD display is equipped with an LED backlight to assist in
reading the display under poor lighting conditions.
15 Datalogging
During datalogging, the instrument displays a disk icon to indicate
that datalogging is enabled. The instrument stores the measured gas
concentration at the end of every sample period (when data logging is
enabled). In addition, the following information is stored: user ID,
site ID, serial number, last calibration date, and alarm limits. All data
are retained (even after the unit is turned off) in non-volatile memory
so that it can be down- loaded at a later time to a PC.
15.1 Datalogging Event
When Datalogging is enabled, measurement readings are being saved.
These data are stored in "groups" or "events." A new event is created
and stored each time the instrument is turned on and is set to
automatic datalogging, or a configuration parameter is changed, or
datalogging is interrupted. The maximum time for one event is 24
hours or 28,800 points. If an event exceeds 24 hours, a new event is
automatically created. Information, such as start time, user ID, site
ID, gas name, serial number, last calibration date, and alarm limits are
recorded.
15.2 Datalogging Sample
After an event is recorded, the unit records a shorter form of the data.
When transferred to a PC running ProRAE Studio, this data is
arranged with a sample number, time, date, gas concentration, and
other related information.
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UltraRAE 3000 User's Guide
15.3 Auto/Manual/Snapshot Datalogging
The instrument has three datalog types:
Auto Default mode. Collects datalog information when the
instrument is sampling.
Manual Datalogging occurs only when the instrument's
datalogging is manually started (see page 63 for
details).
Snapshot Datalogs only during snapshot (single-event capture,
initiated by pressing [MODE]) sampling. See page 65
for details.
Note: You can only choose one datalog type to be active at a time.
16 Accessories
The following accessories are included with the instrument:
• AC Adapter (Battery Charger)
• Travel Charger
• Alkaline battery adapter
• External Filter
• Organic Vapor Zeroing kit
Hard-case kits also include these accessories:
• Calibration gas, if specified
• Calibration adapter
• Calibration regulator and flow controller
• Charging Cradle (instead of Travel Charger)
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UltraRAE 3000 User's Guide
17 Standard Kit & Accessories
17.1 AC Adapter (Battery Charger)
WARNING
To reduce the risk of ignition of hazardous atmospheres, recharge
battery only in area known to be non-hazardous. Remove and
replace battery only in area known to be non-hazardous.
Ne charger les batteries que dans emplacements designes non-
dangereuses.
A battery charging circuit is built into the instrument cradle. It only needs a
regular AC to 12 VDC adapter (wall-mount transformer, part number 500-
0114-000) to charge the instrument.
To charge the battery inside the instrument:
1. Power off the instrument.
2. Connect the AC adapter to the DC jack on the instrument's cradle.
If the instrument is off, it automatically turns on.
3. While charging, the display message shows "Charging." The
Primary LED on the cradle flashes green when charging.
4. When the battery is fully charged, the LED changes to glowing
green continuously, and the message "Fully charged" appears on
the display. If there is a charging error, the LED glows red
continuously.
A completely discharged instrument can be charged to full capacity
within 8 hours. Batteries drain slowly even if an instrument is off.
Therefore, if the instrument has been in storage or has not been
charged for several days or longer, check the charge before using it.
The factory-supplied battery is designed to last for 16 hours of normal
operation (no alarm), for a new battery under the optimum
circumstances. As the battery becomes older or is subject to adverse
conditions (such as cold ambient temperature), its capacity will be
significantly reduced.
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UltraRAE 3000 User's Guide
17.2 External Filter
The external filter is made of PTFE (Teflon®) membrane with a 0.45
micron pore size to prevent dust or other particles from being sucked
into the sensor manifold, which would cause extensive damage to the
instrument. It prolongs the operating life of the sensor. To install the
external filter, simply connect it to the instrument's inlet probe.
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UltraRAE 3000 User's Guide
18 Optional Accessories
18.1 Calibration Adapter
The calibration adapter for the instrument is a simple 6-inch Tygon
tubing with a metal adapter on one end. During calibration, simply
insert the metal adapter into the regular gas inlet probe of the
instrument and the tubing to the gas regulator on the gas bottle.
18.2 Calibration Regulator
The Calibration Regulator is used in the calibration process. It
regulates the gas flow rate from the Span gas cylinder into the gas
inlet of the instrument during calibration process. The maximum flow
rate allowed by the flow controller is about 0.5L/min (500 cc per
min.). Alternatively, a demand-flow regulator or a Tedlar gas bag
may be used to match the pump flow precisely.
18.3 Organic Vapor Zeroing Kit
The Organic Vapor Zeroing Kit is used for filtering organic air
contaminants that may affect the zero calibration reading. To use the
Organic Vapor Zeroing Kit, simply connect the filter to the inlet port
of the instrument.
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UltraRAE 3000 User's Guide
19 Standard Two-Point Calibration
(Zero & Span)
The following diagram shows the instrument's calibrations in
Basic/Hygiene mode.
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UltraRAE 3000 User's Guide
19.1 Entering Calibration
1. Press and hold [MODE] and [N/-] until you see the Password
screen.
Password
§
Enter |
2. In Basic User Level, you do not need a password to perform
calibrations. Instead of inputting a password, enter calibration
by pressing [MODE].
Note: If you inadvertently press [Y/+] and change any of the
numbers, simply press [MODE] and you will be directed to
the calibration menu.
The Calibration screen is now visible with Zero Calibration
highlighted.
Calibration
m&m
Span Calib
Select Back
t
These are your options:
• Press [Y/+] to select the highlighted calibration (Zero Calib
or Span Calib).
• Press [MODE] to exit calibration and return to the main
display and resume measurement.
• Press [N/-] to toggle the highlighted calibration type.
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UltraRAE 3000 User's Guide
19.2 Zero (Fresh Air) Calibration
This procedure determines the zero point of the sensor calibration
curve. To perform a fresh air calibration, use the calibration adapter to
connect the instrument to a "fresh" air source such as from a cylinder
or Tedlar bag (optional accessory). The "fresh" air is clean, dry air
without organic impurities and an oxygen value of 20.9%. If such an
air cylinder is not available, any clean ambient air without detectable
contaminants or a charcoal filter can be used.
At the Zero Calibration menu, you can proceed to perform a Zero
calibration or bypass Zero calibration and perform a Span calibration.
You may also go back to the initial Calibration menu if you want to
exit calibration.
• Press [Y/+] to start calibration.
• Press [MODE] to quit and return to the main calibration
display.
If you have pressed [Y/+] to enter Zero calibration, then you will see
this message:
Please apply zero
gas...
Start Quit
1. Turn on your Zero calibration gas.
2. Press [Y/+] to start calibration.
Note: At this point, you may press [MODE] if you decide
that you do not want to initiate calibration. This will take you
directly to the Calibration menu, highlighted for Span
calibration.
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3. Zero calibration starts a 30-second countdown and displays
this message:
Zeroing...
During the zeroing process, the instrument performs the Zero
calibration automatically and does not require any action on your part.
Note: To abort the zeroing process at any time and proceed to Span
calibration, press [N/-] at any time while zeroing is being performed.
You will see a confirmation message that says "Zero aborted!" and
then the Span calibration menu appears.
When Zero calibration is complete, you see this message:
Zeroing is done!
Reading = 0.0 ppm
The instrument will then show the Calibration menu on its display,
with Span Calib highlighted.
19.3 Span Calibration
This procedure determines the second point of the sensor calibration
curve for the sensor. A cylinder of standard reference gas (span gas)
fitted with a 500 cc/min. flow-limiting regulator or a flow-matching
regulator is the simplest way to perform this procedure. Choose the
500 cc/min. regulator only if the flow rate matches or slightly exceeds
the flow rate of the instrument pump. Alternatively, the span gas can
first be filled into a Tedlar bag or delivered through a demand-flow
regulator. Connect the calibration adapter to the inlet port of the
instrument, and connect the tubing to the regulator or Tedlar bag.
Another alternative is to use a regulator with >500 cc/min flow but
allow the excess flow to escape through a T or an open tube. In the
latter method, the span gas flows out through an open tube slightly
wider than the probe, and the probe is inserted into the calibration
tube.
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At the Span Calibration menu, you perform a Span calibration. You
may also go back to the Zero calibration menu or to the initial
Calibration menu if you want to exit calibration.
• Press [Y/+] to enter Span calibration.
• Press [N/-] to skip Span calibration and return to Zero
calibration.
• Press [MODE] to exit Span calibration and return to the top
calibration menu.
If you have pressed [Y/+] to enter Span calibration, then you will see
the name of your Span gas (the default is isobutylene) and the span
value in parts per million (ppm).
IMPORTANT!
If you are using the UltraRAE 3000 to test for benzene, it is
recommended that you calibrate with 5 ppm benzene calibration gas
from RAE Systems.
You will also see this message that prompts you:
C. Gas = tsobutene
Span = 10® ppm
Please apply gas 1,.
Start Quit
1. Turn on your span calibration gas.
2. Press [Y/+] to initiate calibration.
Note: You may press [MODE] if you decide that you do not
want to initiate calibration. This will abort the span
calibration and take you directly to the Calibration menu for
Zero calibration.
3. Span calibration starts and displays this message:
Calibrating...
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During the Span calibration process, there is a 30-second countdown
and the instrument performs the Span calibration automatically. It
requires no actions on your part.
Note: If you want to abort the Span calibration process, press [N/-] at
any time during the process. You will see a confirmation message that
says "Span is aborted!" and then the Zero calibration menu appears.
You can then proceed to perform a Zero calibration, perform a Span
calibration, or exit to the topmost Calibration menu.
When Span calibration is complete, you see a message similar to this
(the value is an example only):
Span 1 is done!
Reading = 100.0 ppm
The instrument then exits Span calibration and shows the Zero
calibration menu on its display.
Note: The reading should be very close to the span gas value.
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19.4 Exiting Two-Point Calibration In Basic
User Level
When you are done performing calibrations, press [MODE], which
corresponds with "Back" on the display. You will see the following
message:
Updating settings...
The instrument updates its settings and then returns to the main
display. It begins or resumes monitoring.
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20 Three-Point Calibration
For enhanced accuracy, it is possible to perform a second Span
calibration in addition to the Zero and Span calibrations outlined in
the previous section. Your instrument first must be set to allow this
third calibration. This requires using ProRAE Studio software and a
PC, as well as a higher concentration of calibration gas.
Note: Once the third calibration is set, you do not need to use
ProRAE Studio to allow future 3-point calibrations. Also, you can
only disable 3-point calibration capability by using ProRAE Studio
again.
Perform the Zero and Span calibrations. After the first Span
calibration (Span 1) is completed, the display a second Span
calibration (Span 2) can be performed. The process is identical to the
first calibration. As in the Span 1 calibration, you may exit and return
to the Zero calibration screen if you choose not to perform this
calibration or to abort it.
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20.1 Span 2 Calibration
A cylinder of standard reference gas (span gas) fitted with a 500
cc/min. flow-limiting regulator or a flow-matching regulator is the
simplest way to perform this procedure.
Note: This gas should be of a higher concentration than the gas used
for Span 1 calibration.
Choose the 500 cc/min. regulator only if the flow rate matches or
slightly exceeds the flow rate of the instrument pump. Alternatively,
the span gas can first be filled into a Tedlar bag or delivered through a
demand-flow regulator. Connect the calibration adapter to the inlet
port of the instrument, and connect the tubing to the regulator or
Tedlar bag.
Another alternative is to use a regulator with >500 cc/min flow but
allow the excess flow to escape through a T or an open tube. In the
latter method, the span gas flows out through an open tube slightly
wider than the probe, and the probe is inserted into the calibration
tube.
At the Span Calibration menu, you perform a Span calibration. You
may also go back to the Zero calibration menu or to the initial
Calibration menu if you want to exit calibration.
• Press [Y/+] to enter Span 2 calibration.
• Press [N/-] to skip Span calibration and return to Zero
calibration.
• Press [MODE] to exit Span calibration and return to the top
calibration menu.
If you have pressed [Y/+] to enter Span calibration, then you will see
the name of your Span gas (the default is isobutylene) and the span
value in parts per million (ppm). You will also see this message that
prompts you:
Please apply gas...
4. Turn on your span calibration gas.
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5. Press [Y/+] to initiate calibration.
Note: You may press [MODE] if you decide that you do not
want to initiate calibration. This will take you directly to the
Calibration menu for Zero calibration.
6. Span calibration starts a 30-second countdown and displays
this message:
Calibrating...
During the Span calibration process, the instrument performs the
Span calibration automatically and does not require any action on
your part.
Note: If you want to abort the Span calibration process, press [N/-] at
any time during the process. You will see a confirmation message that
says "Span is aborted!" and then the Zero calibration menu will
appear. You can then proceed to perform a Zero calibration, perform
a Span calibration, or exit to the topmost Calibration menu.
When Span calibration is complete, you will see a message similar to
this (the value shown here is for example only):
Span 2 is done!
Reading = 1000 ppm
The instrument then exits Span calibration and shows the Zero
calibration menu on its display.
Note: The reading should be very close to the span gas value.
20.2 Exiting Three-Point Calibration
When you are done performing calibrations, press [MODE], which
corresponds with "Back" on the display. You will see the following
message:
Updating settings...
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The instrument updates its settings and then returns to the main
display. It begins or resumes monitoring.
21 Programming Mode
Programming Mode can be entered from either Hygiene Mode or
Search Mode. If the current user mode is Basic, you must provide a 4-
digit password to enter.
21.1 Entering Programming Mode
1. Press and hold [MODE] and [N/-] until you see the Password
screen.
Password
4* Enter
2. Input the 4-digit password:
• Increase the number from 0 through 9 by pressing [Y/+],
• Step from digit to digit using [N/-].
• Press [MODE] when you are done.
If you make a mistake, you can cycle through the digits by pressing
[N/-] and then using [Y/+] to change the number in each position.
Note: The default password is 0000.
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When you have successfully entered Programming Mode, you see
this screen:
Calibration
fi
999
ppm
**
Select Back —>
Note: The password can only be changed by connecting the
instrument to a PC running ProRAE Studio software. Follow the
instructions in ProRAE Studio to change it.The Calibration label is
shown and its icon is highlighted, but you can press [N/-] to step from
one programming menu to the next, with the name of the menu shown
at the top of the display and the corresponding icon highlighted. As
you repeatedly press [N/-], the selection moves from left to right, and
you see these screens:
Calibration Measurement Alarm Setting
Note: When you reach Monitor Setup and press | N/-|. the menu
cycles back to Calibration.
22 Programming Mode Menus
The Programming Mode allows anyone with the password to change
the instalment's settings, calibrate the instalment, modify the sensor
configuration, enter user information, etc. Programming Mode has
five menus. Each menu includes several sub-menus to perform
additional programming functions.
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This table shows the menus and sub-menus:
LjU
999
pptft
&
i V'l.. J* 1
LJ
Calibration
Measurement
Alarm
Setting
Datalog
Monitor
Setup
Zero
Calibration
Meas. Gas
High
Alarm
Clear
Datalog
Radio
Power
Span
Calibration
Meas. Unit
Low
Alarm
Interval
Op Mode
Tube Selection
STEL
Alarm
Data
Selection
Site ID
TWA
Alarm
Datalog
Type
User ID
Alarm
Mode
User Mode
Buzzer
& Light
Date
Time
Pump Duty
Cycle
Pump Speed
Temperature
Unit
Language
Real Time
Protocol
Power On
Zero
Unit ID
LCD
Contrast
Lamp ID
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Once you enter Programming Mode, the LCD displays the first menu,
Calibration. Each subsequent menu is accessed by pressing [N/-]
repeatedly until the desired menu is displayed. To enter a sub-menu
of a menu, press [Y/+],
22.1 Exiting Programming Mode
To exit Programming Mode and return to normal operation, press
[MODE] once at any of the programming menu displays. You will
see "Updating Settings..." as changes are registered and the mode
changes.
22.2 Navigating Programming Mode Menus
Navigating through the Programming Mode menus is easy and
consistent, using a single interface format of "Select," "Back" and
"Next" at the top level. The three control buttons correspond to these
choices as shown:
Select Back
Note: Pressing [MODE] in the Programming Mode's top level causes
the instrument to exit Programming Mode and return to monitoring.
The three keys perform the following functions in Programming Mode:
Key Function in Programming Mode
[MODE]:
Exit menu when pressed momentarily or exit
data entry mode
[¥/+]:
Increase alphanumerical value for data entry or
confirm (yes) for a question
[N/-]:
Provides a "no" response to a question
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22.3 Calibration
Two types of calibration are available: Zero (fresh air) and Span.
Calibration
m H #
[Meet |
Back | ->
Select Zero or Span Calibration by pressing [N/+]. Once your choice
is highlighted, press [Y/+],
22.3.1 Zero Calibration
The procedure for performing a zero calibration is covered on page
49.
22.3.2 Span Calibration
The procedure for performing a basic span calibration is covered on
page 49.
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22.4 Measurement
The sub-menus for Measurement are Measurement Gas and
Measurement Unit.
22.4.1 Meas. Gas
Measurement gases are organized in four lists:
• My List is a customized list of gases that you create. It contains a
maximum of 10 gases and can only be built in ProRAE Studio on
a PC and transferred to the instrument. Note: The first gas in the
list is always isobutylene (it cannot be removed from the list).
• Last Ten is a list of the last ten gases used by your instrument.
The list is built automatically and is only updated if the gas
selected from Custom Gases or Library is not already in the Last
Ten. This ensures that there is no repetition.
• Gas Library is a library that consists of many of the gases found
in RAE Systems' Technical Note TN-106 (available online at
www.raesystems.com).
• Custom Gases are gases with user-modified parameters. Using
ProRAE Studio, all parameters defining a gas can be modified,
including the name, span value(s), correction factor, and default
alarm limits.
1. Scroll through each list by pressing [N/-].
2. Press [Y/+] to select one (My List, Last Ten, Gas Library, or
Custom Gases).
Measurement
M
Select | Back
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3. Once you are in one of the categories, press [N/-] to scroll
through its list of options and [Y/+] to select one. (If you
press [MODE], you exit to the next submenu.)
4. Press [Y/+] to save your choice or [N/-] to undo your
selection.
Leave the sub-menu and return to the Programming Mode menus by
pressing [MODE],
22.4.2 Meas. Unit
Standard available measurement units include:
Abbreviation
Unit
UltraRAE 3000
ppm
parts per million
Yes
PPb
parts per billion
mg/m3
milligrams per cubic meter
Yes
ug/m3
micrograms per cubic meter
• Scroll through the list by pressing [N/-].
• Select by pressing [Y/+],
• Save your selection by pressing [Y/+] or undo your selection by
pressing [N/-].
Leave the sub-menu and return to the Programming Mode menus by
pressing [MODE],
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22.4.3 Tube Selection
When operating the UltraRAE 3000 in Compound Specific mode, the
internal computer works most effectively when it is told which type
of separation tube is being used.
| Tube Selection
Benzene
O Butadiene
Select
Done
*
1. Scroll through the menu by pressing |N/-|.
2. Press [Y/+] to make a selection.
3. Press [MODE] when you are done.
4. Press [Y/+J to save your choice or [N/-] to undo your selection.
| Tube Selection
Benzene
| O Butadiene
Save
Undo
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22.5 Alarm Setting
During each measurement period, the gas concentration is compared
with the programmed alarm limits (gas concentration alarm limit
settings: Low, High, TWA and STEL). If the concentration exceeds
any of the preset limits, the loud buzzer and red flashing LED are
activated immediately to warn of the alarm condition.
An alarm signal summary is shown on page 42.
In this menu, you can change the High and Low alarm limits, the
STEL limit, and the TWA. Press [Y/+] to to enter the Alarm Setting
menu. Note: All settings are shown in ppb (parts per billion), or
(ig/m3 (micrograms per cubic meter), depending on your setting.
Alarm Setting
s
999
ppm
g
#
Select
Back
1. Scroll through the Alarm Limit sub-menu using the [N/-] key
until the display shows the desired limit to be changed (High
Alarm, Low Alarm, STEL Alarm, and TWA Alarm)
2. Press [Y/+] to select one of the alarm types. The display
shows a flashing cursor on the left-most digit of the
previously stored alarm limit.
3. Press [Y/+] to increase each digit's value.
4. Press [N/-] to advance to the next digit.
5. Again, use [Y/+] to increase the number.
Repeat this process until all numbers are entered.
Press [MODE] when you are done.
• Press [Y/+] to save the changes.
• Press [N/-] to undo the changes and revert to the previous
settings.
When all alarm types have been changed or bypassed, press [MODE]
to exit to the Programming Menu.
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22.5.1 High Alarm
You can change the High Alarm limit value. The value is typically set
by the instrument to match the value for the current calibration gas. It
is expressed in parts per billion (ppb). Note: The default value
depends on the measurement gas.
To change the High Alarm value:
1. Press [Y/+] to increase each digit's value.
2. Press [N/-] to advance to the next digit.
3. Again, use [Y/+] to increase the number.
Repeat this process until all numbers are entered.
When you have completed your selections, press [MODE], You will
see two choices: Save and Undo. You have the opportunity to register
the new settings or to change your mind and revert to your previous
settings.
Press [Y/+] to save the changes.
Press [N/-] to undo the changes and revert to the previous settings.
22.5.2 Low Alarm
You can change the Low Alarm limit value. The value is typically set
by the instrument to match the value for the current calibration gas. It
is expressed in parts per billion (ppb). Note: The default value
depends on the measurement gas.
To change the Low Alarm value:
1. Press [Y/+] to increase each digit's value.
2. Press [N/-] to advance to the next digit.
3. Again, use [Y/+] to increase the number.
Repeat this process until all numbers are entered.
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When you have completed your selections, press [MODE], You will
see two choices: Save and Undo. You have the opportunity to register
the new settings or to change your mind and revert to your previous
settings.
• Press [Y/+] to save the changes.
• Press [N/-] to undo the changes and revert to the previous
settings.
22.5.3 STEL Alarm
You can change the STEL Alarm limit value. The value is typically
set by the instrument to match the value for the calibration gas. It is
expressed in parts per billion (ppb). Note: The default value depends
on the measurement gas.
To change the STEL Alarm value:
1. Press [Y/+] to increase each digit's value.
2. Press [N/-] to advance to the next digit.
3. Again, use [Y/+] to increase the number.
Repeat this process until all numbers are entered.
When you have completed your selections, press [MODE], You will
see two choices: Save and Undo. You have the opportunity to register
the new settings or to change your mind and revert to your previous
settings.
• Press [Y/+] to save the changes.
• Press [N/-] to undo the changes and revert to the previous
settings.
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22.5.4 TWA Alarm
You can change the TWA (time-weighted average) Alarm limit value.
The value is typically set by the instrument to match the value for the
calibration gas. It is expressed in parts per billion (ppb). Note: The
default value depends on the measurement gas.
To change the TWA Alarm value:
1. Press [Y/+] to increase each digit's value.
2. Press [N/-] to advance to the next digit.
3. Again, use [Y/+] to increase the number.
Repeat this process until all numbers are entered.
When you have completed your selections, press [MODE], You will
see two choices:
• Save
• Undo
You have the opportunity to register the new settings or to change
your mind and revert to your previous settings.
• Press [Y/+] to save the changes.
• Press [N/-] to undo the changes and revert to the previous
settings.
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22.5.5 Alarm Mode
There are two selectable alarm modes:
Latched When the alarm is triggered, you can
manually stop the alarm.
The latched setting only controls alarms
for High Alarm, Low Alarm, STEL
Alarm, and TWA alarm.
Note: To clear an alarm when the
instrument is set to "Latched," press
[Y/+] when the main (Reading) display is
shown.
Automatic Reset When the alarm condition is no longer
present, the alarm stops and resets itself.
1. Press [N/-] to step from one alarm mode to the other.
2. Press [Y/+] to select an alarm mode.
When you have completed your selections, press [MODE].
You will see two choices: Save and Undo. You have the
opportunity to register the new settings or to change your mind
and revert to your previous settings.
• Press [Y/+] to save the changes.
• Press [N/-] to undo the changes and revert to the previous
settings.
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22.5.6 Buzzer & Light
The buzzer and light alarms can be programmed to be on or off
individually or in combination. Your choices are:
• Both on
• Light only
• Buzzer only
• Both off
1. Press [N/-] to step from one option to the next.
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates your selection).
3. When you have completed your selections, press [MODE].
You will see two choices: Save and Undo. You have the
opportunity to register the new settings or to change your mind
and revert to your previous settings.
• Press [Y/+] to save the changes.
• Press [N/-] to undo the changes and revert to the previous
settings.
22.6 Datalog
The instrument calculates and stores the concentration and ID of each
sample taken. In the datalog sub-menu, a user can perform the tasks
and functions shown below.
Datalog
999
ppm
&|i| -
Select
Sack
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1. Scroll through the Datalog sub-menu using the [N/-] key until the
display shows the desired parameter to be changed:
Clear Datalog
Interval
Data Selection
Datalog Type
2. Press [Y/+] to make your selection. Exit by pressing [MODE] for
Back.
22.6.1 Clear Datalog
This erases all the data stored in the datalog.
Note: Once the datalog is cleared, the data cannot be recovered.
Press [Y/+] to clear the datalog. The display asks, "Are you sure?"
• Press [Y/+] if you want to clear the datalog. When it has been
cleared, the display shows "Datalog Cleared!"
• Press [N/-] if you do not want to clear the datalog.
The display changes, and you are taken to the next sub-menu,
Interval.
22.6.2 Interval
Intervals are shown in seconds. The default value is 60 seconds. The
maximum interval is 3600 seconds.
1. Press [Y/+] to increase each digit's value.
2. Press [N/-] to advance to the next digit.
3. Again, use [Y/+] to increase the number.
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Repeat this process until all numbers are entered.
When you have completed your selections, press [MODE].
You will see two choices: Save and Undo. You have the opportunity
to register the new settings or to change your mind and revert to your
previous settings.
• Press [Y/+] to save the changes.
• Press [N/-] to undo the changes and revert to the previous
settings.
22.6.3 Data Selection
Data Selection allows you to select which types of data are stored and
made available when you offload your datalog to a computer via
ProRAE Studio software.
You can choose any or all of three types of data (you must choose at
least one):
• Average
• Maximum
• Minimum
1. Press [N/-] to step from one option to the next. The highlighter
indicates your choice.
2. Press [Y/+] to toggle your selection on or off (the check box
indicates "on" with an "X").
3. When you have completed your selections, press [MODE].
You will see two choices: Save and Undo. You have the opportunity
to register the new settings or to change your mind and revert to your
previous settings.
• Press [Y/+] to save the changes.
• Press [N/-] to undo the changes and revert to the previous
settings.
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22.6.4 Datalog Type
The instrument has three datalog types:
Auto Default mode. Collects datalog information when the
instrument is sampling.
Manual Datalogging occurs only when the instrument's
datalogging is manually started (see below for
details).
Snapshot Datalogs only during single-event capture sampling.
Note: You can only choose one datalog type to be active at a time.
1. Press [N/-] to step from one option to the next.
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates "on").
3. When you have completed your selection, press [MODE],
You will see two choices: Save and Undo. You have the opportunity
to register the new settings or to change your mind and revert to your
previous settings.
• Press [Y/+] to save the changes.
Press [N/-] to undo the changes and revert to the previous settings.
22.6.5 Manual Datalog
When the instrument is set to Manual Datalog, you turn datalogging
on and off by stepping through the displays from the Main Display,
and then pressing the keys to select datalog on/off functions.
• When you reach the screen that says "Start Datalog?" press
[Y/+] to start it. You see "Datalog Started," confirming that
datalogging is now on.
When you reach the screen that says "Stop Datalog?" press [Y/+] to
stop it. You see "Datalog Stopped," confirming that datalogging is
now off.
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22.6.6 Snapshot Datalog
When the instrument is in Snapshot datalogging mode, it captures a
single "snapshot" of the data at the moment of your choosing.
Whenever the instrument is on and it is set to Snapshot, all you have
to do is press [MODE] each time you want to capture a snapshot of
the data at that instant.
When you send the data to a computer using ProRAE Studio, the data
snapshots are uniquely identified by time and other parameters.
22.7 Monitor Setup
Many settings can be accessed in this menu, including setting the date
and time and adjusting the pump's on/off duty cycle.
Monitor Setup
0P
J ~S£~
Select I
Back | |
22.7.1 Radio Power
The radio connection can be turned on or off. (The default value is
off.)
1. Press [N/-] to step from one option to the next (on or off).
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates that the option is selected).
3. When you have completed your selection, press [MODE],
• Press [Y/+] to accept the new radio setting (on or off).
• Press [N/-] to discard the change and move to the next sub-
menu.
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22.7.2 Op Mode
Under Monitor Setup is "Op Mode."
Press [Y/+] to select.
You see two options (one is highlighted):
Hygiene
Search
The current mode is indicated by a dark circle within the circle in
front of either Hygiene or Search.
1. Select Hygiene or Search by pressing [N/-]. The highlighting
changes from one to the other each time you press [N/-].
2. Press [Y/+] to select that mode for the instrument.
3. Press [MODE] when you want to register your selection to
place the instrument in the selected mode.
4. Press [Y/+] to commit the change and exit to the Monitor
Setup screen, or press [N/-] to Undo (exit to the Monitor
Setup screen without changing the Mode).
22.7.3 Site ID
Enter an 8-digit alphanumeric/character Site ID in the programming
mode. This Site ID is included in the datalog report.
1. Press [Y/+] and the display shows the current site ID.
Example: "RAE00001." Note that the left-most digit flashes
to indicate it is the selected one.
2. Press [Y/+] to step through all 26 letters (A to Z) and 10
numerals (0 to 9).
Note: The last four digits must be numerals.
3. Press [N/-] to advance to the next digit. The next digit to the
right flashes.
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Repeat this process until all eight digits of the new site ID are
entered.
Press [MODE] to exit.
If there is any change to the existing site ID, the display shows
"Save?" Press [Y/+] to accept the new site ID. Press [N/-] to discard
the change and move to the next sub-menu.
22.7.4 User ID
Enter an 8-digit alphanumeric User ID in the programming mode.
This User ID is included in the datalog report.
1. Press [Y/+] and the display shows the current User ID.
Example: "RAE00001." Note that the left-most digit flashes
to indicate it is the selected one.
2. Press [Y/+] to step through all 26 letters (A to Z) and 10
numerals (0 to 9).
3. Press [N/-] to advance to the next digit. The next digit to the
right flashes.
Repeat this process until all eight digits of the new User ID
are entered.
Press [MODE] to exit.
If there is any change to the existing User ID, the display shows
"Save" Press [Y/+] to accept the new site ID. Press [N/-] to discard
(undo) the change and move to the next sub-menu.
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22.7.5 User Mode
The instrument has two user modes:
Basic Basic users can only see and use a basic set of
functions.
Advanced Advanced users can see all screens and perform all
available functions.
Note: The default value for User Mode is Basic.
To change the User Mode:
1. Press [N/-] to step from one option to the next. The highlighting
changes each time you press [N/-].
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates "on").
3. When you have completed your selection, press [MODE],
4. Press [Y/+] to accept the new User Mode. Press [N/-] to discard
the change and move to the next sub-menu.
22.7.6 Date
The Date is expressed as Month/Day/Year, with two digits for each.
1. Press [Y/+] and the display shows the current date. Note that
the left-most digit flashes to indicate it is selected.
2. Press [Y/+] to step through all 10 numerals (0 to 9).
3. Press [N/-] to advance to the next digit. The next digit to the
right flashes.
Repeat this process until all six digits of the new date are
entered.
Press [MODE] to exit.
• Press [Y/+] to save the new date.
• Press [N/-] to undo the change and move to the next sub-
menu.
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22.7.7 Time
The Time is expressed as Hours/Minutes/Seconds, with two digits for
each. The time is in 24-hour (military) format.
1. Press [Y/+] and the display shows the current time. Note that
the left-most digit flashes to indicate it is selected.
2. Press [Y/+] to step through all 10 numerals (0 to 9).
3. Press [N/-] to advance to the next digit. The next digit to the
right flashes.
Repeat this process until all six digits of the new time are
entered.
Press [MODE] to exit.
• Press [Y/+] to save the new date.
• Press [N/-] to undo the change and move to the next sub-
menu.
22.7.8 Duty Cycle
The pump's duty cycle is the ratio of its on time to off time. The duty
cycle ranges from 50% to 100% (always on; this is the default value),
and the period is 10 seconds. Therefore, a duty cycle of 60% means that
the pump is on for 6 seconds and off for four seconds. Duty cycling is
employed by the instrument to clean the PID. A lower duty cycle has a
greater effect on keeping the PID clean than a higher duty cycle.
Important! Pump duty cycling is interrupted when the instrument
senses a gas. The pump's duty cycle is disabled when the
measurement is greater than the 2ppm threshold and is re-enabled
when the reading falls below 90% of the threshold (1.8 ppm).
1. Press [Y/+] to increase the value.
2. When you have completed your selection, press [MODE],
• Press [Y/+] to save the new duty cycle value.
• Press [N/-] to undo the change and move to the next sub-
menu.
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22.7.9 Temperature Unit
The temperature display can be switched between Fahrenheit and
Celsius units.
1. Press [N/-] to step from one option to the next.
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates "on").
3. When you have completed your selection, press [MODE],
• Press [Y/+] to save the new temperature unit.
• Press [N/-] to undo the change and move to the next sub-
menu.
22.7.10 Pump Speed
The pump can operate at two speeds, high and low. Running at low
speed is quieter and conserves a small amount of power. There is
almost no difference in sampling accuracy.
1. Press [N/-] to step from one option to the next.
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates "on").
3. When you have completed your selection, press [MODE],
• Press [Y/+] to save the new temperature unit.
• Press [N/-] to undo the change and move to the next sub-
menu.
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22.7.11 Language
English is the default language, but other languages can be selected
for the instrument.
1. Press [N/-] to step from one option to the next.
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates "on").
3. When you have completed your selection, press [MODE],
• Press [Y/+] to save your new language choice.
• Press [N/-] to undo it and return to the previous language
selection.
22.7.12 Real Time Protocol
Real Time Protocol is the setting for data transmission.
The choices are:
P2M (cable) Point to multipoint. Data is transferred from the
instrument to multiple locations using a wired
connection. Default data rate: 19200 bps.
P2P (cable) Point to point (default). Data is transferred only
between the instrument and one other location,
such as a computer. Default data rate: 9600 bps.
P2M (wireless) Point to multipoint, wireless. Data is transferred
wirelessly and can be received by multiple
receivers. Use this setting with a RAELink3.
1. Press [N/-] to step from one option to the next.
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates "on").
3. When you have completed your selection, press [MODE],
• Press [Y/+] to save the new real-time communications protocol.
• Press [N/-] to undo the change and move to the next sub-menu.
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22.7.13 Power On Zero
When Power On Zero is on, the instrument is ready to perform a zero
calibration when it is turned on.
1. Press [N/-] to step from one option to the next.
2. Press [Y/+] to make your selection (the dark circle in the "radio
button" indicates your selection).
3. When you have completed your selection, press [MODE],
• Press [Y/+] to save the change.
• Press [N/-] to discard the change and move to the next sub-
menu.
22.7.14 Unit ID
This three-digit number keeps data separated by instrument when
more than one instrument is used in a network. If multiple sensing
units are attempting to communicate with the same Host, then the
units must all have a different Unit ID.
1. Press [Y/+] to step through all 10 numerals (0 to 9). If you pass
the numeral you want, keep pressing [Y/+], After it counts up to
9, it starts counting up from 0 again.
2. Press [N/-] to advance to the next digit. The next digit to the right
flashes.
Repeat this process until all three digits of the Unit ID are entered.
3. Press [MODE] when you are done.
• Press [Y/+] to save the change.
• Press [N/-] to discard the change and move to the next sub-
menu.
Note: If you are using an UltraRAE 3000 with a RAELink3, this unit
ID is displayed by the RAELink3.
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22.7.15 LCD Contrast
The display's contrast can be increased or decreased from its default
setting. You may not need to ever change the default setting, but
sometimes you can optimize the display to suit extreme temperature
and ambient brightness/darkness conditions.
• The minimum value is 20.
• The maximum value is 60.
1. Press [Y/+] to increase the value or [N/-] to decrease the value.
2. Press [MODE] to save your selection.
• Press [Y/+] to save your new contrast value.
• Press [N/-] to undo it and return to the previous value.
22.7.16 Lamp ID
The UltraRAE can automatically identify the type of lamp, or you can
select a lamp type manually.
Lamp ID
®
O 1G.6eV
Auto detect
Select
Done
1. Scroll through the menu by pressing [N/-].
2. Press [Y/+] to make a selection.
3. Press [MODE] when you are done.
4. Press [Y/+] to save your choice or [N/-] to undo your selection.
Lamp ID
®
O 10.6eV
Auto detect
Save
Undo
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23 Humidity Compensation
The UltraRAE 3000 has a humidity sensor and humidity
compensation circuitry. By default it is on, but it can be turned off or
on by using ProRAE Studio software. RAE Systems recommends
testing the humidity sensor once a year. See page 99 for the simple
procedure.
24 Hygiene Mode
The instrument usually operates in Hygiene Mode, which provides
basic functionality. However, it is possible to operate it in a second
mode called Search Mode. Here are the primary differences:
Hygiene Mode: Automatic measurements, continuously
running and datalogging, and calculates
additional exposure values.
Search Mode: Manual start/stop of measurements and display
of certain exposure values.
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24.1 Basic User Level & Hygiene Mode
The default setting is navigated in the following way:
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Pressing [N/-] steps you from screen to screen. Options include
clearing the Peak value and turning on the instrument's PC
Communications for data transfer to a PC.
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24.2 Entering Search Mode From Hygiene
Mode
In order to change the instrument's operational mode from Hygiene
Mode to Search Mode, you must enter the password-protected
Programming Mode:
1. Hold [MODE] and [N/-] until you see the password screen.
2. Use [Y/+] to increment to the number you want for the first
digit. (If you pass by the desired number, press [Y/+] until it
cycles through to 0 again. Then press [Y/+] until you reach
the desired number.)
3. Press [N/-] to advance to the next digit.
4. Again press [Y/+] to increment the number.
5. Press [N/-] to advance to the next digit.
Continue the process until all four numbers of the password have
been input. Then press [MODE] to proceed.
The screen changes to icons with the label "Calibration."
1. Press [N/-] to advance to "Monitor Setup."
2. Press [Y/+] to select Monitor Setup.
Under Monitor Setup, you will see "Op Mode."
Press [Y/+] to select.
You will see:
Hygiene
Search
The current mode is indicated by a dark circle within the circle in
front of either Hygiene or Search.
1. Select Hygiene or Search by pressing [N/-].
2. Press [Y/+] to place the instrument into the selected mode.
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3.
4.
Press [MODE] when you want to register your selection to
place the instrument in the selected mode.
Press |Y/+] to commit the change and exit to the Monitor
Setup screen, or press [N/-] to Undo (exit to the Monitor
Setup screen without changing the Mode).
24.3 Optional Graphic Screen In Search Mode
Using ProRAE Studio, you can set your instrument to show a graphic
display instead of a numeric display of ongoing data. Consult your
ProRAE Studio disc for information.
Calibration needed
Graph
Gas info
t^.iilil—BatterV
PPM Reading
CF=1.00 Isobuten^M^
2*
Y/+ key
"V
-Radio power
-Radio signal
Mode key N/- key
Datalog
Pump
During sampling, the display's readings are shown numerically, plus
the graph tracks the highest readings over time. The numeric reading
alternates between the value and the measurement units, as well:
..ill 1
0.0
CF=1.00 Isobuten^lo]
**
© ^
•I
.¦ill i
ppm
CF=1.00 Isobuten^loJ
&
©
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25 Advanced User Level (Hygiene
Mode Or Search Mode)
The User Mode called Advanced User Level allows a greater number
of parameters to be changed than Basic User Level. It can be used
with either of the Operation Modes, Hygiene Mode or Search Mode.
25.1 Advanced User Level & Hygiene Mode
With the instrument in Operation Mode: Hygiene Mode, enter User
Mode: Advanced User Level (refer to the section called Monitor
Mode for instructions).
Once you are in Advanced User Level and Hygiene Mode together,
you can change the calibration reference and measurement gas, in
addition to performing normal monitoring functions.
Pressing [N/-] progresses through the screens, while pressing [Y/+]
selects options. Pressing [MODE] makes menu choices when it is
shown for "Done" or "Back." Pressing and holding [Mode] whenever
the circle with a vertical line in the middle is shown activates the
countdown to shutoff.
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25.2 Basic User Level & Search Mode
With the instrument in Operation Mode: Search Mode, enter User
Mode and select Basic User Level (refer to the section called User
Mode for instructions).
When the instrument is in Search Mode, it only samples when you
activate sampling. When you see the display that says, "Ready... Start
sampling?" press [Y/+] to start. The pump turns on and the instrument
begins collecting data. To stop sampling, press [N/-] while the main
display is showing. You will see a new screen that says, "Stop
sampling?" Press [Y/+] to stop sampling. Press [N/-] if you want
sampling to continue.
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25.3 Advanced User Level & Search Mode
With the instrument in Operation Mode: Search Mode, enter User
Mode and select Advanced User Level (refer to the section called
Monitor Mode for instructions). Operation is similar to Basic User
Level & Sampling Mode, but now allows you to change calibration
and measurement reference gases. Refer to the section on
measurement gases on page 65 for more details.
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25.4 Diagnostic Mode
IMPORTANT! Diagnostic Mode is designed for servicing and
manufacturing, and therefore is not intended for everyday use, even
by advanced users. It provides raw data from sensors and about
settings, but only allows adjustment of pump stall parameters, which
should only be changed by qualified personnel.
Note: If the instrument is turned on in Diagnostic Mode and you
switch to User Mode, datalog data remains in raw count form. To
change to standard readings, you must restart the instrument.
25.4.1 Entering Diagnostic Mode
Note: To enter Diagnostic Mode, you must begin with the instrument
turned off.
Press and hold [Y/+] and [MODE] until the instrument starts.
The instrument goes through a brief startup, and then displays raw
data for the PID sensor. These numbers are raw sensor readings
without calibration. The instrument is now in Diagnostic Mode.
Note: In Diagnostic Mode, the pump and lamp are normally on.
You can enter Programming Mode and calibrate the instrument as
usual by pressing both [MODE] and [N/-] for three seconds.
You can enter Monitoring Mode by pressing [MODE] and [Y/+]
together for three seconds.
Once the instrument is started up in Diagnostic Mode, you can switch
between Diagnostic Mode and Monitoring Mode by pressing and
holding [MODE] and [Y/+] simultaneously for two seconds.
In Diagnostic mode, you can step through parameter screens by
pressing [MODE],
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25.4.2 Adjusting The Pump Stall Threshold
If the gas inlet is blocked but the pump does not shut down, or the
pump shuts down too easily with a slight blockage, the pump stall
threshold value may be set too high or too low.
Use the following steps to adjust the pump stall threshold:
25.4.3 Pump High
In Diagnostic Mode, press the [MODE] key until "Pump High" is
displayed. The display shows the maximum, minimum, and stall
values for the pump at its high speed. Write down the "Max" reading.
Block the gas inlet and watch the pump current reading (labeled "I")
increase. Write down its blocked reading. Note: If the pump current
reading does not increase significantly (less than 10 counts), then
there may be a leak in the gas inlet or the pump is weak or defective.
Add the two readings you wrote down. This is the average of the
maximum block count and the maximum idle count. Divide that
number by 2. Use the [Y/+] or [N/-] key to increase or decrease the
stall value to equal that number.
Press the [MODE] key to exit this display.
25.4.4 Pump Low
In Diagnostic Mode, press the [MODE] key until "Pump Low" is
displayed. The display shows the maximum, minimum, and stall
values for the pump at its low speed. Write down the "Max" reading.
Block the gas inlet and watch the pump current reading (labeled "I")
increase. Write down its blocked reading. Note: If the pump current
reading does not increase significantly (less than 10 counts), then
there may be a leak in the gas inlet or the pump is weak or defective.
Add the two readings you wrote down. This is the average of the
maximum block count and the maximum idle count. Divide that
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number by 2. Use the [Y/+] or [N/-] key to increase or decrease the
stall value to equal that number.
Press the [MODE] key to exit this display.
25.4.5 Testing The Humidity Sensor
1. Press [MODE] to step through the diagnostic screens until you
reach a screen that says "T.H.P' (for "temperature, humidity,
pressure") at the top.
There are three numbers for the humidity reading ( "H"). The first
number is the current humidity reading from the sensor. The
second is the reference number for 0% humidity, and the third
number is the reference for 100% humidity.
T.H.P.
T 253
H 707 678 866
P 413
S/N GHTJ1W0200
2. Fill a cup with warm water (>25° C/77° F).
3. Put a filter on the UltraRAE 3000's inlet probe.
4. Place the inlet probe over the warm water.
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i==5"" T7>P"
o Q
25° C/77° F
6. Wait a few seconds and check the high-humidity reading.
7. The humidity reading should be within ±10% of the 100%
humidity reading. If it is not, then the THP Sensor (part number
023-3011-000-FRU) should be replaced.
8. Check the low-humidity reading by connecting the inlet probe to
a tank of zero gas (air at 0% humidity).
9. Turn on the zero gas and wait a few seconds for the sensor
reading to stabilize. It should read within 10% of the low-
reference number. If it does not, replace the T.H.P. sensor.
10. Once you have finished testing the humidity sensor, exit
Diagnostic Mode by shutting down the UltraRAE 3000 (hold
[MODE] through the countdown, and then release when it is off).
1 n
25.4.6 Exiting Diagnostic Mode
You can exit Diagnostic Mode and go directly to Programming Mode
or Monitor Mode as outlined above, or you can exit Diagnostic Mode
completely.
To exit Diagnostic Mode so that it cannot be re-entered without a
restart:
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Shut down the instrument. When it is off, restart it by holding the
[MODE] key. Diagnostic Mode cannot be entered until the instrument
is restarted as outlined in "Entering Diagnostic Mode."
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26 Transferring Data To & From
Computer
Once you have connected your instrument cradle to the PC, you can
can transfer data, including a download of the datalog to the computer
and updates of firmware to the instrument (should this ever be
necessary).
26.1 Downloading The Datalog To A PC
1. Connect the data cable to the PC and the cradle.
2. Place the instrument into its cradle. The charging LED should
be illuminated.
3. Start ProRAE Studio on your PC.
4. From ProRAE Studio, select "Operation" and select Setup
Connection.
5. Select the COM port to establish a communication link
between the PC and the instrument.
6. To receive the datalog in the PC, select "Downlog Datalog."
7. When you see "Unit Information," click OK.
During the data transfer, the display shows a progress bar.
When the transfer is done, you will see a screen with the datalog
information. You can now export this datalog for other use or
printing.
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26.2 Uploading Firmware To The instrument
From A PC
Uploading new firmware to your instrument requires connecting the
instrument and PC. Follow these steps to make the connection:
1. Connect the data cable to the PC and the cradle.
2. Place the instrument into its cradle. The charging LED should
be illuminated.
3. Start RAEProgrammer 7000 on your PC.
4. From RAEProgrammer 7000, select "Operation" and select
Setup Connection.
5. Select the COM port to establish a communication link
between the PC and the instrument.
6. Select Operation Download Firmware.
Once communication is established, follow the instructions that
accompany RAEProgrammer 7000 and the firmware to upload the
new firmware to your instrument.
Note: Check for the latest updates to ProRAEProgrammer 7000 at
www.raesystems.com.
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27 Maintenance
The major maintenance items of the instrument are:
• Battery pack
• Sensor module
• PID lamp
• Sampling pump
• Inlet connectors and filters
In addition, you can test the humidity sensor (this should be done
annually, in order to ensure the most accurate operation).
Note: Maintenance should be performed by qualified personnel
only.
NOTE: The printed circuit board of the instrument is connected
to the battery pack even if the power is turned off. Therefore, it is
very important to disconnect the battery pack before servicing or
replacing any components inside the instrument. Severe damage
to the printed circuit board or battery may occur if the battery
pack is not disconnected before servicing the unit.
27.1 Battery Charging & Replacement
When the display shows a flashing empty battery icon, the battery
requires recharging. It is recommended to recharge the instrument
upon returning from fieldwork. A fully charged battery runs a
instrument for 16 hours continuously. The charging time is less than 8
hours for a fully discharged battery. The battery may be replaced in
the field (in areas known to be non-hazardous), if required.
WARNING!
To reduce the risk of ignition of hazardous atmospheres, recharge
battery only in area known to be non-hazardous. Remove and
replace battery only in areas known to be non-hazardous.
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27.1.1 Replacing The Li-ion Battery
1. Turn off the instrument.
2. Located on the rear of the instrument is a battery tab. Slide it down to
unlock the battery.
3. Remove the battery pack from the battery compartment by tilting
4. Replace a fully charged spare battery pack inside the battery
compartment. Make sure the battery pack is oriented properly
inside the compartment.
5. Slide the capture tab back up to its locked position.
27.1.2 Replacing The Alkaline Battery Adapter
An alkaline battery adapter is supplied with each instrument. The
adapter (part number 059-3052-000) accepts four AA alkaline
batteries (use only Duracell MN1500 or Energizer E91) and provides
approximately 12 hours of operation. The adapter is intended to be
used in emergency situations when there is no time to charge the Li-
ion battery pack.
To insert batteries into the adapter:
1. Remove the three hex-socket screws to open the
compartment.
2. Insert four fresh AA batteries as indicated by the polarity (+/-)
markings.
it out.
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3. Replace the cover. Replace the three screws.
To install the adapter in the instrument:
1. Remove the Li-ion battery pack from the battery
compartment by sliding the tab and tilting out the battery.
2. Replace it with the alkaline battery adapter
3. Slide the tab back into place to secure the battery adapter.
IMPORTANT!
Alkaline batteries cannot be recharged. The instrument's internal
circuit detects alkaline batteries and will not allow recharging. If you
place the instrument in its cradle, the alkaline battery will not be
recharged. The internal charging circuit is designed to prevent
damage to alkaline batteries and the charging circuit when alkaline
batteries are installed inside the instrument.
Note: When replacing alkaline batteries, dispose of old ones properly.
WARNING!
To reduce the risk of ignition of hazardous atmospheres, recharge the
battery only in areas known to be non-hazardous. Remove and replace
the battery only in areas known to be non-hazardous.
Note: The internal charging circuit is designed to prevent charging to
alkaline batteries.
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27.2 PID Sensor & Lamp Cleaning/Replacement
The sensor module is made of several components and is attached to
the lamp-housing unit as shown below.
Inlet Probe Assembly
PN 023-3012-000-FRU
O-ring, 35mm x 2mm,
Porous Metal Filter.
Lamp 1/2" (9.8eV)
PN 050-0020-000
Seal Nut
Sensor Body
Assembly
PN 023-3006-
000-FRU
Tube Adapter
Assembly
PN 059-3015-000-FRU
Rubber Adapter
Sensor Detector
PN 023-3010-001
Stainless Steel Washer
O-ring, 36.5mm x 2.65mm
Sensor Module Assembly
PN 023-3005-600-FRU
*THP (temperature, humidity, pressure) Sensor Module
PN 023-3011-000-FRU
Sensor Components
Note: The cleaning procedure is not normally needed. Clean the PID
sensor module, the lamp and the lamp housing only if:
1. The reading is inaccurate even after calibration.
2. The reading is very sensitive to air moisture.
3. A liquid has been sucked into the unit and damaged the unit.
Use of the external filter helps to prevent contamination of the sensor.
To access the sensor components and lamp, gently unscrew the lamp-
housing cap, remove the sensor adapter with the gas inlet probe and
the metal filter all together. Then hold the PID sensor and pull it
straight out. A slight, gentle rocking motion helps release the sensor.
Note: The 10.6eV lamp requires a Teflon O-ring. The 9.8eV and
11.7eV lamps do not require the O-ring.
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27.3 Cleaning The PID Sensor
Place the entire PID sensor module into GC grade methanol. It is
highly recommended that an ultrasound bath to be used to clean the
sensor for at least 15 minutes. Then dry the sensor thoroughly. Never
touch the electrodes of the sensor by hand.
Also use a methanol-soaked cotton swab to wipe off the lamp housing
where it contacts the sensor when the sensor is installed.
Turn over the sensor so that the pins point up and the sensor cavity is
visible. Examine the sensor electrodes for any corrosion, damage, or
bending out of alignment. The metal sensor electrode "fingers"
should be flat and straight. If necessary, carefully bend the sensor
fingers to ensure that they do not touch the Teflon portions and that
they are parallel to each other. Make sure that the nuts on the sensor
pins are snug but not overtight. If the sensor is corroded or otherwise
damaged, it should be replaced.
27.3.1 Cleaning The Lamp Housing Or Changing The
Lamp
If the lamp does not turn on, the instrument will display an error
message to indicate replacement of the lamp may be required.
1. If the lamp is operational, clean the lamp window surface and the
lamp housing by wiping it with GC grade methanol using a cotton
swab using moderate pressure. After cleaning, hold the lamp up
to the light at an angle to detect any remaining film. Repeat the
process until the lamp window is clean. Never use water solutions
to clean the lamp. Dry the lamp and the lamp housing thoroughly
after cleaning.
CAUTION: Never touch the window surface with the fingers
or anything else that may leave a film. Never use acetone or
aqueous solutions.
2. If the lamp does not turn on, remove the lamp from the lamp
housing. Place the lamp O-ring onto the new lamp. Insert the new
lamp, avoiding contact with the flat window surface.
3. Reinstall the PID sensor module.
4. Tighten the Lamp Housing Cap.
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27.3.2 Determining The Lamp Type
The monitor can accommodate three lamp values: 10.6eV (standard),
9.8eV, and 11.7eV. The monitor automatically reads a marking on the
side of the lamp to set the proper Correction Factor. There are two
ways to determine the lamp type:
Remove the lamp and look for markings (bars) on the side:
Nobars: 10.6eV
• 1 bar: 11.7eV
2 bars: 9.8eV
Also, when the monitor is running, the lamp type is shown along with
the calibration and measurement gas and Correction Factor:
C. Gas
= Isobutene
M. Gas
= Isobutene
CF = 1.00
10.6eV
(D
->
Note: This screen can be accessed from the reading screen by
pressing [N/-] four times.
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27.3.3 Sampling Pump
When approaching the end of the specified lifetime of the pump, it
will consume higher amount of energy and reduce its sample draw
capability significantly. When this occurs, it is necessary to replace or
rebuild the pump. When checking the pump flow, make sure that the
inlet connector is tight and the inlet tubing is in good condition.
Connect a flow meter to the gas inlet probe. The flow rate should be
above 450 cc/min when there is no air leakage.
If the pump is not working properly, refer the instrument to qualified
service personnel for further testing and, if necessary, pump repair or
replacement.
27.3.4 Testing The T.H.P. Sensor
It is recommended that you periodically test the humidity sensitivity
of the T.H.P. (temperature/humidity/pressure) sensor. See page 99 for
a simple procedure.
27.3.5 Cleaning The Instrument
Occasional cleaning with a soft cloth is recommended. Do not use
detergents or chemicals.
Visually inspect the contacts at the base of the instrument, on the
battery, and on the charging cradle to make sure they are clean. If
they are not, wipe them with a soft, dry cloth. Never use solvents or
cleaners.
27.3.6 Ordering Replacement Parts
If you need replacement parts, contact your local RAE Systems
distributor. A list is available online:
http: //www. rae systems .com
In the U.S., you can order sensors, replacement batteries, and other
accessories online at:
http://istore.raesystems.com/
110
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UltraRAE 3000 User's Guide
27.4 Special Servicing Note
If the instrument needs to be serviced, contact either:
1. The RAE Systems distributor from whom the instrument was
purchased; they will return the instrument on your behalf.
or
2. The RAE Systems Technical Service Department. Before
returning the instrument for service or repair, obtain a Returned
Material Authorization (RMA) number for proper tracking of
your equipment. This number needs to be on all documentation
and posted on the outside of the box in which the instrument is
returned for service or upgrade. Packages without RMA Numbers
will be refused at the factory.
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28 Troubleshooting
Problem
Possible Reasons & Solutions
Cannot turn on power
after charging the
battery
Reasons:
Solutions:
Discharged battery.
Defective battery.
Chaige or replace battery.
Lost password
Solutions:
Call Technical Support at
+1 408-752-0723 or toll-
free at
+1 888-723-4800
Reading abnormally
High
Reasons:
Dirty filter.
Dirty sensor module.
Excessive moisture and
water condensation.
Incorrect calibration.
Solutions:
Replace filter.
Blow-dry the sensor
module.
Calibrate the unit.
Reading abnormally
Low
Reasons:
Dirty filter.
Dirty sensor module.
Weak or dirty lamp.
Incorrect calibration.
Solutions:
Replace filter.
Remove Calibration
Adapter.
Calibrate the unit.
Check for air leakage.
Buzzer
Inoperative
Reasons:
Solutions:
Bad buzzer.
Check that buzzer is not
turned off.
Call authorized service
center.
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UltraRAE 3000 User's Guide
Inlet flow too low
Reasons:
Pump diaphragm damaged
or has debris.
Flow path leaks.
Solutions:
Check flow path for leaks;
sensor module O-ring, tube
connectors, Teflon tube
compression fitting.
Call Technical Support at
+1 408-752-0723
or toll-free at
+1 888-723-4800
"Lamp" message
during operation
Reasons:
Lamp drive circuit.
Weak or defective PID
lamp, defective.
Solutions:
Turn the unit off and back
on.
Replace UV lamp
29 Technical Support
To contact RAE Systems Technical Support Team:
Monday through Friday, 7:00AM to 5:00PM Pacific (US) Time
Phone (toll-free): +1 888-723-4800
Phone: +1 408-952-8461
Email: tech@raesystems.com
Life-critical after-hours support is available:
+1 408-952-8200 select option 8
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30 RAE Systems Contacts
RAE Systems
World Headquarters
3775 N. First St.
San Jose, CA 95134-1708 USA
Phone: +1 408.952.8200
Fax: +1 408.952.8480
E-mail: customerserv@raesystems.com
Web Site: www.raesystems.com
RAE Systems Technical Support
Monday through Friday, 7:00AM to 5:00PM Pacific Time
Phone: +1.408.952.8461
Email: tech@raesystems.com
Life-critical after-hours support is available:
+1.408.952.8200 select option 8
RAE Systems Europe ApS
Kirstinchoj 23 A
DK-2770 Kastrup
Denmark
Phone:+45 86 52 51 55
Fax: +45 86 52 51 77
orders@raeeurope .com
sales@raeeurope.com
service@raesystems.com
Web: www.raesystems.dk
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RAE Systems UK Ltd
D5 Culham Innovation Centre
Culham Science Centre
Abingdon, Oxon 0X14 3DB
United Kingdom
Phone: +44 1865408368
Fax: +44 1235531119
Mobile:+44 7841362693
Email: raeuk@raeeurope.com
RAE Systems France
336, rue de la fee des eaux
69390 Vernaison
France
Phone: +33 4 78 46 16 65
Fax: +33 4 78 46 25 98
Email: info-france@raeeurope.com
Web: www.raesystems.fr
RAE BeNeLux BV
Rijndal 20
2904 DC Capelle a/d IJssel
Phone: +31 10 4426149
Fax: +31 10 4426148
Email: info@rae.nl
Web: www.rae.nl
RAE Systems Spain, s.l.
Av. Remolar, 31
08820 El Prat de Llobregat
Spain
Phone: +34 933 788 352
Fax: +34 933 788 353
Mobile: +34 687 491 106
Email: mdelgado@raespain.com
Web: www.raespain.com
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UltraRAE 3000 User's Guide
RAE Middle East
Lot 7, Ground Floor, Office 19
Jebel Ali Free Zone
Dubai
United Arab Emirates
Phone: +971 4 887 5562
Fax:+971 4 887 5563
Email: mjorgensen@raesystems.com
RAE Systems (Hong Kong) Ltd.
Room 8, 6/F, Hong Leong Plaza
33 Lok Yip Road
Fanling, N.T, Hong Kong
Phone: +852.2669.0828
Fax: +852.2669.0803
Email: hksales@raesystems.com
RAE Systems Japan
403 Plaza Ochanomizu Bldg. 2-1
Surugadai Kanda Chiyoda-Ku
Tokyo, Japan
Phone: 81-3-5283-3268
Fax: 81-3-5283-3275
Email: jpsales@raesystems.com
RAE Systems Korea
#1010, DaeMyungAnsVill First,
Sang-Dong 412-2, Wonmi-Gu, Bucheon,
Kyungki-Do, Korea
Phone: 82-32-328-7123
Fax: 82-32-328-7127
Email: krsales@raesystems.com
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UltraRAE 3000 User's Guide
31 Regulatory Information
Intrinsic Safety:
Temperature:
Humidity:
US and Canada: Class I, Division 1, Group
A, B, C, D
Europe: ATEX (II 2G EEx ia IIC T4)
-20° C to 50° C (-4° to 122° F)
0% to 95% relative humidity (non-
condensing)
32 Basic Operation
32.1 Turning The Instrument On
1. With the instrument turned off, press and hold [MODE].
2. When the display turns on, release the [MODE] key.
The instrument is now operating and performs self tests. Once the self
tests are complete, the display shows a graph or numerical gas
reading. This indicates that the instrument is fully functional and
ready to use.
32.2 Turning The Instrument Off
1. Press and hold the Mode key for 3 seconds. A 5-second
countdown to shutoff begins.
2. When you see "Unit off..." release your finger from the [MODE]
key. The instrument is now off.
Note: You must hold your finger on the key for the entire shutoff
process. If you remove your finger from the key during the
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UltraRAE 3000 User's Guide
countdown, the shutoff operation is canceled and the instrument
continues normal operation.
33 Alarm Signals
During each measurement period, the gas concentration is compared
with the programmed alarm limits (gas concentration alarm limit
settings). If the concentration exceeds any of the preset limits, the
loud buzzer and red flashing LED are activated immediately to warn
you of the alarm condition.
In addition, the instrument alarms if one of the following conditions
occurs: battery voltage falls below a preset voltage level, failure of
the UV lamp, pump stall, or when the datalog memory is full.
33.1 Alarm Signal Summary
Message
Condition
Alarm Signal
HIGH
Gas exceeds "High
Alarm" limit
3 beeps/flashes per second*
OVR
Gas exceeds
measurement range
3 beeps/flashes per second*
MAX
Gas exceeds electronics'
maximum range
3 beeps/flashes per second*
LOW
Gas exceeds "Low
Alarm" limit
2 beeps/flashes per second*
TWA
Gas exceeds "TWA"
limit
1 Beep/flash per second*
STEL
Gas exceeds "STEL"
limit
1 Beep/flash per second*
Pump
icon
flashes
Pump failure
3 beeps/flashes per second
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UltraRAE 3000 User's Guide
Lamp
PID lamp failure
3 beeps/flashes per second
plus "Lamp" message on
display
Battery
icon
flashes
Low battery
1 flash, 1 beep per minute
plus battery icon flashes on
display
CAL
Calibration failed, or
needs calibration
1 beep/flash per second
NEG
Gas reading measures
less than number stored in
calibration
1 beep/flash per second
34 Preset Alarm Limits & Calibration
The instrument is factory calibrated with standard calibration gas, and
is programmed with defau
t alarm
imits.
Cal Gas
(Isobutylene)
Cal
Span
unit
Low
High
TWA
STEL
ppbRAE
3000
10
ppm
10
25
10
25
MiniRAE
3000
100
ppm
50
100
10
25
MiniRAE
Lite
100
ppm
50
100
10
25
UltraRAE
3000
100
ppm
50
100
10
25
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UltraRAE 3000 User's Guide
35 Charging The Battery
Always fully charge the battery before using the instrument. The
instrument's Li-ion battery is charged by placing the instrument in its
cradle. Contacts on the bottom of the instrument meet the cradle's
contacts, transferring power without other connections.
Note: Before setting the instrument into its charging cradle, visually
inspect the contacts to make sure they are clean. If they are not, wipe
them with a soft cloth. Do not use solvents or cleaners.
Follow this procedure to charge the instrument:
1. Plug the AC/DC adapter's barrel connector into the
instrument's cradle.
2. Plug the AC/DC adapter into the wall outlet.
3. Place the instrument into the cradle, press down, and lean it
back. It locks in place and the LED in the cradle glows.
Note: To release the instrument, press down and tilt the top out
of the cradle and lift up.
The instrument begins charging automatically. The LED on the front
of the cradle marked "Primary" blinks during charging. During
charging, the diagonal lines in the battery icon on the instrument's
display are animated and you see the message "Charging..."
When the instrument's battery is fully charged, the battery icon is no
longer animated and shows a full battery. The message "Fully
charged!" is shown and the Primary LED on the cradle glows
continuously green.
DC 12V IN
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UltraRAE 3000 User's Guide
Note: A spare Li-ion battery (part number 059-3051-000) can be charged
by placing it directly in the charging port on the back of the cradle. It can
be charged at the same time as the instrument. Press the battery in place,
sliding it slightly toward the front of the cradle. This locks it in the
cradle. To release the battery, slide it forward again and tilt it up.
Note: An Alkaline Battery Adapter (part number 059-3052-000),
which uses four AA alkaline batteries (Duracell MN1500 or
Energizer E91), may be substituted for the Li-Ion battery.
WARNING!
To reduce the risk of ignition of hazardous atmospheres, recharge and
replace batteries only in areas known to be non-hazardous. Remove
and replace batteries only in areas known to be non-hazardous.
ATEX WARNING!
To reduce the risk of electrostatic ignition, do not use the instrument
without the rubber boot in place.
35.1 Low Voltage Warning
When the battery's charge falls below a preset voltage, the instrument
warns you by beeping once and flashing once every minute, and the
battery icon blinks once per second. You should turn off the
instrument within 10 minutes and either recharge the battery by
placing the instrument in its cradle, or replace the battery with a fresh
one with a full charge.
35.2 Clock Battery
An internal clock battery is mounted on one of the instrument's
printed circuit boards. This long-life battery keeps settings in memory
from being lost whenever the Li-ion battery or alkaline batteries are
removed. This backup battery should last approximately five years,
and must be replaced by an authorized RAE Systems service
technician. It is not user-replaceable.
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UltraRAE 3000 User's Guide
WARNING
To reduce the risk of ignition of hazardous atmospheres, recharge
battery only in area known to be non-hazardous. Remove and
replace battery only in an area known to be non-hazardous.
35.3 Replacing The Rechargeable Li-Ion
Battery
Caution: Turn off the instrument before removing or replacing the
battery.
35.4 Alkaline Battery Adapter
An alkaline battery adapter is supplied with each instrument. The
adapter (part number 059-3052-000) accepts four AA alkaline
batteries (use only Duracell MN1500 or Energizer E91).
Do not mix old and new batteries or batteries from different
manufacturers.
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UltraRAE 3000 User's Guide
36 Troubleshooting
Problem
Possible Reasons & Solutions
Cannot turn on power
after charging the
battery
Reasons:
Solutions:
Discharged battery.
Defective battery.
Chaige or replace battery.
Lost password
Solutions:
Call Technical Support at
+1 408-752-0723 or toll-
free at
+1 888-723-4800
Reading abnormally
High
Reasons:
Dirty filter.
Dirty sensor module.
Excessive moisture and
water condensation.
Incorrect calibration.
Solutions:
Replace filter.
Blow-dry the sensor
module.
Calibrate the unit.
Reading abnormally
Low
Reasons:
Dirty filter.
Dirty sensor module.
Weak or dirty lamp.
Incorrect calibration.
Solutions:
Replace filter.
Remove Calibration
Adapter.
Calibrate the unit.
Check for air leakage.
Buzzer
Inoperative
Reasons:
Solutions:
Bad buzzer.
Check that buzzer is not
turned off.
Call authorized service
center.
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UltraRAE 3000 User's Guide
Inlet flow too low
Reasons:
Pump diaphragm damaged
or has debris.
Flow path leaks.
Solutions:
Check flow path for leaks;
sensor module O-ring, tube
connectors, Teflon tube
compression fitting.
Call Technical Support at
+1 408-752-0723
or toll-free at
+1 888-723-4800
"Lamp" message
during operation
Reasons:
Lamp drive circuit.
Weak or defective PID
lamp, defective.
Solutions:
Turn the unit off and back
on.
Replace UV lamp
124
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-------
RAE Systems
World Headquarters
3775 N. First St.
San Jose, CA 95134-1708 USA
Phone: 408.952.8200
Fax: 408.952.8480
E-mail: customerserv@raesystems.com
Web Site: www.raesystems.com
Rev. A
May 2008
P/N 059-4023-000
-------
To ran SAFER v. 9.0:
Steps 1-2 - only if you are using a removable drive to store your data, but not to run the
program
1. Connect the removable drive to PC.
2. Copy the appropriate state folder (they can be identified by their two-letter
USPS abbreviation) from the removable drive into C:/GIS Data/World/US A/,
If you wish, you may copy only the counties that you're interested in. The
process is a little more involved, but possible with practice.
Steps 3-end - everyone.
3. Open the STAR Site Manager.
RTSiteMan.exe
y
4. Create a new site by selecting the icon.
5. Name the site and proceed by clicking the , icon.
6. To locate the site, left-click on the map (the V£r icon should already be
selected) near where the incident is located. The coordinates at the location
where you click will appear at the bottom left of the screen. It is NOT critical
at this stage to locate the site exactly. For best results, shoot for +/- 15 miles.
7. Copy the coordinates obtained in step 3 into the boxes at the top left of the
screen. Select the coordinates, then right-click, select 'copy;' right-click and
select 'paste' to paste the coordinates. (If an exact address is known, this may
also be entered).
Once the coordinates have been selected, click the _____
icon. This will
bring up more detailed GIS data around the incident site.
9. Determine the exact location of the incident site by zooming ( t and
icons) and panning ( icon). Use the icon to determine names of
places. After selecting the icon, simply mouse over the place of interest and
hold the left-mouse button
10. After finding the exact incident site location, choose the "A*" icon, and select
that location as the center of the map.
11. Click the
icon.
"ir ;f
12. Locate the weather station (the icon should already be selected) by
clicking on the map.
-------
13. Click the i icon.
14. Select the surface roughness that you wish to use. Try to match the qualitative
surface characteristics of the site. This parameter is most critical in an urban
or dense forest environment.
15. Select the
icon.
16. When back to the main screen, select the
Y
if you want to collect met/sen data, select "Yes.'
icon again. When prompted
17. This will bring you to the Launch Pad. Data Acquisition should start
automatically. Start the Emergency Response program and click on the
Stoplight icon, and model away!
Manual Met Notes:
a. Maximum solar radiation = 1000 W/. Take a fraction of this based on
cloud cover.
b. Stability class can be estimated from wind speed, solar radiation
(qualitative), and ceiling height.
FROM EPA's
'Meteorological Monitoring Guidance for Regulatory Modeling Applications''
(EPA-454/R-99-005, February, 2000)
e
Step 1.
Determine the "Net Radiation Index"
1. If the total cover is 10/10 and the ceiling is less than 7,000 feet,
use net radiation index equal to 0 (whether day or night)
2. For Nighttime: (from one hour before sunset to one hour after sunrise):
a. If total cloud cover — 4/10, use net radiation index equal to -2.
b. If total cloud cover > 4/10, use net radiation index equal to -1.
3. For Daytime
a. Determine the insolation class number as a function of solar
altitude from Table 1, below
b. If total cloud cover — 5/10, use the net radiation index in Table
2 corresponding to the insolation class number.
c. If cloud cover > 5/10, modify the insolation class number using
the following six steps.
1.) Ceiling < 7,000 ft, subtract 2
2.) Ceiling — 7,000 ft, but < 160,000 ft, subtract 1
3.) Total cloud cover equal to 10/10, subtract 1. (This will
only apply to ceiling — 7,000 ft since cases with 10/10
coverage below 7,000 ft are considered in item 1
-------
above.)
4.) If insolation class number has not been modified by
steps 1.), 2.) or 3.) above, assume modified class
number equal to insolation class number.
5.) If modified insolation class number is less than 1, let it
equal 1.
6.) Use the net radiation index in Table 6-4 corresponding to the
modified insolation class number.
Earth
Table 1
Insolation Class as a Function of Solar Altitude
Solar Altitude cl'(degrees)
Insolation
Insolation Class Number
Ol
O
A
strong
4
35 < (i' ^ 60
moderate
3
15 < Cl> < 35
slight
2
^ 15
weak
1
Table 2.
Turner's Key to the P-G Stability Categories
Wind Speed
Net Radiation Index
(knots)
(m/s)
4
3
2
1
0
- 1
- 2
0,1
0 - 0.7
1
1
2
3
4
6
7
2,3
0.8 - 1.8
1
2
2
3
4
6
7
4,5
1.9 - 2.8
1
2
3
4
4
5
6
6
2.9 - 3.3
2
2
3
4
4
5
6
7
3.4 - 3.8
2
2
3
4
4
4
5
8,9
3.9 - 4.8
2
3
3
4
4
4
5
10
4.9 - 5.4
3
3
4
4
4
4
5
11
5.5 - 5.9
3
3
4
4
4
4
4
^ 12
^ 6.0
3
4
4
4
4
4
4
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CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C.
Toxicology Emergency Response Program (DATE)
STANDARD OPERATING PROCEDURE NO. ()
SUBJECT: Data Collection and Management
Description of the SOP. This SOP describes record-keeping processes.
Key Personnel with Responsibility to Manage this Equipment.
Amanda Fincher
Calibration Instructions
1. All instrument calibrations are documented on CTEH Calibration Logs with the following
information: date, time instrument identification, calibration gas/filter identification, user
initials.
2. Calibration logs are stored together in project file.
Sampling Data Collection and Management Instructions
1. Laboratory Samples
a) Sample collection information is documented on CTEH field forms. Sampling information
includes the following: date, time, location, sampler identification, and sample collection
device information (if applicable).
1) Sample collection forms are stored together in project file.
2) Sample collection information is databased using Microsoft Access and/or
summarized on sample collection maps made with ArcGIS.
b) Analysis requests are made on CTEH-prepared chains of custody (COCs). Copies of
original COCs sent to the laboratory are stored together in the project file. The original
COCs are also stored together in the project file, upon receipt from the laboratory.
c) Laboratory results are received in EDD format, in PDF format, and in hard copy data
packets.
1) EDDs and PDFs are stored in an electronic project folder. Hard copies are
stored together in the project file.
2) Laboratory results are compiled and databased using Microsoft Access and/or
summarized on sample collection maps made with ArcGIS. Within the database
and/or map summary, laboratory results are associated with sample collection
information.
2. Instantaneous "Real-Time" Measurements
a) Manually-logged data
1) Instantaneous measurements are documented on CTEH field forms or in bound
notebooks. Information documented includes: date, time, location, instrument
information, sample result, sampler observations, and sampler identification.
-------
2) Copies of measurements from notebooks are stored with field forms in the "real-
time" section of the project file. Notebooks are stored together in the project file.
3) Information from real-time forms and notebooks are databased using Microsoft
Access.
Instrument-logged data
1) Instrument information, location information, and general observations
associated with instrument-logged data are documented either on C TEH real-
time field forms or in bound notebooks. This information is filed in the same
manner as manually-logged data.
2) Instrument-logged data are downloaded from the instrument using the
appropriate software. These data are then databased using Microsoft Access.
Within the database, instrument-logged data are associated with sample
collection information.
3) Sample collection information is mapped using ArcGIS, and associated data are
configured into graphs using SigmaPlot.
Radio-telemeted data
1) Instrument information, location information, and observations are documented
on CTEH field forms or in bound notebooks. This information is filed in the same
manner as manually-logged data.
2) Telemeted data are recorded using software associated with the transmitters.
Stored data are backed up on a da ily basis. These data are then databased
using Microsoft Access. Within the database, instrument-logged data are
associated with sample collection information.
3) Sample collection information is mapped using ArcGIS, and associated data are
configured into graphs using SigmaPlot.
-------
CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L L C.
Toxicology Emergency Response Program (June 15, 2011)
STANDARD OPERATING PROCEDURE NO. (1.0)
SUBJECT: MultiRAE Worker Exposure Monitoring
Description of the SOP. This SOP describes the use of the MultiRAE plus PID as a personal
monitoring device for the collection of real-time worker exposure data.
Key Personnel with Responsibility to Manage this Operation.
Any environmental scientist or IH technician responsible for the collection of real-time worker
exposure data using the MultiRAE plus PID.
MultiRAE Worker Exposure Preparation Instructions
1. Calibration
a) Please follow the CTEH MultiRAE plus PID Standard Operating Procedures Version 1.1,
latest version.
2. Equipment Preparation
a) Connect a 3-4 ft piece of Teflon® tubing using RAE approved connectors to the MultiRAE
inlet. Connect the Teflon® tubing directly to the MultiRAE, do not connect to the water-
trap.
b) Install a water-trap to the inlet end of the Teflon® tubing. Ensure that the inlet of the
Teflon® tubing is equipped with a connection device that can be clipped to the worker's
lapel or clothing in the breathing zone.
3. Instrument Set-Up
a) Ensure that the MultiRAE is NOT in Diagnostics Mode.
b) Set up the MultiRAE to data-log at the appropriate data-log interval. If no specific data-log
interval is desired, use the 5-minute interval.
c) Ensure that the MultiRAE reflects the correct DATE and Time (time zone where sample
will be collected).
d) Ensure that the appropriate sensors are enabled for data-log. Additionally, ensure that
irrelevant sensors are disabled.
4. Instrument Installation on Worker
a) Clip the calibrated MultiRAE onto the belt of the worker. If no belt is available or the
worker is wearing chemical or flame-resistant protective clothing, use an auxiliary belt on
the outside of the chemical or flame-resistant protective clothing.
b) Going across the worker's back, locate the Teflon® tubing inlet in the worker's breathing
zone, clipping the inlet to the worker's lapel or clothing.
c) Ensure that the inlet is located on the outside of any clothing, vest, or other material that
may block the inlet from drawing air from the worker's breathing zone.
-------
Sampling Data Sheet Instructions
1. Use an appropriate field data sheet prior to deploying the MultiRAE to collect worker exposure
data. The data sheet should capture the following information:
a) CTEH Project Number
b) MultiRAE Instrument Serial Number
c) Calibration Information (specifically the: calibration date, calibration gas type, calibration
gas lot number, calibration gas expiration date.)
d) Worker's Full Name, Contact Information, and Company Information,
e) Worker's Job Task,
f) Worker's Work Site Location Information,
g) Sample Information for Co-located samples (i.e. 3M 3500 badge information, sample ID,
etc...),
h) Start Date and Time,
i) Stop Date and Time,
j) Worker's Smoking Habit,
k) Other Potential Cross-Contamination Sources (i.e. bug spray, cologne, hand sanitizer
etc...)
I) Sampler's Name and Contact Information
Post-Sampling Event Collection of MultiRAE and Data Processing
1 .At the end of the worker's job task or work shift, collect the MultiRAE from the worker:
2.Conduct an end of shift interview with the employee to gather information related to work shift
activities
3. Immediately download the MultiRAEs data-logged data using ProRAE suite. Save the data file
in the appropriate project folder location.
4. Replace the MultiRAEs batteries and prepare the instrument for subsequent use of the device.
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CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C.
Toxicology Emergency Response Program (6/17/08)
STANDARD OPERATING PROCEDURE NO. (Version 1.1)
SUBJECT: MultiRAE Plus
Description of the SOP. This SOP describes the set-up and use of the MultiRAE Plus.
Calibration Instructions: Calibration should be done at least once a shift.
To get to Calibration Screen
1) Turn on MultiRAE by pressing and holding the MODE button. Wait for the instrument to
warm up.
2) To get to the calibration screen press the MODE and "No" buttons at the same time.
Hold until screen says "Calibrate Monitor", press Y/+.
3) When the message "Fresh Air Calibration?" appears, make sure before pressing Y/+ you
have either a fresh air environment or are using zero grade air. When calibrating sensors
for the first time, do not Fresh Air calibrate.
For Multiple Sensor Calibration
1) To calibrate multiple sensors at the same time in the MulitRAE, select Y/+ at the multiple
sensor calibration screen.
2) To accept these chemicals for multiple sensor calibration, press Y/+
3) To change the chemicals for the multiple sensor calibration, press N/- at the "OK?"
screen
4) The "Pick" screen will appear. To choose other sensors, press MODE scroll from one
sensor to the next and press Y/+ to select a sensor and N/- to deselect a sensor.
5) An asterisk (*) will appear by the sensors that are selected to be calibrated with the
multiple sensor calibration.
6) The instrument will recognize the Calibration gas and begin counting down from 59
seconds.
7) After 59 seconds, the instrument will show "Calibration Complete"
NOTE: Quad gas allows for the calibration of CO, H2S, 02, and LEL.
For Single Sensor Calibration
1) To calibrate single sensors, select y/+ at the single sensor calibration screen.
2) Use the MODE button to navigate between sensors. Press Y/+ to select the sensor.
-------
3) After pressing Y/+ on the VOC sensor, the MultiRAE will ask you to Apply Gas =
Isobutylene.
4) When you apply the calibration gas to MultiRae, it will begin a countdown from 59 sec.
5) At the end of the 59 sec., the instrument will show "Calibration Complete, Turn off cal
gas"
NOTE: The MultiRae is set to calibrate to a specific concentration of calibration gas. For
each sensor, the calibration gas and concentration will be different.
Using a Different Calibration Gas: If you need to calibrate your instrument with a calibration
gas that is not sold to you by Rae Systems, you will need to check the span gas value which
should equal concentration of the calibration gas.
1) To modify span gas value, press Y/+ when the "Modify Span Gas Value" screen appears.
2) Use the MODE button to scroll from digit to digit and the Y/+ and N/- buttons to adjust
values.
3) Before calibration, the span gas values need to represent the calibration gas
concentrations.
Bump Calibration: This is done to check a sensor's function; this does not take the place of a
standard calibration.
1) Can be done in either diagnostic mode in the raw screen or in standard mode in the
readings screen.
2) Attach the calibration gas that coincides with that sensor to the MultiRAE
3) Expose the instrument to the gas (example: isobutylene to check VOCs)
4) Watch the readings and make sure they reach the correct value. (RAW values have an
acceptable range. The ranges for the most commonly used sensors will be provided at
the end of the SOP)
NOTE: Always record a calibration in the calibration log, there will be an example form at
the end of the SOP.
NOTE: Always calibrate the instrument in the environment it will be used in. If there is too
large a change in humidity and temperature, the instrument will not react properly
NOTE: There are special case calibrations for some sensors.
Example: HCI and HF sensors. These sensors have a 4 minute calibration time.
NOTE: Some sensors need to be "burned in" for a period before fully operable.
Example: CI2, HCL, HF, NO, NH3 sensors: There "burn in" periods are recommended to
be between 12-24 hours.
-------
Equipment Use Instructions (step by step)
Battery Replacement and Monitor Start Up
1) Remove the water trap, if applicable, from the inlet, (replace water trap if there is visible
dirt or it has been in humid environment)
2) Remove the instrument from its casing.
3) Loosen the screws on the backside of the instrument and remove the front cover.
4) Replace the batteries, and screw the cover back on.
5) Press and hold the mode button until the monitor comes on.
6) Place the instrument back into its protective cover and put the water trap back on unless
you are using chemical sensors which call for the water trap to be left off (see MultiRAE
handbook for list of sensors).
7) Allow the MultiRAE to go through its startup procedures.
User Mode- Main Screen Menus
1) While the Instrument is showing readings, press MODE to scroll through the main
screens.
2) Press MODE once to view the PEAK value.
3) Press MODE again to view the MINIMUM value.
4) Press MODE again for the STEL values. STEL values are only shown for TOX1, VOC,
and TOX2.
5) Press MODE again for TWA values. TWA values are also only shown for TOX1, VOC,
and TOX2.
6) Press MODE again to view the Battery Power screen.
7) Press Mode once again to view the Date, Time, Temperature, and Time the instrument
was turned on.
8) Pressing MODE again will take you to the "Start Datalog?" Screen. Press Y/+ to Start
Datalog then the screen will display Stop Datalog. When you stop the datalog, this will
complete one event.
9) Press mode once to view the LEL gas= screen. This tells you what calibration gas your
LEL is set.
10) Press MODE once more to view the calibration gas to which the PID is set.
11) Press MODE again for the "Print Reading?" Screen.
12) Press MODE again for the "Communicate with PC?" screen. To download information off
of the Multi Rae to your computer, press Y/+.
-------
Program Mode -_to go into Program Mode, PRESS and HOLD MODE and N/- for 5 seconds. (It
is sometimes easier to hold the N/- button first then hold MODE)
Change Alarm Limits
1) All sensors come from Rae Systems with a default alarm limit.
2) These limits can be found in the "Change Alarm Limits" screen on the Multi Rae.
3) Press mode and no at the same time. Use the mode button to scroll through the menu.
4) When the "Change Alarm Limits" screen appears, select Y/+.
5) You will have the option of changing the High alarm, Low alarm, STEL alarm, and the
Average alarm limits.
6) Press N/- to scroll to the Alarm limit that you would like to change.
7) Select Y/+ on the alarm limit that you intend to change.
8) Use the MODE button to scroll from digit to digit and the Y/+ and N/- buttons to select
digits.
9) To save your changes, hold down the MODE button.
Change Real Time Clock
1) Hit MODE when the command Monitor Setup? appears on the screen.
2) Select "Change Real Time Clock?" to adjust the date and time showing on the MultiRae,
then use Y/+ and N/- to adjust the time.
NOTE: ALWAYS do this, and double check it, before you start a datalog.
View or Change Datalog
1) Press MODE and N+/ at the same time. Scroll through the menu by pressing the MODE
button.
2) To view or change the Datalog function, press Y/+ at the "View or Change Datalog?"
screen.
3) The first option will be to "Clear all Data?"
4) Select Y/+ to clear all of the data in the datalog memory.
5) The next option is to "Reset the Peak and Minimum?"
6) When you select Y/+ to "Reset the Peak and Minimum?" the Multi Rae will prompt "Are
you sure?"
7) Select Y/+ to reset your values that you see when scrolling the main menu.
8) The next option is to Enable/Disable datalog? If a * is displayed next to a sensor name,
data will be recorded. Use mode to move from sensor to sensor. An asterisk (*) means
-------
the sensor is enabled; no asterisk means the sensor is disabled. Press Y/+ to select, and
N/- to deselect. To save changes, press MODE until Save? appears. Then press Y/+ to
accept. Otherwise, hold MODE to escape and cancel changes.
NOTE: Do not datalog an instrument that is in diagnostic mode, it will record RAW values.
Always restart first then begin datalog.
Change Backlight
1) You can change the backlight mode by pressing Y/+ at the "Change Backlight Mode?"
screen.
2) To turn on the backlight, hold the N/- button down.
Change Pump Speed
1) To change Pump Speed continue until Change Pump Speed? appears on screen. Press
Y+l or N+/ to change speed different than what it is previously set. Once you determine
which speed you prefer then hold the Y+/to save.
2) Low pump speed- (default) used when operating conditions that are slow
to change, prolongs pump motor life, LEL sensor life and battery run time.
3) High pump speed- use for long lengths of tubing or when rapid changes in input
conditions are expected, such as HazMat response or when used for measuring heavy,
low vapor pressure compounds like jet fuel.
NOTE: Make sure to note it somewhere on an equipment tag when you have changed the
pump speed from a default setting, include your initials and date
NOTE: When using tubing as an extension, we must use Teflon tubing. Tygon tubing
readily absorbs volatiles, especially benzene.
Sensor Configuration
1) Hit MODE and N/+at the same time.
2) Change LEL/VOC Gas Selection?
3) Enable/Disable Sensors?
4) Sensors have assigned sockets. These are identified on the PCB. High bias toxic in
socket1/A.
5) Change PID Lamp Type? This only applies to PID monitors. The PID sensor can utilize
either a 10.6 eV or an 11.7 eV UV. Since each lamp type has a different correction factor
table, it is important to select the correct lamp type.
NOTE: 11.7 lamps have a much shorter lifespan, be aware of the expiration date and leave
Tiffani a note when you mobilize with them.
-------
Using the MultiRAE
1) After recognizing your chemical of concern, look in the technical and application notes
and locate the correction factor for that chemical that corresponds with the lamp in your
MultiRAE
2) When two or more chemicals of concern need to be monitored, a general rule of thumb is
to use the highest correction factor and the chemical with the lowest PEL for action level
purposes.
NOTE: Correction factors are very important, for both the VOC and LEL sensors. Look
through both TN-106 (PID) and TN-156 (LEL).
NOTE: The new NH3 sensors are un-biased. However the NO sensors are still high-bias.
How to clean a lamp
1) Acquire a lamp cleaning kit. Make sure it includes cotton swabs, methanol, tweezers.
Gloves can be found in the ER GO BAG if there are none in the kit.
2) Remove the front cover from the instrument.
3) Remove the metal casing from the PID using the tweezers and wearing gloves. Set it
aside.
4) Using the tweezers carefully remove the top of the PID housing, it is usually fairly secure,
do not use too much force. Set it aside.
5) Carefully remove the lamp from the base, and securely hold it while you swab with cotton
soaked in the methanol. Be careful not to allow cotton fibers to stick to the lamp.
6) Give the lamp a few seconds to dry, then place back into base.
7) Carefully swab the metal screen in the top of the PID housing, and give it a few seconds
to dry before replacing.
8) Replace metal casing. If it appears dirty, swab with methanol also.
9) Replace cover on the instrument.
NOTE: If replacing an expired or faulty lamp, please place the old lamp in box the new
lamp came out of. Mark the box with the serial number and date removed, and return to
Tiffani. It may not have expired yet and be available for replacement.
NOTE: Other than lamp cleaning/replacement or sensor changes, do not manipulate the
other components within the instrument. Red tag the unit and return to Tiffani.
-------
Additional media needed for this equipment: (i.e. calibration gas or
chemcassettes)
MultiRAE technical and application notes; MultiRAE users manual
Calibration gases appropriate to the sensors being used.
Lamp cleaning kit.
Notification Procedures for Equipment Failure (i.e. Rae Systems tech support
number and CTEH contact)
RAE Systems 408.723.4800 CTEH- Equipment Room Manager 801.501.8580
RED TAG inoperable equipment properly, example following SOP
References and Further Assistance
Review Date for this SOP
Nathan Williams 4/12/2011
Attachments
Excerpt from TN-123
Calibration Log example
Red Equipment Tag example
-------
CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L L C.
Toxicology Emergency Response Program (June 15, 2011)
STANDARD OPERATING PROCEDURE NO. (1.0)
SUBJECT: MultiRAE Worker Exposure Monitoring
Description of the SOP. This SOP describes the use of the MultiRAE plus PID as a personal
monitoring device for the collection of real-time worker exposure data.
Key Personnel with Responsibility to Manage this Operation.
Any environmental scientist or IH technician responsible for the collection of real-time worker
exposure data using the MultiRAE plus PID.
MultiRAE Worker Exposure Preparation Instructions
1. Calibration
a) Please follow the CTEH MultiRAE plus PID Standard Operating Procedures Version 1.1,
latest version.
2. Equipment Preparation
a) Connect a 3-4 ft piece of Teflon® tubing using RAE approved connectors to the MultiRAE
inlet. Connect the Teflon® tubing directly to the MultiRAE, do not connect to the water-
trap.
b) Install a water-trap to the inlet end of the Teflon® tubing. Ensure that the inlet of the
Teflon® tubing is equipped with a connection device that can be clipped to the worker's
lapel or clothing in the breathing zone.
3. Instrument Set-Up
a) Ensure that the MultiRAE is NOT in Diagnostics Mode.
b) Set up the MultiRAE to data-log at the appropriate data-log interval. If no specific data-log
interval is desired, use the 5-minute interval.
c) Ensure that the MultiRAE reflects the correct DATE and Time (time zone where sample
will be collected).
d) Ensure that the appropriate sensors are enabled for data-log. Additionally, ensure that
irrelevant sensors are disabled.
4. Instrument Installation on Worker
a) Clip the calibrated MultiRAE onto the belt of the worker. If no belt is available or the
worker is wearing chemical or flame-resistant protective clothing, use an auxiliary belt on
the outside of the chemical or flame-resistant protective clothing.
b) Going across the worker's back, locate the Teflon® tubing inlet in the worker's breathing
zone, clipping the inlet to the worker's lapel or clothing.
c) Ensure that the inlet is located on the outside of any clothing, vest, or other material that
may block the inlet from drawing air from the worker's breathing zone.
-------
Sampling Data Sheet Instructions
1. Use an appropriate field data sheet prior to deploying the MultiRAE to collect worker exposure
data. The data sheet should capture the following information:
a) CTEH Project Number
b) MultiRAE Instrument Serial Number
c) Calibration Information (specifically the: calibration date, calibration gas type, calibration
gas lot number, calibration gas expiration date.)
d) Worker's Full Name, Contact Information, and Company Information,
e) Worker's Job Task,
f) Worker's Work Site Location Information,
g) Sample Information for Co-located samples (i.e. 3M 3500 badge information, sample ID,
etc...),
h) Start Date and Time,
i) Stop Date and Time,
j) Worker's Smoking Habit,
k) Other Potential Cross-Contamination Sources (i.e. bug spray, cologne, hand sanitizer
etc...)
I) Sampler's Name and Contact Information
Post-Sampling Event Collection of MultiRAE and Data Processing
1 .At the end of the worker's job task or work shift, collect the MultiRAE from the worker:
2.Conduct an end of shift interview with the employee to gather information related to work shift
activities
3. Immediately download the MultiRAEs data-logged data using ProRAE suite. Save the data file
in the appropriate project folder location.
4. Replace the MultiRAEs batteries and prepare the instrument for subsequent use of the device.
-------
CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L.L.C.
Toxicology Emergency Response Program (6/17/08)
STANDARD OPERATING PROCEDURE NO. (Version 1.1)
SUBJECT: MultiRAE Plus
Description of the SOP. This SOP describes the set-up and use of the MultiRAE Plus.
Calibration Instructions: Calibration should be done at least once a shift.
To get to Calibration Screen
1) Turn on MultiRAE by pressing and holding the MODE button. Wait for the instrument to
warm up.
2) To get to the calibration screen press the MODE and "No" buttons at the same time.
Hold until screen says "Calibrate Monitor", press Y/+.
3) When the message "Fresh Air Calibration?" appears, make sure before pressing Y/+ you
have either a fresh air environment or are using zero grade air. When calibrating sensors
for the first time, do not Fresh Air calibrate.
For Multiple Sensor Calibration
1) To calibrate multiple sensors at the same time in the MulitRAE, select Y/+ at the multiple
sensor calibration screen.
2) To accept these chemicals for multiple sensor calibration, press Y/+
3) To change the chemicals for the multiple sensor calibration, press N/- at the "OK?"
screen
4) The "Pick" screen will appear. To choose other sensors, press MODE scroll from one
sensor to the next and press Y/+ to select a sensor and N/- to deselect a sensor.
5) An asterisk (*) will appear by the sensors that are selected to be calibrated with the
multiple sensor calibration.
6) The instrument will recognize the Calibration gas and begin counting down from 59
seconds.
7) After 59 seconds, the instrument will show "Calibration Complete"
NOTE: Quad gas allows for the calibration of CO, H2S, 02, and LEL.
For Single Sensor Calibration
1) To calibrate single sensors, select y/+ at the single sensor calibration screen.
2) Use the MODE button to navigate between sensors. Press Y/+ to select the sensor.
-------
3) After pressing Y/+ on the VOC sensor, the MultiRAE will ask you to Apply Gas =
Isobutylene.
4) When you apply the calibration gas to MultiRae, it will begin a countdown from 59 sec.
5) At the end of the 59 sec., the instrument will show "Calibration Complete, Turn off cal
gas"
NOTE: The MultiRae is set to calibrate to a specific concentration of calibration gas. For
each sensor, the calibration gas and concentration will be different.
Using a Different Calibration Gas: If you need to calibrate your instrument with a calibration
gas that is not sold to you by Rae Systems, you will need to check the span gas value which
should equal concentration of the calibration gas.
1) To modify span gas value, press Y/+ when the "Modify Span Gas Value" screen appears.
2) Use the MODE button to scroll from digit to digit and the Y/+ and N/- buttons to adjust
values.
3) Before calibration, the span gas values need to represent the calibration gas
concentrations.
Bump Calibration: This is done to check a sensor's function; this does not take the place of a
standard calibration.
1) Can be done in either diagnostic mode in the raw screen or in standard mode in the
readings screen.
2) Attach the calibration gas that coincides with that sensor to the MultiRAE
3) Expose the instrument to the gas (example: isobutylene to check VOCs)
4) Watch the readings and make sure they reach the correct value. (RAW values have an
acceptable range. The ranges for the most commonly used sensors will be provided at
the end of the SOP)
NOTE: Always record a calibration in the calibration log, there will be an example form at
the end of the SOP.
NOTE: Always calibrate the instrument in the environment it will be used in. If there is too
large a change in humidity and temperature, the instrument will not react properly
NOTE: There are special case calibrations for some sensors.
Example: HCI and HF sensors. These sensors have a 4 minute calibration time.
NOTE: Some sensors need to be "burned in" for a period before fully operable.
Example: CI2, HCL, HF, NO, NH3 sensors: There "burn in" periods are recommended to
be between 12-24 hours.
m
-------
Equipment Use Instructions (step by step)
Battery Replacement and Monitor Start Up
1) Remove the water trap, if applicable, from the inlet, (replace water trap if there is visible
dirt or it has been in humid environment)
2) Remove the instrument from its casing.
3) Loosen the screws on the backside of the instrument and remove the front cover.
4) Replace the batteries, and screw the cover back on.
5) Press and hold the mode button until the monitor comes on.
6) Place the instrument back into its protective cover and put the water trap back on unless
you are using chemical sensors which call for the water trap to be left off (see MultiRAE
handbook for list of sensors).
7) Allow the MultiRAE to go through its startup procedures.
User Mode- Main Screen Menus
1) While the Instrument is showing readings, press MODE to scroll through the main
screens.
2) Press MODE once to view the PEAK value.
3) Press MODE again to view the MINIMUM value.
4) Press MODE again for the STEL values. STEL values are only shown for TOX1, VOC,
and TOX2.
5) Press MODE again for TWA values. TWA values are also only shown for TOX1, VOC,
and TOX2.
6) Press MODE again to view the Battery Power screen.
7) Press Mode once again to view the Date, Time, Temperature, and Time the instrument
was turned on.
8) Pressing MODE again will take you to the "Start Datalog?" Screen. Press Y/+ to Start
Datalog then the screen will display Stop Datalog. When you stop the datalog, this will
complete one event.
9) Press mode once to view the LEL gas= screen. This tells you what calibration gas your
LEL is set.
10) Press MODE once more to view the calibration gas to which the PID is set.
11) Press MODE again for the "Print Reading?" Screen.
12) Press MODE again for the "Communicate with PC?" screen. To download information off
of the Multi Rae to your computer, press Y/+.
-------
Program Mode -_to go into Program Mode, PRESS and HOLD MODE and N/- for 5 seconds. (It
is sometimes easier to hold the N/- button first then hold MODE)
Change Alarm Limits
1) All sensors come from Rae Systems with a default alarm limit.
2) These limits can be found in the "Change Alarm Limits" screen on the Multi Rae.
3) Press mode and no at the same time. Use the mode button to scroll through the menu.
4) When the "Change Alarm Limits" screen appears, select Y/+.
5) You will have the option of changing the High alarm, Low alarm, STEL alarm, and the
Average alarm limits.
6) Press N/- to scroll to the Alarm limit that you would like to change.
7) Select Y/+ on the alarm limit that you intend to change.
8) Use the MODE button to scroll from digit to digit and the Y/+ and N/- buttons to select
digits.
9) To save your changes, hold down the MODE button.
Change Real Time Clock
1) Hit MODE when the command Monitor Setup? appears on the screen.
2) Select "Change Real Time Clock?" to adjust the date and time showing on the MultiRae,
then use Y/+ and N/- to adjust the time.
NOTE: ALWAYS do this, and double check it, before you start a datalog.
View or Change Datalog
1) Press MODE and N+/ at the same time. Scroll through the menu by pressing the MODE
button.
2) To view or change the Datalog function, press Y/+ at the "View or Change Datalog?"
screen.
3) The first option will be to "Clear all Data?"
4) Select Y/+ to clear all of the data in the datalog memory.
5) The next option is to "Reset the Peak and Minimum?"
6) When you select Y/+ to "Reset the Peak and Minimum?" the Multi Rae will prompt "Are
you sure?"
7) Select Y/+ to reset your values that you see when scrolling the main menu.
8) The next option is to Enable/Disable datalog? If a * is displayed next to a sensor name,
data will be recorded. Use mode to move from sensor to sensor. An asterisk (*) means
-------
the sensor is enabled; no asterisk means the sensor is disabled. Press Y/+ to select, and
N/- to deselect. To save changes, press MODE until Save? appears. Then press Y/+ to
accept. Otherwise, hold MODE to escape and cancel changes.
NOTE: Do not datalog an instrument that is in diagnostic mode, it will record RAW values.
Always restart first then begin datalog.
Change Backlight
1) You can change the backlight mode by pressing Y/+ at the "Change Backlight Mode?"
screen.
2) To turn on the backlight, hold the N/- button down.
Change Pump Speed
1) To change Pump Speed continue until Change Pump Speed? appears on screen. Press
Y+l or N+/ to change speed different than what it is previously set. Once you determine
which speed you prefer then hold the Y+/to save.
2) Low pump speed- (default) used when operating conditions that are slow
to change, prolongs pump motor life, LEL sensor life and battery run time.
3) High pump speed- use for long lengths of tubing or when rapid changes in input
conditions are expected, such as HazMat response or when used for measuring heavy,
low vapor pressure compounds like jet fuel.
NOTE: Make sure to note it somewhere on an equipment tag when you have changed the
pump speed from a default setting, include your initials and date
NOTE: When using tubing as an extension, we must use Teflon tubing. Tygon tubing
readily absorbs volatiles, especially benzene.
Sensor Configuration
1) Hit MODE and N/+at the same time.
2) Change LEL/VOC Gas Selection?
3) Enable/Disable Sensors?
4) Sensors have assigned sockets. These are identified on the PCB. High bias toxic in
socket1/A.
5) Change PID Lamp Type? This only applies to PID monitors. The PID sensor can utilize
either a 10.6 eV or an 11.7 eV UV. Since each lamp type has a different correction factor
table, it is important to select the correct lamp type.
NOTE: 11.7 lamps have a much shorter lifespan, be aware of the expiration date and leave
Tiffani a note when you mobilize with them.
-------
Using the MultiRAE
1) After recognizing your chemical of concern, look in the technical and application notes
and locate the correction factor for that chemical that corresponds with the lamp in your
MultiRAE
2) When two or more chemicals of concern need to be monitored, a general rule of thumb is
to use the highest correction factor and the chemical with the lowest PEL for action level
purposes.
NOTE: Correction factors are very important, for both the VOC and LEL sensors. Look
through both TN-106 (PID) and TN-156 (LEL).
NOTE: The new NH3 sensors are un-biased. However the NO sensors are still high-bias.
How to clean a lamp
1) Acquire a lamp cleaning kit. Make sure it includes cotton swabs, methanol, tweezers.
Gloves can be found in the ER GO BAG if there are none in the kit.
2) Remove the front cover from the instrument.
3) Remove the metal casing from the PID using the tweezers and wearing gloves. Set it
aside.
4) Using the tweezers carefully remove the top of the PID housing, it is usually fairly secure,
do not use too much force. Set it aside.
5) Carefully remove the lamp from the base, and securely hold it while you swab with cotton
soaked in the methanol. Be careful not to allow cotton fibers to stick to the lamp.
6) Give the lamp a few seconds to dry, then place back into base.
7) Carefully swab the metal screen in the top of the PID housing, and give it a few seconds
to dry before replacing.
8) Replace metal casing. If it appears dirty, swab with methanol also.
9) Replace cover on the instrument.
NOTE: If replacing an expired or faulty lamp, please place the old lamp in box the new
lamp came out of. Mark the box with the serial number and date removed, and return to
Tiffani. It may not have expired yet and be available for replacement.
NOTE: Other than lamp cleaning/replacement or sensor changes, do not manipulate the
other components within the instrument. Red tag the unit and return to Tiffani.
-------
Additional media needed for this equipment: (i.e. calibration gas or
chemcassettes)
MultiRAE technical and application notes; MultiRAE users manual
Calibration gases appropriate to the sensors being used.
Lamp cleaning kit.
Notification Procedures for Equipment Failure (i.e. Rae Systems tech support
number and CTEH contact)
RAE Systems 408.723.4800 CTEH- Equipment Room Manager 801.501.8580
RED TAG inoperable equipment properly, example following SOP
References and Further Assistance
Review Date for this SOP
Nathan Williams 4/12/2011
Attachments
Excerpt from TN-123
Calibration Log example
Red Equipment Tag example
-------
Attachment E
Galson Laboratories SOP for VOCs by OSHA PV-2120
& EPATO-15
-------
CENTER FOR TOXICOLOGY AND ENVIRONMENTAL HEALTH, L L C.
Toxicology Emergency Response Program (June 15, 2011)
STANDARD OPERATING PROCEDURE NO. (1.0)
SUBJECT: 3M 3500_3520 OVM Badge SOP
Description of the SOP. This SOP describes the use of the 3M 3500/3520 Organic Vapor
Monitor (OVM) badge as a passive dosimeter for the collection of analytical worker exposure
data.
Key Personnel with Responsibility to Manage this Operation.
Any environmental scientist or IH technician responsible for the collection of real-time worker
exposure data using the 3M 3500/3520 OVM badge.
3M 3500/3520 OVM Badge Preparation Instructions
1. Calibration
a) Neither calibration, nor flow calibration is required.
2. OVM Badge Preparation
NOTE: While handling un-exposed and/or exposed OVM badges, please consider using
proper media handling techniques. Sample handling should take place in a location,
removed from any areas of contamination or potential sources of cross-contamination.
The researcher should use clean/covered hands, surfaces, and tools when working with
OVM badges.
a) Inspect the badge container to identify potential tampering or un-intentional disturbances
to the OVM badge prior to use. An un-used OVM badge should be housed in a sealed
aluminum canister as sent from the manufacturer or laboratory.
b) Remove the badge from the canister only at the time of sample deployment.
3. OVM Badge Deployment
a) Place the OVM badge on the worker's lapel or clothing within the breathing zone (i.e.
within 10 inches from the nose or mouth as per NIOSH recommendations).
b) Ensure that the OVM badge is located on the outside of any clothing, vest, or other
material that may block the inlet from drawing air from the worker's breathing zone.
c) Instruct the worker to avoid covering the OVM badge with clothing, vests, PPE, etc...
d) Instruct the worker to avoid introducing cross-contamination across the surface of the
OVM badge (i.e. bug spray, cologne, hand sanitizer, etc...)
Sampling Data Sheet Instructions
1. Use an appropriate field data sheet prior to deploying the OVM badge. The data sheet should
capture the following information:
a) CTEH Project Number
b) Sample Identification Number
-------
c) Worker's Full Name, Contact Information, and Company Information,
d) Worker's Job Task,
e) Worker's Work Site Location Information,
f) Sample Information for Co-located samples (i.e. 3M 3500 badge information, sample ID,
etc...),
g) Start Date and Time,
h) Stop Date and Time,
i) Worker's Smoking Habit,
j) Other Potential Cross-Contamination Sources (i.e. bug spray, cologne, hand sanitizer
etc...)
k) Sampler's Name and Contact Information
Post-Sampling OVM Badge Collection and Data Processing
1. At the end of the worker's job task or work shift:
a) collect the exposed OVM badge from the worker,
b) remove the OVM badge's outer ring and permeation membrane,
c) and, place the clear plastic lid over the OVM badge. Ensure that the clear plastic lid
closely firmly.
2. Place the exposed, sealed OVM badge back into the original canister and complete the
canister's label with the appropriate sample information.
3. Conduct the post-sample interview with the sampled worker to identify problems and/or
potential cross contamination to the sample. This information should be entered onto the
Sampling Data Sheet.
4. Document the stop time and date of the sampling event.
5. Place the canister and corresponding OVM badge with the appropriate sample lot and prepare
COC for shipment to the laboratory.
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GALSON LABORATORIES STANDARD OPERATING PROCEDURE
SUBJECT: WHOLE AIR AND SUMMA CAN REGULATOR CALIBRATION AND
CLEANING
1.0 PURPOSE
This SOP describes the calibration and cleaning procedure for flow controllers and the
regulators used to collect samples in 400cc, 450cc, lOOOcc MiniCans or Summa Cans.
2.0 RESPONSIBILITIES
2.1 All technicians performing this procedure are required to read and understand the
SOP as written.
2.2 The Section Supervisor is required to read and understand the SOP as written in
addition to assuming responsibility for the training and continued education of
technicians performing this procedure.
3.0 DEFINITIONS
3.1 SOP - Standard Operation Procedure
3.2 PSI: pounds/sq. inch
3.3 QC: Quality Control
3.4 "Hg: inches of Mercury
3.5 UHP: Ultra High Purity (Nitrogen Grade 4.8 or higher)
3.6 Psig: pounds/sq. inch gauge
3.7 Mini Can: metal canister with valve
3.8 Summa Can: Round Metal Canister with Valve
3.9 Flow controller or regulator: mechanism used to fill Mini can
3.10 LP: Low Pressure
SOP ID:
IN-AIRREG
COPYRIGHT
AUTHOR: Anthony Marchetti
SECTION SUPERVISOR: Gale S. Peterson
QA OFFICER: Wendy Ferro
LABORATORY DIRECTOR: MaryUnangst
4.0 METHOD SUMMARY
4.1 The Mini Can regulator is a high purity flow regulation system used to fill canisters
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(Mini Cans or Summa Cans) at a constant rate from vacuum to within 1 psi of
atmospheric pressure, without requiring power.
4.2 The regulator consists of two main parts; the vacuum controller body and an
interchangeable sapphire restrictor. The vacuum controller maintains a -0.3 to -1 psi
atmospheric pressure regardless of what the vacuum is on the outlet. By changing the
value of the restrictor on the inlet, different flow rates (corresponding to canister fill
times) can be achieved. For any given restrictor, the flow rate can only be changed by
a factor of 2-3x. This is done by adjusting the hex head set screw on the center of the
vacuum controller body. Refer to MS-FORM-1 for restrictor settings for various
applications.
4.3 In the laboratory, regulators are cleaned between each use and set to the flow rate
requested by the client.
4.4 Canisters are leak-checked in the following manner: when can-cleaning has been
completed, each canister is put under full vacuum and the vacuum reading (usually
30" of Mercury) is recorded in the Can-Cleaning Logbook along with the date/time
and analyst's initials. The prep group will check and record the vacuum reading for
each canister before shipping to a client and place a full vacuum sticker along with a
date/sample label. Acceptance criteria are +/- 2" of Hg variance for a >= 24 hour leak
check.
5.0 INTERFERENCES
Not Applicable
6.0 SAFETY
6.1 Safety glasses with side shields are required when working in the laboratory.
7.0 MATERIALS AND APPARATUS
7.1 UHP nitrogen for the cleaning gas.
7.2 Regulators, with a selection of #2 through #5 restrictors. Restek requlators have a #8
restrictor which are comparable to a #5 restrictor.
7.3 Alicat Scientific flow meters: Model #01-39-20035.01 and Model #01-03-200020.
7.4 1/2" and 9/16" open end wrenches and a 1/8" hex key.
8.0 REAGENTS AND STANDARDS
8.1 Nitrogen @ 99.9999% purity (UHP N2)
9.0 PROCEDURE
9.1 For Flow Settings
9.1.1 Select a flow controller with the correct restrictor code. See MS-FORM-1 for
guidelines.
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9.1.2 Ensure all possible leak points are tightened prior to calibration.
9.1.3 The Regulator Calibration Data Sheet located in P:\Prep GroupYPump
Loan\Approved Forms\ Regulator Cal Sheet and update to reflect calibration results.
9.1.4 Connect the appropriate Alicat Scientific flow calibrator to the inlet of the
regulator. Alicat Model #01-39-20035.01 is used with restrictors coded 2 and 3, Model
#01-03-20020 is used with restrictors coded 4 and 5. Verify the gauge is functioning.
9.1.5 Connect an evacuated calibration canister that is between 10 & 30 inches of Hg
(gauge) to the outlet of the flow controller body to start flow.
9.1.6 Allow about 1 minute for the flow to equilibrate, then note the inches of Hg
regulator is reading. Visually observe regulator dial for 30 seconds to verify the
regulator is not leaking (i.e. the inches of Hg is dropping very quickly). Recheck what
regulator is reading when the regulator is calibrated, prior to removing from Alicat, to
ensure it has not leaked. If there is a drastic drop in pressure, place regulator in repair
bin.
9.1.7 Verify that the Alicat is reading 0 when the regulator is removed. If it is not
reading 0, press the reset button and repeat 9.1.3 - 9.1.5. Change the battery if
abnormal fluctuation is noticed on the display of the Alicat during calibration. The
battery of the Alicat should be changed every six months. Attach a label with the date
of battery change and check that it is not past six months before each use. Replace
the label with the correct date anytime the battery is changed.
9.1.8 Remove the hex screw cover located in the center of the regulator body using a
1/8" hex key.
9.1.9 Adjust the set screw using the hex wrench so that the flows agree with MS-
FORM-1 (Figure 1), enter this data into the cells that correspond to the regulator you
are calibrating. Turning the screw clockwise will result in a lower flow rate; turning the
screw counterclockwise raises the flow rate. The adjustment must be done slowly (1/4
of full turn intervals), allowing the regulator body adequate time to "equalize" with any
adjustments made. Add a label with the appropriate hours on it for what the regulator
was calibrated to. Print out "Regulator Calibration Data Sheef'and include in
paperwork that goes to client.
9.1.10 CAUTION: If 1-2 turns do not result in a change of flow rate, STOP and check
the flow calibrator for proper operation or blockages in the inlet plenum. The
internal diaphragm of the regulator may be damaged by over tightening. If flow
readings are unsteady or erratic, select another regulator.
9.2 PROCEDURE FOR CLEANING
9.2.1 Remove all tape or labels added to the regulators. Be sure not to remove the
barcode label or the label containing the serial number.
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9.2.2 Remove back flush port screw from the body of the regulator. This is located to
the right center of the diaphragm housing, it is a 1/8" hex screw.
9.2.3 Remove the restrictor and particulate filter located on the inlet side of the
regulator.
9.2.4 The regulator can be cleaned, by connecting LP UHP N2 hose at 5-10 psi at
the flush port and back flush for about 20 seconds.
9.2.5 The restrictors can be cleaned by using UHP N2 at 30-40 psig to remove any
solid particulate caught in the sapphire orifice (use the dilution manifold). Be
sure to connect the restrictors with the flat side (inlet side) facing out so any
blockages will be blown out.
9.2.6 Clean the particulate filter with UHP N2 by same method as above. Ensuring
positive air flow through the filter.
9.2.7 Reassemble the unit taking great care not to over tighten any screws. Check the
gap between the restrictor and the ferrule nut using the nogo gap gauge at
the 1/4"/ 6mm setting.
9.2.8 Grab regulators must also be flushed briefly with UHP N2 to ensure cleanliness
using the dilution manifold.
10.0 DOCUMENTATION
Not Applicable
11.0 CALCULATIONS
Not Applicable
12.0 QUALITY CONTROL CHECKS AND CRITERIA
Not Applicable
13.0 CORRECTIVE ACTION PLAN
Not Applicable
14.0 WASTE DISPOSAL
Not Applicable
15.0 REFERENCES
15.1 MS-FORM-1
16.0 METHOD MODIFICATIONS
Not Applicable
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Page 5 of 6
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6/22/11
Approval By: wferro Expire Date:6/29/2011
Minican
Setting Guidelines
Minican Setting Guidelines
Regulator
Regulator
400 cc Minican
6 Liter Canister
2
Time (minutes)
5
10
15
30
3 Time (hours) 24
Flow (cc/minute)
72
36
24
72
Flow (cc/minute) 3.8
3
Time (minutes)
15
30
45
60
90
120
4 Time (hours) 24
Flow (cc/minute)
24
12
8
6
4
3
Flow (cc/minute) 3.75
4
Time (hours)
1
1.5
2
3
4**
5 Time (days) 7
Flow (cc/minute)
6
4
3
2
1.5
Flow (cc/minute) 0.54
5
Time (hours)
4**
6
8
10
12
14 16
Flow (cc/minute)
1.5
1
0.75
0.6
0.5
0.43 0.37
450 cc Minican
2
Time (minutes)
5
10
15
30
Note: Minimum \racuum allowable for
Flow (cc/minute)
81
40.5
27
13.5
acceptable minican/canister is -28"Hg
3
Time (minutes)
15
30
45
60
90
120
Note: Flow rate as read from the
Flow (cc/minute)
27
13.5
9
6.8
4.5
3.4
Alicat Scientific flow calibrator
4
Time (hours)
1
1.5
2
3
4**
Note: Regulator setting determined
Flow (cc/minute)
6.75
4.5
3.38
2.25
1.69
by using this formula
5
Time (hours)
4**
6
8
10
12
14 16
Taraet Volume fee}
Total Time (minutes)
Flow (cc/minute)
1.69
1.13
0.84
0.68
0.56
0.48 0.42
1 Liter Minican
4
Time (hours)
1
2
3
4
5
6
Note: When using a 1 Liter can for under
Flow (cc/minute)
15
7.5
5
3.75
3
2.5
8 hours you need to use a #4 restrictor.
5
Time (hours)
8
12
16
18
24
"Preferable to use #4
Flow (cc/minute)
1.87
1.25
0.94
0.83
0.62
restrictor for 4 hour setting
(Figure 1)
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GALSON LABORATORIES STANDARD OPERATING PROCEDURE
SUBJECT: VOLATILE ORGANIC COMPOUNDS BY OSHA PV2120 & EPA TO-15
1.0 PURPOSE
1.1 This SOP describes the procedure for determining contaminants in whole air samples
collected in a fused silica-lined stainless steel canister (following OSHA method
PV2120 and Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air (Method TO-15). This method utilizes GC/MS for the
determination of a wide range of volatile and semi-volatile organic compounds (as listed
in Table 1).
2.0 RESPONSIBILITIES
2.1 All GC/MS analysts performing this method are required to read and understand the
method as written in OSHA PV2120, and are required to meet all QC requirements (as
described in EPA TO-15) before attempting analysis of samples.
2.2 The section supervisor is required to read and understand the method as written, but is
also responsible for the training and continued education of technicians performing this
2.3 The section supervisor is required to review reports and packages to ensure that all data
are valid prior to client receipt.
3.0 DEFINITIONS
3.1 GC/MS: Gas Chromatography/Mass Spectrometry
3.2 Capillary: Analytical column with an internal diameter less than or equal to 0.32 mm
3.3 EICP: Extracted ion current profile: Plot of ion abundance vs. GC retention time for a
single characteristic mass (amu)/charge ratio.
3.4 AMU: Atomic Mass Unit
3.5 ppbv: part per billion by volume for component concentration in the gas phase.
3.6 Mini Can: Canisters ranging from 400mL to lOOOmL in volume; these are associated
with an injection volume of lOOmL.
3.7 Summa Canisters: Canisters with a 6L volume; these are associated with an injection
volumes of 500 to 1000-cc.
SOP ID:
IN-VOCS
COPYRIGHT
AUTHOR: Justin Palmer/ Rob Wilson
SECTION SUPERVISOR: Justin Palmer
QA OFFICER: Wendy Ferro
LABORATORY DIRECTOR: MaryUnangst
method.
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3.8 SCAN: Normal MS acquisition mode where mass ranges from 35 to 300 amu are
scanned to produce a Total Ion Chromatogram.
3.9 SIM: Selective Ion Mode; only scans certain ions per sample to increase sensitivity.
Used for only certain projects that require low level analysis.
4.0 METHOD SUMMARY
4.1 The sample is prepared for analysis by pre-concentration, which removes potential
interference and dries the sample. After the pre-concentration and drying steps are
completed, the analytes are cryo-focused onto the head of the GC column via reduced
temperature trapping, followed by rapid thermal desorption.
4.2 Separation of the analytes is achieved by temperature programming of the GC oven.
4.3 The eluent from the capillary column is introduced directly to the mass spectrometer,
which is operated in the electron impact mode. Identification of target analytes is
accomplished by comparing sample mass spectra with reference spectra generated from
purchased standards on the GC/MS system used to analyze the samples. Quantitation is
achieved using the internal standard technique. The response of a selected quantitation
ion for each analyte relative to the quantitation ion of the designated internal standard
(relative response factor, or RRF) is determined over a minimum five-point calibration
range.
5.0 INTERFERENCES
5.1 Raw GC/MS data from all samples and blanks must be evaluated for interference.
Determine if the source of interference is in the sample introduction system. If so, take
corrective action to eliminate the problem.
5.2 Contamination by carryover can occur whenever high-concentration and low-
concentration samples are sequentially analyzed. Each auto-sampler port is flushed with
nitrogen after use (prior to set-up of the next batch of samples).
5.3 Interferences are minimal by GC/MS as this type of detector allows the determination if
compounds are co-eluting in the chromatographic system. Quantification can be done
on alternate ions so interferences are eliminated in most cases. In other instances, a
dilution may be performed to allow better separation or results may be considered
estimated if the interference cannot be removed.
6.0 SAFETY
6.1 Most volatile compounds are considered hazardous. Always wear gloves and a lab coat
when handling stock standards.
6.2 Safety glasses with side-shields are required whenever working in the laboratory.
6.3 It is very important that special precaution be used when working with liquid nitrogen,
as it can cause serious burns.
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6.4 Be sure that only radiation worker trained personnel handle Mini Cans that have been
screened for radiation. These cans will have an orange dot on them.
7.0 MATERIALS AND APPARATUS
7.1 Agilent (previously Hewlett Packard (HP)- may be used interchangeably) 5890, 6890, or
7890 Series GC, in conjunction with an HP model 5972, 5973, or 5975 mass
spectrometer (capable of scanning from 35 to 300 amu every 1-second or less using 70
volts (nominal) electron energy in the electron impact ionization mode).
7.2 Entech 7032, 7032L, 7032A, or 7016CA autosampler models with the Entech 7100 or
7100A three stage Preconcentrator.
7.2.1 Microscale Purge and Trap (MPT) analysis is performed by utilizing a glass
bead trap in module 1 and a Tenax sorbent trap in module 2. Module 3 contains
an empty trap.
7.2.2 Cold Trap Dehydration analysis (CTD) employs an empty trap in module 1 and a
Tenax trap in module 2. Module 3 contains an empty trap.
7.3 Analytical Chromatography column: 0.32mm ID x 60m length silicone-coated capillary
column with a 1 um film thickness - Restek RTX-1 or equivalent.
7.4 GC/MS Interface - The GC column is directly coupled to the mass spectrometer ion
source. Acceptable tuning and calibration performance must be demonstrated on a daily
basis.
7.5 Data System - The data system used is the HP Chemstation G1701BA with (at
minimum) Revision B.01.00 software package for the HP5972, 5973, or 5975 MS. This
system allows continuous acquisition and storage on machine-readable media of all
mass spectra obtained throughout the duration of the chromatographic program. The
software allows for searching any GC/MS data file for ions of a specific mass, and
plotting such ion abundance versus time or scan number. This type of plot is defined as
an Extracted Ion Current Profile. The software allows integration of the abundance in
any EICP between specified time or scan number limits. The NIST 129K version mass
spectral library is being used for a reference library.
8.0 REAGENTS AND STANDARDS
8.1 Helium @ 99.9999% purity
8.2 Liquid nitrogen
8.3 Stock standards
8.3.1 Stock standard solutions are purchased as certified solutions.
8.3.1.1 TO-15 Subset standard is purchased from Spectra gases
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8.3.1.1.1 (Catalogue # ENT15-25S-6A-1M) or Scott gases (item#
0104AZ00025).
8.3.1.2 TO-14 standard is purchased from Spectra gases
8.3.1.2.1 (Catalogue # ENT14/39S/6A1M) or Scott gases (item#
01049Z90001).
8.3.1.3 Ethylene oxide standard is purchased from Spectra gases
8.3.1.3.1 (ETOX/CGA3501M) or Scott gases (item# 08020001310PAL).
8.3.1.4 4-Phenylcyclohexene standard is purchased from Scott gases (item#
0104P200046).
8.3.1.5 TO-15100-ppbv 75 compound standard
8.3.1.6 TO-1510-ppbvproject specific compound list
8.3.1.6.1 Used for ultra low level SIM analysis.
8.3.2 Stock standard solutions must be stored at room temperature, or as
recommended by the manufacturer.
8.3.3 Stock standard solutions must be replaced after 1 year, or sooner depending on
manufacturer's expiration date.
8.4 Internal Standard and Surrogate
8.4.1 The internal standards are Bromochloromethane, 1,4-Difluorobenzene, and
Chlorobenzene-d5.
8.4.2 The surrogate is Bromofluorobenzene.
8.4.3 Each sample undergoing analysis, as well as all calibration standards must be
spiked with 50-ppbv of each internal standard and surrogate.
8.4.4 A certified stock internal and surrogate standard mixture must be purchased
every 12 months (or sooner, if degradation is observed). (Spectra Gases, TO-14
IS/Surr. mix, catalogue # ENT14ITS-6A-1M) or (Scott Gases, TO-14 IS/Surr.
Mix, P/N 24087828)
8.4.5 Store the internal/surrogate standard at room temperature.
8.5 GC/MS Tuning standard
8.5.1 In a 6L Summa canister, prepare a 100-ppbv standard of Bromofluorobenzene
(BFB). This standard contains the internal standard compounds as well.
8.5.2 The tuning standard is stored at room temperature when not in use. When using
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premixed certified gases, store according to the manufacturer's documented
holding time and storage temperature recommendations.
8.6 Intermediate (working) standards
8.6.1 A working standard of the target compounds is prepared at 5-ppbv, 25-ppbv,
and 100-ppbv for both lOOcc and 500cc injection methods. This is used to
generate the instrument calibration curve. The working standard must contain all
of the analytes of interest. Target compound working standards expire one
month after preparation.
8.6.2 The internal / surrogate working standard is prepared at 100 ppbv. This is also
used as the tuning standard. Working internal standards expire two months from
preparation date.
8.7 Calibration standards
8.7.1 Calibration standards must be analyzed at a minimum of five different
concentrations. One of the calibration standards must correspond to a sample
concentration at or below that necessary to meet the data quality objectives of
the project. The remaining standards must correspond to the range of
concentrations expected to be found in the actual samples. The typical
calibration curve range for TO 15 (Minican) list is 5-ppbv to 150-ppbv for most
analytes. TO-15 (6L Summa can) list is from 1-ppbv to 30-ppbv. TO-15 low
level list is from 0.2-ppbv to 30-ppbv. TO-15 SIM is dependent on project
specific reporting limits. Ethylene Oxide ranges from 20-400-ppbv and 4-
Phenylcyclohexene ranges from 1-20-ppbv.
8.7.2 Internal standards and surrogate are added to all calibration standards during
analysis.
9.0 PROCEDURES
9.1 Sample collection, preservation and handling
9.1.1 Whole air samples are collected in 400cc or lOOOcc fused silica lined stainless
steel canisters (Mini Cans) or 6-liter Summa canisters that are stored at room
temperature until analysis. Sample stability is unknown, therefore samples
should be analyzed as soon as possible.
9.2 Sample Preparation
9.2.1 Once the GCMS group has received the samples, the vacuum in the can is
measured to verify the amount of sample collected. If the vacuum reading is > 5
inches of Hg, the project manager must notify the customer. This can be caused
by either improper sample collection or a malfunction of the regulator. A full
canister will read < 5 inches of Mercury. There should be a partial vacuum
remaining (@1 to <5 inches of Mercury) to evidence that a full sampling
event took place. No measurable vacuum may be an indication that the
canister was not collecting the sample over the full duration of the sampling
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period or that the canister was leaking during sampling. The customer must
be notified if there is no measurable vacuum. Pump group will set regulators
to leave a partial vacuum for the specified sampling time (8 hrs, 24 hrs, or
week). A volume of Nitrogen can be added to bring the volume above 5"
Mercury with the use of the Entech 7100 sample diluter. The initial and final
pressure readings must be recorded in the can dilution logbook. The dilution
factor is calculate according to the equation:
3 Analytical Procedure
9.3.1 Instrument Maintenance
9.3.1.1 Appropriate instrument maintenance must be performed as necessary prior
to initial calibration. Indications of the need for maintenance include poor
peak shape, inadequate sensitivity, and inability to pass BFB tune. Steps that
may be required to address these problems include replacing one or both
traps in the Entech 7100, baking the transfer line and GC column, trimming
or replacing the column, and/or cleaning the ion source.
9.3.2 Instrument conditions for TO-15 regular list and Hydrocarbon analysis:
DF = PSLA
PSIAi
Where PSIAf = final pressure reading
PSIAi = initial pressure reading
Detection limits will be raised proportionately.
The following GC/MS instrument conditions are used:
Injector temperature:
Injection volume:
Carrier gas:
Mass range:
Scan time:
Initial temperature:
Temperature program
Final temperature:
35-300 amu
2.82 scan/sec
34 °C, hold for 5.5 minutes
increase at 5 °C /minute to 70°C, then increase
at 15°C /minute to 170°C, then increase at 25°C/
minute to 240°C, holding there for 1-10
minutes.
240 °C, hold 1-10 minutes after Hexachloro-
1,3-Butadiene elutes.
150 °C
lOOcc
Helium at 20 cm/sec
9.3.3 Instrument conditions for Ethylene Oxide analysis:
Initial temperature:
Temperature program
Final temperature:
Injector temperature:
Injection volume:
Mass range:
28-250 for Ethylene oxide then at 6.9 min. 29-
250 amu
34 °C, hold for 5.5 minutes,
increase at 15 °C /minute to
240 °C, hold 1-10 minutes
150 °C
lOOcc
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Carrier gas: Helium at 20 cm/sec
9.3.4 Instrument conditions for 4-Phenylcyclohexene analysis:
Final temperature:
Injector temperature:
Injection volume:
Carrier gas:
Mass range:
Initial temperature:
Temperature program
SIM Mode (4PCH 74, 108, 158 amu)
50 °C
increase at 10 °C /minute to 200°C, then
increase at 25 °C /minute.
250 °C, hold 1-10 minutes.
150 °C
lOOcc
Helium at 20 cm/sec
9.4 Instrument Calibration
9.4.1 Instrument Performance Check: At the beginning of a 24-hour analysis sequence
it is necessary to show that the GC/MS system meets the instrument
performance criteria. This is accomplished by the analysis of a 50-ppbv injection
of BFB to demonstrate correct mass calibration, mass resolution, and mass
transmission. Any injection containing 50-ppbv of BFB can be used for this
purpose.
9.4.1.1 BFB must meet the criteria listed in 9.4.1.2 before standards and samples
are analyzed. An acceptable BFB tune is demonstrated once at the
beginning of each 24-hour period during which samples or standards are
analyzed. The 24-hour period begins with the injection time of the BFB and
ends after 24 hours according to the system clock. The following abundance
criteria are required to establish instrument tune compliance:
9.4.1.2 Tune acceptance criteria:
Mass | Ion Abundance Criteria
50 8.0-40.0 percent of mass 95
75 30.0-66.0 percent of mass 95
95 base peak, 100 percent relative abundance
96 5.0-9.0 percent of mass 95
173 Less than 2.0 percent of mass 174
174 50.0 - 120 percent of mass 95
175 4.0-9.0 percent of mass 174
176 Greater than 93.0 percent but less than 101.0 percent of mass 174
177 5.0-9.0 percent of mass 176
9.4.1.3 For demonstrating an acceptable tune, the mass spectrum of BFB must be
obtained. This is can be performed by the HP/Agilent Chemstation
Software using the Auto-find BFB function. This function works as follows:
three scans are taken (the peak apex scan, and the scans immediately
preceding and following the apex) and then averaged. Background
subtraction is required, and must be accomplished using a single scan
acquired no more than 20 scans prior to the elution of BFB. The background
subtraction is designed to eliminate column bleed and instrument
background ions. Alternately, the BFB spectrum can be obtained/performed
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manually.
9.4.2 Calibration standards are analyzed concurrently or once BFB meets acceptance
criteria.
9.4.3 Initial Calibration
9.4.3.1 For use with lOOcc-sample injection volume T015 analysis (i.e. 400-1000cc
canisters): A minimum 5-point calibration curve must be analyzed prior to
sample analysis. The internal standards must be added at 50-ppbv to each
curve concentration level. Analyze to determine the instrument sensitivity
and linearity of the GC/MS response for the target compounds. Analyze the
following volumes from the 25 and/or 50-ppbv working standard canister to
obtain the desired concentration. Other standard levels can be used as
needed to meet calibration range criteria. A 5-ppbv standard is utilized
(100-cc injection volume) for the 5-ppbv level on some instruments. A
blank should be run in-between the three highest standards (for example,
between the 100 and 150-ppbv standards).
Standard Level
25-ppbv working standard 50-ppbv working standard
5-ppbv standard
20-ppbv standard
50-ppbv standard
100-ppbv standard
150-ppbv standard
200-ppbv standard
Use 20cc
Use 80cc
Use 200cc
Use 400cc
Use 600cc
N/A
Use lOcc
Use 40cc
UselOOcc
Use 200cc
Use 300cc
Use 400cc
9.4.3.2 For use with 500cc-sample injection volume analysis (i.e. 6-liter canisters):
A minimum 5-point calibration curve must be analyzed prior to sample
analysis. The internal standards must be added at 10-ppbv for each curve
concentration level. Analyze to determine the instrument sensitivity and
linearity of the GC/MS response for the target compounds. Analyze the
following volumes from the 25-ppbv working standard canister to obtain the
desired concentration. Other standard levels can be used as needed to meet
calibration range criteria. Blanks should be run in-between the three highest
standards (for example, between the 20 & 30-ppbv standards).
Standard Level
1-ppbv working
5-ppbv working
25-ppbv working
standard
standard
standard
0.2-ppbv standard
1-ppbv standard
5-ppbv standard
10-ppbv standard
20-ppbv standard
30-ppbv standard
Use lOOcc
N/A
N/A
N/A
N/A
N/A
Use 500cc
Use lOOcc
N/A
N/A
N/A
N/A
N/A
Use 20cc
UselOOcc
Use 200cc
Use 400cc
Use 600cc
9.4.3.3 For use with lOOOcc-sample injection volume analysis (6 liter SIM): A
minimum 5-point calibration curve must be analyzed prior to sample
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analysis. The internal standards must be added at midpoint for each
curve concentration level Analyze to determine the instrument sensitivity
and linearity of the GC/MS response for the target compounds. Analyze
the following volumes from either 0.05-ppbv working standard canister or
1-ppbv working standard canister to obtain the desired concentration.
Other standard levels can be used as needed to meet calibration range
criteria. Blanks should be run in-between the highest standards (for
example, between the 0.4 & 0.6-ppbv standards) and blanks should be run
after the calibration to clean out the system.
Standard Level 0.05-ppbv working standard 1-ppbv working standard
0.005-ppbv standard Use lOOcc N/A
0.025-ppbv standard Use 500cc N/A
0.1-ppbv standard N/A Use lOOcc
0.2-ppbv standard N/A Use 200cc
0.4-ppbv standard N/A Use 400cc
0.6-ppbv standard N/A Use 600cc
9.4.3.4 Calculate the relative response factor for each compound using the
following equation:
RRF = Ax * Cjs
A C
Where:
Ax = Area of the characteristic quant ion for the compound to be measured (see
Table 1 and 2).
Ais = Area of the characteristic quant ion for the designated internal standard (see
Table 1).
C;s = Concentration of the internal standard (ppbv).
Cx = Concentration of the compound to be measured (ppbv).
9.4.3.5 Calculate the average RRF for each analyte in the curve.
9.4.3.6 Calculate the % Relative Standard Deviation (%RSD) of RRF values for the
initial calibration curve using the following equation:
%RSD = Standard Deviation ("n-1) * 100
Average RRF
9.4.3.7 Calculate the average RT for each internal standard over the initial
calibration range.
9.4.4 Calibration acceptance criteria
9.4.4.1 The BFB must meet the specified criteria
9.4.4.2 The %RSD is calculated and must be less than or equal to 30% for all
compounds. This criterion must be met for the initial calibration to be
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valid. However, an exception can be made for up to 2 compounds that may
exceed 30% RSD, but the RSD for these compounds must be <40.0%.
Refer to QC-SOP-12 (current revision) for calibration level rejection
criteria.
Evaluation of IS retention time: The retention time shift for each of the
internal standards at each calibration level must be within 20s of the mean
retention time over the initial calibration range.
Evaluation of target compound retention time: The relative retention time
(RRT) of each target analyte in each calibration level must be within 0.06
RRT units of the mean RRT for that compound
9.5 Calibration verification
9.5.1 Instrument Performance Check: Prior to sample analysis, a 10/50-ppbv
injection of BFB must meet the criteria listed in 9.4.1.2.
9.5.2 Calibration verification standard: The initial calibration must be verified on a
daily basis prior to the analysis of any samples. Analyze a mid-level (10/50-
ppbv)-calibration standard at the beginning and end of each 24-hour working
period after meeting BFB tune criteria.
9.5.2.1 Calculate the % Difference between the average response factor from the
calibration curve and the response factor from the daily standard using the
equation below:
% Difference = IRRF, - RRF J * 100
RRF;
Where:
RRF; = Average relative response factor from initial calibration.
RRFC = Relative response factor from the current calibration check
standard.
The %D in the daily standard must be +/-30% for all compounds.
The %D report is monitored daily to evaluate instrument performance and watch
for trends that might indicate the need for corrective action.
9.6 Method Blank
9.6.1 A Method blank is a volume of a clean reference matrix (Nitrogen @ 99.9999%
purity) carried through the entire analytical procedure. The volume of the
method blank must be approximately equal to the volume of the associated
samples.
9.7 Laboratory Control Sample and Duplicate (LCS/LCSD)
9.4.4.3
9.4.4.4
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9.7.1 A laboratory control sample and duplicate (consisting of a representative list of
target analytes prepared near the mid-level of the calibration curve) are analyzed
daily. The LCS/LCSD are spiked into Mini Cans or 6 liter canisters and are
analyzed in the same manner as client samples. The LCS/LCSD standard must
be from a separate source than that of the calibration standards. Sub-sampling
for an LCS or LCSD from a 6 liter standard stock canister requires the 6 liter
canister to be > or = 10 psig to minimize any sub-sampling biases for the wide
variety of volatile compounds analyzed by this method.
9.8 Detection Limit Standard (DLS)
9.8.1 The lower limit of quantitation is verified daily by the analysis of a standard at
the detection limit (5-ppbv for most compounds in Minican, 0.2-ppbv or 1-ppbv
for 6 liter) in the TO 15 list analysis. The lower limit of quantitation for SIM
analysis will depend on client specifications and targets. Recovery of all
compounds with the DLS should be within the range of 60-140%. The Ethylene
Oxide DLS is analyzed at 20-ppbv and the 4-Phenylcyclohexene DLS is at 1-
ppbv (limits are also 60-140%).
9.9 Sample analysis
9.9.1 Once the instrument check and calibration verification standards have passed the
acceptance criteria, samples may be analyzed.
9.9.2 Add 50cc of the 100-ppbv internal standard/surrogate mixture (for a level of 50-
ppbv for a lOOcc-sample injection and 10-ppbv for a 500cc-sample injection) to
the sample extract obtained from the sample mini-canister.
9.9.3 Analyze the sample on the GC/MS system using the same operating conditions
that were used for the calibration.
9.9.4 If the concentration of any target analyte in the sample exceeds the initial
calibration range of the GC/MS system, the sample must be diluted and
reanalyzed.
9.9.4.1 Dilutions can be automated by using the Entech 7100 system. However, the
smallest sample size that can be analyzed reliably is lOcc. If greater than a
10X dilution is needed on the can, the analyst must pressurize the canister
with nitrogen to further dilute the sample. The pressurization factor is
multiplied by the instrument dilution to obtain the total dilution factor:
Total Df = P„a final x lOOcc x (split factor for loop injector, if used)
PSia initial inj vol
Once the canister is pressurized above atmospheric pressure, or 14.7 Ps;a, the Entech
7032 loop injector may be used to withdraw a 1-cc injection volume. Automated
splitting of the sample stream can further dilute this volume up to a factor of lOx.
If the sample is to be reanalyzed via normal injection, it must be vented to ambient
pressure by depressing the quick-connect pin on the Mini Can.
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9.10 Qualitative analysis
9.10.1 Identification of Target Compounds
The qualitative identification of compounds is based on retention time and
comparison of the sample spectrum with characteristic ions in a reference mass
spectrum. The characteristic ions from the reference mass spectrum are defined
as the three ions of greatest relative intensity, or any ions over 30% relative
intensity, if less than three such ions occur in the reference spectrum. The list
of characteristic ions for each analyte is presented in Table 1. Target
compounds are positively identified when the following criteria are met:
9.10.1.1 The EICPs of the characteristic ions of an analyte must maximize within
one scan of each other.
9.10.1.2 The RRT of the sample component is within +/- 0.06 RRT units of the
RRT of the standard component.
9.10.1.3 The relative intensities of the characteristic ions in the sample analyte
must agree within 30 percent of the relative intensities of these ions in the
reference spectrum from the most recent calibration verification standard.
The analyst must account for deviations from this criterion such as in the
case of interference/co-elution.
9.10.1.4 Structural isomers that produce very similar mass spectra should be
identified as individual isomers if they have sufficiently different GC
retention times. Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25 percent of the sum of the
two peak heights. Otherwise, structural isomers are identified as isomeric
pairs (for example, m- & p-xylene).
9.10.1.5 Identification is hampered when sample components are not resolved
chromatographically and produce mass spectra containing ions contributed
by more than one analyte. When gas chromatographic peaks obviously
represent more than one sample component, appropriate selection of
analyte spectra and background spectra is important. When analytes
coelute the identification criteria can be met, but each analyte spectrum
will contain extraneous ions contributed by the coeluting compound.
9.10.2 Identification of Non-Target Compounds
For samples containing components not associated with the calibration
standards, a library search may be made for the purpose of tentative
identification. Up to 20 organic compounds with greatest concentration
excluding surrogate and internal standards will be identified and reported.
Non-Target compounds identification is not possible in SIM analysis.
9.10.2.1 Major ions in the reference spectrum (ions greater than 10 percent of the
most abundant ion) should be present in the sample spectrum.
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9.10.2.2 The relative intensities of the major ions should agree within +/-20
percent. For example: an ion with an absolute abundance of 50 percent in
the standard spectrum must be between 30 and 70 percent in the
corresponding sample spectrum.
9.10.2.3 Molecular ions present in the reference spectrum should be present in the
sample spectrum.
9.11 Quantitative identification
9.11.1 Once a target compound has been identified, the quantitation of that compound
is based on the total abundance, or EICP integration area, of the primary
characteristic ion.
9.11.2 The concentration of a compound in the sample is determined using the mean
relative response factor determined from the initial calibration.
9.11.3 Concentration is calculated from the equation:
ppbv = (AxYIsYDf)
(Ais)(RRFi)
Where: Ax = Area of the compound characteristic ion in the sample.
Ais = Area of the characteristic ion for the corresponding internal
standard.
Is = Concentration of internal standard in ppbv
RRF; = Mean relative response factor (from initial calibration) for the
compound being measured.
Df= Dilution factor
9.11.4. In all instances where the quantitation report has been edited, or where manual
integration or quantitation has been performed, the GC/MS operator must
identify edits or manual procedures by initialing and dating the changes made
to the report. The data system flags a manual integration on the quantitation
report by placing the symbol "m" next to the area. The analyst who performed
the integration should initial and date this flag.
9.11.5 Samples that contain target analytes above the linear range of the curve must
be diluted to bring the analytes within the curve range. If a dilution was
initially performed and no target analytes are detected above the LOQ, the
sample must be reanalyzed at a more concentrated level.
9.12 Technical Acceptance Criteria for Sample analysis
9.12.1 The samples must be analyzed on a system meeting BFB, initial calibration and
calibration verification criteria.
9.12.2 The sample must have an associated method blank meeting acceptance criteria
(see section 11.2).
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9.12.3 Surrogate recovery must fall within default limits of 80-120% for all samples
and blanks.
9.12.4 The retention time of each internal standard must be within +20s of the
retention time in the most recent calibration verification standard.
9.12.5 The instrumental response (EICP area) for each of the internal standards must
be within ± 40% of the area response in the most recent calibration verification
standard. If analyzed within the same sequence a calibration curve, then the
average of the area responses for all calibration standards can be used for this
criteria comparison.
9.12.6 Concentration of all analytes must be within the calibration range determined
from the initial calibration.
9.12.7 Control Sample/Duplicate must be evaluated to determine if recoveries (and
RPDs) are within control limits.
9.13 Hydrocarbon Analysis
9.13.1 Initial Calibration
9.13.1.1 A copy of the day's data folder is made and renamed "InstID+date+HC."
For example, if the date is 02/25/2011 on instrument J, the new folder
will be named J022511HC. Load the previous hydrocarbon calibration
curve, rename with the current date and save the method.
9.13.1.2 With the global detection limit set to zero, re-quantitate the same data
files used for the TO-15 calibration curve. Q-Edit the files to ensure that
all of the hydrocarbon peaks are correct, using the following table.
Name
Major Peak
Bromochloromethane
130
1,4-Difluorobenzene
114
Chlorobenzene-d5
117
Bromofluorobenzene
174
Total VOC's as n-Heptane
43,57,71,100
Trimethyl Siloxanol
75
Hexmethyl Cyclotrisiloxane
207
Octomethyl Cyclotetrasiloxane
281
Siloxane
267
Note: In standards and blanks, the Trimethyl Siloxanol and Siloxane may not be present.
Highlight the peak around the retention time of where it should be, with the lowest level
present. This is usually the beginning of the peak found.
9.13.1.3 Once the peaks have been selected correctly, clear the calibration
responses in the curve. Update all the levels of the calibration using the
same data files that were used for the TO-15 curve. Ensure that you
select "Quantitate Using Initial Cal RF's" under the "Quant" menu
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before saving the method.
9.13.1.4 Repeat steps 9.4.3.2 - 9.4.3.5 for n-Heptane only. An additional
conversion may be necessary, depending on client, to convert n-Heptane
to Gasoline (M.W. Gasoline divided by M.W. of n-Heptane). Siloxanes
are not calibrated compounds. RSD for siloxanes should be crossed out
and marked "Not calibrated for these compounds." Update the Custom
Report Response factor using the Average of the Total VOC's as n-
Heptane.
9.14 SIM Analysis
9.14.1 SIM analysis is a technique used to increase sensitivity with GCMS for for
target compounds using only specific ions. The only ions scanned for are
those that are characteristic of target compounds only. As a result non target
compounds are not able to be detected using SIM analysis.
9.14.2 SIM analysis can be done upon client request for compounds that require
lower detection limits than the low level 0.2-ppbv standard.
9.14.3 Target compounds will depend on client target list and will be ordered at a
lower level primary standard if needed (example: Order a 10-ppbv standard if
client requests detection limit of0.005-ppbv)
9.14.4 If the detection limits can be meet with a standard SCAN TO-15 method but
client requests SIM analysis, the same stock and working standards used for
SCAN analysis can be used.
9.14.5 Target compounds will be quantitated from the primary ion for each
respective compound with at least 1 secondary ion for qualitative
identification. Retention time will be the primary method of identification per
9.10.1.
9.14.6 SIM analysis will be set up using a separate chemstation method using only
the ions for compounds that require SIM analysis. This will keep from
scanning non target compound ions which will increase sensitivity. Target
ions will depend on client request and the ions used should be seen in regular
TO-15 SCAN ECIP.
9.14.7 SIM methods will be made per client project to maximize sensitivity by
minimizing dwell time by the mass spectrometer. See section supervisor or
alternate for any questions.
9.14.8 Blank should be run after any QC until system is fully cleaned out before
running any client samples. This will ensure that client samples are free from
any possible carry over effects from working standards used for QC. Blanks
should be run at the end of client sample batch to ensure that there is no carry
over. Blanks should be run in between any client samples with a hit at or
greater than the mid point calibration level, to ensure that subsequent client
samples are not contaminated with carry over.
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9.15 Corrective Action
9.15.1 Corrective Action for sample analysis: the sample technical acceptance criteria
must be met. If any samples do not meet acceptance criteria, consult with the
section supervisor to determine whether reanalysis is required.
9.15.2 Corrective Action for surrogate recovery failure: check calculations and examine
the chromatogram for interference. If no interference is noted, reanalyze any
sample that exceeds criteria. If the sample meets criteria upon reanalysis, report
the reanalysis only. If the sample produced similar results upon reanalysis, the
problem may be matrix-related. Contact the project manager so the client may be
notified.
9.15.3 Corrective Action for Internal Standard Response failures: if any internal
standard exceeds acceptance criteria, check calculations. Verify that the standard
concentration is accurate, and that the instrument did not malfunction. Reanalyze
the sample to see if the problem was matrix related. If the reanalysis meets
criteria, report the reanalysis only. If the reanalysis produced similar results,
consult with the section supervisor and project manager to determine the best
course of action.
9.15.4 Corrective Action for Internal Standard Retention Time: if any internal standard
exceeded retention time criteria, follow the same guidelines used in Section
9.14.3.
9.15.5 Corrective Action for Instrument Contamination: if an instrument has come into
contact with a PPM level of analytes, the instrument might need extra cleaning
to ensure that there is no carry-over to other client samples. Block access to the
ports affected on the Entech autosampler until they go through at least 5 flush
and bake cycles. Test the ports, as room air blanks, to see if there is carry-over.
If there no carry-over, go ahead and use the ports during the next run. If there is
carry-over, see section supervisor for other possible actions, which may include
cleaning the source.
10.0 DOCUMENTATION
10.1 The raw data is archived to CD-ROM and is stored in a secured area. Hard copies
of raw data are kept for a period of ~1 year in the laboratory and then stored for a
total time of 5 years before disposal.
10.2 Chain of custody forms, instrument maintenance logs, standards preparation logs,
analytical run logs, and corrective action logs must be filled out in a timely manner.
These records are maintained in the laboratory for five years.
11.0 CALCULATIONS
All calculations are covered in Section 9.
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.0 QUALITY CONTROL CHECKS & CRITERIA
12.1 Instrument performance must be monitored to ensure that all of the tuning, initial
calibration and calibration verification criteria requirements are met.
12.2 Method blanks
12.2.1 A method blank is a volume of a clean reference matrix (nitrogen @ 99.9999%
purity) carried through the entire analytical procedure. The volume of the
method blank must be approximately equal to the volume of the associated
samples. The purpose of the method blank is to determine the level of
contamination associated with the preparation and analysis of samples.
12.2.2 Method blanks must be analyzed with each batch of samples, or at a minimum
frequency of 1 for every 20 samples.
12.2.3 A method blank is analyzed following the calibration verification standard under
the same conditions as the standards and samples before any samples may be
analyzed.
12.2.4 The method blank must contain no targets above the LOQ of 5-ppbv (lOOcc
injection for Minican) and 0.2-ppbv (500cc injection for 6-L Summa canisters)
for the TO 15 list. They should contain no targets above client specific
detection limits for SIM analysis. The LOQ for Ethylene Oxide is 20-ppbv and
the 4-Phenylcyclohexene LOQ is 1-ppbv.
12.2.5 If the method blank does not meet this criterion, repeat the analysis until an
acceptable blank is obtained. Sample analysis may not begin until a method
blank meeting criteria has been successfully analyzed.
12.2.6 If the surrogate recovery in the method blank does not meet control limits,
reanalyze the method blank. If the surrogate recovery is still outside control
limits, it may be necessary to re-prepare the internal standard/surrogate mixture
or recalibrate the instrument.
12.3 Laboratory Control Sample/ Laboratory Control Sample Duplicate
12.3.1 A laboratory control sample & duplicate (LCS/LCSD) consist of an aliquot of a
clean reference matrix (UHP nitrogen), spiked with a representative list of the
target analytes at the mid-level of the calibration curve. The spiking standard
must be from a source different from that of the calibration standards.
12.3.2 The LCS & LCSD must be analyzed with each analytical run. The recoveries
should fall within the range of 70-130%. For compounds 1,2,4-Trichlorobenzene
and Hexachloro-1, 3-Butadiene, separate limits have been established based on
historical laboratory data (these compounds are no longer in the TO-15 regular
list). RPD method default limits of 25% are used to assess analytical precision.
If recovery and/or RPD are not within this range, the possible effect(s) on the
sample data must be determined. The data may be qualified or the LCS/LCSD
sample may be reanalyzed.
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12.4 Surrogate Recoveries
12.4.1 All samples, including quality control samples, are spiked with 50ppbv
Bromofluorobenzene as a surrogate.
12.4.2 The surrogate (BFB) recovery control limits are 80-120%. All samples should
meet the surrogate recovery criterion. If BFB recovery falls outside control limits
for any sample, the sample must be reanalyzed. If the reanalysis produces similar
results, contact the project manager.
12.5 Duplicate analysis.
12.5.1 A sample is analyzed in duplicate to assess precision. Duplicates must be
analyzed with each batch of samples, or at a minimum frequency of 1 for every
24-hour analytical sequence. The relative percent difference (RPD) between
measurements should be 25% or less.
12.6 Initial Demonstration of Proficiency (IDP)
12.6.1 Demonstration of proficiency is established by generating data of acceptable
accuracy and precision for target analytes for each preparative method and
matrix by analyzing reference samples. On-going demonstration is performed on
a semiannual basis.
12.6.2 Four reference samples are prepared so that each analyst tests 4 samples of
unknown concentration containing all analytes of interest. Analyst One prepares
two different stock standards independently and fills two sample canisters from
each. The preparing analyst labels the canisters with the injection volume to use
and gives them a sample ID. This results in 4 different concentrations for each
analyst. A second analyst repeats the process for any other analysts. The
standards must be made from stock standards prepared independently from those
used for calibration. The concentration of targets in the four reference samples
may be anywhere within the current calibration range of the instrument.
12.6.3 Analyze the four reference samples by the same procedure used for analyzing
actual samples. Calculate both the average recoveries in ppbv and the relative
standard deviations of the recovery for each analyte of interest. The average
recovery should fall within the in-house generated control limits for each
analyte.
12.6.4 IDP procedures must be repeated whenever new staff is trained or significant
changes in preparative or analytical methods are made.
12.7 Verification of Method Detection Limit
12.7.1 Instrument reporting limits are verified (at least) annually by analyzing 7
replicates at the reporting limit. All compounds must be within 60-140%
recovery for the detection limit standard (DLS) when using a nominal sample
injection volume of 100-cc for MiniCan, 500-cc for Summa Canisters or 1000-
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cc for SIM analysis.
12.7.2 Alternatively, an MDL study can be performed if needed. MDL is the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the analyte concentration is greater than zero. The MDL is
determined by the analysis of seven replicate injections of each compound of
interest at a level near the expected detection limit. The standard deviation of
the seven measurements multiplied by 3.14 (Student's t value for 99%
confidence for seven values) defines the MDL for each analyte.
12.7.3 MDLs are determined only if needed for each instrument, as the detection limit
studies (described in 12.7.1) are used to verify instrument-reporting limits.
12.7.4 For SIM analysis, detection limits should meet or exceed client specifications.
12.8 Additional Control Procedures
12.8.1 Logbook Review Procedure:
The supervisor or designee will review GCMS run logs and maintenance logs
weekly. The logbooks will be reviewed for content and for the absence of cross
outs. All forms will be verified to be the most recent approved version.
Logbooks will be initialed and dated as to the date of review. MS-Form-6 will
be used to document that all logbooks are reviewed as per their set schedule.
The preventative maintenance log will be reviewed as the maintenance is done
(some is weekly, some monthly and also some at 6-12 month intervals). The
standards logbooks are reviewed each time a standard is made. Can cleaning
logbooks and canister dilution logbooks will be reviewed weekly.
12.8.2 Forms Control Procedure:
In addition to forms being reviewed on a weekly basis new forms once approved
(notification through email) will be printed and a new logbook made by the end
of the next business day. Previous logbooks will be closed out and archived.
12.8.3 Preventative Action Plan Initiation/Review Policy:
A PAP should be initiated whenever an action can be initiated to prevent a
future problem. Consultation with the QC group will be used to determine if a
PAP is required. PAPs will be reviewed at least weekly until completed.
12.8.4 Entech auto-sampler ports are flushed before use and this is indicated on system
injection log.
12.8.5 All working standard numbers (IH numbers) will be verified on hard copy
reports and in LIMS to ensure accuracy and traceability for standard
documentation.
12.8.6 Sample Canister Cleaning Approval Procedure.
This procedure is used to ensure sample analysis is complete before sample
canisters are cleaned. After a sample analysis sequence is complete, canisters are
placed in project holding bin (red or purple) waiting for approval of all Quality
control and sample results. If any re-analysis is required, those samples are kept
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in this bin until re-analysis is performed. When approval is given by supervisor
and/or designee to clean sample canisters, canisters are then transferred to the
"approved for cleaning bin" (black or blue) by verifying sample identification
using Galson Login number and individual sample number. This bin is then
taken to the sample cleaning area.
13.0 CORRECTIVE ACTION
13.1 See section 9.14 for corrective actions.
14.0 WASTE DISPOSAL
14.1 Refer to Galson Laboratories SOP LF-DISPO (current revision).
15.0 REFERENCES
15.1 Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs)
In Air Collected I Specially-Prepared Canisters And Analyzed By Gas
Chromatography/Mass Spectrometry (GC/MS), Second Edition, U. S. Environmental
Protection Agency, Research Triangle Park, NC 27711, EPA/626/R-96/010b, January
1999.
15.2 PV2120: Volatile Organic Compounds in Air, U. S. Department of Labor -
Occupational Safety & Health Administration, Control Number T-PV2120-01-0305-
ACT, May 2003
16.0 METHOD MODIFICATIONS
Method PV2120:
The samples arrive in the lab at ~ 15 psia (atmospheric pressure, 0 psig) and this is
adequate to sample without pressurizing (diluting) the sample up to 30 psig (45 psia).
Method TO-15: (parentheses denote method-referenced sections)
(10.7.5)
Daily blank limit is set at 5-ppbv for TO 15 list (the normal reporting limit for most
compounds), not 3x the MDL.
(8.4.1.2)
Can leak-checks are done by evacuating cans to ~ 30" of Mercury (vacuum reading),
and then checking them before sample shipment. If vacuum falls to <28" of Mercury
within 24 hours, a can is considered to be leaking (TO-15 leak-checks by pressurizing
cans to 30 psig and has pass/fail criteria of <+/- 2 psig) in 24 hours.
(8.4.1.6)
Cans containing less than 2-ppm of individual contaminants are cleaned in batches
where a representative can is tested to demonstrate cleanliness of the batch. For cans
containing analytes greater than 2-ppm, these cans are tested individually to verify
cleanliness. Can cleaning limits are higher (refer to section 9.2.2.2). For MiniCans: the
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representative can cleaning blank limit (or individual can) for TO-15 list is set at 5-
ppbv, the normal reporting limit. The warning limit is 2.5-ppbv. Quantitation in general
is not reliable below 5-ppbv. Cans are generally re-cleaned if above 2.5-ppbv for any
analyte. For 6-L Summa Canisters: the cleaning blank limit is 0.2-ppbv (IDL for most
compounds), anything less than 0.2-ppbv is considered clean. Correspondingly, for
Ethylene Oxide the limit is 20-ppbv and for 4-Phenylcyclohexene the limit is 1 ppbv.
(10.8.1)
For Minican analysis: lOOmL-sample injection volume is used when sampling is done
with 400mL and 1-liter canisters rather than 6-liter summa canisters. Therefore, MDL
limits, etc. are ~ 5x higher because the sample injection volume is 5x less.
(9.2.2.3)
For Minican analysis: Internal standard/surrogate levels are spiked at 50-ppbv rather
than 10-ppbv to be consistent with calibration levels for TO 15 list analyses.
(10.7.2)
A blank is not always analyzed after a high level sample. If the compound that was high
is detected in samples injected after the high level sample, those samples would be
reanalyzed after the system was shown to be clean.
(10.7.5)
Internal standard area limit of +/- 40% is calculated versus the daily standard for all
injections that day (24 hour window) not versus the most recent calibration curve
average areas.
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Table 1
Characteristic Ions, PQLs
COMPOUND
EI
EI
EI
PQL ppb
PRIMARY
SECONDARY
TERTIARY
Summa
Minican
Propylene
41
39
0.2
5
Freon-12
85
87
0.2
5
Chlorom ethane
50
52
0.2
5
Freon-114
85
135
87
0.2
5
Vinyl Chloride
62
64
0.2
5
1,3-Butadiene
39
54
0.2
5
Bromomethane
94
96
0.2
5
Chloro ethane
64
66
0.2
5
Vinyl Bromide
106
108
0.2
5
Freon-11
101
103
105
0.2
5
[sopropyl Alcohol
45
43
0.2
5
Acetone
43
58
0.2
5
1,1 -Dichloroethene
96
61
98
0.2
5
Methylene Chloride
84
86
49
0.2
5
Freon-113
101
101
151
0.2
5
Allyl chloride
76
41
39
0.2
5
Carbon Disulfide
76
78
0.2
5
Trans-1,2-Dichloroethene
61
96
98
0.2
5
Methyl Tert-Butyl Ether
73
41
57
0.2
5
1,1 -Dichloroethane
63
65
0.2
5
Vinyl Acetate
43
86
0.2
5
Methyl Ethyl Ketone
43
57
72
0.2
5
:is-1,2-Dichloroethylene
61
96
98
0.2
5
Hexane
57
41
43
0.2
5
Ethyl Acetate
43
45
61
0.2
5
Chloroform
83
85
47
0.2
5
T etrahydrofuran
42
71
72
0.2
5
COMPOUND
EI
EI
EI
PQL ppb
PRIMARY
SECONDARY
TERTIARY
Summa
Minican
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1,2-Dichloroethane
62
64
0.2
5
1,1,1 -Trichloro ethane
97
99
61
0.2
5
Cyclohexane
56
41
84
0.2
5
Carbon T etrachloride
117
119
0.2
5
Benzene
78
77
50
0.2
5
1,4-Dioxane
88
58
0.8
20
2,2,4-Trimethylpentane
57
41
56
0.2
5
Heptane
43
57
71
0.2
5
1,2-Dichloropropane
63
41
62
0.2
5
T richloro ethylene
130
132
95
0.2
5
Bromodichloromethane
83
85
0.2
5
sis-1,3 -Dichloropropene
75
39
77
0.2
5
Trans-1,3 -Dichloropropene
75
39
77
0.2
5
1,1,2-Trichloroethane
97
83
61
0.2
5
Toluene
92
91
92
0.2
5
Dibromochloromethane
129
127
0.2
5
Methyl Isobutyl Ketone
43
57
58
0.8
20
Methyl Butyl Ketone
43
57
58
0.8
20
1,2-Dibromomethane
107
109
0.2
5
T etrachloroethylene
164
166
131
0.2
5
Chlorobenzene
112
77
114
0.2
5
Ethylbenzene
91
106
0.2
5
Bromoform
173
175
0.2
5
Styrene
104
78
103
0.2
5
~-xylene
91
106
0.2
5
m- & p-xylene (co-elute)
91
106
0.4
10
1,1,2,2-T etrachloro ethane
83
85
0.2
5
4-Ethyltoluene
105
120
0.2
5
1,3,5-Trim ethylbenzene
105
120
0.2
5
COMPOUND
EI
EI
EI
PQL ppb
PRIMARY
SECONDARY
TERTIARY
Summa
Minican
1,2,4-Trim ethylbenzene
105
120
0.2
5
1,3 -Dichlorobenzene
146
148
111
0.2
5
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Benzyl Chloride
91
126
0.2
5
1,4-Dichlorobenzene
146
148
111
0.2
5
1,2-Dichlorobenzene
146
148
111
0.2
5
1,2,4-Trichlorobenzene
180
182
184
0.2
5
Hexachloro-1,3 -Butadiene
225
227
223
0.2
5
Ethylene Oxide
44
29
NA
20
4-Phenylcyclohexene
104
158
78
1
Bromofluorobenzene (surrogate)
95
-
*Bromochlorom ethane
128
-
* 1,4-Difluorobenzene
114
-
* Chlorobenzene-d5
117
-
*Indicates internal standard
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Table 2
Volatile Internal Standards with Corresponding Analytes
Assigned for Quantitation
*Bromochloromethane
* 1,4-Difluorobenzene
* Chlorob enzene -d5
Propylene
1,1,1 -Trichloroethane
Toluene
Freon-12
Cyclohexane
Dibromochloromethane
Chloromethane
Carbon Tetrachloride
Methyl Isobutyl ketone
Freon-114
Benzene
Methyl Butyl ketone
Vinyl Chloride
1,4-Dioxane
1,2-Dibromoethane
1,3-Butadiene
2,2,4-Trimethylpentane
T etrachloro ethylene
Bromomethane
Heptane
Chlorobenzene
Chloro ethane
1,2-Dichloropropane
Ethylbenzene
Vinyl bromide
T richloro ethylene
m- & p-xylene (co-elute)
Freon-11
Bromodichloromethane
Styrene
Isopropyl alcohol
cis-1,3 -Dichloropropene
o-xylene
Acetone
trans-1,3 -Dichloropropene
Bromoform
1,1 -Dichloroethene
1,1,2-Trichloroethane
1,1,2,2-T etrachloro ethane
Methylene Chloride
4-Ethyltoluene
Freon-113
1,3,5-Trimethylbenzene
Allyl chloride
1,2,4-Trimethylbenzene
Carbon disulfide
Benzyl chloride
Trans-1,2-Dichloroethene
1,3 -Dichlorobenzene
Methyl tert-butyl ether
1,4-Dichlorobenzene
1,1 -Dichloroethane
1,2-Dichlorobenzene
Vinyl acetate
1,2,4-Trichlorobenzene
Methyl ethyl ketone (2-butanone)
Hexachloro-1,3 -Butadiene
Cis-1,2-Dichloro ethylene
Bromofluorobenzene (surrogate)
Hexane
4-Phenylcyclohexene
Ethyl acetate
Chloroform
T etrahydro furan
1,2-Dichloroethane
Ethylene Oxide
Page 25 of 25
-------
Enbridge Energy, Limited Partnership
1601 Pratt Avenue
Marshall, Michigan 49068
'nbridge*
September 9, 2011
Mr. Ralph Dollhopf
Federal On-Scene Coordinator and Incident Commander
U.S. Environmental Protection Agency
801 Garfield Avenue, #229
Traverse City, Ml 49686
Re: In the Matter of Enbridge Energy Partners, L.P, et al,
Docket No. CWA 1321-5-10-001
Dear Mr. Dollhopf:
Enbridge Energy, Limited Partnership (Enbridge) is requesting that the United States
Environmental Protection Agency (U.S. EPA) consider the following modification to the 2011 Air
Monitoring and Sampling Addendum dated June 21, 2011. The proposed modifications are
being requested for immediate implementation.
The specific request includes modification of Community Air Sampling laboratory analysis turn-
around time. This request excludes Odor Response sampling activities which will continue with
expedited shipping and 24-hour analytical turnaround times for samples collected. In
accordance with the approved Plan, based on community monitoring and sampling analytical
results obtained throughout the 2011 work activities, we are requesting the Community Air
Sampling laboratory analysis turn-around time be changed from a 24-hour analytical period to a
5 day analytical turn-around time period.
This request for modification is supported by 411 work area perimeter samples and 815
Community Air samples over 67 days with only 10 individual detections of four Target
Analytesabove the Human Health Screening Levels. Detections above screening levels for
Target Analytes include 1,2,4 Trimethylbenzene (1 sample), benzene (1 sample), toluene (4
samples), and xylene (4 samples). In addition, we have collected over 12,000 real-time
community monitoring readings for VOCs, H2S, S02, and benzene (all non-detect) throughout
the monitoring period.
Assessment of community air sampling and monitoring results lead us to conclude:
• That our analytical data set is established,
• Concentrations of Target Analytes in community air are stable,
• Work activities do not influence air sampling results, and
• The necessity for expedited analytical turn-around times reduced.
-------
Page 2, Mr. Ralph Dollhopf, September 9, 2011
Enbridge welcomes the opportunity to present additional information regarding our sampling
and monitoring strategy, a review of data collected, and a detailed assessment of results. If you
have any questions regarding this request, please do not hesitate to contact me.
CC: Joel W. Kanvik, Enbridge
John Sobojinski, Enbridge
Bob Steede, Enbridge
Leon Zupan, Enbridge
Leslie Kirby-Miles, EPA Region 5 [kirby-miles.leslie@epa.gov]
Jeff Kimble, EPA Region 5 [kimble.jeff@epa.gov]
Enbridge@EPA.gov
Mark DuCharme, MDEQ
Mike Alexander, MDEQ
Sincerely,
ENBRIDGE ENERGY, LIMITED
PARTNERSHIP
By Enbridge Pipelines (Lakehead) L L C.
Its General Partner
Richard Adams
Vice President, U.S. Operations
-------
Enbridge Energy, Limited Partnership
1601 Pratt Avenue
Marshall, Michigan49068
October 13, 2011
Mr. Ralph Dollhopf
Federal On-Scene Coordinator and Incident Commander
U.S. Environmental Protection Agency
801 Garfield Avenue, #229
Traverse City, MI49686
Re: In the Matter of Enbridge Energy Partners, L.P, et al,
Docket No. CWA 1321-5-10-001
Dear Mr. Dollhopf:
Enbridge Energy, Limited Partnership (Enbridge) is requesting the United States Environmental
Protection Agency (U.S. EPA) approve the following modification to the 2011 Air Monitoring and
Sampling Addendum (dated June 21, 2011) of the Sampling and Analysis Plan (SAP) (dated
August 2010). The proposed modifications are being requested for immediate implementation.
Enbridge is requesting an indefinite suspension of all Community Air Sampling and Monitoring
activities, Work Area Monitoring, and elimination of River Opening Sampling effective
immediately. The air sampling and monitoring program was designed to protect worker safety
and public health during assessment and recovery operations. Work activities during these air
sampling and monitoring periods included overbank surface soil oil recovery, overbank
excavation oil recovery, and submerged oil recovery during a wide range of atmospheric
conditions over the 2011 work periods. This request excludes Odor Response sampling
activities which will continue with expedited shipping and 24-hour analytical turnaround times for
samples collected.
This request for modification is supported by 2,059 Work Area and Community Air samples
collected during 2010 and 1,266 Work Area and Community Air samples collected in 2011, as of
September 16, 2011. In addition to the lab analyzed samples, we have collected 66,922 real-
time community readings in 2010 and 18,662 in 2011, as of September 16, 2011for VOCs, H2S,
S02, and benzene (all non-detect above screening limits).
Between June 3, 2011 and September 16, 2011, a total of 10 Target Analytes have been
detected above Human Health Air Screening Levels (HHASLs) in 2011 along with 22 detections
of Non-Target Analytes above HHASLs, which are not related to crude oil released from Line 6B
MP 608. Detections of both Target and Non-Target Analytes have been inconsistent and do not
alter our conclusions regarding air sampling and monitoring results. In addition, efforts have
been taken to evaluate potential lab related issues for select contaminants including isopropyl
alcohol and acetone, which revealed these contaminants along with carbonyl sulfide in the
laboratory carrier gas. It is important to note that these are 8-, 12-, and 24-hour samples (acute
exposure) being compared to chronic exposure based screening levels (greater than one year).
Therefore we also compared measures of central tendency (including median and mean values)
of contaminant levels over the sampling duration in 2011, which indicated values well below the
applicable HHASLs.
The attached tables and figures provide details regarding chemicals detected and comparisons
with applicable HHASLs. Please refer to the attached Table 1: Cumulative Air Sample
Summary - Target Analytes and Table 2: Cumulative Air Sample Summary - Non-Target
-------
Page 2
Analvtes for a summary of analytical results from June 3, 2011 to September 16, 2011 for
Target Analytes and Non-Target Analytes, respectively. In addition, see attached figures for
visual depictions of sampling results compared against applicable HHASLs for each of the
detected Target Analytes and specific Non-Target Analytes of interest.
Enbridge is also requesting the elimination of River Opening Sampling and Monitoring, as
included in Memorandum -RE: Modification of the 2011 Air Monitoring and Sampling Addendum
to the Sampling and Analysis Plan, dated July 6, 2011, due to the lack of applicability based on
the extensive Work Area and Community Air Sampling and Monitoring conducted in 2010 and
2011 with minimal detections of Target Analytes as outlined in the above text and associated
tables and figures.
Assessment of Community Air Sampling and Monitoring results lead us to conclude that our
analytical data set is well established, concentrations of Target Analytes in ambient air
throughout the community are stable and below levels of concern, and that work activities do
not negatively influence ambient air concentrations. Additionally, as ambient air temperatures
continue to decrease for the remainder of 2011, weather conditions substantiate a lesser
potential for volatilization of chemicals in comparison to the higher ambient air temperatures
observed during the sample collection conducted in 2011 to date. Therefore, Enbridge believes
it has been demonstrated that continued air sampling and monitoring is unnecessary.
Enbridge welcomes the opportunity to present additional information regarding our sampling
and monitoring strategy, a review of data collected, and a detailed assessment of results. If you
have any questions regarding this request, please do not hesitate to contact me.
CC: Joel W. Kanvik, Enbridge
John Sobojinski, Enbridge
Bob Steede, Enbridge
Leon Zupan, Enbridge
Leslie Kirby-Miles, EPA Region 5 [kirby-miles.leslie@epa.gov]
Jeff Kimble, EPA Region 5 [kimble.jeff@epa.gov]
Enbridge@EPA.gov
Mark DuCharme, MDEQ
Mike Alexander, MDEQ
Sincerely,
ENBRIDGE ENERGY, LIMITED
PARTNERSHIP
By Enbridge Pipelines (Lakehead) L L C.
Its General Partner
Richard Adams
Vice President, U.S.Operations
-------
Table 1. Cumulative Air Sample Summary - Target Analytes
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Target Analytes - Predominant
Human Health Air
All Sample Durationst
8-hour Target Period
12-hour Target Period
24-hour Target Period
Crude Oil VOCs Detected by TO-15
CAS NO
Screening Level
Source
N
Ndet
Average
Max
N
Ndet
Average
Max
N Ndet
Average
Max
N
Ndet
Average
Max
Analysis (including TICs)
(PPbv)
Level**
(PPbv)
Level**
(PPbv)
Level**
(PPbv)
Level**
(PPbv)
1,2,4-Tri methyl benzene
95-63-6
1.5
EPA RfCf)
1266
1
1.0
3.0
364
117 0
ND
785
1
1.0
3.0
Benzene
71-43-2
3
ATSDR Chr. MRLO
1266
4
1.0
4.0
364
ND
117 0
ND
ND
785
4
1.0
4.0
2-Methylbutane*
78-78-4
6000
MDEQO
1266
43
10.4
83.0
364
0
ND
ND
117 0
ND
ND
785
43
10.4
83.0
Cyclohexane
110-82-7
2000
EPA RfCO
1266
25
1.0
63.0
364
1
5.0
63.0
117 0
ND
785
24
1.0
20.0
1,3-Dimethylcyclohexane*
591-21-9
NA
NA
1266
0
ND
ND
364
rt
ND
ND
117 0
ND
785
(!
ND
Methylcyclopentane*
96-37-7
200
MDEQ(')
1266
2
2.6
3.7
364
ND
ND
117 0
ND
785
2
2.6
3.7
cis-1,3-Dimethylcyclohexane*
638-04-0
NA
NA
1266
ND
ND
364
rt
ND
117 0
ND
785
li
ND
Butylcyclohexane*
1678-93-9
NA
NA
1266
364
ND
ND
117 0
ND
785
Ethylcyclohexane*
1678-91-7
NA
NA
1266
u
ND
ND
364
0
ND
ND
117 0
ND
ND
785
(!
ND
Methylcyclohexane*
108-87-2
4000
MDEQ(')
1266
2
3.9
4.6
364
ND
ND
117 0
ND
ND
785
2
3.9
4.6
Propylcyclohexane*
1678-92-8
NA
1266
Is
ND
ND
364
!\
ND
ND
117 0
ND
ND
785
li
ND
1,1-Dimethylcyclopentane*
1638-26-2
NA
NA
1266
ND
ND
364
ND
ND
117 0
ND
ND
785
trans-1,3-Dimethylcyclopentane*
1759-58-6
NA
NA
1266
u
ND
ND
364
! ?!
ND
ND
117 0
M{"»
ND
785
(!
ND
trans-1,2-Dimethylcyclopentane*
822-50-4
0.025
MDEQO
1266
ND
364
ND
117 0
ND
ND
785
ND
3-Methylheptane*
589-81-1
NA
NA
1266
u
ND
ND
364
rt
ND
117 0
ND
ND
785
(!
ND
2,6-Dimethyl-2-Octene*
4057-42-5
NA
1266
364
ND
117 0
ND
785
Decane*
124-18-5
NA
NA
1266
3
4.7
8.9
364
rt
ND
ND
117 0
ND
ND
785
3
4.7
8.9
Dodecane*
112-40-3
NA
1266
4
2.5
5.6
364
ND
ND
117 0
ND
ND
785
4
2.5
5.6
Ethylbenzene
100-41-4
60
ATSDR Chr. MRLO
1266
3
1.0
3.0
364
0
ND
ND
117 0
ND
ND
785
3
1.0
3.0
4-Ethyltoluene
622-96-8
70
MDEQO
1266
1
1.0
1.0
364
ND
ND
117 0
ND
785
1
1.0
1.0
n-Heptane
142-82-5
850
MDEQO
1266
13
1.0
14.0
364
t\
II
ND
117 0
ND
ND
785
13
1.0
14.0
n-Hexane
110-54-3
200
EPA RfCO
1266
18
1.0
3.0
364
117 0
ND
785
18
1.0
3.0
Naphthalene*
91-20-3
1
ATSDR Chr. MRLO
1266
!;
ND
ND
364
0
ND
ND
117 0
ND
ND
785
is
ND
Nonane*
111-84-2
40
EPA RfC(')
1266
1
18.0
18.0
364
ND
117 0
ND
ND
785
1
18.0
18.0
2-Methylhexane*
591-76-4
850
MDEQO
1266
4
18.3
35.0
364
1
35.0
35.0
117 0
ND
ND
785
3
12.7
29.0
Octane*
111-65-9
NA
1266
ND
ND
364
117 0
ND
ND
785
ND
3-Methyloctane*
2216-33-3
NA
NA
1266
! 1
ND
ND
364
si
ND
ND
117 0
ND
ND
785
(!
ND
2-Methylpentane*
107-83-5
5000
MDEQO
1266
1
1.7
1.7
364
117 0
ND
ND
785
1
1.7
1.7
Toluene
108-88-3
80
ATSDR Chr. MRLO
1266
256
4.5
270.0
364
3
5.0
54.0
117 1
5.0
17.0
785
252
3.9
270.0
3-Methylhexane*
589-34-4
850
MDEQO
1266
4
16.5
48.0
364
ND
117 0
ND
785
4
16.5
48.0
2-Methylheptane*
592-27-8
NA
1266
u
ND
ND
364
t\
ND
ND
117 0
ii'jn
ND
785
(!
ND
1,1,3- Trimethylcyclohexane*
3073-66-3
NA
1266
ND
364
ND
ND
117 0
ND
ND
785
:: '¦» ¦¦
1,3,5-Tri methyl benzene
108-67-8
45
MDEQO
1266
ND
ND
364
t\
ND
ND
117 0
ND
785
(!
ND
Undecane*
1120-21-4
NA
NA
1266
1
1.5
1.5
364
ND
117 0
ND
785
1
1.5
1.5
m&p-Xylene
179601-23-1
50
EPA RfCO
1266
6
2.0
10.0
364
i)
ND
ND
117 0
ND
ND
785
6
2.0
10.0
o-Xylene
95-47-6
50
EPA RfC(')
1266
3
1.0
3.0
364
0
NU
NU
117 0
NU
ND
785
3
1.0
3.0
PPBV- Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects. Average Levels for
compounds that were detected in >5% of samples are the mean using the detection limit for non-detects. Average Levels for tentatively identified compounds are
the mean of detects.
tSamples reported do not include instantaneous 'grab' samples. Samples with 8-24 hour target sample periods are included.
NA - Not Available/ND - Not Detected
N - Number of samples analyzed/NDET - Number of detections
(') - Unless otheiwise noted, the screening level was obtained from Enbridge Oil Spill Human Health Air Screening Levels, August 31, 2011.
ATSDR Chr. MRL- Agency for Toxic Substances and Disease Registry - Chronic Minimal Risk Level for Inhalation
EPA RfC - If no Chronic MRL is available, the screening level is the EPA Chronic Reference Concentration (RfC).
EPA RSL- If none of the above are available, the EPA Regional Screening Level (RSL) is used.
MDEQ - If none of the above are available, the Michigan DEQ Air Quality Division, Air Toxics Screening Level is the screening level. Page 1 of 1
-------
Table 2. Cumulative Air Sample Summary - Non-Target Analytes
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Human Health Air
All Sample Durationst
8-hour Target Period
12-hour Target Period
24-hour Target Period
Non-Target Analytes (including TICs)
CAS NO
Screening Level
Source
N
Ndet
Average
Max
N
Ndet *Vera9e
Level**
Max
^ Average Max
N Ndet
Level** (ppbv)
N
Ndet
Average
Max
(PPbv)
Level**
(PPbv)
(PPbv)
Level**
(ppbv)
1,1,1 -f richloroethane
71-55-6
1000
EPA RfC(1)
1266
0.0
364
!Ml "t
117 0 ND ND
785
1,1,2,2-Tetrachloroethane
79-34-5
0.006
EPA RSL(1)
1266
ND
364
117 0 ND ND
785
1,1,2-Trichloro-1,2,2-trifluoroetharre
76-13-1
4000
EPA RSL(1)
1266
0
ND
0.0
364
0 ND
ND
785
f!
1,1,2-Trichloroethane
79-00-5
0.04
EPA RfC(1)
1266
364
P IM *
785
1,1-Dichloroethane
75-34-3
0.4
EPA RSL(1)
1266
0
ND
0.0
364
0 ND
ND
117 0 ND ND
785
f!
ND
1,1-Dichloroethene
75-35-4
50
EPA RfC(1)
1266
364
117 0 ND ND
785
1,2,4-Trichlorobenzene
120-82-1
0.3
EPARfC(')
1266
0
ND
0.0
364
0 ND
ND
117 0 ND ND
785
f!
ND
1,2-Dibromoethane
106-93-4
1
EPA RfC(1)
1266
364
785
1,2-Dichloro-1,1,2,2-Tetrafluoroethane
76-14-2
9900
MDEQ(1)
1266
0
ND
0,0
364
0 ND
ND
117 0 ND ND
785
f!
ND
1,2-Dichlorobenzene
95-50-1
30
EPA RfC(1)
1266
364
785
1,2-Dichloroethane
107-06-2
600
ATSDR Chr. MRL(1)
1266
2
1
3.0
364
0 ND
ND
117 0 ND ND
785
2
1.0
3.0
1,2-Dichloropropane
78-87-5
1
EPA RfC(1)
1266
364
785
1,2-PENTADIENE*
591-95-7
NA
NA
1266
1
1.6
1.6
364
0 ND
ND
117 0 ND ND
785
1
1.6
1.6
1,3-Butadiene
106-99-0
1
EPA RfC(1)
1266
364
785
ND
1,3-BUTADIENE, 2-METHYL-*
78-79-5
NA
NA
1266
4
2.7
6.4
364
1 6.4
6.4
117 0 ND ND
785
3
1.5
1.6
1,3-Dichlorobenzene
541-73-1
0.5
MDEQ(1)
1266
364
785
1,3-PENTADIENE*
504-60-9
NA
1266
2
8.4
8.9
364
0 ND
ND
117 0 ND ND
785
2
8.4
8.9
1,3-PENTADIENE, (E)-*
2004-70-8
1266
2
1.8
1.9
364
ND
785
2
1.8
1.9
1,4-Dichlorobenzene
106-46-7
10
ATSDR Chr. MRLf1)
1266
0
NID
0.0
364
0 ND
ND
117 0 ND ND
785
0
ND
1,4-Dioxane
123-91-1
1000
ATSDR Chr. MRL(1)
1266
364
785
1-DECENE*
872-05-9
NA
NA
1266
0
ND
0,0
364
0 ND
ND
117 0 ND ND
785
f!
ND
1-HEPTANAL, 3,5,5-TRIETHYL-*
1000160-77-0
NA
1266
4
14.6
29.0
364
117 0 ND ND
785
4
14.6
29.0
1-HEPTANOL, 2-PROPYL-*
10042-59-8
NA
NA
1266
1
1.5
1.5
364
0 ND
ND
117 0 ND ND
785
1
1.5
1.5
1-HEXENE, 4-METHYL-*
3769-23-1
NA
1266
1
5.6
5.6
364
785
1
5.6
5.6
1 -METHYL-2-METHYLENECYCLOHEXANE*
2808-75-5
NA
NA
1266
1
1.2
1.2
364
0 ND
ND
117 0 ND ND
785
1
1.2
1.2
1 -METHYLDECAHYDRONAPHTHALENE*
2958-75-0
1266
7
10.9
26.0
364
785
7
10.9
26.0
1-TRIDECENE*
2437-56-1
NA
NA
1266
1
1.3
1.3
364
0 ND
ND
117 0 ND ND
785
1
1.3
1.3
2(1 H)-NAPHTHALENONE, OCTAHYDRO-4.. .*
938-06-7
1266
1
29
29.0
364
0 ND
785
1
29.0
29.0
2,2,4-T rimethylpentarie
540-84-1
750
MDEQ(1)
1266
1
1
1.0
364
0 ND
ND
117 0 ND ND
785
1
1.0
1.0
2,2,7,7-TETRAMETHYLOCTANE*
1071-31-4
NA
1266
1
1.2
1.2
364
117 0 ND ND
785
1
1.2
1.2
2,3,4,5-TETRAHYDROPYRIDAZINE*
694-06-4
NA
NA
1266
1
2.2
2.2
364
0 ND
117 0 ND ND
785
1
2.2
2.2
2-BUTENAL*
4170-30-3
3
MDEQ(1)
1266
1
1.7
1.7
364
0 ND
785
1
1.7
1.7
2-BUTENAL, (E)-*
123-73-9
NA
NA
1266
4
1.9
2.7
364
0 ND
ND
117 0 ND ND
785
4
1.9
2.7
2-BUTENOIC ACID, METHYL ESTER, (Z)-*
4358-59-2
NA
1266
1
8
8.0
364
0 ND
785
1
8.0
8.0
2-Chloro-1,3-butadiene
126-99-8
6
EPA RfC(')
1266
0
ND
0,0
364
0 ND
ND
117 0 ND ND
785
f!
ND
2-DECENAL, (E)-*
3913-81-3
NA
1266
364
0 ND
785
2-HEPTANONE*
110-43-0
500
MDEQO
1266
1
11
11.0
364
0 ND
ND
117 0 ND ND
785
1
11.0
11.0
2-PENTANONE*
107-87-9
1500
MDEQ(1)
1266
2
23.5
29.0
364
785
2
23.5
29.0
2-PROPANOL, 2-METHYL-*
75-65-0
600
MDEQO)
1266
6
47.6
120.0
364
0 ND
ND
117 2 120.0 120.0
785
4
11.4
18.0
3,5-DECADIENE, 2,2-DIMETHYL-, (Z...*
55638-50-1
NA
1266
1
6.4
6.4
364
0 ND
785
1
6.4
6.4
3,5-OCTADIENE, 4,5-DIETHYL-*
67652-84-0
NA
NA
1266
1
10
10.0
364
0 ND
ND
117 0 ND ND
785
1
10.0
10.0
3-Chloropropene
107-05-1
32
EPA RfC(1)
1266
364
0 ND
785
3-HEPTANONE*
106-35-4
NA
NA
1266
1
2.4
2.4
364
0 ND
ND
117 0 ND ND
785
1
2.4
2.4
4-DECENE, 2,2-DIMETHYL-, (E)-*
55534-69-5
NA
1266
364
0 ND
117 0 ND ND
785
4-NONENE, 5-BUTYL-*
7367-38-6
NA
NA
1266
1
3.9
3.9
364
0 ND
ND
117 0 ND ND
785
1
3.9
3.9
4-TRIFLUOROACETOXYTRIDECANE*
1000245-47-3
1266
364
117 0 ND ND
785
5-OCTEN-2-YN-4-OL*
1000196-87-1
NA
NA
1266
1
11
11.0
364
0 ND
ND
117 0 ND ND
785
1
11.0
11.0
Page 1 of 5
-------
Table 2. Cumulative Air Sample Summary - Non-Target Analytes
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Human Health Air
All Sample Durationst
8-hour Target Period
12-hour Target Period
24-hour Target Period
Non-Target Analytes (including TICs)
CAS NO
Screening Level
Source
N
Ndet
Average
Max
N
Ndet
Average Max
N Ndet 7era,9e
Level**
Max
N
Ndet
Average
Max
(PPbv)
Level**
(PPbv)
Level** (ppbv)
(ppbv)
Level**
(ppbv)
7-METHYLBICYCLO[4.2.0]OCTANE*
1000210-90-2
NA
NA
1266
1
4.5
4.5
364
0
ND ND
117 0 ND
ND
785
1
4.5
4.5
7-NORBORNYL T-BUTYL ETHER*
3391-07-9
NA
1266
1
14
14.0
364
n
ND ND
117 0 ND
ND
785
1
14.0
14.0
ACETALDEHYDE*
75-07-0
5
EPA RfC(1)
1266
26
6.9
15.0
364
5
7.7 10.0
117 3 8.2
11.0
785
18
6.5
15.0
ACETIC ACID, 1,1-DIMETHYLETHYL ESTER*
540-88-5
2000
MDEQO
1266
1
2.2
2.2
364
ij
ND ND
117 0 ND
ND
785
1
2.2
2.2
ACETIC ACID, 2-ETHYLHEXYL ESTER*
103-09-3
2
MDEQO
1266
1
6.2
6.2
364
117 1 6.2
6.2
785
ACETOACETIC ACID, 1-THIO-, S-ALLYL*
15780-65-1
NA
NA
1266
3
1.6
1.8
364
0
ND ND
117 0 ND
ND
785
3
1.6
1.8
Acetone
67-64-1
13000
EPA RSL(1)
1266
1096
8.1
300.0
364
339
9.9 120.0
117 116 17.3
300.0
785
641
5.9
89.0
ACETONITRILE*
75-05-8
36
EPA RfC(1)
1266
62
7.7
47.0
364
5
8.3 12.0
117 2 5.9
6.4
785
55
7.7
47.0
Acrylonitrile
107-13-1
1
EPA RfC(1)
1266
364
785
ALPHA-PINENE*
80-56-8
200
MDEQO)
1266
2
7.1
13.0
364
IS
ND ND
117 0 ND
ND
785
2
7.1
13.0
BENZENE, 1,3,5-TRICHLORO-*
108-70-3
NA
NA
1266
364
117 0 ND
785
BENZENE, 1,3-DIETHYL-*
141-93-5
NA
NA
1266
1
1.9
1.9
364
0
ND ND
117 0 ND
ND
785
1
1.9
1.9
BENZENE, 1 -METHYL-4-(1-METHYLETHYL)*
99-87-6
1.8
MDEQ(1)
1266
1
2.7
2.7
364
785
1
2.7
2.7
Benzyl chloride
100-44-7
0.2
EPA RfC(1)
1266
o
ND
0.0
364
IS
ND ND
117 0 ND
ND
785
f!
ND
BETA-PINENE*
127-91-3
200
MDEQ(1)
1266
364
785
Bromodichloromethane
75-27-4
0.01
EPA RSLO
1266
0
ND
0.0
364
0
ND ND
117 0 ND
ND
785
f!
ND
Bromoform
75-25-2
0.2
EPA RSL(1)
1266
0.0
364
785
BROMOMETHANE
74-83-9
5
ATSDR Chr. MRL(')
1266
10
1
23.0
364
1
5.0 15.0
117 3 5.0
23.0
785
6
1.0
7.1
BUTANAMIDE, 3,3-DIMETHYL-*
926-04-5
NA
1266
1
5.6
5.6
364
785
1
5.6
5.6
BUTANE*
106-97-8
10000
MDEQ(1)
1266
7
4.8
10.0
364
u
ND ND
117 0 ND
ND
785
7
4.8
10.0
BUTANOIC ACID, 2-METHYLPROPYL ESTER*
539-90-2
NA
1266
1
1.9
1.9
364
ND ND
785
1
1.9
1.9
BUTANOIC ACID, BUTYL ESTER*
109-21-7
NA
NA
1266
1
14
14.0
364
IS
ND ND
117 0 ND
ND
785
1
14.0
14.0
BUTANOIC ACID, ETHYL ESTER*
105-54-4
NA
1266
1
17
17.0
364
785
1
17.0
17.0
BUTANOIC ACID, METHYL ESTER*
623-42-7
NA
NA
1266
1
4.8
4.8
364
0
ND ND
117 0 ND
ND
785
1
4.8
4.8
BUTANOIC ACID, PROPYL ESTER*
105-66-8
1266
1
16
16.0
364
ND ND
785
1
16.0
16.0
CARBON DISULFIDE
75-15-0
200
EPA RfC(')
1266
60
2
120.0
364
IS
ND ND
117 0 ND
ND
785
60
3.1
120.0
Carbon tetrachloride
56-23-5
30
ATSDR Chr. MRL(1)
1266
364
785
CARBONYL SULFIDE*
463-58-1
4
MDEQO
1266
5
2.3
5.2
364
0
ND ND
117 0 ND
ND
785
5
2.3
5.2
Chlorobenzene
108-90-7
10
EPA RfC(1)
1266
364
ND ND
785
Chloroethane
75-00-3
4000
EPARfCO
1266
0
ND
0,0
364
IS
!!¦.:: ff "¦!. Mirv
117 0 ND
ND
785
f!
ND
Chloroform
67-66-3
20
ATSDR Chr. MRL(1)
1266
364
ND
785
Chloromethane
74-87-3
50
ATSDR Chr. MRL(')
1266
0
ND
0,0
364
0
ND ND
117 0 ND
ND
785
f!
!!\.iil! J
cis-1,2-dichloroethene
156-59-2
9
MDEQO
1266
364
785
cis-1,3-Dichloropropene
10061-02-6
4
MDEQO
1266
0
ND
0,0
364
f!
ND ND
117 0 ND
ND
785
f!
ND
Cumene
98-82-8
80
EPA RfC(1)
1266
364
ND ND
785
CYCLODECENE, 1-METHYL-*
66633-38-3
NA
NA
1266
2
4.7
5.2
364
0
ND ND
117 0 ND
ND
785
2
4.7
5.2
CYCLODODECANE*
294-62-2
NA
1266
1
1.7
1.7
364
785
1
1.7
1.7
CYCLODODECENE*
1501-82-2
NA
NA
1266
1
8.6
8.6
364
IS
ND ND
117 0 ND
ND
785
1
8.6
8.6
CYCLODODECENE, (E)-*
1486-75-5
1266
1
7.7
7.7
364
785
1
7.7
7.7
CYCLOHEXANE, 1,2,3-TRIMETHYL-*
7667-55-2
NA
NA
1266
1
3.8
3.8
364
0
ND ND
117 0 ND
ND
785
1
3.8
3.8
CYCLOHEXANE, 2-BUTYL-1,1,3-TRIMETHYL-*
54676-39-0
1266
4
22.8
48.0
364
785
4
22.8
48.0
CYCLOHEXANOL, 3-(3,3-DIMETHYLBUTYL)-*
40564-98-5
NA
NA
1266
3
10.2
15.0
364
IS
ND ND
117 0 ND
ND
785
3
10.2
15.0
CYCLOHEXANONE, 2,3-DIMETHYL-*
13395-76-1
1266
1
26
26.0
364
785
1
26.0
26.0
CYCLOPENTANE*
287-92-3
6000
MDEQO
1266
2
3.4
5.1
364
0
ND ND
117 0 ND
ND
785
2
3.4
5.1
CYCLOPENTANE, 1,1'-ETHYLIDENEBIS-*
4413-21-2
1266
1
9.7
9.7
364
785
1
9.7
9.7
CYCLOPENTANE, 1-HYDROXYMETHYL-*
1000156-73-8
NA
NA
1266
1
6.1
6.1
364
IS
117 0 ND
ND
785
1
6.1
6.1
CYCLOPENTANE, 1 -PE NTYL-2-PROPYL-*
62199-51-3
NA
NA
1266
1
1.1
1.1
364
0
ND ND
117 0 ND
ND
785
1
1.1
1.1
Page 2 of 5
-------
Table 2. Cumulative Air Sample Summary - Non-Target Analytes
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Human Health Air
All Sample Durationst
8-hour Target Period
12-hour Target Period
24-hour Target Period
Non-Target Analytes (including TICs)
CAS NO
Screening Level
Source
N
Ndet
Average
Max
N
Ndet
Average Max
N Ndet 7era,9e
Level**
Max
N
Ndet
Average
Max
(PPbv)
Level**
(PPbv)
Level** (ppbv)
(ppbv)
Level**
(ppbv)
CYCLOPENTANE, PROPYL-*
2040-96-2
NA
NA
1266
1
6.1
6.1
364
0
117 0 ND
ND
785
1
6.1
6.1
DECANAL*
112-31-2
1266
2
7.9
8.7
364
ND ND
785
2
7.9
8.7
DECANE, 2,2,4-TRIMETHYL-*
62237-98-3
Nft
NA
1266
1
1.1
1.1
364
0
ND ND
117 0 ND
ND
785
1
1.1
1.1
DECANE, 2,2,6-TRIMETHYL-*
62237-97-2
NA
1266
1
4.3
4.3
364
785
1
4.3
4.3
DECANE, 2,2,8-TRIMETHYL-*
62238-01-1
NA
NA
1266
1
14
14.0
364
0
ND ND
117 0 ND
ND
785
1
14.0
14.0
DECANE, 2,2-DIMETHYL-*
17302-37-3
1266
1
1.3
1.3
364
785
1
1.3
1.3
DECANE, 2,3,4-TRIMETHYL-*
62238-15-7
NA
NA
1266
1
1.5
1.5
364
0
ND ND
117 0 ND
ND
785
1
1.5
1.5
DECANE, 2,3,5-TRIMETHYL-*
62238-11-3
NA
1266
1
6.1
6.1
364
ND ND
117 0 ND
ND
785
1
6.1
6.1
DECANE, 2,6,7-TRIMETHYL-*
62108-25-2
NA
NA
1266
1
6.6
6.6
364
0
ND ND
117 0 ND
ND
785
1
6.6
6.6
DIACETYL*
431-03-8
NA
1266
1
1.8
1.8
364
785
1
1.8
1.8
Dibromochloromethane
124-48-1
0.01
EPA RSLO
1266
ii
ND
0.0
364
0
ND ND
117 0 ND
ND
785
f!
ND
DICHLOROACETIC ACID, 4-TRIDECYL ESTER*
1000280-64-3
NA
1266
364
ND ND
785
Dichlorodifluoromethane
75-71-8
20
EPA RfC(')
1266
ii
ND
0.0
364
fi
ND ND
117 0 ND
ND
785
f!
ND
DIMETHYL ETHER*
115-10-6
35
MDEQO
1266
364
785
DISULFIDE, DIMETHYL*
624-92-0
7.3
MDEQO
1266
1
2.4
2.4
364
y
ND ND
117 0 ND
ND
785
1
2.4
2.4
DISULFIDE, FLUOROMETHYL METHYL*
60307-49-5
NA
NA
1266
1
2
2.0
364
785
1
2.0
2.0
DODECANE, 2,2,11,11 -TETRAMETHYL-*
127204-12-0
NA
NA
1266
1
6.6
6.6
364
f!
ND ND
117 0 ND
ND
785
1
6.6
6.6
DODECANE, 2,6,11-TRIMETHYL-*
31295-56-4
NA
NA
1266
1
1.6
1.6
364
ND ND
785
1
1.6
1.6
DODECANE, 6-METHYL-*
6044-71-9
NA
NA
1266
1
1.7
1.7
364
0
ND ND
117 0 ND
ND
785
1
1.7
1.7
ETHANE, 1,1-DIFLUORO-*
75-37-6
14800
EPA RfC(1)
1266
9
6
12.0
364
ND ND
785
9
6.0
12.0
ETHYL ACETATE
141-78-6
890
MDEQO)
1266
67
3
76.0
364
2
5.0 76.0
117 0 ND
ND
785
65
1.6
33.0
ETHYL ALCOHOL*
64-17-5
10000
MDEQ(1)
1266
29
68.9
220.0
364
1
CO
CO
117 1 15.0
15.0
785
27
73.2
220.0
EUCALYPTOL*
470-82-6
NA.
NA
1266
1
6.9
6.9
364
0
ND ND
117 1 6.9
6.9
785
u
ND
FURAN, 2,3-DIHYDRO-3-METHYL-*
1708-27-6
1266
1
1.5
1.5
364
ND ND
785
1
1.5
1.5
HENEICOSANE*
629-94-7
NA
NA
1266
0
ND
0.0
364
0
ND ND
117 0 ND
ND
785
f!
ND
HEPTADECANE, 7-METHYL-*
20959-33-5
1266
1
1.4
1.4
364
785
1
1.4
1.4
HEPTANE, 2,2,3,4,6,6-HEXAMETHYL-*
62108-32-1
NA
NA
1266
2
3.9
6.5
364
0
ND ND
117 0 ND
ND
785
2
3.9
6.5
HEPTANE, 2,2,4,6,6-PENTAMETHYL-*
13475-82-6
NA
1266
2
3.1
3.9
364
ND
785
2
3.1
3.9
HEPTANE, 2,2,4-TRIMETHYL-*
14720-74-2
NA
NA
1266
1
13
13.0
364
0
!M!i!"n MlfV
117 0 ND
ND
785
1
13.0
13.0
HEPTANE, 2,2-DIMETHYL-*
1071-26-7
NA
1266
1
57
57.0
364
ND ND
ND
785
1
57.0
57.0
HEPTANE, 4-ETHYL-2,2,6,6-TETRAMER*
62108-31-0
NA
NA
1266
1
6.4
6.4
364
0
ND ND
117 0 ND
ND
785
1
6.4
6.4
Hexachlorobutadiene
87-68-3
0.01
EPA RSL(1)
1266
364
785
HEXADECANE*
544-76-3
NA
NA
1266
1
1.5
1.5
364
0
ND ND
117 0 ND
ND
785
1
1.5
1.5
HEXADECANE, 2,6,10,14-TETRAMETHYL-*
638-36-8
NA
NA
1266
1
29
29.0
364
ND ND
785
1
29.0
29.0
HEXANAL*
66-25-1
0.49
MDEQ(1)
1266
7
3.9
9.2
364
1
6.0 6.0
117 0 ND
ND
785
6
3.6
9.2
HEXANE, 2,2,5,5-TETRAMETHYL-*
1071-81-4
1266
1
1.2
1.2
364
785
1
1.2
1.2
HEXANE, 2,2,5-TRIMETHYL-*
3522-94-9
NA
NA
1266
2
3.5
5.2
364
0
ND ND
117 0 ND
ND
785
2
3.5
5.2
HEXANE, 2,3,4-TRIMETHYL-*
921-47-1
NA
1266
1
15
15.0
364
ND ND
785
1
15.0
15.0
HEXANE, 2,4-DIMETHYL-*
589-43-5
NA
NA
1266
3
5
8.8
364
0
ND ND
117 0 ND
ND
785
3
5.0
8.8
HEXANOIC ACID, METHYL ESTER*
106-70-7
NA
1266
1
2.4
2.4
364
785
1
2.4
2.4
HEXATRIACONTANE*
630-06-8
NA
NA
1266
1
5.2
5.2
364
0
ND ND
117 0 ND
ND
785
1
5.2
5.2
HEXYL N-VALERATE*
1117-59-5
NA
1266
1
2.2
2.2
364
ND ND
785
1
2.2
2.2
ISOBUTANE*
75-28-5
10000
MDEQO
1266
37
11.7
38.0
364
10
13.2 38.0
117 0 ND
ND
785
27
11.1
38.0
Isopropyl Alcohol
67-63-0
3000
EPA RfC(1)
1266
1098
11.8
530.0
364
274
11.9 150.0
117 113 22.8
130.0
785
711
10.1
530.0
LIMONENE*
138-86-3
NA
NA
1266
6
7.9
21.0
364
1
21.0 21.0
117 0 FMD
ND
785
5
5.3
8.1
METHYL 3-BUTENOATE*
3724-55-8
1266
2
5.1
8.8
364
785
2
5.1
8.8
Methyl butyl ketone
591-78-6
10
EPA RfCO
1266
0
ND
0.0
364
0
ND ND
117 0 ND
ND
785
n
ND
Page 3 of 5
-------
Table 2. Cumulative Air Sample Summary - Non-Target Analytes
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Human Health Air
All Sample Durationst
8-hour Target Period
12-hour Target Period
24-hour Target Period
Non-Target Analytes (including TICs)
CAS NO
Screening Level
Source
N
Ndet
Average
Max
N
Ndet
Average Max
N Ndet 7era,9e
Level**
Max
N
Ndet
Average
Max
(PPbv)
Level**
(PPbv)
Level** (ppbv)
(ppbv)
Level**
(ppbv)
METHYL ETHYL KETONE
78-93-3
2000
EPA RfC(1)
1266
48
1
120.0
364
0
ND ND
117 1 5.0
30.0
785
47
1.7
120.0
Methyl isobutyl ketone
108-10-1
700
EPA RfC(1)
1266
0
0,0
364
0
ND ND
117 0 ND
ND
785
0
ND
Methyl tert-butyl ether
1634-04-4
700
ATSDR Chr. MRL(1)
1266
364
ND
785
METHYLENE CHLORIDE
75-09-2
300
ATSDR Chr. MRL(')
1266
18
1
9.0
364
f!
ND ND
117 0 ND
ND
785
18
1.0
9.0
NAPHTHALENE, 2-(1,1-DIMETHYLETHY...*
54934-96-2
1266
1
7.8
7.8
364
785
1
7.8
7.8
NAPHTHALENE, DECAHYDRO-1,6-DIMET.. *
1750-51-2
MA
NA
1266
1
7.2
7.2
364
0
ND ND
117 0 ND
ND
785
1
7.2
7.2
NAPHTHALENE, DECAHYDRO-2.6-DIMETHYL-*
1618-22-0
NA
1266
2
6.8
6.9
364
ND
785
2
6.8
6.9
NAPHTHALENE, DECAHYDRO-2-METHYL-*
2958-76-1
NA
NA
1266
4
10
23.0
364
0
ND ND
117 0 ND
ND
785
4
10.0
23.0
NONANAL*
124-19-6
1266
17
3.5
13.0
364
1
13.0 13.0
117 1 9.1
9.1
785
15
2.4
9.1
NONANE, 2,2,3-TRIMETHYL-*
55499-04-2
NA
NA
1266
1
1.1
1.1
364
0
ND ND
117 0 ND
ND
785
1
1.1
1.1
NONANE, 2-METHYL-*
871-83-0
1266
1
16
16.0
364
785
1
16.0
16.0
NONANE, 3-METH YL-5-PROPYL-*
31081-18-2
NA
NA
1266
2
4.4
5.6
364
0
ND ND
117 0 ND
ND
785
2
4.4
5.6
OCTADECANE, 2,6-DIMETHYL-*
75163-97-2
1266
1
7.8
7.8
364
785
1
7.8
7.8
OCTANAL*
124-13-0
NA
NA
1266
1
1.1
1.1
364
0
ND ND
117 0 ND
ND
785
1
1.1
1.1
OCTANE, 2,2-DIMETHYL-*
15869-87-1
1266
1
2.5
2.5
364
ND
785
1
2.5
2.5
OCTANE, 2,3,3-TRIMETHYL-*
62016-30-2
NA
NA
1266
1
5.7
5.7
364
0
ND ND
117 0 ND
ND
785
1
5.7
5.7
OCTANE, 2,6-DIMETHYL-*
2051-30-1
1266
3
12.3
25.0
364
785
3
12.3
25.0
OCTANE, 2,7-DIMETHYL-*
1072-16-8
NA
NA
1266
1
4.8
4.8
364
0
ND ND
117 0 ND
ND
785
1
4.8
4.8
OCTANE, 4-ETHYL-*
15869-86-0
1266
1
14
14.0
364
785
1
14.0
14.0
o-Veratramide*
1521-39-7
NA
NA
1266
1
24
24.0
364
0
ND ND
117 0 ND
ND
785
1
24.0
24.0
PENTADECANE, 2,6,10,14-TE TRAM ETHYL-*
1921-70-6
1266
1
1.1
1.1
364
785
1
1.1
1.1
PENTANE*
109-66-0
300
EPA RfC(1)
1266
59
21.2
180.0
364
12
10.5 51.0
117 0 ND
ND
785
47
23.9
180.0
PENTANE, 2,3-DIMETHYL-*
565-59-3
850
MDEQO
1266
2
9.2
16.0
364
ND
785
2
9.2
16.0
PENTANE, 3-ETHYL-2.2-DIMETHYL-*
16747-32-3
NA
NA
1266
1
4.6
4.6
364
0
ND ND
117 0 ND
785
1
4.6
4.6
PENTANE, 3-METHYL-*
96-14-0
1000
MDEQO
1266
1
1.4
1.4
364
785
1
1.4
1.4
PROPANE*
74-98-6
NA
NA
1266
10
4.4
25.0
364
1
o
o
117 0 ND
ND
785
9
4.1
25.0
PROPANOIC ACID, 2-OXO-*
127-17-3
1266
1
5.5
5.5
364
785
1
5.5
5.5
PROPYLENE
115-07-1
2000
EPA RfC(')
1266
18
1
1.0
364
0
ND ND
117 0 ND
ND
785
18
1.0
1.0
STYRENE
100-42-5
200
ATSDR Chr. MRL(1)
1266
2
1
5.0
364
785
2
1.0
5.0
SULFUROUS ACID, BUTYL HEPTADECYL...*
1000309-18-4
NA
NA
1266
1
6.1
6.1
364
0
ND ND
117 0 ND
ND
785
1
6.1
6.1
TETRACHLOROETHYLENE
127-18-4
40
ATSDR Chr. MRL(1)
1266
1
1
2.0
364
785
1
1.0
2.0
TETRADECANE*
629-59-4
NA
NA
1266
1
1.3
1.3
364
0
ND ND
117 0 ND
ND
785
1
1.3
1.3
TETRADECANE, 2,2-DIMETHYL-*
59222-86-5
NA
1266
1
34
34.0
364
785
1
34.0
34.0
TETRAHYDROFURAN
109-99-9
6
MDEQO
1266
4
1
44.0
364
1
5.0 44.0
117 0 ND
ND
785
3
1.0
3.0
TRANS,TRANS-1,8-DIMETHYLSPIRO[4....*
1000111-72-8
Nft
1266
1
6.3
6.3
364
785
1
6.3
6.3
traris-1,2-Dichloroethene
156-60-5
15
EPA RfC(1)
1266
0
ND
0.0
364
0
ND ND
117 0 ND
ND
785
f!
ND
trans-1,3-Dichloropropene
10061-01-5
0.5
MDEQO
1266
364
785
TRANS-DECALIN, 2-METHYL-*
1000152-47-3
NA
1266
1
11
11.0
364
0
ND ND
117 0 ND
ND
785
1
11.0
11.0
Trichloroethene
79-01-6
2
EPA RfC(1)
1266
1
1
1.0
364
785
1
1.0
1.0
Trichlorofluoromethane
75-69-4
130
EPA RfCO
1266
0
ND
0,0
364
0
ND ND
117 0 ND
ND
785
f!
ND
TRICOSYL PENTAFLUOROPROPIONATE*
1000351-81-0
NA
1266
1
1.9
1.9
364
785
1
1.9
1.9
TRIDECANE*
629-50-5
NA
NA
1266
1
10
10.0
364
0
ND ND
117 0 ND
ND
785
1
10.0
10.0
TRIDECANE, 4,8-DIMETHYL-*
55030-62-1
1266
1
4.8
4.8
364
785
1
4.8
4.8
TRIDECANE, 6-METHYL-*
13287-21-3
NA
NA
1266
1
45
45.0
364
0
ND ND
117 0 ND
ND
785
1
45.0
45.0
TRIDECYL HEPTAFLUOROBUTYRATE*
1000351-82-8
1266
364
785
TRIETHYLAMINE*
121-44-8
2
EPA RfCO
1266
2
12.9
18.0
364
0
ND ND
117 0 ND
ND
785
2
12.9
18.0
TRISULFIDE, DIMETHYL*
3658-80-8
NA
NA
1266
1
5.1
5.1
364
0
ND ND
117 0 ND
ND
785
1
5.1
5.1
Page 4 of 5
-------
Table 2. Cumulative Air Sample Summary - Non-Target Analytes
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Human Health Air
All Sample Durationst
8-hour Target Period
12-hour Target Period
24-hour Target Period
Non-Target Analytes (including TICs)
CAS NO
Screening Level
(PPbv)
Source
N
Ndet
Average
Level**
Max
(PPbv)
N
Ndet Average Max
Level** (ppbv)
.. Average Max
N Ndet
Level** (ppbv)
N
Ndet
Average
Level**
Max
(PPbv)
UNDEGANE, 2,2-DIMETHYL-*
17312-64-0
NA
NA
1266
1
2.7
2.7
364
117 0 ND ND
785
1
2.7
2.7
UNDECANE, 2,6-DIMETHYL-*
17301-23-4
1266
6
13.4
52.0
364
0 ND ND
785
6
13.4
52.0
UNDECANE, 3,6-DIMETHYL-*
17301-28-9
MA
Mi
1266
2
8.7
16.0
364
0 ND ND
117 0 ND ND
785
2
8.7
16.0
UNDECANE, 3,9-DIMETHYL-*
17301-31-4
NA
1266
1
4.9
4.9
364
785
1
4.9
4.9
UNDECANE, 5-METHYL-*
1632-70-8
NA
NA
1266
1
1.2
1.2
364
0 ND ND
117 0 ND ND
785
1
1.2
1.2
UNKNOWN*
78-99-9
1266
1
1.6
1.6
364
785
1
1.6
1.6
UNKNOWN*
288-47-1
NA
NA
1266
1
1.2
1.2
364
0 ND ND
117 0 ND ND
785
1
1.2
1.2
UNKNOWN*
62-55-5
NA
1266
2
1.4
1.4
364
785
2
1.4
1.4
Vinyl acetate
108-05-4
10
ATSDR Int. MRL(1)
1266
3
1
2.0
364
0 ND ND
117 0 ND ND
785
3
1.0
2.0
Vinyl bromide
593-60-2
1
EPA RfC(1)
1266
0 0
364
117 0 ND ND
785
Vinyl chloride
75-01-4
30
ATSDR Int. MRL(')
1266
u
ND
0.0
364
0 ND ND
117 0 ND ND
785
u
PPBV - Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects. Average Levels for compounds that were
detected in >5% of samples are the mean using the detection limit for non-detects. Average Levels for tentatively identified compounds are the mean of detects.
tSamples reported do not include instantaneous 'grab' samples. Samples with 8-24 hour target sample periods are included.
NA - Not Available/ND - Not Detected
N - Number of samples analyzed/NDET - Number of detections
C) - Unless otherwise noted, the screening level was obtained from Enbridge Oil Spill Human Health Air Screening Levels, August 31, 2011.
ATSDR Chr. MRL - Agency for Toxic Substances and Disease Registry - Chronic Minimal Risk Level for Inhalation
EPA RfC - If no Chronic MRL is available, the screening level is the EPA Chronic Reference Concentration (RfC). For 2 chemicals, vinyl
acetate and vinyl chloride, the ATSDR Intermediate (Int.) MRL was selected. These were developed more recently than the EPA RfC and
were lower than the EPA RfC.
EPA RSL- If none of the above are available, the EPA Regional Screening Level (RSL) is used.
MDEQ- If none of the above are available, the Michigan DEQ Air Quality Division, Air Toxics Screening Level is the screening level.
Page 5 of 5
-------
1.6
Comparison of Average Air Levels with Human Health Screening Levels
1,2,4-Trimethylbenzene
1.4
1.2
1.0
| 0.8
Cl
0.6
0.4
0.2
0.0
Average Level (ppbv)*
Screening Level (ppbv)
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Benzene
3.0
2.5
2.0
>
CO
Q.
Q.
1.5
1.0
0.5
Average Level (ppbv)*
Screening Level (ppbv)
0.0
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
2-Methylbutane*
6000
5000
4000
>
CO
Q.
Q.
3000
2000
1000
0
Average Level (ppbv)**
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Cyclohexane
2000
1800
1600
1400
1200
>
CO
Q.
Q.
1000
800
600
400
200
0
Average Level (ppbv)*
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Methylcyclopentane*
200
180
160
140
120
>
£ 100
Q.
80
60
40
20
0
Average Level (ppbv)**
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Methylcyclohexane*
4000
3500
3000
2500
>
£ 2000
Q.
1500
1000
500
0
Average Level (ppbv)**
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Ethyl benzene
60 mm—mmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmimmmm.
50
40
| 30
Cl
20
i Average Level (ppbv)*
• Screening Level (ppbv)
10
N=1266
0
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
4-Ethyltoluene
70
60
50
40
>
CO
Q.
Q.
30
20
10
0
Average Level (ppbv)*
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
900
Comparison of Average Air Levels with Human Health Screening Levels
n-Heptane
800
700
600
500
>
CO
Q.
Q.
400
300
200
100
0
Average Level (ppbv)*
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
n-Hexane
200
180
160
140
120
>
£ 100
Q.
80
60
40
20
0
Average Level (ppbv)*
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Nonane*
40
35
30
25
| 20
Cl
15
10
0
N=1266
Average Level (ppbv)**
Screening Level (ppbv)
PPBV - Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
2-Methylhexane*
900
800
700
600
500
>
CO
Q.
Q.
400
300
200
100
0
Average Level (ppbv)**
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
2-Methylpentane*
5000
4500
4000
3500
3000
Q.
Q.
2000
1500
1000
500
0
Average Level (ppbv)**
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Toluene
80
70
60
50
>
CO
Q.
Q.
40
30
20
10
0
Average Level (ppbv)*
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
900
Comparison of Average Air Levels with Human Health Screening Levels
3-Methylhexane*
800
700
600
500
>
CO
Q.
Q.
400
I Average Level (ppbv)**
•Screening Level (ppbv)
300
200
100
N=1266
0
PPBV - Parts Per Billion Volume
* - TIC (tentatively identified compound)
** - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
m&p-Xylene
50
45
40
35
30
Q.
Q.
20
Average Level (ppbv)*
Screening Level (ppbv)
15
10
5
0 N=1266
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
50
Comparison of Average Air Levels with Human Health Screening Levels
o-Xylene
45
40
35
30
>
£ 25
Q.
20
15
10
0
Average Level (ppbv)*
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Acetone
14000 -i
12000
10000
>
CO
Q.
Q.
8000
6000
4000
Average Level (ppbv)*
Screening Level (ppbv)
2000
N=1266
0
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
Comparison of Average Air Levels with Human Health Screening Levels
Isopropyl Alcohol
3000
2500
2000
>
CO
Q.
Q.
1500
1000
500
0
Average Level (ppbv)*
Screening Level (ppbv)
N=1266
PPBV - Parts Per Billion Volume
* - Average Levels for compounds that were detected in <5% of samples are the median value using the detection limit for non-detects.
Average Levels for compounds that were detected in >5% of samples are the mean using the detection limit for non-detects.
Average Levels for tentatively identified compounds are the mean of detects.
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
September 20, 2011
Enbridge Energy, Limited Partnership
c/o Mr. Rich Adams
Vice President, Operations
Superior City Centre
Second Floor
1409 Hammond Ave.
Superior, Wisconsin 54880
Re: Approval of Enbridge Energy, Limited Partnership's September 9,2011 requested
modification of the 2011 Air Monitoring and Sampling Addendum dated June 21,2011
submitted in response to the Administrative Order issued by U.S. EPA on July 27, 2010
and Supplement to the Administrative Order issued by U.S. EPA on September 23, 2010,
pursuant to §311(c) of the Clean Water Act (Docket No. CWA 1321-5-10-001).
Dear Mr. Adams:
On September 9, 2011 Enbridge Energy, Limited Partnership, Enbridge Pipelines (Lakehead)
L.L.C., Enbridge Pipelines (Wisconsin), and Enbridge Energy Partners, L.P. (herein collectively
referred to as "Enbridge") submitted a letter to U.S. EPA requesting a modification of the 2011
Air Monitoring and Sampling Addendum dated June 21, 2011.
U.S. EPA has completed its review of the requested modification; specifically to modify the
laboratory turn-around time (TAT) for Community Air Sampling from a 24-hour TAT to a 5-day
Pursuant to Paragraph 18 of the Order and Paragraph 6 of the Supplement, this letter provides written
confirmation of my September 16,2011 verbal approval of Enbridge's request.
If you have any questions regarding this approval, please contact me immediately at (231) 301-
TAT.
0559.
Sincerely,
Ralph Dollhopf
Federal On-Scene Coordinator and Incident Commander
U.S. EPA, Region 5
cc: L. Kirby-Miles, U.S. EPA, ORC
-------
J. Cahn. U.S. EPA. ORG
J, Kimble. U.S. HP A
M. Durno, U.S. EPA
[. Edwards. U.S. EPA
S. Wolfe. U.S. I;.PA
S. Vega, U.S. EPA
M. Dueharme. MDEQ
M. Alexander. MDEQ
I.. Dykema. MDCH
Records Center. U.S. EPA. Re
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
'*t raerf"
October 26, 201 I
Enbridge Energy. Limited Partnership
c/o Mr. Rich Adams
Vice President. Operations
Superior City Centre
Second Floor
1409 I ianimond A\ e.
Superior. Wisconsin 54880
Re: Approval with Mollifications of Enbridge Energy, Limited Partnership's October 13,
2011 requested modification of the 2011 Air Monitoring and Sampling Addendum dated
June 21, 2011 submitted in response to the Administrative Order issued by IIS, EPA on
July 27, 2010 and Supplement to the Administrative Order issued by U.S. EPA on
September 23, 2010, pursuant to §311(c) of the (.'lean Water Act (Docket No. €WA 1321-5-
10-001).
Dear Mr. Adams:
On October 13. 2011 I in bridge Energy, Limited Partnership. Enhridge Pipelines I Lakehead)
L.L..C.. Lnbridge Pipelines (Wiseonsin), and Enbridge Lnerg} Partners. I.,P. (herein eollecthely
referred to us "Enbridge") submitted a letter to I'.S. EPA requesting a modification of the 2011
Air Monitoring and Sampling Addendum dated June 21. 2011.
US. EPA has completed its re\ iew of the requested modification; specilkalh to "indefinite!)
suspend all Community Air Sampling and Monitoring activities. Work Area Monitoring, and
eliminate River Opening Sampling, effective immediately."
Although LPA does not agree with Enbridge's justification for the requested suspension of air
monitoring and sampling. EPA agrees that a decrease in the prescribed le\ el of air monitoring
and sampling under the current plan is warranted based on EP.Vs own review of the daih air
monitoring and sampling data. Therefore, pursuant to Paragraph IS of the Order and Paragraph 6
of the Supplement. U.S. EPA approves the Enbridge request with modifications described below.
• Remo\e the term "indefinitely". Air monitoring and sampling will be required when
work ramp-up in the spring occurs, as approved by I :,S. EPA.
• Air monitoring must be continued in current work areas to ensure that workers are not
exposed to unacceptable lexels of oil-related contaminants: specifically during
excavations such as Talmadge Creek MP 0.5, MP 2.75 and 6.0, the island at MP 15.0.
and any other pending work areas.
-------
• Work area perimeter sampling must be performed in areas in close proximitx to
residential areas as directed by I .S.FTA.
• The plum to assess acetaldehvde air leveU must siill be completed as requested b\ the
Michigan Deparimetn ol'Communit) Health in a letter dated August 23, 2011 and
discussed during the 2l) \ueust meeting with I \S, EPA and MIX'H representatives.
• Odor complaint response capability must be maintained as required in the 2011 Air
Monitoring urn! Sampling Addendum in the Sampling and Anuh Plait Submitted: June
15, 2011. Approved: June 21, 20J1
If \ mi ha\ c any questions regarding this approval, please contact nie immediate!} at (23 l's 3D 1 -
1155*-).
Kaipn uomiopi
Federal On-Scene Coordinator and Incident Commander
U.S. CPA. Region 5
cc: F. Kirby-Milcs. U.S. HI'A. ORG
J. Cahn. U.S. FPA. ORC
J Kimble. U.S. FPA
M. Durtio. U.S. I*PA
T, Edwards. U.S. HP.\
S. Wolfe. U.S. F.PA
S. Vega. U.S. F.PA
ML Dueharme, MF>HQ
M. Alexander, MDE\>
L. Djkema. MDCH
Records Center, 1 '.S, f PA. Reg. V
Sincerely.
2
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Approved
Enbridge Line 6B MP 608
Marshall, Ml Pipeline Release
Air Monitoring and Sampling
Addendum to the Sampling and Analysis Plan
Prepared for United States Environmental Protection Agency
Enbridge Energy, Limited Partnership
Originally Submitted: December 9, 2011
Resubmitted: January 31, 2012
Resubmitted: March 28, 2012
Resubmitted: May 3, 2012
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Approved
I.0 INTRODUCTION AND PURPOSE 1
2.0 ADAPTIVE MANAGEMENT 1
3.0 AIR SAMPLING METHODS 2
4.0 METEOROLOGICAL DATA 2
5.0 WORK AREA & PERIMETER EVALUATIONS 3
5.1 Work Area Real-Time Monitoring 3
5.2 Work Area Perimeter Real-Time Monitoring 3
5.3 Work Area Perimeter Sampling 4
6.0 ODOR INVESTIGATIONS 5
7.0 DATA QUALITY AND MANAGEMENT 6
8.0 AIR MONITORING AND SAMPLING REPORTING 6
9.0 PROJECT ORGANIZATION 8
10.0 CALIBRATION AND MAINTENANCE OF FIELD INSTRUMENTS 8
II.0 CHAIN OF CUSTODY (COC) 8
12.0 SAMPLE LABELS 9
13.0 PACKAGING AND SHIPPING 9
14.0 REFERENCES 9
ATTACHMENTS
Attachment A
Attachment B
Attachment C
Attachment D
VOCs Detected by TO-15 Analysis
Enbridge Oil Spill Human Health Screening Levels
Field Standard Operating Procedures
Galson Laboratories SOP for VOCs by OSHA PV-2120 & EPA TO-15
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Approved
LIST OF ACRONYMS
coc
Chain of Custody
Enbridge
Enbridge Energy, Limited Partnership
GPS
global positioning system
H2S
hydrogen sulfide
Line 6B
The pipeline owned by Enbridge Energy, Limited Partnership that runs
just south of Marshall, Michigan
MDCH
Michigan Department of Community Health
MP
Mile Post
NWS
National Weather Service
OSHA
Occupational Safety and Health Administration
PPm
parts per million
QA/QC
Quality Assurance/Quality Control
SCRIBE
SCRIBE is a software tool developed by EPA to assist in the process of
managing environmental data.
SOP
Standard Operating Procedure
TIC
Tentatively Identified Compound
U.S. EPA
United States Environmental Protection Agency
U.S. EPA Order
U.S. EPA Removal Administrative Order Under Section 311(c) of the
Clean Water Act, issued on July 27, 2010 to Enbridge Energy
Partners, L.P., Docket Number: CWA 1321-5-10-001
VOCs
Volatile Organic Compounds
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Approved
1.0 INTRODUCTION AND PURPOSE
Enbridge Energy, Limited Partnership (Enbridge) will conduct air monitoring and sampling to
evaluate worker safety and public health during assessment and recovery operations.
Enbridge was given verbal direction on June 2, 2011, verified in a letter dated June 17, 2011
by United States Environmental Protection Agency (U.S. EPA) to conduct real-time air
monitoring and/or air sampling in the following areas:
• Real-time air monitoring in work areas where oil recovery activities occur;
• Real-time air monitoring for work area perimeters, if elevated volatile organic
compounds (VOCs) or benzene are detected during work area air monitoring, within
close proximity to residential areas;
• Air sampling for work area perimeters, if continuous elevated VOCs or benzene
levels are detected during work area perimeter air monitoring, within close proximity
to residential areas as directed by U.S. EPA, and
• Air monitoring and sampling in other areas in response to odor complaints.
The real-time air monitoring will include VOCs, hydrogen sulfide (H2S), and benzene. Air
sampling will only be conducted for VOCs.
Data gathered in the above mentioned areas will be used to assess the potential for worker
and community exposures associated with oil and oil recovery efforts. All field work and
data collection will be conducted in accordance with approved work plans and standard
operating procedures (SOPs). More detailed discussions of air sampling and real-time air
monitoring and air sampling can be found in the following sections.
2.0 ADAPTIVE MANAGEMENT
Many of the activities described in this Addendum are investigative in nature and are
designed to provide scientific information that can be used to further evaluate worker safety
and public health. Therefore, future findings of assessment activities may affect the viability
and/or effectiveness of activities described herein. Findings of air monitoring and sampling
activities shall be evaluated and considered in an iterative fashion when determining
tactics and strategies to accomplish the overall objectives of the work. However, any
changes to the activities described must be approved by the U.S. EPA prior to changing
this Addendum and/or implementation of activities.
1
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Approved
3.0 AIR SAMPLING METHODS
Air samples for VOCs will be collected by subatmospheric sampling using evacuated
canisters in accordance with the field SOP included in Attachment C. The collected whole-
air samples will be analyzed according to modified U.S. EPA Method TO-15 and
Occupational Safety and Health Administration (OSHA) PV-2120. Attachment D presents
the laboratory SOP for this sampling. The compounds detected by TO-15 analysis are
presented in Attachment A. The laboratory will also provide a report of Tentatively Identified
Compounds (TICs) detected in each canister sample. Please note that acetaldehyde will be
included as a calibrated laboratory standard analyte, and not as a TIC as in previous
analysis.
Canister samples will consist of either grab (instantaneous) or 24-hour collections. The
collection time will be based on sampling objectives. For instance, a grab sample may be
collected in response to odor complaints. A 24-hour sample will be collected for evaluating
the potential for long-term exposure at work area perimeter sites. The 24-hour samples will
be positioned both upwind (one sample) and downwind (two samples) of oil recovery work
areas near residential areas to evaluate VOC vapors on-site and as background (further
described in Section 5.1 below). All extended duration samples will be collected using critical
flow orifices and pressure regulators calibrated by the laboratory to collect a specified target
volume into the canister over the desired period. Details of the flow rate settings and
pressure limits of the flow controllers are contained in the applicable SOP.
Samples will be sent to Galson Laboratories, an American Industrial Hygiene Association
accredited laboratory, in Syracuse, NY. Samples will be analyzed on a five-day turnaround
time for sample results.
4.0 METEOROLOGICAL DATA
Meteorological data is an important consideration for deploying canisters and for interpreting
air sampling results. National Weather Service (NWS) data will be used to support air
sampling.
In areas where work area perimeter air sampling is conducted, NWS data from Battle Creek
(call sign KBTL) or Kalamazoo (call sign KAZO), whichever is in closer physical proximity,
will be used to produce wind roses and classify upwind/downwind samples. The
2
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Approved
observations of meteorological data (specifically temperature, wind speed, and wind
direction) will be downloaded from the internet daily.
Forecasts issued by the NWS, accessed via the NWS web site, will be used to plan sample
deployment. Samples will be placed in patterns so as to capture (as best possible)
conditions both upwind and downwind of an oil recovery work area based on these
forecasts. Predicted shifts in winds due to frontal passages will be taken into consideration
in sample placement.
5.0 WORK AREA & PERIMETER EVALUATIONS
5.1 Work Area Real-Time Monitoring
Real-time air monitoring for VOCs, H2S, and benzene, will be conducted using a MultiRAE
Plus (or similar) and UltraRAE or Gastec Pump with benzene colorimetric tubes within all the
work zones. Enbridge Safety or safety designee will coordinate work area air monitoring
activities. Air monitoring readings will be documented once each hour. If the Health and
Safety monitoring indicates a VOC alarm above applicable action levels, benzene checks
will be initiated with a real-time benzene monitor along with appropriate protective action as
described in the Health and Safety Plan. The benzene checks will be recorded on an air
monitoring log form or by entry into a handheld data collection device.
5.2 Work Area Perimeter Real-Time Monitoring
In the event work area real-time air monitoring reveals a detection of VOCs in exceedance of
300 parts per million (ppm) for two consecutive 1-minute readings or benzene in
exceedance of 0.5 ppm (American Conference of Governmental Industrial Hygienists
(ACGIH) Threshold Limit Value (TLV)), work area perimeter real-time air monitoring will be
initiated if the work area is in close proximity to residential areas. Close proximity to
residential areas shall be determined through a review by Enbridge of oil recovery activities
on the GIS mapping system. Enbridge will document distances between oil recovery
activities and residential dwellings and review factors including, but not limited to: natural
and man-made features, topography, and prevailing wind direction to make a determination
on whether the oil recovery activity is in close proximity to a residential area. This
determination and supporting documentation will be e-mailed to U.S. EPA air support staff
for final determination. Air monitoring will be conducted as outlined in Section 5.1 in a
3
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Approved
minimum of three locations to ensure both upwind (one location) and downwind (two
locations) capture zones from work operations to evaluate VOC vapors on-site and as
background. Air monitoring will be conducted by means of one MultiRAE Plus monitor (or
similar), moving between each of the three locations, during periods of active oil recovery.
The air monitoring will be conducted at a rate of approximately 30 minutes at each location
commencing at the initiation of oil recovery activities and ending at the completion of oil
recovery activities for a single work day (i.e. one full work day of air monitoring). If the air
monitoring indicates a sustained VOC alarm (i.e. two consecutive 1-minute readings) above
the detection limit (i.e. 0.1 ppm), a benzene check will be initiated with a real-time benzene
monitor (i.e. UltraRAE or Gastec Pump with benzene colorimetric tubes). Work area
monitoring will continue during work area perimeter air monitoring. Work area perimeter air
monitoring will be discontinued and revert back to only work area air monitoring, if no
sustained detections, as defined above, are revealed.
5.3 Work Area Perimeter Sampling
Work area perimeter air samples will be collected at work sites involving submerged oil
recovery, dredged sediment recovery, and overbank excavation, if both the following
conditions exist:
1. Work area perimeter air monitoring (triggered by work area air monitoring) reveals
two consecutive 1-minute sustained detections of VOCs in exceedance of 300 ppm
or benzene in exceedance of 0.5 ppm, and
2. Work area is in close proximity to residential areas.
Within 24-hours of the existence of the above two conditions, three canister samples will be
collected simultaneously over a 24-hour period along the perimeter work areas, coinciding
with work activity (e.g. 0700 to 0700 sampling period). Sample locations will be selected
based on anticipated activities and forecast wind directions. The purpose is to select
locations with the greatest opportunity to detect volatile organic compounds, if any, that are
present during recovery activities. Work area samples will be positioned to ensure both
upwind (one sample) and downwind (two samples) capture zones from work operations to
evaluate VOC vapors on-site and as background. Sample canisters will be placed as close
as practical to the actual removal activities, without compromising site safety or work efforts.
All sample locations will be documented using global positioning system (GPS) devices.
4
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Approved
Following the initial response, perimeter air sampling will continue at identified work
locations (i.e. work locations where the above two conditions exist), as directed by U.S. EPA
for a period of 12 work days, or until results can be evaluated for an initial 6-day period, or
until completion of work (whichever is the shorter duration). Enbridge and U.S. EPA will
review all sampling results from the initial period, and determine the perimeter sampling
frequency and strategy needed for ongoing operations.
6.0 ODOR INVESTIGATIONS
Enbridge will provide an Odor Response Team. During periods of active oil recovery, the
Odor Response Team will be contacted and response initiated by contacting the
complainant within 30 minutes (maximum) after receiving odor complaints/concerns from the
Enbridge Hotline between 0700 and 1900 Monday through Saturday. The initial complaint
information will be collected through the Hotline and evaluated for response. Complaints
received during periods when there is no active oil recovery, or on weekends or holidays, will
be addressed on the next scheduled working day, and will be communicated as such to the
complainant via the Hotline answering service. Nuisance complaints or complaints logged
from areas outside of the geographic areas reasonably expected to be impacted will be
addressed. Enbridge will relay all initial odor reports to U.S. EPA and Michigan Department
of Community Health (MDCH) and the three entities will work together (corresponding via e-
mail or phone) within a timely manner to determine if a response is appropriate. U.S. EPA
will make the final ruling on response if the parties cannot agree.
Personnel responding to the odor event will attempt to contact the complainant and schedule
sampling and monitoring at the location where the report originated. Real-time air
monitoring data and analytical "grab" canister sample data will be collected at the reported
location. Short-term real-time readings will be taken for VOCs, H2S, and sulfur dioxide (S02)
using a MultiRAE Plus monitor (or similar) and benzene using an UltraRAE monitor or
Gastec pump with benzene specific colorimetric tubes. These readings will be reported to
the complainant if present, and recorded in log books. At least one canister sample will be
obtained, with additional long term (24 hour) canisters possible depending on the situation
encountered. The canister samples will be analyzed using the same analytical approach
and target compound list as routine samples (Attachment A), with an expedited 24-hour turn-
around-time for odor response. In addition, at the time of sampling, the Odor Response
5
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Approved
Team will document the presence or absence of odors and the subjective quality of the
odors. The odor event location will also be documented using GPS.
After completion of the field visit, the Odor Response Team will relay the collected
information to Enbridge. Enbridge will provide U.S. EPA with a summary of all Odor
Response Team activities utilizing the Odor Complaint Response Action Tracker. Upon
receipt of canister sampling results, Enbridge contractor will prepare a follow-up letter report,
to be transmitted to the complainant, MDCH, and U.S. EPA.
7.0 DATA QUALITY AND MANAGEMENT
Air samples will be sent to Galson Laboratories located in Syracuse, N.Y or other approved
laboratory. Preliminary results will be provided to Enbridge's designated representative and
to any other designated representative or organization within five days of receipt by the
laboratory. Analytical results will be flagged in instances where the contaminant is also
detected in the laboratory blanks. Data will be submitted to the U.S. EPA SCRIBE database
through Enbridge data management system. In addition, Enbridge will provide daily
sampling and monitoring summaries to U.S. EPA, when such activities are being conducted,
as outlined in Section 8.0.
Duplicate samples will be collected at a frequency of 1 per 10 (10%).
8.0 AIR MONITORING AND SAMPLING REPORTING
Enbridge will provide on a weekly basis (every Monday) the following deliverables, during
periods of air sampling:
• An overview of air sampling activities conducted each day.
• The overview for air sampling will consist of a map of the oil recovery work area
perimeter and community area, or the geographical extent of air sampling activities.
The map will include the following layers:
o Locations of discrete analytical samples collected the previous day. Labels
will include a common name (e.g. Ceresco) or project marker name (e.g. MP
24.75), discrete sample identifiers, and identification of work area (e.g.
polygon showing approximate excavation area).
6
-------
Approved
o Windrose(s) generated from meteorological data downloaded the previous
day.
Air monitoring data for work areas will be submitted weekly (every Monday) summarized
from the previous day(s) in a table format identifying the work area location, number of
sampling points recorded, and detections as applicable.
An overview of the latest full day of air sampling laboratory results received. The overview
will consist of one map of the area(s) encompassing all locations where samples were
collected and any compounds were detected. The map will include the following layers:
• Locations of all discrete analytical samples. Labels will include a unique location
code for each symbol, as well as common name or project marker name.
• Chart listing concentrations and applicable screening levels of all analytes detected
in the locations included in the extent of the map.
• Windrose(s) generated from meteorological data collected the day of sampling.
These deliverables will be provided following an internal Quality Assurance/Quality Control
(QA/QC) process. The analytical data is received and reviewed by a qualified individual
(project manager/industrial hygienist and/or toxicologist). The data will be reviewed on a
daily basis to ensure that necessary actions are implemented if required (such as the need
for: additional real-time air monitoring, air sampling, or additional canister placement and/or
real-time monitoring). Deliverables will be disseminated to the air group, including U.S. EPA
representative and MDCH representative, via e-mail following the internal QA/QC process.
Raw analytical data will be available through the SCRIBE database following data validation.
A final report will be produced upon completion of air monitoring/sampling activities detailed
in this plan. The final report will consist of a compilation of real-time and analytical data,
physical parameters such as wind direction, and geographical area. An evaluation of the
results will be conducted to determine if "target analytes" were present during the oil
recovery operations and if those "target analyte" concentrations exceeded applicable Human
Health Air Screening Levels included in Attachment B.
7
-------
Approved
9.0 PROJECT ORGANIZATION
Enbridge will utilize Environmental Consultants for responsibility of the following:
• Toxicological support,
• Air sampling,
• Air monitoring for odor response,
• Air data quality assurance/quality control, and
• Data evaluation and reporting.
Enbridge Safety will be utilized for real-time air monitoring activities in work areas where oil
recovery activities occur.
10.0 CALIBRATION AND MAINTENANCE OF FIELD INSTRUMENTS
The calibration and maintenance of field equipment and instrumentation will be in
accordance with each manufacturer's specifications or applicable test/method specifications,
and will be recorded in Enbridge's or Consultant's calibration logs. All field real-time air
monitoring instruments or equipment will be calibrated prior to use in the field. Real-time
instruments will be calibrated daily or as needed, according to manufacturer
recommendations. Specifically, MultiRAE Plus (or similar meter with photoionization
detector) will be calibrated with a known concentration of isobutylene gas or zeroed using
zero-grade air or at background site locations. Gastec chemical specific colorimetric
detector tubes are hermetically sealed and are calibrated by the manufacturer, and
therefore, do not require field calibration. Calibrations will be conducted in accordance with
user manuals included in the 2011 Air Monitoring and Sampling Addendum to the Sampling
and Analysis Plan, approved by the U.S. EPA on June 21, 2011 (Enbridge, 2011).
11.0 CHAIN OF CUSTODY (COC)
Each sample will be identified on a COC record. The air sample numbering system will
include site name, date, analyte, and identification code unique to each sample.
8
-------
Approved
12.0 SAMPLE LABELS
Sample labels will be securely affixed to the sample container. They will clearly identify the
particular sample and should include the following information:
• Sampling location,
• Date the sample was collected, and
• Unique identifier.
13.0 PACKAGING AND SHIPPING
Packaging and shipping of air samples will be conducted following method
recommendations. Canisters will be shipped in a box via carrier service (e.g. FedEx). Air
samples do not require sample preservation in the field. However, caps will be placed on
canisters and regulators or critical orifices will be detached during shipment. The person
packaging the samples is responsible to ensure that the sample packaging is in suitable
condition for shipping.
14.0 REFERENCES
Enbridge, 2011. Enbridge Line 6B Pipeline Release, Marshall, Michigan; 2011 Air Monitoring
and Sampling Addendum to the Sampling and Analysis Plan. June 21, 2011.
9
-------
Attachment A
VOCs Detected by TO-15 Analysis
-------
Attachment A - Analyte Type List
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Predominant Crude Oil VOCs Detected by TO-15 Analysis1
Target Analyte
CAS No.
Laboratory LOQ (ppbv)
Benzene
71-43-2
5
Butane, 2-methyl-*
78-78-4
NA
Cyclohexane
110-82-7
5
Cyclohexane, 1,3-dimethyl*
591-21-9
NA
Cyclopentane, methyl-*
96-37-7
NA
Cyclohexane, 1,3-dimethyl-, cis-*
638-04-0
NA
Cyclohexane, butyl-*
1678-93-9
NA
Cyclohexane, ethyl-*
1678-91-7
NA
Cyclohexane, methyl-*
108-87-2
NA
Cyclohexane, propyl-*
1678-92-8
NA
Cyclopentane, 1,1-dimethyl*
1638-26-2
NA
Cyclopentane, 1,3-dimethyl-, trans*
1759-58-6
NA
Cyclopentane, 1,2-dimethyl-, trans*
822-50-4
NA
Heptane, 3-methyl-*
589-81-1
NA
2-Octene, 2,6-dimethyl-*
4057-42-5
NA
Decane*
124-18-5
NA
Dodecane*
112-40-3
NA
Ethylbenzene
100-41-4
5
Ethyltoluene, 4-
622-96-8
5
Heptane, n-
142-82-5
5
Hexane, n-
110-54-3
5
Naphthalene*
91-20-3
NA
Nonane*
111-84-2
NA
Hexane, 2-methyl*
591-76-4
NA
Octane*
111-65-9
NA
Octane, 3-methyl-*
2216-33-3
NA
Pentane, 2-methyl-*
107-83-5
NA
Toluene
108-88-3
5
Benzene, 1,2,4-trimethyl
95-63-6
5
Hexane, 3-methyl*
589-34-4
NA
Heptane, 2-methyl-*
592-27-8
NA
Cyclohexane-1,1,3-trimethyl*
3073-66-3
NA
Benzene, 1,3,5-trimethyl
108-67-8
5
Undecane*
1120-21-4
NA
Xylene, m&p-
179601-23-1
10
Xylene, o-
95-47-6
5
1The laboratory will also be asked to report on all analytes included in their TO-15 method standard
analyte list.
"Tentatively identified compound (TIC)
NA - Not Applicable
Sheet 1 of 3
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Attachment A - Analyte Type List
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Predominant Crude Oil VOCs Detected by TO-15 Analysis1
Non-Target Analyte
CAS NO
Laboratory LOQ (ppbv)
ALPHA-PINENE*
80-56-8
NA
1,1,1 -TRICH LOROETHAN E
71-55-6
5
1,1,2,2-TETRACHLOROETHANE
79-34-5
5
1,1,2-TRICHLOROETHANE
79-00-5
5
1,1-DICHLOROETHANE
75-34-3
5
1,1-DICHLOROETHENE
75-35-4
5
1,2-DIBROMOETHANE
106-93-4
5
1,2-DICHLOROBENZENE
95-50-1
5
1,2-DICHLOROETHANE
107-06-2
5
1,2-DICHLOROPROPANE
78-87-5
5
1,3-BUTADIENE
106-99-0
5
1,3-BUTADIENE, 2-METHYL-*
78-79-5
NA
1,3-DICHLOROBENZENE
541-73-1
5
1,4-DICHLOROBENZENE
106-46-7
5
1,4-DIOXANE
123-91-1
20
1-HEPTANOL, 2-PROPYL-*
10042-59-8
NA
2,2,4-TRIMETHYLPENTANE
540-84-1
5
2,2,7,7-TETRAMETHYLOCTANE*
1071-31-4
NA
2,3,4,5-TETRAHYDROPYRI DAZIN E*
694-06-4
NA
2-HEPTANONE*
110-43-0
NA
2-PENTANONE*
107-87-9
NA
2-PROPANOL, 2-METHYL-*
75-65-0
NA
3-HEPTANONE*
106-35-4
NA
ACETALDEHYDE2
75-07-0
1
ACETIC ACID, 2-ETHYLHEXYL ESTER*
103-09-3
NA
ACETONITRILE*
75-05-8
NA
ALLYL CHLORIDE
107-05-1
5
BENZENE, 1-METHYL-4-(1-METHYLETHYL)*
99-87-6
NA
BENZYL CHLORIDE
100-44-7
5
BROMODICHLOROMETHANE
75-27-4
5
BROMOFORM
75-25-2
5
BROMOM ETHANE
74-83-9
5
BUTANE*
106-97-8
NA
BUTANOIC ACID, 2-METHYLPROPYL ESTER*
539-90-2
NA
BUTANOIC ACID, BUTYL ESTER*
109-21-7
NA
BUTANOIC ACID, ETHYL ESTER*
105-54-4
NA
BUTANOIC ACID, METHYL ESTER*
623-42-7
NA
BUTANOIC ACID, PROPYL ESTER*
105-66-8
NA
CARBON DISULFIDE
75-15-0
10
CARBON TETRACHLORIDE
56-23-5
5
CARBONYL SULFIDE*
463-58-1
NA
CHLOROBENZENE
108-90-7
5
CHLOROETHANE
75-00-3
5
CHLOROFORM
67-66-3
5
CHLOROMETHANE
74-87-3
5
1The laboratory will also be asked to report on all analytes included in their TO-15 method standard analyte list.
2Acetaldehyde was added as a standard analyte in 2011 based on continuous detections of this compound as a TIC in community air
samples
^Tentatively identified compound (TIC)
NA- Not Applicable
Sheet 2 of 3
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Attachment A - Analyte Type List
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Predominant Crude Oil VOCs Detected by TO-15 Analysis1
Non-Target Analyte
CAS NO
Laboratory LOQ (ppbv)
CIS-1,2-DICHLOROETHYLENE
156-59-2
5
CIS-1,3-DICHLOROPROPENE
10061-01-5
5
CYCLOPENTANE, 1,1'-ETHYLIDENEBIS-*
4413-21-2
NA
DECANE, 2,2,4-TRIMETHYL-*
62237-98-3
NA
DECANE, 2,3,4-TRIMETHYL-*
62238-15-7
NA
DECANE, 2,3,5-TRIMETHYL-*
62238-11-3
NA
DIACETYL*
431-03-8
NA
DIBROMOCHLOROMETHANE
124-48-1
5
DISULFIDE, DIMETHYL*
624-92-0
NA
DISULFIDE, FLUOROMETHYL METHYL*
60307-49-5
NA
ETHANE, 1,1-DIFLUORO-*
75-37-6
NA
ETHYL ACETATE
141-78-6
5
ETHYL ALCOHOL*
64-17-5
NA
EUCALYPTOL*
470-82-6
NA
FREON 11
75-69-4
5
FREON 113
76-13-1
5
FREON 114
76-14-2
5
FREON 12
75-71-8
5
FURAN, 2.3-DIHYDRO-3-M ETHYL-*
1708-27-6
NA
HEPTANE, 2,2,3,4,6,6-HEXAMETHYL-*
62108-32-1
NA
HEPTANE, 2,2,4,6,6-PENTAMETHYL-*
13475-82-6
NA
HEPTANE, 2,2-DIMETHYL-*
1071-26-7
NA
HEPTANE, 4-ETHYL-2,2,6,6-TETRAMER*
62108-31-0
NA
H EXADECAN E, 2,6,10,14-TETRAMETHYL-*
638-36-8
NA
HEXANAL*
66-25-1
NA
HEXANE, 2,2,5-TRIMETHYL-*
3522-94-9
NA
HEXANE, 2,4-DIMETHYL-*
589-43-5
NA
HEXANOIC ACID, METHYL ESTER*
106-70-7
NA
HEXYL N-VALERATE*
1117-59-5
NA
ISOBUTANE*
75-28-5
NA
LIMONENE*
138-86-3
NA
METHYL 3-BUTENOATE*
3724-55-8
NA
METHYL BUTYL KETONE
591-78-6
20
1The laboratory will also be asked to report on all analytes included in their TO-15 method standard analyte list.
2Acetaldehyde was added as a standard analyte in 2011 based on continuous detections of this compound as a TIC in community air
samples
^Tentatively identified compound (TIC)
NA- Not Applicable
Sheet 3 of 3
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Attachment B
Enbridge Oil Spill Human Health Screening Levels
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Enbridge Oil Spill
Human Health Air Screening Levels
August 31, 2011
Chemical
Screening
Level in
Chemical Name
Abstract
Service
Number
parts per
billion by
volume
(ppbv)
Source of
Screening Level
1,1,1-trichloroethane
71-55-6
1,000
EPA RfC
1,1,2,2-T etrachloroethane
79-34-5
0.006
EPA RSL
1,1,2-Trichloro-1,2,2-trifluoroethane
76-13-1
4,000
EPA RSL
1,1,2-Trichloroethane
79-00-5
0.04
EPA RfC
1,1-Dichloroethane
75-34-3
0.4
EPA RSL
1,1-Dichloroethene
75-35-4
50
EPA RfC
1,2,4-T richlorobenzene
120-82-1
0.3
EPA RfC
1,2,4-T rimethylbenzene
95-63-6
1.5
EPA RfC
1,2-Dibromoethane
106-93-4
1
EPA RfC
1,2-Dichloro-1,1,2,2-Tetrafluoroethane
76-14-2
9,900
MDEQ
1,2-Dichlorobenzene
95-50-1
30
EPA RfC
1,2-Dichloroethane
107-06-2
600
ATSDR Chr. MRL
1,2-Dichloropropane
78-87-5
1
EPA RfC
1,3-Butadiene
106-99-0
1
EPA RfC
1,3,5-T rimethylbenzene
108-67-8
45
MDEQ
1,3-Dichlorobenzene
541-73-1
0.5
MDEQ
1,4-Dichlorobenzene
106-46-7
10
ATSDR Chr. MRL
1,4-Dioxane
123-91-1
1,000
ATSDR Chr. MRL
2,2,4-T rimethylpentane
540-84-1
750
MDEQ
2-Chloro-1,3-butadiene
126-99-8
6
EPA RfC
2-Propanol
67-63-0
3,000
EPA RfC
3-Chloropropene
107-05-1
32
EPA RfC
Acetaldehyde
75-07-0
5
EPA RfC
Acetone
67-64-1
13,000
ATSDR Chr. MRL
Acetonitrile
75-05-8
36
EPA RfC
Acrylonitrile
107-13-1
1
EPA RfC
Benzene
71-43-2
3
ATSDR Chr. MRL
Benzyl chloride
100-44-7
0.2
EPA RfC
Bromodichloromethane
75-27-4
0.01
EPA RSL
Bromoform
75-25-2
0.2
EPA RSL
Bromomethane
74-83-9
5
ATSDR Chr. MRL
Butane
106-97-8
10,000
MDEQ
Carbon disulfide
75-15-0
200
EPA RfC
Carbon tetrachloride
56-23-5
30
ATSDR Chr. MRL
Chlorobenzene
108-90-7
10
EPA RfC
Chloroethane
75-00-3
4,000
EPA RfC
Chloroform
67-66-3
20
ATSDR Chr. MRL
Chloromethane
74-87-3
50
ATSDR Chr. MRL
cis-1,2-dichloroethene
156-59-2
9
MDEQ
cis-1,3-Dichloropropene*
10061-02-6
4
MDEQ
Cumene
98-82-8
80
EPA RfC
Cyclohexane
110-82-7
2,000
EPA RfC
Cyclohexane, methyl
108-87-2
4,000
MDEQ
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Chemical
Screening
Level in
Chemical Name
Abstract
Service
Number
parts per
billion by
volume
(ppbv)
Source of
Screening Level
Cyclopentane
287-92-3
6,000
MDEQ
Dibromochloromethane
124-48-1
0.01
EPA RSL
Dichlorodifluoromethane
75-71-8
20
EPA RfC
Ethyl Acetate
141-78-6
890
MDEQ
Ethyl benzene
100-41-4
60
ATSDR Chr. MRL
Heptane
142-82-5
850
MDEQ
Hexachlorobutadiene
87-68-3
0.01
EPA RSL
Hexane
110-54-3
200
EPA RfC
Isobutane
75-28-5
10,000
MDEQ
Methyl butyl ketone
591-78-6
10
EPA RfC
Methyl ethyl ketone
78-93-3
2,000
EPA RfC
Methyl isobutyl ketone
108-10-1
700
EPA RfC
Methyl tert-butyl ether
1634-04-4
700
ATSDR Chr. MRL
Methylene chloride
75-09-2
300
ATSDR Chr. MRL
Napthalene
91-20-3
1
ATSDR Chr. MRL
Nonane
111-84-2
40
EPA RfC
Pentane
109-66-0
300
EPA RfC
Propene
115-07-1
2,000
EPA RfC
Styrene
100-42-5
200
ATSDR Chr. MRL
Tetrachloroethene
127-18-4
40
ATSDR Chr. MRL
Tetrahydrofuran
109-99-9
6
MDEQ
Toluene
108-88-3
80
ATSDR Chr. MRL
trans-1,2-Dichloroethene
156-60-5
15
EPA RfC
trans-1,3-Dichloropropene*
10061-01-5
0.5
MDEQ
Trichloroethene
79-01-6
2
EPA RfC
Trichlorofluoromethane
75-69-4
130
EPA RfC
Vinyl acetate
108-05-4
10
ATSDR Int. MRL
Vinyl bromide
593-60-2
1
EPA RfC
Vinyl chloride
75-01-4
30
ATSDR Int. MRL
Xylenes
1330-20-7
50
EPA RfC
* MDEQ provisional screening value for Dichloropropene based on a 1 in 100,000 cancer risk
ATSDR Chr. MRL - The Agency for Toxic Substances and Disease Registry Chronic Minimal
Risk Level (MRL) is the preferred screening level. The MRL is protective of daily human
inhalation exposure for longer than a year, including sensitive individuals such as children, the
elderly, and those with pre-existing illnesses.
EPA RfC - If no Chronic MRL is available, the screening level is the EPA Reference
Concentration (RfC). The RfC is protective of daily human inhalation exposure over a lifetime,
including sensitive individuals. For 2 chemicals, vinyl acetate and vinyl chloride, the ATSDR
Intermediate (Int.) MRL was selected. These were developed more recently than the EPA RfC
and were lower than the EPA RfC.
EPA RSL - If none of the above are available, the EPA Regional Screening Level (RSL) is used.
The RSLs are protective of daily human inhalation exposure over a lifetime, including sensitive
individuals.
MDEQ - If none of the above are available, the Michigan DEQ Air Quality Division, Air Toxics
Screening Level is the screening level. The MDEQ screening levels are protective of daily
human inhalation exposure over a lifetime, including sensitive individuals.
-------
Attachment C
Field Standard Operating Procedures
-------
Standard Operation Procedure:
6L SUMMA Canister Sampling
METHOD SUMMARY
Sub atmospheric pressure sampling uses an initially cleaned and evacuated stainless steel
canister. The canister has a hand valve and fixed orifice to regulate flow. Sub atmospheric
pressure sampling is performed with a 24-hr critical orifice and low pressure regulator for 24-
hour sampling or without the flow metering for taking grab samples. With this configuration, a
grab sample of ambient air is drawn into a pre-evacuated Summa passivated canister. The
canister is placed in the Breathing Zone (between 3 and 6 feet above ground surface). For 24-
hour sampling the hand valve is opened to full and the canister allowed to fill as regulated by the
metering equipment. With the grab sample, the hand valve is opened a quarter turn until the
sound changes as it nears atmospheric pressure, and the hand valve is then closed. Normal
documentation, chain of custody and sealing of the sample(s) are completed and the package is
readied for shipping.
SAMPLE PRESERVATION, CONTAINERS HANDLING, AND STORAGE
After the air sample is collected, the canister valve is closed, flow regulator removed, cap is
installed, an identification tag is attached to the canister, and the canister is transported to a
laboratory for analysis. Upon receipt at the laboratory, the canister tag data is recorded. Sample
holding times and expiration are to be determined prior to initiating field activities.
Care must be taken not to exceed 40 psi in the canister (do not heat canister above 140°F).
Canisters should not be dented or punctured. They should be stored in a cool dry place and
always be placed in their cardboard shipping boxes or similar protective carrier during transport
and storage.
EQUIPMENT/MATERIALS REQUIRED
The following equipment/apparatus is required:
• Sub atmospheric Pressure Sampling Equipment
-------
• VOC canister sampler - whole air sampler capable of filling an initially evacuated
canister by action of the hand valve from vacuum to near atmospheric pressure.
PROCEDURE
1. Prior to sampling collection, the appropriate information is completed on the Field Data
Sheet and brass cap is removed with 9/16 inch end wrench.
2. Place canister at the "Breathing Zone height".
3. A canister, (which is evacuated to at least 26 inches Hg) hand valve is opened to the
atmosphere containing the air to be sampled. The pressure differential causes the
sample to flow into the canister.
4. The sampling duration depends on the degree to which the flow is restricted.
5. A fixed orifice flow restrictor will have a decrease in the flow rate as the vacuum canister
approaches atmospheric (which is indicated by a change in pitch or sound level). Shut
off hand valve following completion of sampling interval.
6. Upon sample completion at the location, the appropriate information is recorded on the
Field Data Sheet and labels (Note the final vacuum reading on canister by separate
gauge on each canister. Separate gauge will need to be attached and removed. Cap
the SUMMA Canister with the cap and tighten with wrench slightly to seal vacuum.
7. Place canister into a cardboard box labeled for shipping with the Field Data Sheet
information, chain of custody, and labels.
QUALITY ASSURANCE/QUALITY CONTROL
The following general quality assurance procedures apply:
1. All data must be documented on standard chain of custody records, field data sheets, or site
logbooks.
2. All instrumentation must be operated in accordance with operating instructions as supplied by
the manufacturer, unless otherwise specified in the work plan. Equipment checkout and
calibration activities must occur prior to sampling/operation, and they must be documented.
-------
3. Duplicate samples will be taken as 1 in 10 samples.
4. Blank samples or "zero air," (sample not taken) will be returned at a rate of 1 per week of
sampling.
-------
Attachment D
Galson Laboratories SOP for VOCs by OSHA PV-2120
& EPATO-15
-------
in-vocs Ver: 18 Appr/Eff Date: 12/1/11 - 12/15/11 Approval By: wferro Expire Date: 12/22/2011
GALSON LABORATORIES STANDARD OPERATING PROCEDURE
SUBJECT: VOLATILE ORGANIC COMPOUNDS BY OSHA PV2120 & EPA TO-15
1.0 PURPOSE
1.1 This SOP describes the procedure for determining contaminants in whole air samples
collected in a fused silica-lined stainless steel canister (following OSHA method
PV2120 and Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air (Method TO-15). This method utilizes GC/MS for the
determination of a wide range of volatile and semi-volatile organic compounds (as listed
in Table 1).
2.0 RESPONSIBILITIES
2.1 All GC/MS analysts performing this method are required to read and understand the
method as written in OSHA PV2120, and are required to meet all QC requirements (as
described in EPA TO-15) before attempting analysis of samples.
2.2 The section supervisor is required to read and understand the method as written, but is
also responsible for the training and continued education of technicians performing this
2.3 The section supervisor is required to review reports and packages to ensure that all data
are valid prior to client receipt.
3.0 DEFINITIONS
3.1 GC/MS: Gas Chromatography/Mass Spectrometry
3.2 Capillary: Analytical column with an internal diameter less than or equal to 0.32 mm
3.3 EICP: Extracted ion current profile: Plot of ion abundance vs. GC retention time for a
single characteristic mass (amu)/charge ratio.
3.4 AMU: Atomic Mass Unit
3.5 ppbv: part per billion by volume for component concentration in the gas phase.
3.6 Mini Can: Canisters ranging from 400mL to lOOOmL in volume; these are associated
with an injection volume of lOOmL.
3.7 Summa Canisters: Canisters with a 6L volume; these are associated with an injection
volumes of 500cc to lOOOcc.
SOP ID:
IN-VOCS
COPYRIGHT
AUTHOR: Justin Palmer/ Rob Wilson
SECTION SUPERVISOR: Justin Palmer
QA OFFICER: Wendy Ferro
LABORATORY DIRECTOR: MaryUnangst
method.
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3.8 SCAN: Normal MS acquisition mode where mass ranges from 35 to 300 amu are
scanned to produce a Total Ion Chromatogram.
3.9 SIM: Selective Ion Mode; only scans certain ions per sample to increase sensitivity.
Used for only certain projects that require low level analysis.
4.0 METHOD SUMMARY
4.1 The sample is prepared for analysis by pre-concentration, which removes potential
interference and dries the sample. After the pre-concentration and drying steps are
completed, the analytes are cryo-focused onto the head of the GC column via reduced
temperature trapping, followed by rapid thermal desorption.
4.2 Separation of the analytes is achieved by temperature programming of the GC oven.
4.3 The eluent from the capillary column is introduced directly to the mass spectrometer,
which is operated in the electron impact mode. Identification of target analytes is
accomplished by comparing sample mass spectra with reference spectra generated from
purchased standards on the GC/MS system used to analyze the samples. Quantitation is
achieved using the internal standard technique. The response of a selected quantitation
ion for each analyte relative to the quantitation ion of the designated internal standard
(relative response factor, or RRF) is determined over a minimum five-point calibration
range.
5.0 INTERFERENCES
5.1 Raw GC/MS data from all samples and blanks must be evaluated for interference.
Determine if the source of interference is in the sample introduction system. If so, take
corrective action to eliminate the problem.
5.2 Contamination by carryover can occur whenever high-concentration and low-
concentration samples are sequentially analyzed. Each auto-sampler port is flushed with
nitrogen after use (prior to set-up of the next batch of samples).
5.3 Interferences are minimal by GC/MS as this type of detector allows the determination if
compounds are co-eluting in the chromatographic system. Quantification can be done
on alternate ions so interferences are eliminated in most cases. In other instances, a
dilution may be performed to allow better separation or results may be considered
estimated if the interference cannot be removed.
6.0 SAFETY
6.1 Most volatile compounds are considered hazardous. Always wear gloves and a lab coat
when handling stock standards.
6.2 Safety glasses with side-shields are required whenever working in the laboratory.
6.3 It is very important that special precaution be used when working with liquid nitrogen,
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as it can cause serious burns.
6.4 Be sure that only radiation worker trained personnel handle Mini Cans that have been
screened for radiation. These cans will have an orange dot on them.
7.0 MATERIALS AND APPARATUS
7.1 Agilent (previously Hewlett Packard (HP)- may be used interchangeably) 5890, 6890, or
7890 Series GC, in conjunction with an HP model 5972, 5973, or 5975 mass
spectrometer (capable of scanning from 35 to 300 amu every 1-second or less using 70
volts (nominal) electron energy in the electron impact ionization mode).
7.2 Entech 7032, 7032L, 7032A, or 7016CA autosampler models with the Entech 7100 or
7100A three stage Preconcentrator.
7.2.1 Microscale Purge and Trap (MPT) analysis is performed by utilizing a glass
bead trap in module 1 and a Tenax sorbent trap in module 2. Module 3 contains
an empty trap.
7.2.2 Cold Trap Dehydration analysis (CTD) employs an empty trap in module 1 and a
Tenax trap in module 2. Module 3 contains an empty trap.
7.3 Analytical Chromatography column: 0.32mm ID x 60m length silicone-coated capillary
column with a 1 um film thickness - Restek RTX-1 or equivalent.
7.4 GC/MS Interface - The GC column is directly coupled to the mass spectrometer ion
source. Acceptable tuning and calibration performance must be demonstrated on a daily
basis.
7.5 Data System - The data system used is the HP Chemstation G1701BA with (at
minimum) Revision B.01.00 software package for the HP5972, 5973, or 5975 MS. This
system allows continuous acquisition and storage on machine-readable media of all
mass spectra obtained throughout the duration of the chromatographic program. The
software allows for searching any GC/MS data file for ions of a specific mass, and
plotting such ion abundance versus time or scan number. This type of plot is defined as
an Extracted Ion Current Profile. The software allows integration of the abundance in
any EICP between specified time or scan number limits. The NIST 129K version mass
spectral library is being used for a reference library.
8.0 REAGENTS AND STANDARDS
8.1 Helium @ 99.9999% purity
8.2 Liquid nitrogen
8.3 Stock standards
8.3.1 Stock standard solutions are purchased as certified solutions.
8.3.1.1 TO-15 Subset standard is purchased from Spectra gases
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8.3.1.1.1 (Catalogue # ENT15-25S-6A-1M) or Scott gases (item#
0104AZ00025).
8.3.1.2 TO-14 standard is purchased from Spectra gases
8.3.1.2.1 (Catalogue # ENT14/39S/6A1M) or Scott gases (item#
01049Z90001).
8.3.1.3 Ethylene oxide standard is purchased from Spectra gases
8.3.1.3.1 (ETOX/CGA3501M) or Scott gases (item# 08020001310PAL).
8.3.1.4 4-Phenylcyclohexene standard is purchased from Scott gases (item#
0104P200046).
8.3.1.5 TO-15100-ppbv 75 compound standard Vapor Intrusion stock standard
is purchased from Scott gases (item# MAZ00090-Z-7AL). Two different
lots are purchased for calibration and alternate source. This stock
contains Naphthalene.
8.3.1.6 TO-15 10-ppbv project specific compound list
8.3.1.6.1 Used for ultra low level SIM analysis.
8.3.2 Stock standard solutions must be stored at room temperature, or as
recommended by the manufacturer.
8.3.3 Stock standard solutions must be replaced after 1 year, or sooner depending on
manufacturer's expiration date.
8.4 Internal Standard and Surrogate
8.4.1 The internal standards are Bromochloromethane, 1,4-Difluorobenzene, and
Chlorobenzene-d5.
8.4.2 The surrogate is Bromofluorobenzene.
8.4.3 Each sample undergoing analysis, as well as all calibration standards must be
spiked with 50 ppbvof each internal standard and surrogate (based on a lOOcc
injection volume). For a 500cc injection volume this equates to 10 ppbv and
lOOOcc injection volume gives 5 ppbv.
8.4.4 A certified stock internal and surrogate standard mixture must be purchased
every 12 months (or sooner, if degradation is observed). (Spectra Gases, TO-14
IS/Surr. mix, catalogue # ENT14ITS-6A-1M) or (Scott Gases, TO-14 IS/Surr.
Mix, P/N 24087828)
8.4.5 Store the internal/surrogate standard at room temperature.
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8.5 GC/MS Tuning standard
8.5.1 In a 6L Summa canister, prepare a 100-ppbv standard of Bromofluorobenzene
(BFB). This standard contains the internal standard compounds as well.
8.5.2 The tuning standard is stored at room temperature when not in use. When using
premixed certified gases, store according to the manufacturer's documented
holding time and storage temperature recommendations.
8.6 Intermediate (working) standards
8.6.1 A working standard of the target compounds is prepared at 5-ppbv, 25-ppbv,
and 100-ppbv for both lOOcc and 500cc injection methods. This is used to
generate the instrument calibration curve. The working standard must contain all
of the analytes of interest. Target compound working standards expire one
month after preparation. Standards may be prepared at lower concentrations to
meet project specific detection limits. For 75 compound list with 0.2 ppbv
reporting limit, working standards are currently prepared at 2 and 10 ppbv.
8.6.2 The internal / surrogate working standard is prepared at 100 ppbv. This is also
used as the tuning standard. Working internal standards expire two months from
preparation date.
8.7 Calibration standards
8.7.1 Calibration standards must be analyzed at a minimum of five different
concentrations. One of the calibration standards must correspond to a sample
concentration at or below that necessary to meet the data quality objectives of
the project. The remaining standards must correspond to the range of
concentrations expected to be found in the actual samples. The typical
calibration curve range for TO 15 (Minican) list is 5-ppbv to 150-ppbv for most
analytes. TO-15 (6L Summa can) list is from 1-ppbv to 30-ppbv. TO-15 low
level list is from 0.2-ppbv up to 30-ppbv. TO-15 SIM is dependent on project
specific reporting limits. Ethylene Oxide ranges from 20-400-ppbv and 4-
Phenylcyclohexene ranges from 1-20-ppbv.
8.7.2 Internal standards and surrogate are added to all calibration standards during
analysis.
9.0 PROCEDURES
9.1 Sample collection, preservation and handling
9.1.1 Whole air samples are collected in 400cc or lOOOcc fused silica lined stainless
steel canisters (Mini Cans) or 6-liter Summa canisters that are stored at room
temperature until analysis. Sample stability is unknown, therefore samples
should be analyzed as soon as possible.
9.2 Sample Preparation
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9.2.1 Once the GCMS group has received the samples, the vacuum in the can is
measured to verify the amount of sample collected. If the vacuum reading is > 5
inches of Hg, the project manager must notify the customer. This can be caused
by either improper sample collection or a malfunction of the regulator. A full
canister will read < 5 inches of Mercury. There should be a partial vacuum
remaining (@1 to <5 inches of Mercury) to evidence that a full sampling
event took place. No measurable vacuum may be an indication that the
canister was not collecting the sample over the full duration of the sampling
period or that the canister was leaking during sampling. The customer must
be notified if there is no measurable vacuum. Pump group will set regulators
to leave a partial vacuum for the specified sampling time (8 hrs, 24 hrs, or
week). A volume of Nitrogen can be added to bring the volume above 5"
Mercury with the use of the Entech 7100 sample diluter. The initial and final
pressure readings must be recorded in the can dilution logbook. The dilution
factor is calculate according to the equation:
9.3 Analytical Procedure
9.3.1 Instrument Maintenance
9.3.1.1 Appropriate instrument maintenance must be performed as necessary prior
to initial calibration. Indications of the need for maintenance include poor
peak shape, inadequate sensitivity, and inability to pass BFB tune. Steps that
may be required to address these problems include replacing one or both
traps in the Entech 7100, baking the transfer line and GC column, trimming
or replacing the column, and/or cleaning the ion source.
9.3.2 Instrument conditions for TO-15 regular list, TO-15 0.2ppbv reporting level,
and Hydrocarbon analysis:
DF = PSLA
PSIAi
Where PSIAf = final pressure reading
PSIAi = initial pressure reading
Detection limits will be raised proportionately.
The following GC/MS instrument conditions are used:
Injector temperature:
Injection volume:
Carrier gas:
Mass range:
Scan time:
Initial temperature:
Temperature program
Final temperature:
35-300 amu
2.82 scan/sec
34 °C, hold for 5.5 minutes
increase at 5 °C /minute to 70°C, then increase
at 15°C /minute to 170°C, then increase at 25°C/
minute to 240°C, holding there for 1-10
minutes.
240 °C, hold 1-10 minutes after Hexachloro-
1,3-Butadiene elutes.
150 °C
lOOcc
Helium at 20 cm/sec
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9.3.3 Instrument conditions for Ethylene Oxide analysis:
Injection volume:
Carrier gas:
Mass range:
Initial temperature:
Temperature program
Final temperature:
Injector temperature:
28-250 for Ethylene oxide then at 6.9 min. 29-
250 amu
34 °C, hold for 5.5 minutes,
increase at 15 °C /minute to
240 °C, hold 1-10 minutes
150 °C
lOOcc
Helium at 20 cm/sec
9.3.4 Instrument conditions for 4-Phenylcyclohexene analysis:
Final temperature:
Injector temperature:
Injection volume:
Carrier gas:
Mass range:
Initial temperature:
Temperature program
SIM Mode (4PCH 74, 108, 158 amu)
50 °C
increase at 10 °C /minute to 200°C, then
increase at 25 °C /minute.
250 °C, hold 1-10 minutes.
150 °C
lOOcc
Helium at 20 cm/sec
9.4 Instrument Calibration
9.4.1 Instrument Performance Check: At the beginning of a 24-hour analysis sequence
it is necessary to show that the GC/MS system meets the instrument
performance criteria. This is accomplished by the analysis of a 50-ppbv injection
of BFB to demonstrate correct mass calibration, mass resolution, and mass
transmission. Any injection containing 50-ppbv of BFB can be used for this
purpose (based on lOOcc injection volume).
9.4.1.1 BFB must meet the criteria listed in 9.4.1.2 before standards and samples
are analyzed. An acceptable BFB tune is demonstrated once at the
beginning of each 24-hour period during which samples or standards are
analyzed. The 24-hour period begins with the injection time of the BFB and
ends after 24 hours according to the system clock. The following abundance
criteria are required to establish instrument tune compliance:
9.4.1.2 Tune acceptance criteria:
Mass | Ion Abundance Criteria
50 8.0-40.0 percent of mass 95
75 30.0-66.0 percent of mass 95
95 base peak, 100 percent relative abundance
96 5.0-9.0 percent of mass 95
173 Less than 2.0 percent of mass 174
174 50.0 - 120 percent of mass 95
175 4.0-9.0 percent of mass 174
176 Greater than 93.0 percent but less than 101.0 percent of mass 174
177 5.0-9.0 percent of mass 176
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9.4.1.3 For demonstrating an acceptable tune, the mass spectrum of BFB must be
obtained. This is can be performed by the HP/Agilent Chemstation
Software using the Auto-find BFB function. This function works as follows:
three scans are taken (the peak apex scan, and the scans immediately
preceding and following the apex) and then averaged. Background
subtraction is required, and must be accomplished using a single scan
acquired no more than 20 scans prior to the elution of BFB. The background
subtraction is designed to eliminate column bleed and instrument
background ions. Alternately, the BFB spectrum can be obtained/performed
manually.
9.4.2 Calibration standards are analyzed concurrently or once BFB meets acceptance
criteria.
9.4.3 Initial Calibration
9.4.3.1 For use with lOOcc-sample injection volume T015 analysis (i.e. 400-1000cc
canisters): A minimum 5-point calibration curve must be analyzed prior to
sample analysis. The internal standards must be added at 50-ppbv to each
curve concentration level. Analyze to determine the instrument sensitivity
and linearity of the GC/MS response for the target compounds. Analyze the
following volumes from the 25 and/or 50-ppbv working standard canister to
obtain the desired concentration. Other standard levels can be used as
needed to meet calibration range criteria. A 5-ppbv standard is utilized
(100-cc injection volume) for the 5-ppbv level on some instruments. A
blank should be run in-between the three highest standards (for example,
between the 100 and 150-ppbv standards).
Standard Level
25-ppbv working standard 50-ppbv working standard
5-ppbv standard
20-ppbv standard
50-ppbv standard
100-ppbv standard
150-ppbv standard
200-ppbv standard
Use 20cc
Use 80cc
Use 200cc
Use 400cc
Use 600cc
N/A
Use lOcc
Use 40cc
UselOOcc
Use 200cc
Use 300cc
Use 400cc
9.4.3.2 For use with 500cc-sample injection volume analysis (i.e. 6-liter canisters):
A minimum 5-point calibration curve must be analyzed prior to sample
analysis. The internal standards must be added at 10-ppbv for each curve
concentration level. Analyze to determine the instrument sensitivity and
linearity of the GC/MS response for the target compounds. Analyze the
following volumes from the 25-ppbv working standard canister to obtain the
desired concentration. Other standard levels can be used as needed to meet
calibration range criteria. Blanks should be run in-between the three highest
standards (for example, between the 20 & 30-ppbv standards).
Standard Level
1-ppbv working
5-ppbv working
25-ppbv working
standard
standard
standard
0.2-ppbv standard
Use lOOcc
Use 500cc
N/A
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1-ppbv standard
N/A
Use lOOcc
Use 20cc
5-ppbv standard
N/A
N/A
UselOOcc
10-ppbv standard
N/A
N/A
Use 200cc
20-ppbv standard
N/A
N/A
Use 400cc
30-ppbv standard
N/A
N/A
Use 600cc
9.4.3.3 For use with lOOOcc sample injection volume analysis (i.e. 6-liter
canisters): A minimum 5-point calibration curve must be analyzed prior
to sample analysis. The internal standards must be added at 5-ppbv for
each curve concentration level. Analyze to determine the instrument
sensitivity and linearity of the GC/MS response for the target compounds.
Analyze the following volumes from the 2 and 10-ppbv working standard
canisters to obtain the desired concentration. Other standard levels can be
used as needed to meet calibration range criteria. Blanks may need to be
run in-between the highest standards (for example, between the 4 & 6-
ppbv standards).
Standard Level
2-ppbv working standard 10-ppbv working standard
0.2-ppbv standard
1-ppbv standard
2-ppbv standard
3-ppbv standard
4-ppbv standard
6-ppbv standard
Use lOOcc
N/A
N/A
N/A
N/A
N/A
N/A
Use lOOcc
Use 200cc
Use 300cc
Use 400cc
Use 600cc
9.4.3.4 For use with lOOOcc sample injection volume analysis (6 liter SIM): A
minimum 5-point calibration curve must be analyzed prior to sample
analysis. The internal standards must be added at midpoint for each
curve concentration level. Analyze to determine the instrument sensitivity
and linearity of the GC/MS response for the target compounds. Analyze
the following volumes from either 0.05-ppbv working standard canister or
1-ppbv working standard canister to obtain the desired concentration.
Other standard levels can be used as needed to meet calibration range
criteria. Blanks should be run in-between the highest standards (for
example, between the 0.4 & 0.6-ppbv standards) and blanks should be run
after the calibration to clean out the system.
Standard Level
0.05-ppbv working standard 1-ppbv working standard
0.005-ppbv standard
0.025-ppbv standard
0.1-ppbv standard
0.2-ppbv standard
0.4-ppbv standard
0.6-ppbv standard
Use lOOcc
Use 500cc
N/A
N/A
N/A
N/A
N/A
N/A
UselOOcc
Use 200cc
Use 400cc
Use 600cc
9.4.3.5 Calculate the relative response factor for each compound using the
following equation:
RRF = A, * Cis
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A C
Where:
Ax = Area of the characteristic quant ion for the compound to be measured (see
Table 1 and 2).
Ais = Area of the characteristic quant ion for the designated internal standard (see
Table 1).
C;s = Concentration of the internal standard (ppbv).
Cx = Concentration of the compound to be measured (ppbv).
9.4.3.6 Calculate the average RRF for each analyte in the curve.
9.4.3.7 Calculate the % Relative Standard Deviation (%RSD) of RRF values for the
initial calibration curve using the following equation:
%RSD = Standard Deviation (n-1) * 100
Average RRF
9.4.3.8 Calculate the average RT for each internal standard over the initial
calibration range.
9.4.4 Calibration acceptance criteria
9.4.4.1 The BFB must meet the specified criteria
9.4.4.2 The %RSD is calculated and must be less than or equal to 30% for all
compounds. This criterion must be met for the initial calibration to be
valid. However, an exception can be made for up to 2 compounds that may
exceed 30% RSD, but the RSD for these compounds must be <40.0%.
Refer to QC-SOP-12 (current revision) for calibration level rejection
criteria.
9.4.4.3 Evaluation of IS retention time: The retention time shift for each of the
internal standards at each calibration level must be within 20s of the mean
retention time over the initial calibration range.
9.4.4.4 Evaluation of target compound retention time: The relative retention time
(RRT) of each target analyte in each calibration level must be within 0.06
RRT units of the mean RRT for that compound
9.5 Calibration verification
9.5.1 Instrument Performance Check: Prior to sample analysis, a 10/50-ppbv
injection of BFB must meet the criteria listed in 9.4.1.2.
9.5.2 Calibration verification standard: The initial calibration must be verified on a
daily basis prior to the analysis of any samples. Analyze a mid-level (10/50-
ppbv)-calibration standard at the beginning and end of each 24-hour working
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period after meeting BFB tune criteria.
9.5.2.1 Calculate the % Difference between the average response factor from the
calibration curve and the response factor from the daily standard using the
equation below:
% Difference = |RRF, - RRiv| * 100
RRF;
Where:
RRF; = Average relative response factor from initial calibration.
RRFC = Relative response factor from the current calibration check
standard.
The %D in the daily standard must be +/-30% for all compounds.
The %D report is monitored daily to evaluate instrument performance and watch
for trends that might indicate the need for corrective action.
9.6 Method Blank
9.6.1 A Method blank is a volume of a clean reference matrix (Nitrogen @ 99.9999%
purity) carried through the entire analytical procedure. The volume of the
method blank must be approximately equal to the volume of the associated
samples.
9.7 Laboratory Control Sample and Duplicate (LCS/LCSD)
9.7.1 A laboratory control sample and duplicate (consisting of a representative list of
target analytes prepared near the mid-level of the calibration curve) are analyzed
daily. The LCS/LCSD are spiked into Mini Cans or 6 liter canisters and are
analyzed in the same manner as client samples. The LCS/LCSD standard must
be from a separate source than that of the calibration standards. Sub-sampling
for an LCS or LCSD from a 6 liter standard stock canister requires the 6 liter
canister to be > or = 10 psig to minimize any sub-sampling biases for the wide
variety of volatile compounds analyzed by this method.
9.8 Detection Limit Standard (DLS)
9.8.1 The lower limit of quantitation is verified daily by the analysis of a standard at
the detection limit (5-ppbv for most compounds in Minican, 0.2-ppbv or 1-ppbv
for 6 liter) in the TO 15 list analysis. The lower limit of quantitation for SIM
analysis will depend on client specifications and targets. Recovery of all
compounds with the DLS should be within the range of 60-140%. The Ethylene
Oxide DLS is analyzed at 20-ppbv and the 4-Phenylcyclohexene DLS is at 1-
ppbv (limits are also 60-140%).
9.9 Sample analysis
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9.9.1 Once the instrument check and calibration verification standards have passed the
acceptance criteria, samples may be analyzed.
9.9.2 Add 50cc of the 100-ppbv internal standard/surrogate mixture (for a level of 50-
ppbv for a lOOcc-sample injection and 10-ppbv for a 500cc-sample injection) to
the sample extract obtained from the sample mini-canister. For lOOOcc sample
injection this equates to 5 ppbv.
9.9.3 Analyze the sample on the GC/MS system using the same operating conditions
that were used for the calibration.
9.9.4 If the concentration of any target analyte in the sample exceeds the initial
calibration range of the GC/MS system, the sample must be diluted and
reanalyzed.
9.9.4.1 Dilutions can be automated by using the Entech 7100 system. However, the
smallest sample size that can be analyzed reliably is lOcc. If greater than a
10X dilution is needed on the can, the analyst must pressurize the canister
with nitrogen to further dilute the sample. The pressurization factor is
multiplied by the instrument dilution to obtain the total dilution factor:
Total Df = P„a final x lOOcc x (split factor for loop injector, if used)
PSia initial inj vol
Once the canister is pressurized above atmospheric pressure, or 14.7 Ps;a, the Entech
7032 loop injector may be used to withdraw a 1-cc injection volume. Automated
splitting of the sample stream can further dilute this volume up to a factor of lOx.
If the sample is to be reanalyzed via normal injection, it must be vented to ambient
pressure by depressing the quick-connect pin on the Mini Can.
9.10 Qualitative analysis
9.10.1 Identification of Target Compounds
The qualitative identification of compounds is based on retention time and
comparison of the sample spectrum with characteristic ions in a reference mass
spectrum. The characteristic ions from the reference mass spectrum are defined
as the three ions of greatest relative intensity, or any ions over 30% relative
intensity, if less than three such ions occur in the reference spectrum. The list
of characteristic ions for each analyte is presented in Table 1. Target
compounds are positively identified when the following criteria are met:
9.10.1.1 The EICPs of the characteristic ions of an analyte must maximize within
one scan of each other.
9.10.1.2 The RRT of the sample component is within +/- 0.06 RRT units of the
RRT of the standard component.
9.10.1.3 The relative intensities of the characteristic ions in the sample analyte
must agree within 30 percent of the relative intensities of these ions in the
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reference spectrum from the most recent calibration verification standard.
The analyst must account for deviations from this criterion such as in the
case of interference/co-elution.
9.10.1.4 Structural isomers that produce very similar mass spectra should be
identified as individual isomers if they have sufficiently different GC
retention times. Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25 percent of the sum of the
two peak heights. Otherwise, structural isomers are identified as isomeric
pairs (for example, m- & p-xylene).
9.10.1.5 Identification is hampered when sample components are not resolved
chromatographically and produce mass spectra containing ions contributed
by more than one analyte. When gas chromatographic peaks obviously
represent more than one sample component, appropriate selection of
analyte spectra and background spectra is important. When analytes
coelute the identification criteria can be met, but each analyte spectrum
will contain extraneous ions contributed by the coeluting compound.
9.10.2 Identification of Non-Target Compounds
For samples containing components not associated with the calibration
standards, a library search may be made for the purpose of tentative
identification. Up to 20 organic compounds with greatest concentration
excluding surrogate and internal standards will be identified and reported.
Non-Target compounds identification is not possible in SIM analysis.
9.10.2.1 Major ions in the reference spectrum (ions greater than 10 percent of the
most abundant ion) should be present in the sample spectrum.
9.10.2.2 The relative intensities of the major ions should agree within +/-20
percent. For example: an ion with an absolute abundance of 50 percent in
the standard spectrum must be between 30 and 70 percent in the
corresponding sample spectrum.
9.10.2.3 Molecular ions present in the reference spectrum should be present in the
sample spectrum.
9.11 Quantitative identification
9.11.1 Once a target compound has been identified, the quantitation of that compound
is based on the total abundance, or EICP integration area, of the primary
characteristic ion.
9.11.2 The concentration of a compound in the sample is determined using the mean
relative response factor determined from the initial calibration.
9.11.3 Concentration is calculated from the equation:
ppbv = (AxYIsYDfl
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(Ais)(RRFi)
Where: Ax = Area of the compound characteristic ion in the sample.
Ais = Area of the characteristic ion for the corresponding internal
standard.
Is = Concentration of internal standard in ppbv
RRF; = Mean relative response factor (from initial calibration) for the
compound being measured.
Df= Dilution factor
9.11.4. In all instances where the quantitation report has been edited, or where manual
integration or quantitation has been performed, the GC/MS operator must
identify edits or manual procedures by initialing and dating the changes made
to the report. The data system flags a manual integration on the quantitation
report by placing the symbol "m" next to the area. The analyst who performed
the integration should initial and date this flag.
9.11.5 Samples that contain target analytes above the linear range of the curve must
be diluted to bring the analytes within the curve range. If a dilution was
initially performed and no target analytes are detected above the LOQ, the
sample must be reanalyzed at a more concentrated level.
9.12 Technical Acceptance Criteria for Sample analysis
9.12.1 The samples must be analyzed on a system meeting BFB, initial calibration and
calibration verification criteria.
9.12.2 The sample must have an associated method blank meeting acceptance criteria
(see section 11.2).
9.12.3 Surrogate recovery must fall within default limits of 80-120% for all samples
and blanks.
9.12.4 The retention time of each internal standard must be within +20s of the
retention time in the most recent calibration verification standard.
9.12.5 The instrumental response (EICP area) for each of the internal standards must
be within ± 40% of the area response in the most recent calibration verification
standard. If analyzed within the same sequence a calibration curve, then the
average of the area responses for all calibration standards can be used for this
criteria comparison.
9.12.6 Concentration of all analytes must be within the calibration range determined
from the initial calibration.
9.12.7 Control Sample/Duplicate must be evaluated to determine if recoveries (and
RPDs) are within control limits.
9.13 Hydrocarbon Analysis
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9.13.1 Initial Calibration
9.13.1.1 A copy of the day's data folder is made and renamed "InstlD+date+HC."
For example, if the date is 02/25/2011 on instrument J, the new folder
will be named J022511HC. Load the previous hydrocarbon calibration
curve, rename with the current date and save the method.
9.13.1.2 With the global detection limit set to zero, re-quantitate the same data
files used for the TO-15 calibration curve. Q-Edit the files to ensure that
all of the hydrocarbon peaks are correct, using the following table.
Name
Major Peak
Bromochloromethane
130
1,4-Difluorobenzene
114
Chlorobenzene-d5
117
Bromofluorobenzene
174
Total VOC's as n-Heptane
43,57,71,100
Trimethyl Siloxanol
75
Hexmethyl Cyclotrisiloxane
207
Octomethyl Cyclotetrasiloxane
281
Siloxane
267
Note: In standards and blanks, the Trimethyl Siloxanol and Siloxane may not be present.
Highlight the peak around the retention time of where it should be, with the lowest level
present. This is usually the beginning of the peak found.
9.13.1.3 Once the peaks have been selected correctly, clear the calibration
responses in the curve. Update all the levels of the calibration using the
same data files that were used for the TO-15 curve. Ensure that you
select "Quantitate Using Initial Cal RF's" under the "Quant" menu
before saving the method.
9.13.1.4 Repeat steps 9.4.3.2 - 9.4.3.5 for n-Heptane only. An additional
conversion may be necessary, depending on client, to convert n-Heptane
to Gasoline (M.W. Gasoline divided by M.W. of n-Heptane). Siloxanes
are not calibrated compounds. RSD for siloxanes should be crossed out
and marked "Not calibrated for these compounds." Update the Custom
Report Response factor using the Average of the Total VOC's as n-
Heptane.
9.14 SIM Analysis
9.14.1 SIM analysis is a technique used to increase sensitivity with GCMS for for
target compounds using only specific ions. The only ions scanned for are
those that are characteristic of target compounds only. As a result non target
compounds are not able to be detected using SIM analysis.
9.14.2 SIM analysis can be done upon client request for compounds that require
lower detection limits than the low level 0.2-ppbv standard.
9.14.3 Target compounds will depend on client target list and will be ordered at a
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lower level primary standard if needed (example: Order a 10-ppbv standard if
client requests detection limit of0.005-ppbv)
9.14.4 If the detection limits can be meet with a standard SCAN TO-15 method but
client requests SIM analysis, the same stock and working standards used for
SCAN analysis can be used.
9.14.5 Target compounds will be quantitated from the primary ion for each
respective compound with at least 1 secondary ion for qualitative
identification. Retention time will be the primary method of identification per
9.10.1.
9.14.6 SIM analysis will be set up using a separate chemstation method using only
the ions for compounds that require SIM analysis. This will keep from
scanning non target compound ions which will increase sensitivity. Target
ions will depend on client request and the ions used should be seen in regular
TO-15 SCAN ECIP.
9.14.7 SIM methods will be made per client project to maximize sensitivity by
minimizing dwell time by the mass spectrometer. See section supervisor or
alternate for any questions.
9.14.8 Blank should be run after any QC until system is fully cleaned out before
running any client samples. This will ensure that client samples are free from
any possible carry over effects from working standards used for QC. Blanks
should be run at the end of client sample batch to ensure that there is no carry
over. Blanks should be run in between any client samples with a hit at or
greater than the mid point calibration level, to ensure that subsequent client
samples are not contaminated with carry over.
9.15 Corrective Action
9.15.1 Corrective Action for sample analysis: the sample technical acceptance criteria
must be met. If any samples do not meet acceptance criteria, consult with the
section supervisor to determine whether reanalysis is required.
9.15.2 Corrective Action for surrogate recovery failure: check calculations and examine
the chromatogram for interference. If no interference is noted, reanalyze any
sample that exceeds criteria. If the sample meets criteria upon reanalysis, report
the reanalysis only. If the sample produced similar results upon reanalysis, the
problem may be matrix-related. Contact the project manager so the client may be
notified.
9.15.3 Corrective Action for Internal Standard Response failures: if any internal
standard exceeds acceptance criteria, check calculations. Verify that the standard
concentration is accurate, and that the instrument did not malfunction. Reanalyze
the sample to see if the problem was matrix related. If the reanalysis meets
criteria, report the reanalysis only. If the reanalysis produced similar results,
consult with the section supervisor and project manager to determine the best
course of action.
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9.15.4 Corrective Action for Internal Standard Retention Time: if any internal standard
exceeded retention time criteria, follow the same guidelines used in Section
9.14.3.
9.15.5 Corrective Action for Instrument Contamination: if an instrument has come into
contact with a PPM level of analytes, the instrument might need extra cleaning
to ensure that there is no carry-over to other client samples. Block access to the
ports affected on the Entech autosampler until they go through at least 5 flush
and bake cycles. Test the ports, as room air blanks, to see if there is carry-over.
If there no carry-over, go ahead and use the ports during the next run. If there is
carry-over, see section supervisor for other possible actions, which may include
cleaning the source.
10.0 DOCUMENTATION
10.1 The raw data is archived to CD-ROM and is stored in a secured area. Hard copies
of raw data are kept for a period of ~1 year in the laboratory and then stored for a
total time of 5 years before disposal.
10.2 Chain of custody forms, instrument maintenance logs, standards preparation logs,
analytical run logs, and corrective action logs must be filled out in a timely manner.
These records are maintained in the laboratory for five years.
11.0 CALCULATIONS
All calculations are covered in Section 9.
12.0 QUALITY CONTROL CHECKS & CRITERIA
12.1 Instrument performance must be monitored to ensure that all of the tuning, initial
calibration and calibration verification criteria requirements are met.
12.2 Method blanks
12.2.1 A method blank is a volume of a clean reference matrix (nitrogen @ 99.9999%
purity) carried through the entire analytical procedure. The volume of the
method blank must be approximately equal to the volume of the associated
samples. The purpose of the method blank is to determine the level of
contamination associated with the preparation and analysis of samples.
12.2.2 Method blanks must be analyzed with each batch of samples, or at a minimum
frequency of 1 for every 20 samples.
12.2.3 A method blank is analyzed following the calibration verification standard under
the same conditions as the standards and samples before any samples may be
analyzed.
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12.2.4 The method blank must contain no targets above the LOQ of 5-ppbv (lOOcc
injection for Minican) and 0.2-ppbv (500cc injection or lOOOcc for 6-L Summa
canisters) for the TO 15 list. They should contain no targets above client
specific detection limits for SIM analysis. The LOQ for Ethylene Oxide is 20-
ppbv and the 4-Phenylcyclohexene LOQ is 1-ppbv.
12.2.5 If the method blank does not meet this criterion, repeat the analysis until an
acceptable blank is obtained. Sample analysis may not begin until a method
blank meeting criteria has been successfully analyzed.
12.2.6 If the surrogate recovery in the method blank does not meet control limits,
reanalyze the method blank. If the surrogate recovery is still outside control
limits, it may be necessary to re-prepare the internal standard/surrogate mixture
or recalibrate the instrument.
12.3 Laboratory Control Sample/ Laboratory Control Sample Duplicate
12.3.1 A laboratory control sample & duplicate (LCS/LCSD) consist of an aliquot of a
clean reference matrix (UHP nitrogen), spiked with a representative list of the
target analytes at the mid-level of the calibration curve. The spiking standard
must be from a source different from that of the calibration standards.
12.3.2 The LCS & LCSD must be analyzed with each analytical run. The recoveries
should fall within the range of 70-130%. For compounds 1,2,4-Trichlorobenzene
and Hexachloro-1, 3-Butadiene, separate limits have been established based on
historical laboratory data (these compounds are no longer in the TO-15 regular
list). RPD method default limits of 25% are used to assess analytical precision.
If recovery and/or RPD are not within this range, the possible effect(s) on the
sample data must be determined. The data may be qualified or the LCS/LCSD
sample may be reanalyzed.
12.4 Surrogate Recoveries
12.4.1 All samples, including quality control samples, are spiked with 50ppbv
Bromofluorobenzene as a surrogate for lOOcc sample injection volume (this
equates to 10 and 5ppbv for 500cc and lOOOcc injection volumes).
12.4.2 The surrogate (BFB) recovery control limits are 80-120%. All samples should
meet the surrogate recovery criterion. If BFB recovery falls outside control limits
for any sample, the sample must be reanalyzed. If the reanalysis produces similar
results, contact the project manager.
12.5 Duplicate analysis.
12.5.1 A sample is analyzed in duplicate to assess precision. Duplicates must be
analyzed with each batch of samples, or at a minimum frequency of 1 for every
24-hour analytical sequence. The relative percent difference (RPD) between
measurements should be 25% or less.
12.6 Initial Demonstration of Proficiency (IDP)
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12.6.1 Demonstration of proficiency is established by generating data of acceptable
accuracy and precision for target analytes for each preparative method and
matrix by analyzing reference samples. On-going demonstration is performed on
a semiannual basis.
12.6.2 Four reference samples are prepared so that each analyst tests 4 samples of
unknown concentration containing all analytes of interest. Analyst One prepares
two different stock standards independently and fills two sample canisters from
each. The preparing analyst labels the canisters with the injection volume to use
and gives them a sample ID. This results in 4 different concentrations for each
analyst. A second analyst repeats the process for any other analysts. The
standards must be made from stock standards prepared independently from those
used for calibration. The concentration of targets in the four reference samples
may be anywhere within the current calibration range of the instrument.
12.6.3 Analyze the four reference samples by the same procedure used for analyzing
actual samples. Calculate both the average recoveries in ppbv and the relative
standard deviations of the recovery for each analyte of interest. The average
recovery should fall within the in-house generated control limits for each
analyte.
12.6.4 IDP procedures must be repeated whenever new staff is trained or significant
changes in preparative or analytical methods are made.
12.7 Verification of Method Detection Limit
12.7.1 Instrument reporting limits are verified (at least) annually by analyzing 7
replicates at the reporting limit. All compounds must be within 60-140%
recovery for the detection limit standard (DLS) when using a nominal sample
injection volume of 100-cc for MiniCan, 500cc-1000cc fox Summa Canisters or
1 OOOcc for SIM analysis.
12.7.2 Alternatively, an MDL study can be performed if needed. MDL is the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the analyte concentration is greater than zero. The MDL is
determined by the analysis of seven replicate injections of each compound of
interest at a level near the expected detection limit. The standard deviation of
the seven measurements multiplied by 3.14 (Student's t value for 99%
confidence for seven values) defines the MDL for each analyte.
12.7.3 MDLs are determined only if needed for each instrument, as the detection limit
studies (described in 12.7.1) are used to verify instrument-reporting limits.
12.7.4 For SIM analysis, detection limits should meet or exceed client specifications.
12.8 Additional Control Procedures
12.8.1 Logbook Review Procedure:
The supervisor or designee will review GCMS run logs and maintenance logs
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weekly. The logbooks will be reviewed for content and for the absence of cross
outs. All forms will be verified to be the most recent approved version.
Logbooks will be initialed and dated as to the date of review. MS-Form-6 will
be used to document that all logbooks are reviewed as per their set schedule.
The preventative maintenance log will be reviewed as the maintenance is done
(some is weekly, some monthly and also some at 6-12 month intervals). The
standards logbooks are reviewed each time a standard is made. Can cleaning
logbooks and canister dilution logbooks will be reviewed weekly.
12.8.2 Forms Control Procedure:
In addition to forms being reviewed on a weekly basis new forms once approved
(notification through email) will be printed and a new logbook made by the end
of the next business day. Previous logbooks will be closed out and archived.
12.8.3 Preventative Action Plan Initiation/Review Policy:
A PAP should be initiated whenever an action can be initiated to prevent a
future problem. Consultation with the QC group will be used to determine if a
PAP is required. PAPs will be reviewed at least weekly until completed.
12.8.4 Entech auto-sampler ports are flushed before use and this is indicated on system
injection log.
12.8.5 All working standard numbers (IH numbers) will be verified on hard copy
reports and in LIMS to ensure accuracy and traceability for standard
documentation.
12.8.6 Sample Canister Cleaning Approval Procedure.
This procedure is used to ensure sample analysis is complete before sample
canisters are cleaned. After a sample analysis sequence is complete, canisters are
placed in project holding bin (red or purple) waiting for approval of all Quality
control and sample results. If any re-analysis is required, those samples are kept
in this bin until re-analysis is performed. When approval is given by supervisor
and/or designee to clean sample canisters, canisters are then transferred to the
"approved for cleaning bin" (black or blue) by verifying sample identification
using Galson Login number and individual sample number. This bin is then
taken to the sample cleaning area.
13.0 CORRECTIVE ACTION
13.1 See section 9.14 for corrective actions.
14.0 WASTE DISPOSAL
14.1 Refer to Galson Laboratories SOP LF-DISPO (current revision).
15.0 REFERENCES
15.1 Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs)
In Air Collected I Specially-Prepared Canisters And Analyzed By Gas
Chromatography/Mass Spectrometry (GC/MS), Second Edition, U. S. Environmental
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Protection Agency, Research Triangle Park, NC 27711, EPA/626/R-96/010b, January
1999.
15.2 PV2120: Volatile Organic Compounds in Air, U. S. Department of Labor -
Occupational Safety & Health Administration, Control Number T-PV2120-01-0305-
ACT, May 2003
16.0 METHOD MODIFICATIONS
Method PV2120:
The samples arrive in the lab at ~ 15 psia (atmospheric pressure, 0 psig) and this is
adequate to sample without pressurizing (diluting) the sample up to 30 psig (45 psia).
Method TO-15: (parentheses denote method-referenced sections)
(10.7.5)
Daily blank limit is set at 5-ppbv for TO 15 list (the normal reporting limit for most
compounds), not 3x the MDL.
(8.4.1.2)
Can leak-checks are done by evacuating cans to ~ 30" of Mercury (vacuum reading),
and then checking them before sample shipment. If vacuum falls to <28" of Mercury
within 24 hours, a can is considered to be leaking (TO-15 leak-checks by pressurizing
cans to 30 psig and has pass/fail criteria of <+/- 2 psig) in 24 hours.
(8.4.1.6)
Cans containing less than 2-ppm of individual contaminants are cleaned in batches
where a representative can is tested to demonstrate cleanliness of the batch. For cans
containing analytes greater than 2-ppm, these cans are tested individually to verify
cleanliness. Can cleaning limits are higher (refer to section 9.2.2.2). For MiniCans: the
representative can cleaning blank limit (or individual can) for TO-15 list is set at 5-
ppbv, the normal reporting limit. The warning limit is 2.5-ppbv. Quantitation in general
is not reliable below 5-ppbv. Cans are generally re-cleaned if above 2.5-ppbv for any
analyte. For 6-L Summa Canisters: the cleaning blank limit is 0.2-ppbv (LOQ for most
compounds), anything less than 0.2-ppbv is considered clean. Correspondingly, for
Ethylene Oxide the limit is 20-ppbv and for 4-Phenylcyclohexene the limit is 1 ppbv.
(10.8.1)
For Minican analysis: lOOcc sample injection volume is used when sampling is done
with 400mL and 1-liter canisters rather than 6-liter summa canisters. Therefore, MDL
limits, etc. are ~ 5x higher because the sample injection volume is 5x less.
(9.2.2.3)
For Minican analysis: Internal standard/surrogate levels are spiked at 50-ppbv rather
than 10-ppbv to be consistent with calibration levels for TO 15 list analyses.
(10.7.2)
A blank is not always analyzed after a high level sample. If the compound that was high
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is detected in samples injected after the high level sample, those samples would be
reanalyzed after the system was shown to be clean.
(10.7.5)
Internal standard area limit of +/- 40% is calculated versus the daily standard for all
injections that day (24 hour window) not versus the most recent calibration curve
average areas.
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Table 1
Characteristic Ions, PQLs
COMPOUND
EI
EI
EI
PQL ppb
PRIMARY
SECONDARY
TERTIARY
Summa
Minican
Propylene
41
39
0.2
5
Freon-12
85
87
0.2
5
Chlorom ethane
50
52
0.2
5
Freon-114
85
135
87
0.2
5
Vinyl Chloride
62
64
0.2
5
1,3-Butadiene
39
54
0.2
5
Bromomethane
94
96
0.2
5
Chloro ethane
64
66
0.2
5
Vinyl Bromide
106
108
0.2
5
Freon-11
101
103
105
0.2
5
[sopropyl Alcohol
45
43
0.2
5
Acetone
43
58
0.2
5
1,1 -Dichloroethene
96
61
98
0.2
5
Methylene Chloride
84
86
49
0.2
5
Freon-113
101
101
151
0.2
5
Allyl chloride
76
41
39
0.2
5
Carbon Disulfide
76
78
0.2
5
Trans-1,2-Dichloroethene
61
96
98
0.2
5
Methyl Tert-Butyl Ether
73
41
57
0.2
5
1,1 -Dichloroethane
63
65
0.2
5
Vinyl Acetate
43
86
0.2
5
Methyl Ethyl Ketone
43
57
72
0.2
5
:is-1,2-Dichloroethylene
61
96
98
0.2
5
Hexane
57
41
43
0.2
5
Ethyl Acetate
43
45
61
0.2
5
Chloroform
83
85
47
0.2
5
T etrahydrofiiran
42
71
72
0.2
5
COMPOUND
EI
EI
EI
PQL ppb
PRIMARY
SECONDARY
TERTIARY
Summa
Minican
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1,2-Dichloroethane
62
64
0.2
5
1,1,1 -Trichloro ethane
97
99
61
0.2
5
Cyclohexane
56
41
84
0.2
5
Carbon T etrachloride
117
119
0.2
5
Benzene
78
77
50
0.2
5
1,4-Dioxane
88
58
0.8
20
2,2,4-Trimethylpentane
57
41
56
0.2
5
Heptane
43
57
71
0.2
5
1,2-Dichloropropane
63
41
62
0.2
5
T richloro ethylene
130
132
95
0.2
5
Bromodichloromethane
83
85
0.2
5
sis-1,3 -Dichloropropene
75
39
77
0.2
5
Trans-1,3 -Dichloropropene
75
39
77
0.2
5
1,1,2-Trichloroethane
97
83
61
0.2
5
Toluene
92
91
92
0.2
5
Dibromochloromethane
129
127
0.2
5
Methyl Isobutyl Ketone
43
57
58
0.8
20
Methyl Butyl Ketone
43
57
58
0.8
20
1,2-Dibromomethane
107
109
0.2
5
T etrachloroethylene
164
166
131
0.2
5
Chlorobenzene
112
77
114
0.2
5
Ethylbenzene
91
106
0.2
5
Bromoform
173
175
0.2
5
Styrene
104
78
103
0.2
5
~-xylene
91
106
0.2
5
m- & p-xylene (co-elute)
91
106
0.4
10
1,1,2,2-T etrachloro ethane
83
85
0.2
5
4-Ethyltoluene
105
120
0.2
5
1,3,5-Trim ethylbenzene
105
120
0.2
5
1,2,4-Trim ethylbenzene
105
120
0.2
1,3 -Dichlorobenzene
146
148
111
0.2
COMPOUND
EI
EI
EI
PQL ppb
PRIMARY
SECONDARY
TERTIARY
Summa
Minican
Benzyl Chloride
91
126
0.2
5
1,4-Dichlorobenzene
146
148
111
0.2
5
1,2-Dichlorobenzene
146
148
111
0.2
5
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1,2,4-Trichlorobenzene
180
182
184
0.2
5
Hexachloro-1,3 -Butadiene
225
227
223
0.2
5
Ethylene Oxide
44
29
NA
20
4-Phenylcyclohexene
104
158
78
1
Naphthalene
128
102
NA
0.2
5
Bromofluorobenzene (surrogate)
95
-
*Bromochlorom ethane
128
-
* 1,4-Difluorobenzene
114
-
* Chlorobenzene-d5
117
-
*Indicates internal standard
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Table 2
Volatile Internal Standards with Corresponding Analytes
Assigned for Quantitation
*Bromochloromethane
* 1,4-Difluorobenzene
* Chlorob enzene -d5
Propylene
1,1,1 -Trichloroethane
Toluene
Freon-12
Cyclohexane
Dibromochloromethane
Chloromethane
Carbon Tetrachloride
Methyl Isobutyl ketone
Freon-114
Benzene
Methyl Butyl ketone
Vinyl Chloride
1,4-Dioxane
1,2-Dibromoethane
1,3-Butadiene
2,2,4-Trimethylpentane
T etrachloro ethylene
Bromomethane
Heptane
Chlorobenzene
Chloro ethane
1,2-Dichloropropane
Ethylbenzene
Vinyl bromide
T richloro ethylene
m- & p-xylene (co-elute)
Freon-11
Bromodichloromethane
Styrene
Isopropyl alcohol
cis-1,3 -Dichloropropene
o-xylene
Acetone
trans-1,3 -Dichloropropene
Bromoform
1,1 -Dichloroethene
1,1,2-Trichloroethane
1,1,2,2-T etrachloro ethane
Methylene Chloride
4-Ethyltoluene
Freon-113
1,3,5-Trimethylbenzene
Allyl chloride
1,2,4-Trimethylbenzene
Carbon disulfide
Benzyl chloride
Trans-1,2-Dichloroethene
1,3 -Dichlorobenzene
Methyl tert-butyl ether
1,4-Dichlorobenzene
1,1 -Dichloroethane
1,2-Dichlorobenzene
Vinyl acetate
1,2,4-Trichlorobenzene
Methyl ethyl ketone (2-butanone)
Hexachloro-1,3 -Butadiene
Cis-1,2-Dichloro ethylene
Bromofluorobenzene (surrogate)
Hexane
4-Phenylcyclohexene
Ethyl acetate
Naphthalene
Chloroform
T etrahydro furan
1,2-Dichloroethane
Ethylene Oxide
Page 26 of 26
-------
ENBRIDGE
August 17, 2012
Mr. Ralph Dollhopf
Federal On-Scene Coordinator and Incident Commander
U.S. Environmental Protection Agency
801 Garfield Avenue, #229
Traverse City, Ml 49686
RE: Request for Modification of the Air Monitoring and Sampling Addendum to the Sampling
and Analysis Plan,
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Dear Mr. Dollhopf:
Enbridge Energy, Limited Partnership (Enbridge) is requesting the United States Environmental
Protection Agency (U.S. EPA) approve the following modification to the Air Monitoring and
Sampling Addendum to the Sampling and Analysis Plan (AMSA) approved by the U.S. EPA on
January 31, 2012. The proposed modifications are being requested for immediate
implementation.
Enbridge continues to meet obligations related to air monitoring and sampling under the current
AMSA, which specifically requires work area air monitoring for all oil recovery activities, and the
ability to respond to odor complaints. Enbridge is requesting a suspension of all work area air
monitoring activities and odor response requirements effective immediately.
As you are aware, the air monitoring and sampling program was designed to protect worker
safety and public health during assessment and oil recovery activities. Enbridge has been
conducting, collecting, and reporting air monitoring and sampling since July 27, 2010. This has
been a comprehensive and collaborative effort that has involved not only real-time and
analytical data collection, but at minimum weekly reviews and discussion of data involving an air
sampling and monitoring group that includes: Enbridge, U.S. EPA, and Michigan Department of
Community Health (MDCH). In addition, Enbridge has supported and provided extensive
scientific studies as informally requested by U.S. EPA and MDCH to ensure air sampling
activities support the safety of workers and public health.
Air monitoring and sampling conducted in 2010, 2011, and 2012 for the Line 6B release has
resulted in the compilation of robust data sets from all types of oil recovery activities including,
but not limited to, free product recovery, overbank surface oil recovery, overbank excavation,
and submerged oil recovery. These activities were conducted over a broad range of
atmospheric conditions and through degradation of the released oil from free product to
weathered tar patties and submerged oil. As a result, a negative exposure assessment for
potential inhalation exposure has been derived from which Enbridge is confident that there is
not an inhalation exposure risk to their workers or the community with respect to remaining oil
recovery activities.
Enbridge Energy, Limited Partnership
1601 Pratt Ave.
Marshall, Michigan 49068
P. 269-781-1195
F. 269-781-1110
-------
Page 2, Mr. Dollhopf, August 17, 2012
The following summarizes pertinent data with respect to air monitoring and sampling to support
the suspension of the air monitoring and sampling program for the Line 6B release.
Air Monitoring Data
Air monitoring has been utilized as a screening tool throughout the Line 6B release to assess
potential exposures to workers and the community. Real-time air monitoring included the
collection of data for concentrations of airborne volatile organic compounds (VOCs), benzene,
hydrogen sulfide (H2S), and sulfur dioxide (S02) associated with oil recovery activities.
Work Zone
Throughout 2010, 2011, and 2012, work zones (also known as 'work areas') were monitored to
assess potential exposures to airborne concentrations of chemicals of potential concern, which
are a subset of "target analytes" (a list of crude oil related constituents, specifically related to
Enbridge Line 6B crude oil, and enclosed as Table 1). Real-time air monitoring conducted in
work zones is compared to Occupational Exposure Standards and Guidelines that were
compiled by the Enbridge Public Health Unit during initial response activities. The exposure
criteria, presented in the enclosed Table 2, outline the applicable occupational exposure
standards and guidelines established by the Occupational Safety & Health Administration
(OSHA), Michigan OSHA, and American Conference of Governmental Industrial Hygienists. In
2011, a total of 21,169 real-time work zone monitoring readings were collected which resulted in
a total of 44 detections (27 S02 and 17 VOC detections) all linked through field notes to boat
motor exhaust odors. 6,378 real-time work zone monitoring readings were collected in 2012
(through July 31, 2012). There were 28 VOC detections and 16 carbon monoxide (CO)
detections during 2012 work area monitoring. The VOC detections were not sustained
readings, were indicative of boat motors, and coincide with the CO detections. All detections of
CO were attributed to boat motors.
Community
As a screening tool for determining air sampling locations and in addition to work zone air
monitoring, community air monitoring (which also included work zone perimeter air monitoring)
was conducted in 2010 and 2011. A total of 66,922 real-time community air monitoring readings
were collected in 2010, with no detections. From June 3, 2011 through and including October
27, 2011 a total of 33,424 real-time community air monitoring readings were also collected with
no detections.
Enbridge has made an undeniable commitment to the communities and people affected by the
Line 6B release, which is further supported by the community air sampling program.
Specifically between August 16, 2010 through and including November 10, 2010, a total of
1,531 24-hour duration community air samples were collected. Enbridge continued the
community air sampling program with the collection of another 1,702 24-hour duration
community air samples between June 3, 2011 through and including January 23, 2012 during oil
recovery activities.
Community Air Sampling
To evaluate potential exposures during oil recovery activities, a list of target analytes was
developed based on modified U.S. EPA Method TO-15 laboratory analysis of volatiles which
could potentially be released from Line 6B crude oil. All other chemicals are referred to as "non-
target analytes". Developed as a baseline for comparison to assess potential community
exposure to VOCs from the Line 6B crude oil, the 2011 Enbridge Oil Spill Human Health Air
Screening Levels (HHASLs), included as Attachment A, were compiled by local and state health
-------
Page 3, Mr. Dollhopf, August 17, 2012
departments and regulatory agencies using State and Federal exposure criteria. It's important
to note that these HHASLs are concentrations that are likely to be without appreciable risk of
deleterious non-cancer effects during a long term continuous exposure at or greater than the
reference concentrations. They are not a direct estimator of risk but rather a reference point to
gauge potential effects. At exposures to a chemical increasingly greater than the HHASL, the
potential for adverse health effects increases. A long term continuous exposure above the
HHASLs does not imply that an adverse health effect would necessarily occur, just that risk
increases.
Enbridge has utilized the above referenced HHASLs to compare the subset of air sampling data
from 2010, 2011, and 2012 filtered, specifically to include only 24-hour duration samples and
target analytes, to evaluate potential community exposure to chemicals that may be related to
Enbridge crude oil and associated oil recovery activities. An initial assessment of this data
revealed that, when segregated by target analytes, greater than 99% of the air sampling data
set is below the method detection limit (MDL) for their respective analytes, with the exception of
toluene which showed greater than 85% of samples below the MDL. The air sampling data set
was evaluated through the use of U.S. EPA ProUCL Version 4.00.02 (ProLICL) statistical
analysis software to adequately evaluate all results, including those below the MDL. Based on
a general statistical analysis through ProUCL for each of the target analytes with MDLs (i.e. not
including tentatively identified compounds), the Kaplan-Meier (KM) method was recommended
for a more refined statistical evaluation of the analytical data set. Copies of the ProUCL
statistical analysis outputs for these target analytes are included as Attachment B.
In conjunction with the use of statistical analysis to evaluate data in comparison to HHASLs,
Enbridge developed charts for select target analytes (target analytes with at least one detection
and a comparable HHASL) and one non-target analyte (acetaldehyde) that has been of interest
to the air sampling and monitoring group. These charts display a chronology of detections for
each of the analytes from August 16, 2010 through and including January 23, 2012, including: a
depiction of the KM calculated mean (where applicable for analytes with MDLs), respective
HHASL, number of detections, analyte concentrations, and number of samples analyzed. It is
important to note that the charts only reflect analyte concentrations above the MDL. However,
for select parameters analyzed in 2010 the MDL may be higher than the current HHASL and is
noted as such on the respective charts. These charts are also enclosed with this
correspondence.
As shown in these charts, the detection frequency of target analytes is low and mean values,
where appropriate, are well below respective HHASLs. In addition, the total number of
detections above HHASLs for each of the contaminants in comparison to the total number of
samples analyzed is significant.
Odor Response Monitoring & Sampling
The Odor Response Team responded to 11 odor complaints between June 3, 2011 through and
including October 13, 2011 at which a combination of real-time air monitoring data and canister
air samples (grab and/or 24-hour canister samples) were collected. Real-time readings were
collected for VOCs, benzene, H2S, and S02 at each response. There were no detections above
the instrument detection limits on any occasion. Grab and 24-hour duration samples collected
during the response were analyzed for VOCs by U.S. EPA Method TO-15. Laboratory results
indicated no detections for target analytes above HHASLs.
-------
Page 4, Mr. Dollhopf, August 17, 2012
Supported by limited number of odor complaints (the last complaint occurring on October 13,
2011) and air monitoring and sampling data collected to date, Enbridge is requesting to
discontinue the current odor response requirements.
Enbridge understands that there are a variety of ways to sort, analyze, and present the air
sampling and monitoring data from the Line 6B release and all parties may not all agree on the
selected technical approach. Data has been presented in multiple formats for review and
comment by the U.S. EPA including, but not limited to: daily deliverables, SCRIBE.net, Monthly
Reports, and Report of Findings Air Monitoring and Sampling reports. In the professional
opinion of our engineers and scientists, there is conclusive evidence to support suspension of
the air monitoring and sampling program. Enbridge is certainly open to the opportunity to
present additional information and is willing to accept comments and/or suggestions regarding
the analysis of data collected through our air monitoring and sampling program.
If you have any questions regarding this request, please do not hesitate to contact Jim Snider at
(269)781-1195.
Sincerely,
ENBRIDGE ENERGY, LIMITED PARTNERSHIP
By Enbridge Pipelines (Lakehead) L.L.C.
Its General Partner
Richard Adams
Vice President, U.S. Field Operations
Enclosures: Table 1: Predominant Crude Oil VOCs Detected by TO-15 Analysis
Table 2: Occupational Exposure Standards and Guidelines
Attachment A. 2011 Enbridge Oil Spill Human Health Air Screening Levels
Attachment B. ProUCL Statistical Output for Target Analytes
Attachment C. Charts for Select Analytes
CC: John Sobojinski, Enbridge
Michelle DeLong, MDEQ
-------
Tables
-------
Table 1. Predominant Crude Oil VOCs Detected by TO-15 Analysis
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Predominant Crude Oil VOCs Detected by TO-15 Analysis1
Target Analyte
CAS No.
Laboratory LOQ (ppbv)
Benzene
71-43-2
1.0
Butane, 2-methyl-*
78-78-4
NA
Cyclohexane
110-82-7
1.0
Cyclohexane, 1,3-dimethyl*
591-21-9
NA
Cyclopentane, methyl-*
96-37-7
NA
Cyclohexane, 1,3-dimethyl-, cis-*
638-04-0
NA
Cyclohexane, butyl-*
1678-93-9
NA
Cyclohexane, ethyl-*
1678-91-7
NA
Cyclohexane, methyl-*
108-87-2
NA
Cyclohexane, propyl-*
1678-92-8
NA
Cyclopentane, 1,1-dimethyl*
1638-26-2
NA
Cyclopentane, 1,3-dimethyl-, trans*
1759-58-6
NA
Cyclopentane, 1,2-dimethyl-, trans*
822-50-4
NA
Heptane, 3-methyl-*
589-81-1
NA
2-Octene, 2,6-dimethyl-*
4057-42-5
NA
Decane*
124-18-5
NA
Dodecane*
112-40-3
NA
Ethylbenzene
100-41-4
1.0
Ethyltoluene, 4-
622-96-8
1.0
Heptane, n-
142-82-5
1.0
Hexane, n-
110-54-3
1.0
Naphthalene*
91-20-3
NA
Nonane*
111-84-2
NA
Hexane, 2-methyl*
591-76-4
NA
Octane*
111-65-9
NA
Octane, 3-methyl-*
2216-33-3
NA
Pentane, 2-methyl-*
107-83-5
NA
Toluene
108-88-3
1.0
Benzene, 1,2,4-trimethyl
95-63-6
1.0
Hexane, 3-methyl*
589-34-4
NA
Heptane, 2-methyl-*
592-27-8
NA
Cyclohexane-l,l,3-trimethyl*
3073-66-3
NA
Benzene, 1,3,5-trimethyl
108-67-8
1.0
Undecane*
1120-21-4
NA
Xylene, m&p-
179601-23-1
2.0
Xylene, o-
95-47-6
1.0
Sheet 1 of 4
-------
Table 1. Predominant Crude Oil VOCs Detected by TO-15 Analysis
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Non-Target Analyte
CAS NO
Laboratory LOQ (ppbv)
ALPHA-PINENE*
80-56-8
NA
1,1,1-TRICHLOROETHANE
71-55-6
1.0
1,1,2,2-TETRACHLOROETHANE
79-34-5
1.0
1,1,2-TRICHLOROETHANE
79-00-5
1.0
1,1-DICHLOROETHANE
75-34-3
1.0
1,1-DICHLOROETHENE
75-35-4
1.0
1,2-DIBROMOETHANE
106-93-4
1.0
1,2-DICHLOROBENZENE
95-50-1
1.0
1,2-DICHLOROETHANE
107-06-2
1.0
1,2-DICHLORO PRO PANE
78-87-5
1.0
1,3-BUTADIENE
106-99-0
1.0
1,3-BUTADIENE, 2-METHYL-*
78-79-5
NA
1,3-DICHLOROBENZENE
541-73-1
1.0
1,4-DICHLOROBENZENE
106-46-7
1.0
1,4-DIOXANE
123-91-1
4.0
1-HEPTANOL, 2-PROPYL-*
10042-59-8
NA
2,2,4-TRIMETHYLPENTANE
540-84-1
1.0
2,2,7,7-TETRAMETHYLOCTANE*
1071-31-4
NA
2,3,4,5-TETRAHYDROPYRIDAZINE*
694-06-4
NA
2-HEPTANONE*
110-43-0
NA
2-PENTANONE*
107-87-9
NA
2-PROPANOL, 2-METHYL-*
75-65-0
NA
3-HEPTANONE*
106-35-4
NA
ACETALDEHYDE*
75-07-0
NA
ACETIC ACID, 2-ETHYLHEXYL ESTER*
103-09-3
NA
ACETONITRILE*
75-05-8
NA
ALLYL CHLORIDE
107-05-1
1.0
BENZENE, l-METHYL-4-(l-METHYLETHYL)*
99-87-6
NA
BENZYL CHLORIDE
100-44-7
1.0
BROMODICHLOROMETHANE
75-27-4
1.0
BROMOFORM
75-25-2
1.0
BROMOMETHANE
74-83-9
1.0
BUTANE*
106-97-8
NA
BUTANOIC ACID, 2-METHYLPROPYL ESTER*
539-90-2
NA
BUTANOIC ACID, BUTYL ESTER*
109-21-7
NA
BUTANOIC ACID, ETHYL ESTER*
105-54-4
NA
BUTANOIC ACID, METHYL ESTER*
623-42-7
NA
BUTANOIC ACID, PROPYL ESTER*
105-66-8
NA
CARBON DISULFIDE
75-15-0
2.0
CARBON TETRACHLORIDE
56-23-5
1.0
CARBONYL SULFIDE*
463-58-1
NA
Sheet 2 of 4
-------
Table 1. Predominant Crude Oil VOCs Detected by TO-15 Analysis
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Non-Target Analyte
CAS NO
Laboratory LOQ (ppbv)
CHLOROBENZENE
108-90-7
1.0
CHLOROETHANE
75-00-3
1.0
CHLOROFORM
67-66-3
1.0
CHLOROMETHANE
74-87-3
1.0
CIS-l,2-DICHLOROETHYLENE
156-59-2
1.0
CIS-l,3-DICHLOROPROPENE
10061-01-5
1.0
CYCLOPENTANE, 1,1'-ETHYLIDENEBIS-*
4413-21-2
NA
DECANE, 2,2,4-TRIMETHYL-*
62237-98-3
NA
DECANE, 2,3,4-TRIMETHYL-*
62238-15-7
NA
DECANE, 2,3,5-TRIMETHYL-*
62238-11-3
NA
DIACETYL*
431-03-8
NA
DIBROMOCHLOROMETHANE
124-48-1
1.0
DISULFIDE, DIMETHYL*
624-92-0
NA
DISULFIDE, FLUOROMETHYL METHYL*
60307-49-5
NA
ETHANE, 1,1-DIFLUORO-*
75-37-6
NA
ETHYL ACETATE
141-78-6
1.0
ETHYL ALCOHOL*
64-17-5
NA
EUCALYPTOL*
470-82-6
NA
FREON 11
75-69-4
1.0
FREON 113
76-13-1
1.0
FREON 114
76-14-2
1.0
FREON 12
75-71-8
1.0
FURAN, 2,3-DIHYDRO-3-METHYL-*
1708-27-6
NA
HEPTANE, 2,2,3,4,6,6-H EXAM ETHYL-*
62108-32-1
NA
HEPTANE, 2,2,4,6,6-PENTAMETHYL-*
13475-82-6
NA
HEPTANE, 2,2-DIMETHYL-*
1071-26-7
NA
HEPTANE, 4-ETHYL-2,2,6,6-TETRAMER*
62108-31-0
NA
HEXADECANE, 2,6,10,14-TETRAMETHYL-*
638-36-8
NA
HEXANAL*
66-25-1
NA
HEXANE, 2,2,5-TRIMETHYL-*
3522-94-9
NA
HEXANE, 2,4-DIMETHYL-*
589-43-5
NA
HEXANOIC ACID, METHYL ESTER*
106-70-7
NA
HEXYL N-VALERATE*
1117-59-5
NA
ISOBUTANE*
75-28-5
NA
LIMONENE*
138-86-3
NA
METHYL 3-BUTENOATE*
3724-55-8
NA
METHYL BUTYL KETONE
591-78-6
4.0
METHYL ETHYL KETONE
78-93-3
1.0
METHYL ISOBUTYL KETONE
108-10-1
4.0
METHYL TERTIARY BUTYL ETHER
1634-04-4
1.0
METHYLENE CHLORIDE
75-09-2
1.0
Sheet 3 of 4
-------
Table 1. Predominant Crude Oil VOCs Detected by TO-15 Analysis
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Non-Target Analyte
CAS NO
Laboratory LOQ (ppbv)
NONANAL*
124-19-6
NA
NONANE, 3-METHYL-5-PROPYL-*
31081-18-2
NA
OCTANE, 2,2-DIMETHYL-*
15869-87-1
NA
OCTANE, 2,7-DIMETHYL-*
1072-16-8
NA
o-Veratramide*
1521-39-7
NA
PENTANE*
109-66-0
NA
PENTANE, 3-METHYL-*
96-14-0
NA
PROPANE*
74-98-6
NA
PROPANOIC ACID, 2-OXO-*
127-17-3
NA
PROPYLENE
115-07-1
1.0
STYRENE
100-42-5
1.0
TETRACHLOROETHYLENE
127-18-4
1.0
TETRADECANE*
629-59-4
NA
TETRADECANE, 2,2-DIMETHYL-*
59222-86-5
NA
TETRAHYDROFURAN
109-99-9
1.0
TRANS-l,2-DICHLOROETHENE
156-60-5
1.0
TRANS-l,3-DICHLOROPROPENE
10061-02-6
1.0
TRICHLOROETHYLENE
79-01-6
1.0
TRIDECANE, 6-METHYL-*
13287-21-3
NA
TRISULFIDE, DIMETHYL*
3658-80-8
NA
UNDECANE, 2,2-DIMETHYL-*
17312-64-0
NA
UNDECANE, 2,6-DIMETHYL-*
17301-23-4
NA
UNDECANE, 3,6-DIMETHYL-*
17301-28-9
NA
THIAZOLE*
288-47-1
NA
THIOACETAMIDE*
62-55-5
NA
1,1-DICHLORO PRO PANE*
78-99-9
NA
VINYL ACETATE
108-05-4
1.0
VINYL BROMIDE
593-60-2
1.0
VINYL CHLORIDE
75-01-4
1.0
^he laboratory will also be asked to report on all analytes included in their TO-15 method
standard analyte list.
Tentatively identified compound (TIC)
NA - Not Applicable
ppbv - parts per billion by volume
Sheet 4 of 4
-------
Table 2. Occupational Exposure Standards and Guidelines
Enbridge Line 6B MP 608 Marshall, Ml Pipeline Release
Enbridge Energy, Limited Partnership
Chemical
OSHA
PEL-
TWA(a)
OSHA
PEL-
STEL(b)
OSHA
PEL-
Ceiling(c)
ACGIH
TLV-
TWA(d)
ACGIH
TLV-
STEL(e)
MIOSHA
PEL-
TWA(f)
MIOSHA
PEL-
STEL(g)
Benzene
1 ppm
5 ppm
NE
0.5 ppm
2.5 ppm
1 ppm
5 ppm
Ethyl
Benzene
100 ppm
NE
NE
20 ppm
125 ppm
NE
NE
n-Hexane
500 ppm
NE
NE
50 ppm
NE
NE
NE
Toluene
200 ppm
NE
300 ppm
20 ppm
NE
NE
NE
Xylene
100 ppm
NE
NE
100 ppm
NE
NE
NE
a. OSHA PEL-TWA = The permissible concentration in air of a substance that shall not be exceeded in an 8-
hour work shift or a 40-hour work week (OSHA, 1989).
b. OSHA PEL-STEL = The time-weighted average exposure that should not be exceeded for any 15-minute
period (OSHA, 1989).
c. OSHA PEL-Ceiling = The exposure limit that shall at no time be exceeded. If instantaneous monitoring is not
feasible, then the ceiling shall be assessed as a 15-minute time-weighted average exposure, which shall not
be exceeded at any time during the workday (OSHA, 1989).
d. ACGIH TLV-TWA = The Threshold Limit Value-TWA is the concentration for a normal 8-hour workday and a
40-hour work week, to which nearly all workers may be repeatedly exposed, day after day, without adverse
effect (ACGIH, 2011).
e. ACGIH TLV-STEL = The time-weighted average exposure that should not be exceeded for any 15-minute
period (ACGIH, 2011).
f. MIOSHA PEL-TWA = The permissible concentration in air of a substance that shall not be exceeded in an 8-
hour work shift or a 40-hour work week (R 325.77103 Rule 3 (1) MIOSHA Reference of OSHA Permissible
Exposure Limits).
g. MIOSHA PEL-STEL = The time-weighted average exposure that should not be exceeded for any 15-minute
period (R 325.77103 Rule 3 (2) MIOSHA Reference of OSHA Permissible Exposure Limits).
NE - Not Established
ppm - parts per million
Sheet 1 of 1
-------
Attachment A
2011 Enbridge Oil Spill Human Health Air Screening Levels
-------
Enbridge Oil Spill
Human Health Air Screening Levels
August 31, 2011
Chemical
Screening
Level in
Chemical Name
Abstract
Service
Number
parts per
billion by
volume
(ppbv)
Source of
Screening Level
1,1,1-trichloroethane
71-55-6
1,000
EPA RfC
1,1,2,2-T etrachloroethane
79-34-5
0.006
EPA RSL
1,1,2-Trichloro-1,2,2-trifluoroethane
76-13-1
4,000
EPA RSL
1,1,2-Trichloroethane
79-00-5
0.04
EPA RfC
1,1-Dichloroethane
75-34-3
0.4
EPA RSL
1,1-Dichloroethene
75-35-4
50
EPA RfC
1,2,4-T richlorobenzene
120-82-1
0.3
EPA RfC
1,2,4-T rimethylbenzene
95-63-6
1.5
EPA RfC
1,2-Dibromoethane
106-93-4
1
EPA RfC
1,2-Dichloro-1,1,2,2-Tetrafluoroethane
76-14-2
9,900
MDEQ
1,2-Dichlorobenzene
95-50-1
30
EPA RfC
1,2-Dichloroethane
107-06-2
600
ATSDR Chr. MRL
1,2-Dichloropropane
78-87-5
1
EPA RfC
1,3-Butadiene
106-99-0
1
EPA RfC
1,3,5-T rimethylbenzene
108-67-8
45
MDEQ
1,3-Dichlorobenzene
541-73-1
0.5
MDEQ
1,4-Dichlorobenzene
106-46-7
10
ATSDR Chr. MRL
1,4-Dioxane
123-91-1
1,000
ATSDR Chr. MRL
2,2,4-T rimethylpentane
540-84-1
750
MDEQ
2-Chloro-1,3-butadiene
126-99-8
6
EPA RfC
2-Propanol
67-63-0
3,000
EPA RfC
3-Chloropropene
107-05-1
32
EPA RfC
Acetaldehyde
75-07-0
5
EPA RfC
Acetone
67-64-1
13,000
ATSDR Chr. MRL
Acetonitrile
75-05-8
36
EPA RfC
Acrylonitrile
107-13-1
1
EPA RfC
Benzene
71-43-2
3
ATSDR Chr. MRL
Benzyl chloride
100-44-7
0.2
EPA RfC
Bromodichloromethane
75-27-4
0.01
EPA RSL
Bromoform
75-25-2
0.2
EPA RSL
Bromomethane
74-83-9
5
ATSDR Chr. MRL
Butane
106-97-8
10,000
MDEQ
Carbon disulfide
75-15-0
200
EPA RfC
Carbon tetrachloride
56-23-5
30
ATSDR Chr. MRL
Chlorobenzene
108-90-7
10
EPA RfC
Chloroethane
75-00-3
4,000
EPA RfC
Chloroform
67-66-3
20
ATSDR Chr. MRL
Chloromethane
74-87-3
50
ATSDR Chr. MRL
cis-1,2-dichloroethene
156-59-2
9
MDEQ
cis-1,3-Dichloropropene*
10061-02-6
4
MDEQ
Cumene
98-82-8
80
EPA RfC
Cyclohexane
110-82-7
2,000
EPA RfC
Cyclohexane, methyl
108-87-2
4,000
MDEQ
-------
Chemical
Screening
Level in
Chemical Name
Abstract
Service
Number
parts per
billion by
volume
(ppbv)
Source of
Screening Level
Cyclopentane
287-92-3
6,000
MDEQ
Dibromochloromethane
124-48-1
0.01
EPA RSL
Dichlorodifluoromethane
75-71-8
20
EPA RfC
Ethyl Acetate
141-78-6
890
MDEQ
Ethyl benzene
100-41-4
60
ATSDR Chr. MRL
Heptane
142-82-5
850
MDEQ
Hexachlorobutadiene
87-68-3
0.01
EPA RSL
Hexane
110-54-3
200
EPA RfC
Isobutane
75-28-5
10,000
MDEQ
Methyl butyl ketone
591-78-6
10
EPA RfC
Methyl ethyl ketone
78-93-3
2,000
EPA RfC
Methyl isobutyl ketone
108-10-1
700
EPA RfC
Methyl tert-butyl ether
1634-04-4
700
ATSDR Chr. MRL
Methylene chloride
75-09-2
300
ATSDR Chr. MRL
Napthalene
91-20-3
1
ATSDR Chr. MRL
Nonane
111-84-2
40
EPA RfC
Pentane
109-66-0
300
EPA RfC
Propene
115-07-1
2,000
EPA RfC
Styrene
100-42-5
200
ATSDR Chr. MRL
Tetrachloroethene
127-18-4
40
ATSDR Chr. MRL
Tetrahydrofuran
109-99-9
6
MDEQ
Toluene
108-88-3
80
ATSDR Chr. MRL
trans-1,2-Dichloroethene
156-60-5
15
EPA RfC
trans-1,3-Dichloropropene*
10061-01-5
0.5
MDEQ
Trichloroethene
79-01-6
2
EPA RfC
Trichlorofluoromethane
75-69-4
130
EPA RfC
Vinyl acetate
108-05-4
10
ATSDR Int. MRL
Vinyl bromide
593-60-2
1
EPA RfC
Vinyl chloride
75-01-4
30
ATSDR Int. MRL
Xylenes
1330-20-7
50
EPA RfC
* MDEQ provisional screening value for Dichloropropene based on a 1 in 100,000 cancer risk
ATSDR Chr. MRL - The Agency for Toxic Substances and Disease Registry Chronic Minimal
Risk Level (MRL) is the preferred screening level. The MRL is protective of daily human
inhalation exposure for longer than a year, including sensitive individuals such as children, the
elderly, and those with pre-existing illnesses.
EPA RfC - If no Chronic MRL is available, the screening level is the EPA Reference
Concentration (RfC). The RfC is protective of daily human inhalation exposure over a lifetime,
including sensitive individuals. For 2 chemicals, vinyl acetate and vinyl chloride, the ATSDR
Intermediate (Int.) MRL was selected. These were developed more recently than the EPA RfC
and were lower than the EPA RfC.
EPA RSL - If none of the above are available, the EPA Regional Screening Level (RSL) is used.
The RSLs are protective of daily human inhalation exposure over a lifetime, including sensitive
individuals.
MDEQ - If none of the above are available, the Michigan DEQ Air Quality Division, Air Toxics
Screening Level is the screening level. The MDEQ screening levels are protective of daily
human inhalation exposure over a lifetime, including sensitive individuals.
-------
Attachment B
ProLICL Statistical Output for Target Analytes
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
1,2,4-TMB
General Statistics
Number of Valid Data 3232 Number of Detected Data 10
Number of Distinct Detected Data 5 Number of Non-Detect Data 3222
Percent Non-Detects 99.69%
Raw Statistics
Minimum Detected 1
Maximum Detected 9
Mean of Detected 3.32
SD of Detected 2.432
Minimum Non-Detect 1
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 2.197
Mean of Detected 1.009
SD of Detected 0.625
Minimum Non-Detect 0
Maximum Non-Detect 3.219
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect
Number treated as Detected
Single DL Non-Detect Percentage
3232
0
100.00%
-------
Normal Distribution Test with Detected Values OnID
Shapiro Wilk Test Statistic
5% Shapiro Wilk Critical Value
Data not Normal at 5% Significance Level
UCL Statistics
0.75D
0.0 42
Lognormal Distribution Test with Detected Values OnID
Shapiro Wilk Test Statistic
5% Shapiro Wilk Critical Value
Data appear Lognormal at 5% Significance Level
0.907
0.0 42
D ssuming Normal Distribution
DL/2 Substitution Method
Mean 1.515
SD 1.069
95% DL/2 (t) UCL 1.546
ssuming Lognormal Distribution
DL/2 Substitution Method
Mean
SD
95% D -Stat (DL/2) UCL
0.117
0.D 06
Maximum Likelihood D stimate(MLD) Method
MLD method failed to converge properlD
N/0
Log ROS Method
Mean in Log Scale -4.20D
SD in Log Scale 1.7D
Mean in Original Scale 0.0716
SD in Original Scale 0.276
95% Percentile Bootstrap UCL 0.0D 01
95% BCD Bootstrap UCL 0.0D 15
Gamma Distribution Test with Detected Values OnID
k star (bias corrected) 2.00D
Theta Star 1.653
nu star 40.17
Data Distribution Test with Detected Values OnID
Data appear Lognormal at 5% Significance Level
D-D Test Statistic 0.74
5% D -D Critical Value 0.733
K-S Test Statistic 0.733
5% K-S Critical Value 0.269
Data not Gamma Distributed at 5% Significance Level
D ssuming Gamma Distribution
Gamma ROS Statistics using D xtrapolated Data
Minimum 0.00676
Maximum 103.3
Mean 67.69
Median 72.06
SD 25.07
kstar 4.4D4
Theta star 15.1
Nustar 2D9D3
D ppChi2 20 50 0
95% Gamma 0 pproximate UCL 60.62
95% 0 dOusted Gamma UCL 60.62
Note: DL/2 is not a recommended method.
Nonparametric Statistics
Kaplan-Meier (KM) Method
Mean 1.01
SD 0.195
SD of Mean 0.00404
95% KM (t) UCL 1.017
95% KM (0) UCL 1.017
95% KM (Oackknife) UCL 1.652
95% KM (bootstrap t) UCL 1.010
95% KM (BCO ) UCL 2.01
95% KM (Percentile Bootstrap) UCL 2.009
95% KM (ChebO shev) UCL 1.020
97.5% KM (ChebO shev) UCL 1.035
99% KM (ChebO shev) UCL 1.05
Potential UCLs to Use
95% KM (t) UCL 1.017
95% KM (% Bootstrap) UCL 2.009
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
1,3,5-TMB
Number of Valid Data
Number of Distinct Detected Data
General Statistics
3232
2
Number of Detected Data 3
Number of Non-Detect Data 3229
Percent Non-Detects 99.91%
Raw Statistics
Minimum Detected 1
Maximum Detected 2
Mean of Detected 1.333
SD of Detected 0.577
Minimum Non-Detect 1
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 0.693
Mean of Detected 0.231
SD of Detected 0.4
Minimum Non-Detect 0
Maximum Non-Detect 3.219
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect 3232
Number treated as Detected 0
Single DL Non-Detect Percentage 100.00%
Warning: Data set has only 2 Distinct Detected Values.
This may not be adequate enough to compute meaningful and reliable test statistics and estimates.
The Project Team may decide to use alternative site specific values to estimate environmental parameters (e.g., EPC, BTV).
Unless Data Quality Objectives (DQOs) have been met, it is suggested to collect additional observations.
The number of detected data may not be adequate enough to perform GOF tests, bootstrap, and ROS methods.
Those methods will return a 'N/A' value on your output display!
It is necessary to have 4 or more Distinct Values for bootstrap methods.
However, results obtained using 4 to 9 distinct values may not be reliable.
It is recommended to have 10 to 15 or more observations for accurate and meaningful results and estimates.
-------
Normal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic
5% Shapiro Wilk Critical Value
Data not Normal at 5% Significance Level
Assuming Normal Distribution
DL/2 Substitution Method
Mean
SD
95% DL/2 (t) UCL
Maximum Likelihood Estimate(MLE) Method
MLE method failed to converge properly
Gamma Distribution Test with Detected Values Only
k star (bias corrected)
Theta Star
nu star
A-D Test Statistic
5% A-D Critical Value
K-S Test Statistic
5% K-S Critical Value
Data not Gamma Distributed at 5% Significance Level
Assuming Gamma Distribution
Gamma ROS Statistics using Extrapolated Data
Minimum
Maximum
Mean
Median
SD
k star
Theta star
Nu star
AppChi2
95% Gamma Approximate UCL
95% Adjusted Gamma UCL
Note: DL/2 is not a recommended method.
UCL Statistics
Lognormal Distribution Test with Detected Values Only
0.75 Shapiro Wilk Test Statistic 0.75
0.767 5% Shapiro Wilk Critical Value 0.767
Data not Lognormal at 5% Significance Level
Assuming Lognormal Distribution
DL/2 Substitution Method
1.507 Mean 0.113
1.05D SD 0.D 04
1.530 95% H-Stat (DL/2) UCL N/A
N/A Log ROS Method
Mean in Log Scale -5.032
SD in Log Scale 1.652
Mean in Original Scale 0.025
SD in Original Scale 0.0754
95% Percentile Bootstrap UCL 0.0273
95% BCA Bootstrap UCL 0.027D
Data Distribution Test with Detected Values Only
N/A Data do not follow a Discernable Distribution (0.05)
N/A
N/A
N/A Nonparametric Statistics
N/A Kaplan-Meier (KM) Method
N/A Mean 1.001
N/A SD 0.0247
SE of Mean 0.000747
95% KM (t) UCL 1.002
95% KM (D) UCL 1.002
95% KM (jackknife) UCL 1.002
N/A 95% KM (bootstrap t) UCL N/A
N/A 95% KM (BCA) UCL N/A
N/A 95% KM (Percentile Bootstrap) UCL 2
N/A 95% KM (Chebyshev) UCL 1.004
N/A 97.5% KM (Chebyshev) UCL 1.005
N/A 99% KM (Chebyshev) UCL 1.000
N/A
N/A Potential UCLs to Use
N/A 95% KM (t) UCL 1.002
N/A 95% KM (% Bootstrap) UCL 2
N/A
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
4-Ethyltoluene
Number of Valid Data
Number of Distinct Detected Data
General Statistics
3232
Number of Detected Data 3
Number of Non-Detect Data 3229
Percent Non-Detects 99.91%
Raw Statistics
Minimum Detected 1
Maximum Detected 2
M ea n of Detected 1.333
SD of Detected 0.577
Minimum Non-Detect 1
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 0.693
Mean of Detected 0.231
SD of Detected 0.4
Minimum Non-Detect 0
Maximum Non-Detect 3.219
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect 3232
Number treated as Detected 0
Single DL Non-Detect Percentage 100.00%
Warning: Data set has only 2 Distinct Detected Values.
This may not be adequate enough to compute meaningful and reliable test statistics and estimates.
The Project Team may decide to use alternative site specific values to estimate environmental parameters (e.g., EPC, BTV).
Unless Data Quality Objectives (DQOs) have been met, it is suggested to collect additional observations.
The number of detected data may not be adequate enough to perform GOF tests, bootstrap, and ROS methods.
Those methods will return a 'N/A' value on your output display!
It is necessary to have 4 or more Distinct Values for bootstrap methods.
However, results obtained using 4 to 9 distinct values may not be reliable.
It is recommended to have 10 to 15 or more observations for accurate and meaningful results and estimates.
-------
UCL Statistics
Normal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic
5% Shapiro Wilk Critical Value
Data not Normal at 5% Significance Level
Lognormal Distribution Test with Detected Values Only
0.75 Shapiro Wilk Test Statistic 0.75
0.767 5% Shapiro Wilk Critical Value 0.767
Data not Lognormal at 5% Significance Level
Assuming Normal Distribution
DL/2 Substitution Method
Mean 1.507
SD 1.05D
95% DL/2 (t) UCL 1.530
Assuming Lognormal Distribution
DL/2 Substitution Method
Mean 0.113
SD 0.D 04
95% H-Stat (DL/2) UCL N/A
Maximum Likelihood Estimate(MLE) Method N/A Log ROS Method
MLE method failed to converge properly Mean in Log Scale -5.032
SD in Log Scale 1.652
Mean in Original Scale 0.025
SD in Original Scale 0.0754
95% Percentile Bootstrap UCL 0.0273
95% BCA Bootstrap UCL 0.0274
Gamma Distribution Test with Detected Values Only
k star (bias corrected) N/A
Theta Star N/A
nu star N/A
Data Distribution Test with Detected Values Only
Data do not follow a Discernable Distribution (0.05)
A-D Test Statistic
N/A
Nonparametric Statistics
5% A-D Critical Value
N/A
Kaplan-Meier (KM) Method
K-S Test Statistic
N/A
Mean
1.001
5% K-S Critical Value
N/A
SD
0.0247
ta not Gamma Distributed at 5% Significance Level
SE of Mean
0.000747
95% KM (t) UCL
1.002
Assuming Gamma Distribution
95% KM (D) UCL
1.002
Gamma ROS Statistics using Extrapolated Data
95% KM (jackknife) UCL
1.002
Minimum
N/A
95% KM (bootstrap t) UCL
N/A
Maximum
N/A
95% KM (BCA) UCL
2
Mean
N/A
95% KM (Percentile Bootstrap) UCL
2
Median
N/A
95% KM (Chebyshev) UCL
1.004
SD
N/A
97.5% KM (Chebyshev) UCL
1.005
k star
N/A
99% KM (Chebyshev) UCL
1.00D
Theta star
N/A
Nu star
N/A
Potential UCLs to Use
AppChi2
N/A
95% KM (t) UCL
1.002
95% Gamma Approximate UCL
N/A
95% KM (% Bootstrap) UCL
2
95% Adjusted Gamma UCL
N/A
Note: DL/2 is not a recommended method.
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File C:\Users\loppor\Desktop\acetaldehyde.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
Acetaldehyde
General Statistics
Number of Valid Data 104 Number of Detected Data 15
Number of Distinct Detected Data 7 Number of Non-Detect Data 89
Percent Non-Detects 85.58%
Raw Statistics
Minimum Detected 1
Maximum Detected 15
Mean of Detected 5.533
SD of Detected 5.878
Minimum Non-Detect 1
Maximum Non-Detect 4
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 2.708
Mean of Detected 1.101
S D of Detected 1.157
Minimum Non-Detect 0
Maximum Non-Detect 1.386
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect
Number treated as Detected
Single DL Non-Detect Percentage
99
5
95.19%
-------
Normal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic
5% Shapiro Wilk Critical Value
Data not Normal at 5% Significance Level
Assuming Normal Distribution
DL/2 Substitution Method
Mean
SD
95% DL/2 (t) UCL
Maximum Likelihood Estimate(MLE) Method
MLE yields a negative mean
Gamma Distribution Test with Detected Values Only
k star (bias corrected)
Theta Star
nu star
A-D Test Statistic
5% A-D Critical Value
K-S Test Statistic
5% K-S Critical Value
Data not Gamma Distributed at 5% Significance Level
Assuming Gamma Distribution
Gamma ROS Statistics using Extrapolated Data
Minimum
Maximum
Mean
Median
SD
k star
Theta star
Nu star
AppChi2
95% Gamma Approximate UCL
95% Adjusted Gamma UCL
Note: DL/2 is not a recommended method.
UCL Statistics
Lognormal Distribution Test with Detected Values Only
0.724 Shapiro Wilk Test Statistic 0.793
0.881 5% Shapiro Wilk Critical Value 0.881
Data not Lognormal at 5% Significance Level
Assuming Lognormal Distribution
DL/2 Substitution Method
1.24 Mean -0.421
2.803 SD 0.771
1.697 95% H-Stat (DL/2) UCL 0.886
N/A Log ROS Method
Mean in Log Scale -3.18
SD in Log Scale 2.691
Mean in Original Scale 0.877
SD in Original Scale 2.899
95% Percentile Bootstrap UCL 1.381
95% BCA Bootstrap UCL 1.482
Data Distribution Test with Detected Values Only
0.807 Data do not follow a Discernable Distribution (0.05)
6.86
24.2
1.469 Nonparametric Statistics
0.765 Kaplan-Meier (KM) Method
0.765 Mean 1.654
0.228 SD 2.681
SE of Mean 0.272
95% KM (t) UCL 2.106
95% KM (z) UCL 2.102
95% KM (jackknife) UCL 2.093
1E-09 95% KM (bootstrap t) UCL 2.342
150.8 95% KM (BCA) UCL 2.106
57.95 95% KM (Percentile Bootstrap) UCL 2.135
50.57 95% KM (Chebyshev) UCL 2.841
47.44 97.5% KM (Chebyshev) UCL 3.354
0.48 99% KM (Chebyshev) UCL 4.362
120.6
99.93 Potential UCLs to Use
77.87 95% KM (BCA) UCL 2.106
74.36
74.62
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
Benzene
Number of Valid Data
Number of Distinct Detected Data
General Statistics
3234
4
Number of Detected Data 5
Number of Non-Detect Data 3229
Percent Non-Detects 99.85%
Raw Statistics
Minimum Detected 1
Maximum Detected 4
Mean of Detected 2.2
SD of Detected 1.304
Minimum Non-Detect 0.2
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 1.386
Mean of Detected 0.636
SD of Detected 0.63
Minimum Non-Detect -1.609
Maximum Non-Detect 3.219
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect 3234
Number treated as Detected 0
Single DL Non-Detect Percentage 100.00%
Warning: There are only 4 Distinct Detected Values in this data
Note: It should be noted that even though bootstrap may be performed on this data set
the resulting calculations may not be reliable enough to draw conclusions
It is recommended to have 10-15 or more distinct observations for accurate and meaningful results.
-------
Normal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic
5% Shapiro Wilk Critical Value
Data appear Normal at 5% Significance Level
UCL Statistics
0.902
0.0 62
Lognormal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic
5% Shapiro Wilk Critical Value
Data appear Lognormal at 5% Significance Level
0.886
0.D 62
D ssuming Normal Distribution
DL/2 Substitution Method
Mean 1.509
SD 1.059
95% DL/2 (t) UCL 1.539
ssuming Lognormal Distribution
DL/2 Substitution Method
Mean
SD
95% D -Stat (DL/2) UCL
0.113
0.806
Maximum Likelihood D stimate(MLD) Method
MLD method failed to converge properly
N/0
Log ROS Method
Mean in Log Scale -6.315
SD in Log Scale 2.2D 8
Mean in Original Scale 0.0223
SD in Original Scale 0.133
95% Percentile Bootstrap UCL 0.0263
95% BCD Bootstrap UCL 0.02D3
Gamma Distribution Test with Detected Values Only
k star (bias corrected) 1.505
Theta Star 1.462
nu star 15.05
Data Distribution Test with Detected Values Only
Data appear Normal at 5% Significance Level
D-D Test Statistic 0.365
5% D -D Critical Value 0.682
K-S Test Statistic 0.682
5% K-S Critical Value 0.359
Data appear Gamma Distributed at 5% Significance Level
D ssuming Gamma Distribution
Nonparametric Statistics
Kaplan-Meier (KM) Method
Mean 1.004
SD 0.092
SD of Mean 0.00253
95% KM (t) UCL 1.008
95% KM (z) UCL 1.008
ROS Statistics using D xtrapolated Data
95% KM (Oackknife)
UCL
1.000
Minimum
0.151
95% KM (bootstrap t)
UCL
1.009
Maximum
4
95% KM (BCD )
UCL
3.001
Mean
1.101
95% KM (Percentile Bootstrap)
UCL
2.004
Median
1.028
95% KM (Chebyshev)
UCL
1.015
SD
0.621
90.5% KM (Chebyshev)
UCL
1.019
k star
2.635
99% KM (Chebyshev)
UCL
1.029
Theta star
0.418
Nu star
10 046
Potential UCLs to Use
D ppChi2
160 43
95% KM (t)
UCL
1.008
95% Gamma D pproximate UCL
1.121
95% KM (Percentile Bootstrap)
UCL
2.004
95% D dDusted Gamma UCL
1.121
Note: DL/2 is not a recommended method.
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
Cyclohexane
General Statistics
Number of Valid Data 3234 Number of Detected Data 30
Number of Distinct Detected Data 10 Number of Non-Detect Data 3204
Percent Non-Detects 99.07%
Raw Statistics
Minimum Detected 1
Maximum Detected 20
Mean of Detected 4.333
SD of Detected 5.208
Minimum Non-Detect 0.5
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 2.996
Mean of Detected 0.979
SD of Detected 0.941
Minimum Non-Detect -0.693
Maximum Non-Detect 3.219
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect
Number treated as Detected
Single DL Non-Detect Percentage
3234
0
100.00%
-------
Normal Distribution D est with Detected Values Only
Shapiro Wilk D est Statistic
5% Shapiro Wilk Critical Value
Data not Normal at 5% Significance Level
D ssuming Normal Distribution
DL/2 Substitution Method
Mean
SD
95% DL/2 (t) UCL
Maximum Likelihood D stimate(MLD) Method
MLD method failed to converge properly
Gamma Distribution D est with Detected Values Only
k star (bias corrected)
D heta Star
nu star
D -D D est Statistic
5% D -D Critical Value
K-S D est Statistic
5% K-S Critical Value
Data not Gamma Distributed at 5% Significance Level
D ssuming Gamma Distribution
Gamma ROS Statistics using D xtrapolated Data
Minimum
Maximum
Mean
Median
SD
k star
D heta star
Nu star
D ppChi2
95% Gamma D pproximate UCL
95% D dDusted Gamma UCL
Note: DL/2 is not a recommended method.
UCL Statistics
Lognormal Distribution D est with Detected Values Only
0.654 Shapiro Wilk D est Statistic 0.871
0.927 5% Shapiro Wilk Critical Value 0.927
Data not Lognormal at 5% Significance Level
D ssuming Lognormal Distribution
DL/2 Substitution Method
1.541 Mean 0.126
1.195 SD 0.81
1.575 95% D -Stat (DL/2) UCL N/0
N/0 Log ROS Method
Mean in Log Scale -5.355
SD in Log Scale 2.441
Mean in Original Scale 0.0876
SD in Original Scale 0.667
95% Percentile Bootstrap UCL 0.108
95% BCD Bootstrap UCL 0.114
Data Distribution D est with Detected Values Only
1.07 Data do not follow a Discernable Distribution (0.05)
4.05
64.2
1.822 Nonparametric Statistics
0.771 Kaplan-Meier (KM) Method
0.771 Mean 1.037
0.164 SD 0.599
SD of Mean 0.0111
95% KM (t) UCL 1.055
95% KM (D) UCL 1.055
95% KM (Dackknife) UCL 1.055
0.783 95% KM (bootstrap t) UCL 1.063
20 95% KM (BCD ) UCL 1.056
2.577 95% KM (Percentile Bootstrap) UCL 1.056
2.536 95% KM (Chebyshev) UCL 1.086
1.154 97.5% KM (Chebyshev) UCL 1.107
5.118 99% KM (Chebyshev) UCL 1.148
0.504
33102 Potential UCLs to Use
32680 95% KM (t) UCL 1.055
2.611 95% KM (% Bootstrap) UCL 1.056
2.611
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
Ethylbenzene
Number of Valid Data
Number of Distinct Detected Data
General Statistics
3232
Number of Detected Data 6
Number of Non-Detect Data 3226
Percent Non-Detects 99.81%
Raw Statistics
Minimum Detected 1
Maximum Detected 6
Mean of Detected 2.667
SD of Detected 1.862
Minimum Non-Detect 1
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 1.792
Mean of Detected 0.78
SD of Detected 0.7
Minimum Non-Detect 0
Maximum Non-Detect 3.219
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect 3232
Number treated as Detected 0
Single DL Non-Detect Percentage 100.00%
Warning: There are only 4 Distinct Detected Values in this data
Note: It should be noted that even though bootstrap may be performed on this data set
the resulting calculations may not be reliable enough to draw conclusions
It is recommended to have 10-15 or more distinct observations for accurate and meaningful results.
-------
UCL Statistics
Normal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic 0.861
5% Shapiro Wilk Critical Value 0.788
Data appear Normal at 5% Significance Level
Lognormal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic 0.913
5% Shapiro Wilk Critical Value 0.788
Data appear Lognormal at 5% Significance Level
ssuming Normal Distribution
DL/2 Substitution Method
Mean 1.511
SD 1.061
95% DL/2 (t) UCL 1.541
ssuming Lognormal Distribution
DL/2 Substitution Method
Mean
SD
95% D -Stat (DL/2) UCL
0.114
0.805
Maximum Likelihood Estimate(MLE) Method
MLE method failed to converge properly
N/0
Log ROS Method
Mean in Log Scale -5.605
SD in Log Scale 2.079
Mean in Original Scale 0.0308
SD in Original Scale 0.165
95% Percentile Bootstrap UCL 0.0361
95% BCD Bootstrap UCL 0.0369
Gamma Distribution Test with Detected Values Only
k star (bias corrected) 1.436
Theta Star 1.858
nu star 17.23
Data Distribution Test with Detected Values Only
Data appear Normal at 5% Significance Level
D-D Test Statistic 0.343
5% D -D Critical Value 0.702
K-S Test Statistic 0.702
5% K-S Critical Value 0.335
Data appear Gamma Distributed at 5% Significance Level
D ssuming Gamma Distribution
Gamma ROS Statistics using Extrapolated Data
Minimum 0.274
Maximum 306.4
Mean 179.5
Median 188.2
SD 81.72
k star 2.947
Theta star 60.92
Nu star 19047
D ppChi2 18727
95% Gamma D pproximate UCL 182.6
95% D dDusted Gamma UCL 182.6
Note: DL/2 is not a recommended method.
Nonparametric Statistics
Kaplan-Meier (KM) Method
Mean 1.005
SD 0.115
SE of Mean 0.00263
95% KM (t) UCL 1.009
95% KM (z) UCL 1.009
95% KM (Dackknife) UCL 1.009
95% KM (bootstrap t) UCL 1.009
95% KM (BCD ) UCL 3.002
95% KM (Percentile Bootstrap) UCL 2.005
95% KM (Chebyshev) UCL 1.016
97.5% KM (Chebyshev) UCL 1.021
99% KM (Chebyshev) UCL 1.031
Potential UCLs to Use
95% KM (t) UCL 1.009
95% KM (Percentile Bootstrap) UCL 2.005
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
m,p-Xylene
General Statistics
Number of Valid Data 3232
Number of Distinct Detected Data 7
Raw Statistics
Minimum Detected 2
Maximum Detected 19
M ea n of Detected 5.818
SD of Detected 5.4
Minimum Non-Detect 2
Maximum Non-Detect 50
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number of Detected Data 11
Number of Non-Detect Data 3221
Percent Non-Detects 99.66%
Log-transformed Statistics
Minimum Detected 0.693
Maximum Detected 2.944
Mean of Detected 1.445
SD of Detected 0.794
Minimum Non-Detect 0.693
Maximum Non-Detect 3.912
Number treated as Non-Detect 3232
Number treated as Detected 0
Single DL Non-Detect Percentage 100.00%
-------
UCL Statistics
Normal Distribution D est with Detected Values Only Lognormal Distribution D est with Detected Values Only
Shapiro Wilk D est Statistic 0.752
5% Shapiro Wilk Critical Value 0.85
Data not Normal at 5% Significance Level
Shapiro Wilk D est Statistic 0.869
5% Shapiro Wilk Critical Value 0.85
Data appear Lognormal at 5% Significance Level
ssuming Normal Distribution
DL/2 Substitution Method
Mean 3.028
SD 2.131
95% DL/2 (t) UCL 3.089
ssuming Lognormal Distribution
DL/2 Substitution Method
Mean
SD
95% D -Stat (DL/2) UCL
0.809
0.805
Maximum Likelihood D stimate(MLD) Method
MLD method failed to converge properly
N/0
Log ROS Method
Mean in Log Scale -5.698
SD in Log Scale 2.448
Mean in Original Scale 0.062
SD in Original Scale 0.488
95% Percentile Bootstrap UCL 0.0769
95% BCD Bootstrap UCL 0.0804
Gamma Distribution D est with Detected Values Only
k star (bias corrected)
D heta Star
nu star
Data Distribution D est with Detected Values Only
1.32 Data Follow D ppr. Gamma Distribution at 5% Significance Level
4.408
29.04
D -D D est Statistic 0.752
5% D -D Critical Value 0.741
K-S D est Statistic 0.741
5% K-S Critical Value 0.259
Data follow D ppr. Gamma Distribution at 5% Significance Level
D ssuming Gamma Distribution
Gamma ROS Statistics using D xtrapolated Data
Minimum 1D -09
Maximum 694.8
Mean 391.7
Median 408
SD 190.2
k star 2.356
D heta star 166.3
Nu star 15227
D ppChi2 14941
95% Gamma D pproximate UCL 399.2
95% D dDusted Gamma UCL 399.2
Note: DL/2 is not a recommended method.
Nonparametric Statistics
Kaplan-Meier (KM) Method
Mean 2.015
SD 0.382
SD of Mean 0.00731
95% KM (t) UCL 2.027
95% KM (D) UCL 2.027
95% KM (Dackknife) UCL 2.027
95% KM (bootstrap t) UCL 2.037
95% KM (BCD ) UCL 2.034
95% KM (Percentile Bootstrap) UCL 2.03
95% KM (Chebyshev) UCL 2.047
97.5% KM (Chebyshev) UCL 2.061
99% KM (Chebyshev) UCL 2.088
Potential UCLs to Use
95% KM (t) UCL 2.027
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
n-Heptane
General Statistics
Number of Valid Data 3232
Number of Distinct Detected Data 6
Raw Statistics
Minimum Detected 1
Maximum Detected 14
M ea n of Detected 3.118
SD of Detected 3.551
Minimum Non-Detect 1
Maximum Non-Detect 25
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number of Detected Data 17
Number of Non-Detect Data 3215
Percent Non-Detects 99.47%
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 2.639
Mean of Detected 0.708
SD of Detected 0.885
Minimum Non-Detect 0
Maximum Non-Detect 3.219
Number treated as Non-Detect 3232
Number treated as Detected 0
Single DL Non-Detect Percentage 100.00%
-------
UCL Statistics
Normal Distribution D est with Detected Values OnID Lognormal Distribution D est with Detected Values OnID
Shapiro Wilk D est Statistic 0.666 Shapiro Wilk D est Statistic 0.793
5% Shapiro Wilk Critical Value 0.892 5% Shapiro Wilk Critical Value 0.892
Data not Normal at 5% Significance Level Data not Lognormal at 5% Significance Level
ssuming Normal Distribution
DL/2 Substitution Method
Mean 1.52
SD 1.091
95% DL/2 (t) UCL 1.552
ssuming Lognormal Distribution
DL/2 Substitution Method
Mean 0.119
SD 0.806
95% H-Stat (DL/2) UCL N/0
Maximum Likelihood D stimate(MLD) Method N/0 Log ROS Method
MLD method failed to converge properlD Mean in Log Scale -5.995
SD in Log Scale 2.417
Mean in Original Scale 0.0439
SD in Original Scale 0.354
95% Percentile Bootstrap UCL 0.0549
95% BCD Bootstrap UCL 0.0583
Gamma Distribution D est with Detected Values OnID
k star (bias corrected) 1.117
D heta Star 2.792
nu star 37.96
Data Distribution D est with Detected Values OnID
Data do not follow a Discernable Distribution (0.05)
D -D D est Statistic
1.627
Nonparametric Statistics
5% D -D Critical Value
0.76
Kaplan-Meier (KM) Method
K-S D est Statistic
0.76
Mean
1.013
5% K-S Critical Value
0.214
SD
0.3
ta not Gamma Distributed at 5% Significance Level
SD of Mean
0.00567
95% KM (t) UCL
1.023
D ssuming Gamma Distribution
95% KM (D) UCL
1.023
Gamma ROS Statistics using D xtrapolated Data
95% KM (Dackknife) UCL
1.022
Minimum
1D -09
95% KM (bootstrap t) UCL
1.03
Maximum
545.4
95% KM (BCD ) UCL
1.023
Mean
284.4
95% KM (Percentile Bootstrap) UCL
1.023
Median
290.4
95% KM (ChebD shev) UCL
1.038
SD
154.9
97.5% KM (ChebD shev) UCL
1.049
k star
1.697
99% KM (ChebD shev) UCL
1.07
D heta star
167.6
Nu star
10969
Potential UCLs to Use
D ppChi2
10727
95% KM (t) UCL
1.023
95% Gamma D pproximate UCL
290.8
95% KM (% Bootstrap) UCL
1.023
95% D dDusted Gamma UCL
290.8
Note: DL/2 is not a recommended method.
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
n-Hexane
Number of Valid Data
Number of Distinct Detected Data
General Statistics
3234
Number of Detected Data
Number of Non-Detect Data
Percent Non-Detects
Raw Statistics
Minimum Detected 1
Maximum Detected 3
M ea n of Detected 1.619
SD of Detected 0.74
Minimum Non-Detect 0.5
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected
Maximum Detected
Mean of Detected
SD of Detected
Minimum Non-Detect
Maximum Non-Detect
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect
Number treated as Detected
Single DL Non-Detect Percentage
Warning: There are only 3 Distinct Detected Values in this data set
The number of detected data may not be adequate enough to perform GOF tests, bootstrap, and ROS methods.
Those methods will return a 'N/A' value on your output display!
It is necessary to have 4 or more Distinct Values for bootstrap methods.
However, results obtained using 4 to 9 distinct values may not be reliable.
It is recommended to have 10 to 15 or more observations for accurate and meaningful results and estimates.
21
3213
99.35%
0
1.099
0.388
0.437
-0.693
3.219
3234
0
100.00%
-------
UCL Statistics
Normal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic
5% Shapiro Wilk Critical Value
Data not Normal at 5% Significance Level
Lognormal Distribution Test with Detected Values Only
0.755 Shapiro Wilk Test Statistic 0.75
0.908 5% Shapiro Wilk Critical Value 0.908
Data not Lognormal at 5% Significance Level
Assuming Normal Distribution
DL/2 Substitution Method
Mean 1.514
SD 1.057
95% DL/2 (t) UCL 1.544
Assuming Lognormal Distribution
DL/2 Substitution Method
Mean 0.118
SD 0.803
95% H-Stat (DL/2) UCL N/A
Maximum Likelihood D stimate(MLD) Method
MLD method failed to converge properly
N/A
Log ROS Method
Mean in Log Scale -3.074
SD in Log Scale 1.338
Mean in Original Scale 0.112
SD in Original Scale 0.224
95% Percentile Bootstrap UCL 0.119
95% BCA Bootstrap UCL 0.119
Gamma Distribution Test with Detected Values Only
k star (bias corrected) 4.737
Theta Star 0.342
nu star 198.9
Data Distribution Test with Detected Values Only
Data do not follow a Discernable Distribution (0.05)
A-D Test Statistic 2.411
5% A-D Critical Value 0.745
K-S Test Statistic 0.745
5% K-S Critical Value 0.19
Data not Gamma Distributed at 5% Significance Level
Assuming Gamma Distribution
Gamma ROS Statistics using D xtrapolated Data
Minimum 1
Maximum 3
Mean 1.963
Median 1.993
SD 0.128
kstar 211.5
Theta star 0.00928
Nu star 1367784
AppChi2 1365064
95% Gamma Approximate UCL 1.967
95% AdDusted Gamma UCL 1.967
Note: DL/2 is not a recommended method.
Nonparametric Statistics
Kaplan-Meier (KM) Method
Mean 1.008
SD 0.107
SD of Mean 0.00271
95% KM (t) UCL 1.012
95% KM (D) UCL 1.012
95% KM (Dackknife) UCL 1.012
95% KM (bootstrap t) UCL 1.014
95% KM (BCA) UCL 1.012
95% KM (Percentile Bootstrap) UCL 1.012
95% KM (Chebyshev) UCL 1.02
97.5% KM (Chebyshev) UCL 1.025
99% KM (Chebyshev) UCL 1.035
Potential UCLs to Use
95% KM (t) UCL 1.012
95% KM (% Bootstrap) UCL 1.012
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
Toluene
Number of Valid Data
Number of Distinct Detected Data
General Statistics
3234
62
Number of Detected Data 457
Number of Non-Detect Data 2777
Percent Non-Detects 85.87%
Raw Statistics
Minimum Detected 1
Maximum Detected 270
Mean of Detected 8.492
SD of Detected 24.39
Minimum Non-Detect 0.4
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 5.598
Mean of Detected 1.088
SD of Detected 1.169
Minimum Non-Detect -0.916
Maximum Non-Detect 3.219
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect
Number treated as Detected
Single DL Non-Detect Percentage
3206
28
99.13%
-------
UCL Statistics
Normal Distribution Test with Detected Values OnID
Lilliefors Test Statistic
5% Lilliefors Critical Value
Data not Normal at 5% Significance Level
Lognormal Distribution Test with Detected Values OnID
0.379 Lilliefors Test Statistic 0.19
0.0414 5% Lilliefors Critical Value 0.0414
Data not Lognormal at 5% Significance Level
ssuming Normal Distribution
DL/2 Substitution Method
Mean 2.609
SD 9.515
95% DL/2 (t) UCL 2.885
ssuming Lognormal Distribution
DL/2 Substitution Method
Mean
SD
95% D -Stat (DL/2) UCL
0.342
0.912
Maximum Likelihood D stimate(MLD) Method N/0 Log ROS Method
MLD D ields a negative mean Mean in Log Scale -1.799
SD in Log Scale 2.044
Mean in Original Scale 1.517
SD in Original Scale 9.611
95% Percentile Bootstrap UCL 1.803
95% BCD Bootstrap UCL 1.863
Gamma Distribution Test with Detected Values OnID
k star (bias corrected) 0.587
Theta Star 14.46
nu star 536.6
Data Distribution Test with Detected Values OnID
Data do not follow a Discernable Distribution (0.05)
D -D Test Statistic
47.5
Nonparametric Statistics
5% D -D Critical Value
0.814
Kaplan-Meier (KM) Method
K-S Test Statistic
0.814
Mean
2.146
5% K-S Critical Value 0.0447
SD
9.522
ta not Gamma Distributed at 5% Significance Level
SD of Mean
0.168
95% KM (t) UCL
2.422
D ssuming Gamma Distribution
95% KM (D) UCL
2.422
Gamma ROS Statistics using D xtrapolated Data
95% KM (Dackknife) UCL
2.422
Minimum
1D -09
95% KM (bootstrap t) UCL
2.505
Maximum
301.8
95% KM (BCD ) UCL
2.438
Mean
79.61
95% KM (Percentile Bootstrap) UCL
2.445
Median
52.68
95% KM (ChebD shev) UCL
2.878
SD
81.73
97.5% KM (ChebD shev) UCL
3.195
k star
0.23
99% KM (ChebD shev) UCL
3.817
Theta star
345.6
Nu star
1490
Potential UCLs to Use
D ppChi2
1401
95% KM (BCD ) UCL
2.438
95% Gamma D pproximate UCL
84.65
95% D dDusted Gamma UCL
84.65
Note: DL/2 is not a recommended method.
-------
General UCL Statistics for Data Sets with Non-Detects
User Selected Options
From File WorkSheet.wst
Full Precision OFF
Confidence Coefficient 95%
Number of Bootstrap Operations 2000
o-Xylene
Number of Valid Data
Number of Distinct Detected Data
General Statistics
3232
Number of Detected Data 6
Number of Non-Detect Data 3226
Percent Non-Detects 99.81%
Raw Statistics
Minimum Detected 1
Maximum Detected 4
Mean of Detected 2.5
SD of Detected 1.049
Minimum Non-Detect 1
Maximum Non-Detect 25
Log-transformed Statistics
Minimum Detected 0
Maximum Detected 1.386
Mean of Detected 0.828
SD of Detected 0.486
Minimum Non-Detect 0
Maximum Non-Detect 3.219
Note: Data have multiple DLs - Use of KM Method is recommended
For all methods (except KM, DL/2, and ROS Methods),
Observations < Largest ND are treated as NDs
Number treated as Non-Detect 3232
Number treated as Detected 0
Single DL Non-Detect Percentage 100.00%
Warning: There are only 4 Distinct Detected Values in this data
Note: It should be noted that even though bootstrap may be performed on this data set
the resulting calculations may not be reliable enough to draw conclusions
It is recommended to have 10-15 or more distinct observations for accurate and meaningful results.
-------
UCL Statistics
Normal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic 0.96
5% Shapiro Wilk Critical Value 0.D 88
Data appear Normal at 5% Significance Level
Lognormal Distribution Test with Detected Values Only
Shapiro Wilk Test Statistic 0.918
5% Shapiro Wilk Critical Value 0.D 88
Data appear Lognormal at 5% Significance Level
ssuming Normal Distribution
DL/2 Substitution Method
Mean 1.51
SD 1.059
95% DL/2 (t) UCL 1.541
ssuming Lognormal Distribution
DL/2 Substitution Method
Mean
SD
95% D -Stat (DL/2) UCL
0.115
0.805
Maximum Likelihood D stimate(MLD) Method
MLD method failed to converge properly
N/0
Log ROS Method
Mean in Log Scale -3.959
SD in Log Scale 1.598
Mean in Original Scale 0.06D 4
SD in Original Scale 0.189
95% Percentile Bootstrap UCL 0.0D 32
95% BCD Bootstrap UCL 0.0D 35
Gamma Distribution Test with Detected Values Only
k star (bias corrected) 3.033
Theta Star 0.824
nu star 36.4
Data Distribution Test with Detected Values Only
Data appear Normal at 5% Significance Level
D-D Test Statistic 0.316
5% D -D Critical Value 0.698
K-S Test Statistic 0.698
5% K-S Critical Value 0.333
Data appear Gamma Distributed at 5% Significance Level
D ssuming Gamma Distribution
Gamma ROS Statistics using D xtrapolated Data
Minimum 0.93D
Maximum 36.96
Mean 26.96
Median 28.68
SD D .680
k star 8.382
Theta star 3.216
Nu star 541D8
D ppChi2 53638
95% Gamma D pproximate UCL 2D .23
95% D dDusted Gamma UCL 2D .23
Note: DL/2 is not a recommended method.
Nonparametric Statistics
Kaplan-Meier (KM) Method
Mean 1.005
SD 0.10D
SD of Mean 0.00289
95% KM (t) UCL 1.01
95% KM (D) UCL 1.01
95% KM (Dackknife) UCL 1.649
95% KM (bootstrap t) UCL 1.01
95% KM (BCD ) UCL 3.001
95% KM (Percentile Bootstrap) UCL 2.00D
95% KM (Chebyshev) UCL 1.018
90.5% KM (Chebyshev) UCL 1.024
99% KM (Chebyshev) UCL 1.034
Potential UCLs to Use
95% KM (t) UCL 1.01
95% KM (Percentile Bootstrap) UCL 2.00D
-------
Attachment C
Charts for Select Analytes
-------
24-Hour Community Air Sampling Data
Benzene Detections
Time Period: 8/16/2010 -1/23/2012
4.5
4
3.5
Total Number of Samples = 3,234
Total Number of Detections at or above
Method Detection Limit (MDL) = 5
Kaplan-Meier Mean = 1.004 ppbv
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Canisters (6 L Summa Canisters were used in 2011 & 2012). Therefore, the MDL for
Benzene in 2010 was 5 ppbv (1 ppbv in 2011 & 2012), which is over the current
HHASL, but below the 2010 HHASL of 6 ppbv.
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-------
24-Hour Community Air Sampling Data
1,2,4-TMB Detections
Time Period: 8/16/2010 -1/23/2012
10
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Total Number of Samples = 3,234
Total Number of Detections at or above
Method Detection Limit (MDL) = 10
Kaplan-Meier Mean = 1.01 ppbv
Please note that air samples collected in 2010 were collected using 1 L Summa
Canisters (6 L Summa Canisters were used in 2011 & 2012). Therefore, the MDL for
1,2,4-TMB in 2010 was 5 ppbv (1 ppbv in 2011 & 2012), which is over the HHASL of
1.5 ppbv in 2010.
Human Health Air Screening Level = 1.5 parts per billion by volume (ppbv)
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^¦1,2,4-TMB Detections ^"Human Health Air Screening Level Kaplan-Meier Mean
-------
24-Hour Community Air Sampling Data
1,3/5-TMB Detections
Time Period: 8/16/2010 -1/23/2012
50
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Human Health Air Screening Level = 45 parts per billion by volume (ppbv)
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Total Number of Samples = 3,234
Total Number of Detections at or above
Method Detection Limit (MDL) = 3
Kaplan-Meier Mean = 1.001 ppbv
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^¦1,3,5-TMB Detections ^"Human Health Air Screening Level Kaplan-Meier Mean
-------
24-Hour Community Air Sampling Data
Cyclohexane Detections
Time Period: 8/16/2010 -1/23/2012
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Total Number of Samples = 3,234
Total Number of Detections at or above
Method Detection Limit (MDL) = 30
Kaplan-Meier Mean = 1.037 ppbv
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80
70
24-Hour Community Air Sampling Data
4-Ethyltoluene Detections
Time Period: 8/16/2010 -1/23/2012
Human Health Air Screening Level = 70 parts per billion by volume (ppbv)
60
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3
C
o
to
4->
c
0)
u
c
o
u
0)
4->
_>
to
c
<
50
40
30
Total Number of Samples = 3,232
Total Number of Detections at or above
Method Detection Limit (MDL) = 3
Kaplan-Meier Mean = 1.001 ppbv
20
10
($y <$y jy ^ $ <$yjy jyjy ^ ^ ^ ^ & $ <
-------
70
60
> 50
Q.
3
C
o
+3 40
ro
4->
c
0)
u
§ 30
u
a>
4->
_>
to
= 20
24-Hour Community Air Sampling Data
Ethylbenzene Detections
Time Period: 8/16/2010 -1/23/2012
Total Number of Samples = 3,232
Total Number of Detections at or above
Method Detection Limit (MDL) = 6
Kaplan-Meier Mean = 1.005 ppbv
10
($y <$y jy ^ $ <$yjy jyjy ^ ^ ^ ^ & $ <
-------
60
50
24-Hour Community Air Sampling Data
m,p-Xylene Detections
Time Period: 8/16/2010 -1/23/2012
Human Health Air Screening Level = 50 parts per billion by volume (ppbv)
>
-Q
Q.
40
£
O
+¦»
S 30
u
c
o
u
0)
4->
_> 20
ro
c
<
10
Total Number of Samples = 3,232
Total Number of Detections at or above
Method Detection Limit (MDL) = 11
Kaplan-Meier Mean = 2.015 ppbv
($y <$y ^ ^ $ <$yjy jyjy ^ ^ ^ ^ ^ &<$'
-------
24-Hour Community Air Sampling Data
n-Heptane Detections
Time Period: 8/16/2010 -1/23/2012
900
800
700
Human Health Air Screening Level = 850 parts per billion by volume (ppbv)
>
-Q
Q.
3
C
o
5
to
4->
c
0)
u
c
o
u
0)
4->
_>
to
c
<
600
500
400
_> 300
Total Number of Samples = 3,232
Total Number of Detections at or above
Method Detection Limit (MDL) = 17
Kaplan-Meier Mean = 1.013 ppbv
200
100
^ ^ ^ ^ ^ ^ &
Date (M/D/YYYY)
^¦n-Heptane Detections ^"Human Health Air Screening Level ^—Kaplan-Meier Mean
-------
24-Hour Community Air Sampling Data
n-Hexane Detections
Time Period: 8/16/2010 -1/23/2012
250
Human Health Air Screening Level = 200 parts per billion by volume (ppbv)
200
>
CO
O.
Q-
O 150
5
to
4->
c
0)
u
c
o
u ioo
0)
%
to
c
<
50
Total Number of Samples = 3,234
Total Number of Detections at or above
Method Detection Limit (MDL) = 21
Kaplan-Meier Mean = 1.008 ppbv
^ ^ ^ ^ jyjy <&<$"$'$' ^ <$y<$y <$y
Date (M/D/YYYY)
^¦n-Hexane Detections ^"Human Health Air Screening Level Kaplan-Meier Mean
-------
60
50
24-Hour Community Air Sampling Data
o-Xylene Detections
Time Period: 8/16/2010 -1/23/2012
Human Health Air Screening Level = 50 parts per billion by volume (ppbv)
>
-Q
Q.
40
£
O
+¦»
S 30
u
c
o
u
0)
4->
_> 20
ro
c
<
Total Number of Samples = 3,232
Total Number of Detections at or above
Method Detection Limit (MDL) = 5
Kaplan-Meier Mean = 1.005 ppbv
10
($y <$y ^ ^ $ <$yjy jyjy ^ ^ ^ ^ ^ &<$'
-------
24-Hour Community Air Sampling Data
Toluene Detections
Time Period: 8/16/2010 -1/23/2012
300
250
>
-Q
Q.
3
C
o
5
to
4->
c
0)
u
c
o
u
0)
4->
_>
to
c
<
200
150
Total Number of Samples = 3,234
Total Number of Detections at or above
Method Detection Limit (MDL) = 457
Kaplan-Meier Mean = 2.146 ppbv
_> 100
Human Health Air Screening Level = 80 parts per billion by volume (ppbv)
^ ^ ^ ^ & $ <&jy <§yjy ^ &
Date (M/D/YYYY)
^¦Toluene Detections ^"Human Health Air Screening Level Kaplan-Meier Mean
-------
24-Hour Community Air Sampling Data
Methylcyclopentane Detections
Time Period: 8/16/2010 -1/23/2012
250
200
>
-Q
Q.
3
§ 150
'+¦»
(D
Total Number of Samples = 3,234
Methylcyclopentane is a Tentatively Identified Compound
and does not have a Method of Detection Limit (MDL)
Number of detections = 2
50
^ ^ ^ ^ ^ ^ &
V V ' V ' V
V V 'V ' V
Date (M/D/YYYY)
Methylcyclopentane
•Human Health Air Screening Level
-------
45
40
24-Hour Community Air Sampling Data
Nonane Detections
Time Period: 8/16/2010 -1/23/2012
Human Health Air Screening Level = 40 parts per billion by volume (ppbv)
35
>
-Q
Q.
3
C
o
to
4->
c
0)
u
c
o
u
0)
30
25
20
>" 15
ro
c
<
10
Total Number of Samples = 3,234
Nonane is a Tentatively Identified Compound
and does not have a Method of Detection Limit (MDL)
Number of detections = 2
^ ¦$>£'¥4- *
-------
24-Hour Community Air Sampling Data
2-Methylpentane Detections
Time Period: 8/16/2010 -1/23/2012
6000
5000
Human Health Air Screening Level = 5,000 parts per billion by volume (ppbv)
>
-Q
£ 4000
£
O
5
to
= 3000
a)
u
c
o
u
ai
>¦ 2000
as
c
<
1000
Total Number of Samples = 3,234
2-Methylpentane is a Tentatively Identified Compound
and does not have a Method of Detection Limit (MDL)
Number of detections = 1
^ ^ <$y jy
-------
24-Hour Community Air Sampling Data
2-Methylbutane Detections
Time Period: 8/16/2010 -1/23/2012
7000
6000
_> 5000
Q.
3
c
4000
ro
4-»
c
OJ
u
§ 3000
u
a>
4->
_>
to
= 2000
Total Number of Samples = 3,234
2-Methlybutane is a Tentatively Identified Compound
and does not have a Method of Detection Limit (MDL)
Number of detections = 74
1000
^ ^ <$y jy
-------
24-Hour Community Air Sampling Data
Methylcyclohexane Detections
Time Period: 8/16/2010 -1/23/2012
4500
4000
Human Health Air Screening Level = 4,000 parts per billion by volume (ppbv)
3500
>
-Q
Q.
3
C
o
5
to
4->
c
0)
u
c
o
u
0)
4->
_>
to
c
<
3000
2500
Total Number of Samples = 3,234
Methylcyclohexane is a Tentatively Identified Compound
and does not have a Method of Detection Limit (MDL)
Number of detections = 2
2000
_> 1500
1000
500
^ ^ <$y jy
-------
24-Hour Community Air Sampling Data
2-Methylhexane Detections
Time Period: 8/16/2010 -1/23/2012
900
800
Human Health Air Screening Level = 850 parts per billion by volume (ppbv)
700
>
-Q
Q.
3
C
o
5
to
4->
c
0)
u
c
o
u
0)
600
500
400
Total Number of Samples = 3,234
2-Methlyhexane is a Tentatively Identified Compound
and does not have a Method of Detection Limit (MDL)
Number of detections = 6
_> 300
ro
c
<
200
100
<$> <$> 4?&& *
-------
24-Hour Community Air Sampling Data
3-Methylhexane Detections
Time Period: 8/16/2010 -1/23/2012
900
800
Human Health Air Screening Level = 850 parts per billion by volume (ppbv)
700
>
-Q
Q.
3
C
o
5
to
4->
c
0)
u
c
o
u
0)
600
500
400
Total Number of Samples = 3,234
3-Methylhexane is a Tentatively Identified Compound
and does not have a Method of Detection Limit (MDL)
Number of detections = 8
_> 300
ro
c
<
200
100
<$> <$> 4?&& *
-------
24-Hour Community Air Sampling Data
AcetaldehydeDetections
Time Period: 8/16/2010 -1/23/2012
180
140
S"
-Q
a. 120
c
o
to
100
£
0)
u
c 80
o
u
0)
>• 60
ro
c
<
40
20
<$> <$> v&jr#' 4?$ 4?$ v *
-------
-------
Table of Contents
1. Purpose 3
2. Air Monitoring 4
2.1 Monitoring Frequency and Coverage 5
3. Noise Monitoring 5
4. Air Sampling 6
5. Air Sampling Locations 8
6. Odor Investigations 9
7. Response to Detections 9
8. Data Quality and Management 10
9. Project Organization 10
10. Calibration and Maintenance of Field 10
11. Chain of Custody 10
12. Sample Labels 10
13. Packaging and Shipping 11
Table of Tables
1. Real-Time Air Monitoring Equipment 4
2. Noise Exposure Levels 5
3. NIOSH 7300 Metals 6
4. Primary TO-15 VOC's 8
5. Analytical Sampling Methods 7
Table of Figures
Ceresco Community Map 4
Analytical Sampling Locations 5
Appendices
NIOSH 0500 Appendix 1a
NIOSH 7300 Appendix 1b
Quality Assurance Project Plan Appendix 2
2
-------
1. Purpose
Center for Toxicology and Environmental Health, L.L.C. (CTEH®) was requested to respond in support
of site operations for the Enbridge Energy crude oil release on Monday, July 26, 2010. CTEH® is
providing air monitoring, air sampling, and toxicology support to address public health concerns resulting
from the crude oil spill and subsequent dredging operations. CTEH® has been conducting community air
monitoring and sampling in communities to protect human health.
This work plan addresses air monitoring and sampling in the Ceresco community, and surrounding areas
to ensure air quality is not adversely impacted by the dredging activities. The purpose of this sampling
includes the following:
• Air monitoring and sampling in the community potentially impacted by the presence of
crude oil and suspended particulates during work activities.
• Air monitoring and sampling throughout the community during remediation activities to
evaluate the potential for exposure.
• Perform air monitoring and sampling in response to reports of odors in the community.
• Provide personnel monitoring for CTEH and EPA contractors performing air sampling and
monitoring to protect against overexposure to chemicals in crude oil vapors and/or fumes.
CTEH® will conduct community air monitoring in support of Unified Command actions. Data from air
monitoring and sampling will be evaluated to make decisions regarding the need for additional
monitoring and sampling. Data will be reported to Unified Command, Enbridge representatives, and the
USEPA, on a daily basis.
Two types of air monitoring will be conducted, analytical and real-time. These are discussed at greater
length in the following sections of this report.
2. Air Monitoring
CTEH personnel will perform continuous air monitoring in and around the Ceresco community (Figure 1)
using the MultiRAE Plus, UltraRAE, UltraRAE 3000, Gastec pump with benzene specific colorimetric
tubes, and the TS1 AM510. Real-time data using these instruments will be collected for volatile organic
3
-------
compounds (VOCs), hydrogen sulfide (HiS), benzene, and particulate matter (2.5um and lOum). A
summary of the air monitoring equipment to be used is listed in Table 1.
Figure 1
Cereseo Community
Table 1
Real-Time Air Monitoring Equipment
AM510 with 2.Sum impactor
Particulate
O
O
o
AM510 with 10urn impactor
Particulate
E
CD
O
O
O
MultiRAE 10.6 PID
VOCs
0.1 ppm
MultiRAE H2S electrochemical sensor
H2S
1 ppm
UltraRAE 3000 PID with benzene sep filters
Benzene
0.05 ppm
UltraRAE PID with benzene sep filters
Benzene
0.01 ppm
Gastec detector tube with pump
Benzene
0.05 ppm*
4
-------
* Gastec detection limits are based upon detector tubes used
2.1 Monitoring Frequency and Coverage
CTEH personnel will conduct air monitoring within the Ceresco community, and surrounding areas, for
the duration of dredging operations. Monitoring emphasis will be placed on community areas along the
effected portion of the waterway, areas located downwind of the dewatering/soil staging area, and within
the work zone.
Real-Time readings will be taken at various locations in and around the Ceresco community, as well as
within the work zone. At each location a VOC, H2S, PM10, and PM2.5 reading will be recorded.
Multiple readings in the same location will be used as one method to determine if detects from
instantaneous readings from real-time instrumentation are due to transient elevations, spikes in air
concentration, or if the concentrations are sustained. If sustained, further air monitoring and/or sampling
would be initiated. In the case of benzene, readings will be taken in all areas with detectable VOCs or
where odor is present.
3. Noise Monitoring
Noise monitoring will be conducted within the community as well as the work area.
The Questpro DX noise dosimeter will be utilized to determine real-time noise expose levels. The
detection limit for this instrument is 40 dB. Noise readings will be used by Enbridge as well as various
regulators to determine what, if any, actions should be taken to reduce community and/or worker noise
exposure. Exposure values are listed in Table 2.
Table 2
Noise Exposure Levels
Sound Pressure Level
90 dBA (100% dose)
85 dBA
(SPL)
5
-------
4. Air Sampling
Analytical air sampling will be conducted in community areas near the Ceresco Dam dredging operations.
Analytical samples will be taken in fixed community locations near dredging operations (Figure 2),
around the de-watering/soil staging area (Figure 2), and as needed due to changing site conditions, odor
complaints, wind direction, and in areas where elevated reading are recorded.
Air samples will be collected once at each location during a 12-hour period (5um Polyvinyl Chloride
cassette), and once during a 24-hour period (evacuated canisters) each day. The criteria used in selecting
sampling locations include proximity of residences to the Kalamazoo River, location of dredging
operations, and location of potential receptors surrounding the de-watering/soil staging area._Air samples
collected using 5um PVC cassettes will be analyzed for total dust according to NIOSH 0500, as well as
for metals using NIOSH 7300 (Table 3). Evacuated canister samples will be analyzed for VOCs using
EPA Method TO-15 (Table 4). Air Sampling Methods are summarized in Table 5. Each analytical
method can be found in Appendix 1.
Figure 2
Analytical Air Sampling Locations
-------
Table 3
Metal Analysis NIOSH 7300
NIOSH 7300-Metals
Aluminium
Molybdenum
Antmony
Nickel
Arsenic
Potassium
Barium
Phosphorus
Beryllium
Selenium
Cadmium
Silver
Calcium
Strontium
Chromium
Tellurium
Cobat
Tin
Copper
Thallium
Iron
Titanium
Lead
Tungsten
Lanthanum
Vanadium
Lithium
Yittarium
Magnesium
Zinc
Manganese
Zirconium
Table 4
Predominant Crude Oil VOCs Detected by TO-15
Benzene
Heptane, n-
Butane, 2-methyl-*
Hexane, n-
Cyclohexane
Naphthalene
Cyclohexane, 1,3-dimethyl-*
Nonane*
Cyclohexane, 1,3-dimethyl-, cis-*
Octane*
Cyclohexane, butyl-*
Octane, 4-methyl-*
Cyclohexane, ethyl-*
Pentane, 2-methyl-*
Cyclohexane, methyl-*
Toluene
Cyclohexane, propyl-*
Trimethylbenzene, 1,2,4-
Decane*
Trimethylbenzene, 1,3,5-
Dodecane*
Undecane*
Ethylbenzene
Xylene, m&p-
Ethyltoluene, 4-
Xylene, o-
*- Tentatively identified compound (TIC)
7
-------
Table 5
Summary of Analytical Air Sampling Methods
VOCs
EPA TO-15
Canisters
NA
Total Dust
NIOSH 0500
37mm PVC 5um
2000
Metals
NIOSH 7300
37mm PVC 5um
2000
Evacuated canisters will also be used to collect air samples to address community concerns about odors.
Canister samples will consist of either grab or 24-hour collections. The collection time will be based on
monitoring needs. For instance, a grab sample will be collected for confirmatory purposes in response to
data from real-time instruments. Longer sampling times may be appropriate for evaluation of air
concentrations over time. For example, 24-hour sampling would be appropriate for evaluating the
potential for exposure at certain receptor sites like homes and schools.
All collected air samples will be sent to Galson Laboratories, an American Industrial Hygiene Association
(AIHA) accredited laboratory, in East Syracuse, New York. Samples will be expedited for shipping and
analysis. A 1 - 2 day turnaround is anticipated for data is anticipated.
5. Air Sampling Locations
Real-time and integrated sampling locations will be selected based on the presence of communities near
impacted waterways (Figure 1) and in addressing specific community concerns. Manually logged real-
time data will be collected and uploaded to the CTEH® data management system using MC55 handheld
data collection devices.
6. Odor Investigations
A CTEH team will be available as an Odor Response Team. The Odor Response Team will be deployed
as soon as possible after receiving odor complaints/concerns_referred by the hotline, Enbridge, and
8
-------
Unified Command staff. The response team will additionally include representatives USEPA and/or the
Calhoun County Public Health Department, as available. Air monitoring equipment (e.g. MultiRAE Plus,
AreaRAE, Gastec colorimetric detector tubes, and/or UltraRAE) will be used to evaluate the levels of
VOCs and specific oil-related chemicals in the air. The evaluation of the results should follow the
decision process described below.
7. Response to Detections
A decision process has been developed for the evaluation of air monitoring results for dust, VOCs, TO-
15, and real-time detections for benzene. For VOC detections, a trigger level of 1 ppm will be used to
designate the need for chemical-specific sampling. The decision process for the evaluation of benzene
levels from Ultra RAE, GASTEC, and HAP analysis (Tedlar bag collection). If benzene levels are
detected above 200 ppb, then confirmation with the HAP instrument should be employed. If benzene
levels exceed 60 ppb, then an 8-24 hr time-weighted sample should be collected. For particulates,
additional engineering controls will be utilized if real-time instrumentation detect concentrations that
meet or exceed 75% of the National Ambient Air Quality Standards (NAAQS) for PM2.5 and/or PM10
(Table 5).
Table 5
National Ambient Air Quality Standards (NAAQS) for PM2.5 and PM10
Primary Standard
Level
Averaging Time
Particulate
Matter (PMio)
150 |ig/m3
24-hour(1)
Particulate
Matter (PM2.s)
35 |ig/m3
24-hour
(1) Not to be exceeded more than once per year on average over 3 years.
8. Data Quality and Management
Integrated air samples will be sent to Galson Laboratories located in Syracuse, N.Y. Air sampling
preliminary results will be provided to Enbridge Energy's designated representative and the USEPA
within 1-2 days of receipt by the laboratory. The expedited turnaround time for Galson is one business
9
-------
day. All air sampling and air monitoring data will be provided to Unified Command in a format
compatible with SCRIBE. The Quality Assurance Project Plan can be found in Appendix 2.
9. Project Organization
CTEH will be responsible for the following:
• Toxicological support
• Air data quality assurance/quality control
• Data evaluation and reporting
10. Calibration and Maintenance of Field Instruments
The calibration and maintenance of field equipment and instrumentation will be in accordance with each
manufacturer's specifications or applicable test/method specifications, and will be recorded in CTEH
calibration logs.
11. Chain of Custody (COC)
Each sample will be identified on a chain of custody record. The integrated sample numbering system
will include site name, date, analyte, and identification code unique to each sample.
12. Sample Labels
Sample labels will be securely affixed to the sample container. They will clearly identify the
particular sample and should include the following information:
¦ Sampling location
¦ Date and time the sample was collected.
¦ Analysis requested.
¦ Unique identifier
10
-------
13. Packaging and Shipping
Packaging and shipping of samples will vary depending upon sample media, contaminant concentration,
preservation technique, and sample container. The person packaging the samples is responsible to ensure
that the sample packaging is in suitable condition for shipping.
11
-------
PARTICULATES NOT OTHERWISE REGULATED, TOTAL 0500
DEFINITION: total aerosol mass CAS: NONE RTECS: NONE
METHOD: 0500, Issue 2 EVALUATION: FULL Issue 1:15 February 1984
Issue 2:15 August 1994
OSHA: 15 mg/m3 PROPERTIES: contains no asbestos and quartz less than 1%
NIOSH: no REL
ACGIH: 10 mg/m3, total dust less than 1% quartz
SYNONYMS: nuisance dusts; particulates not otherwise classified
SAMPLING
MEASUREMENT
SAMPLER:
FILTER
TECHNIQUE:
GRAVIMETRIC (FILTER WEIGHT)
(tared 37-mm, 5-nm PVC filter)
ANALYTE:
airborne particulate material
FLOW RATE:
1 to 2 L/min
BALANCE:
0.001 mg sensitivity; use same balance
VOL-MIN:
7 L @ 15 mg/m3
before and after sample collection
-MAX:
133 L @ 15 mg/m3
CALIBRATION:
National Institute of Standards and
SHIPMENT:
routine
Technology Class S-1.1 weights or ASTM
Class 1 weights
SAMPLE
STABILITY:
indefinitely
RANGE:
0.1 to2mg per sample
BLANKS:
2 to 10 field blanks per set
ESTIMATED LOD:
0.03 mg per sample
BULK
PRECISION (St):
0.026 [2]
SAMPLE:
none required
ACCURACY
RANGE STUDIED: 8 to 28 mg/m3
BIAS:
0.01%
OVERALL PRECISION (S[T): 0.056 [1 ]
ACCURACY:
±11.04%
APPLICABILITY: The working range is 1 to 20 mg/m3 for a 100-Lair sample. This method is nonspecific and determines the
total dust concentration to which a worker is exposed. It may be applied, e.g., to gravimetric determination of fibrous glass
[3] in addition to the other ACGIH particulates not otherwise regulated [4].
INTERFERENCES: Organic and volatile particulate matter may be removed by dry ashing [3],
OTHER METHODS: This method is similar to the criteria document method for fibrous glass [3] and Method 5000 for carbon
black. This method replaces Method S349 [5]. Impingers and direct-reading instruments may be used to collect total dust
samples, but these have limitations for personal sampling.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
PARTICULATES NOT OTHERWISE REGULATED, TOTAL: METHOD 0500, Issue 2, dated 15 August 1994 - Page 2 of 3
EQUIPMENT:
1. Sampler: 37-mm PVC, 2- to 5-nm pore size membrane or equivalent hydrophobic filter and
supporting pad in 37-mm cassette filter holder.
2. Personal sampling pump, 1 to 2 L/min, with flexible connecting tubing.
3. Microbalance, capable of weighing to 0.001 mg.
4. Static neutralizer: e.g., Po-210; replace nine months after the production date.
5. Forceps (preferably nylon).
6. Environmental chamber or room for balance (e.g., 20 °C ± 1 °C and 50% ± 5% RH).
SPECIAL PRECAUTIONS: None.
PREPARATION OF FILTERS BEFORE SAMPLING:
1. Equilibrate the filters in an environmentally controlled weighing area or chamber for at least 2 h.
NOTE: An environmentally controlled chamber is desirable, but not required.
2. Number the backup pads with a ballpoint pen and place them, numbered side down, in filter
cassette bottom sections.
3. Weigh the filters in an environmentally controlled area or chamber. Record the filter tare weight,
(mg).
a. Zero the balance before each weighing.
b. Handle the filter with forceps. Pass the filter over an antistatic radiation source. Repeat this step if
filter does not release easily from the forceps or if filter attracts balance pan. Static electricity can
cause erroneous weight readings.
4. Assemble the filter in the filter cassettes and close firmly so that leakage around the filter will not
occur. Place a plug in each opening of the filter cassette. Place a cellulose shrink band around the
filter cassette, allow to dry and mark with the same number as the backup pad.
SAMPLING:
5. Calibrate each personal sampling pump with a representative sampler in line.
6. Sample at 1 to 2 L/min for a total sample volume of 7 to 133 L. Do not exceed a total filter loading of
approximately 2 mg total dust. Take two to four replicate samples for each batch of field samples for
quality assurance on the sampling procedure.
SAMPLE PREPARATION:
7. Wipe dust from the external surface of the filter cassette with a moist paper towel to minimize
contamination. Discard the paper towel.
8. Remove the top and bottom plugs from the filter cassette. Equilibrate for at least 2 h in the balance
room.
9. Remove the cassette band, pry open the cassette, and remove the filter gently to avoid loss of dust.
NOTE: If the filter adheres to the underside of the cassette top, very gently lift away by using the dull
side of a scalpel blade. This must be done carefully or the filter will tear.
CALIBRATION AND QUALITY CONTROL:
10. Zero the microbalance before all weighings. Use the same microbalance for weighing filters before
and after sample collection. Maintain and calibrate the balance with National Institute of Standards
and Technology Class S-1.1 or ASTM Class 1 weights.
11. The set of replicate samples should be exposed to the same dust environment, either in a laboratory
dust chamber [7] or in the field [8]. The quality control samples must be taken with the same
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
PARTICULATES NOT OTHERWISE REGULATED, TOTAL: METHOD 0500, Issue 2, dated 15 August 1994 - Page 3 of 3
equipment, procedures, and personnel used in the routine field samples.The relative standard
deviation calculated from these replicates should be recorded on control charts and action taken
when the precision is out of control [7].
MEASUREMENT:
12. Weigh each filter, including field blanks. Record the post-sampling weight, W2 (mg). Record anything
remarkable about a filter (e.g., overload, leakage, wet, torn, etc.)
CALCULATIONS:
13. Calculate the concentration of total particulate^ (mg/m3), in the air volume sampled,!/ (L):
c = V_ x 1 gi mg/m
V
where: Wy = tare weight of filter before sampling (mg),
l/l/2 = post-sampling weight of sample-containing filter (mg),
6, = mean tare weight of blank filters (mg),
B1 = mean post-sampling weight of blank filters (mg).
EVALUATION OF METHOD:
Lab testing with blank filters and generated atmospheres of carbon black was done at 8 to 28 mg/m3
[2,6]. Precision and accuracy data are given on page 0500-1.
REFERENCES:
[1] NIOSH Manual of Analytical Methods, 3rd ed., NMAM 5000, DHHS (NIOSH) Publication No. 84-100
(1984).
[2] Unpublished data from Non-textile Cotton Study, NIOSH/DRDS/EIB.
[3] NIOSH Criteria for a Recommended Standard ... Occupational Exposure to Fibrous Glass, U.S.
Department of Health, Education, and Welfare, Publ. (NIOSH) 77-152,119-142 (1977).
[4] 1993-1994 Threshold Limit Values and Biological Exposure Indices, Appendix D, ACGIH, Cincinnati,
OH (1993).
[5] NIOSH Manual of Analytical Methods, 2nd ed.,V. 3, S349, U.S. Department of Health, Education, and
Welfare, Publ. (NIOSH) 77-157-C (1977).
[6] Documentation of the NIOSH Validation Tests, S262 and S349, U.S. Department of Health,
Education, and Welfare, Publ. (NIOSH) 77-185 (1977).
[7] Bowman, J.D., D.L. Bartley, G.M. Breuer, LJ. Doemeny, and D.J. Murdock. Accuracy Criteria
Recommended for the Certification of Gravimetric Coal Mine Dust Personal Samplers. NTIS Pub. No.
PB 85-222446 (1984).
[8] Breslin, J.A., S.J. Page, and R.A. Jankowski. Precision of Personal Sampling of Respirable Dust in Coal
Mines, U.S. Bureau of Mines Report of Investigations #8740 (1983).
METHOD REVISED BY:
Jerry Clere and Frank Hearl, P.E., NIOSH/DRDS.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
Esta pagina en Espanoi
ELEMENTS by ICP 7300
(Nitric/Perchloric Acid Ashing)
MW: Table 1 CAS: Table 2 RTECS: Table 2
METHOD: 7300, Issue 3
EVALUATION: PARTIAL
Issue 1: 15August1990
Issue 3: 15 March 2003
OS HA: Table 2
NIOSH: Table 2
ACGIH: Table 2
PROPERTIES: Table 1
ELEMENTS: aluminum*
calcium
lanthanum
nickel
strontium
tungsten*
antimony*
chromium*
lithium*
potassium
tellurium
vanadium*
arsenic
cobalt*
magnesium
phosphorus
tin
yittrium
barium
copper
manganese*
selenium
thallium
zinc
beryllium*
iron
molybdenum*
silver
titanium
zirconium*
cadmium
lead*
"Some compounds of these elements require special sample treatment.
SAMPLING
MEASUREMENT
SAMPLER:
FILTER
TECHNIQUE:
INDUCTIVELY COUPLED ARGON
(0.8-pm, cellulose ester membrane, or
PLASMA, ATOMIC EMISSION
5.0-(jm, polyvinyl chloride membrane)
SPECTROSCOPY (ICP-AES)
FLOWRATE:
1 to 4 L/min
ANALYTE:
elements above
VOL-MIN:
Table 1
ASHING
-MAX:
Table 1
REAGENTS:
conc. HNOa/ conc. HCI04 (4:1), 5 mL;
2mL increments added as needed
SHIPMENT:
routine
CONDITIONS:
room temperature, 30 min; 150 °Cto near
SAMPLE
dryness
STABILITY:
stable
FINAL
SOLUTION:
4% HNOa, 1% HCI04, 25 mL
BLANKS:
2 to 10 field blanks per set
WAVELENGTH:
depends upon element; Table 3
ACCURACY
BACKGROUND
CORRECTION:
spectral wavelength shift
RANGE STUDIED:
not determined
CALIBRATION:
elements in 4% HN03, 1% HCIO,
BIAS:
not determined
RANGE:
varies with element [1]
OVERALL PRECISION (SrT): not determined
ESTIMATED LOD: Tables 3 and 4
ACCURACY:
not determined
PRECISION (S):
Tables 3 and 4
APPLICABILITY: The working range of this method is 0.005 to 2.0 mg/m3 for each element in a 500-L air sample. This is
simultaneous elemental analysis, not compound specific. Verify that the types of compounds in the samples are soluble with
the ashing procedure selected.
INTERFERENCES: Spectral interferences are the primary interferences encountered in ICP-AES analysis. These are
minimized by judicious wavelength selection, interelement correction factors and background correction [1-4].
OTHER METHODS: This issue updates issues 1 and 2 of Method 7300, which replaced P&CAM 351 [3] for trace elements.
Flame atomic absorption spectroscopy (e.g., Methods 70XX) is an alternate analytical technique for many of these elements.
Graphite furnace AAS (e.g., 7102 for Be, 7105 for Pb) is more sensitive.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
ELEMENTS (ICP): METHOD 7300, Issue 3, dated 15 March 2003 - Page 2 of 8
REAGENTS:
1. Nitric acid (HN03), conc., ultra pure.
2. Perchloric acid (HCI04), conc., ultra pure.*
3. Ashing acid: 4:1 (v/v) HN03:HCI04. Mix 4
volumes conc. HN03 with 1 volume conc.
HCI04.
4. Calibration stock solutions, 1000 pg/mL.
Commercially available, or prepared per
instrument manufacturer's recommendation
(see step 12).
5. Dilution acid, 4% HNOs, 1% HCI04. Add 50
mL ashing acid to 600 mL water; dilute to 1 L.
6. Argon.
7. Distilled,deionized water.
See SPECIAL PRECAUTIONS.
EQUIPMENT:
1. Sampler: cellulose ester membrane filter,
0.8-|jm pore size; or polyvinyl chloride
membrane, 5.0-pm pore size; 37-mm
diameter, in cassette filter holder.
2. Personal sampling pump, 1 to 4 L/min, with
flexible connecting tubing.
3. Inductively coupled plasma-atomic emission
spectrometer, equipped as specified by the
manufacturer for analysis of elements of
interest.
4. Regulator, two-stage, for argon.
5. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
with watch glass covers.**
6. Volumetric flasks, 10-, 25-,100-mL., and 1-L**
7. Assorted volumetric pipets as needed.**
8. Hotplate, surface temperature 150 °C.
** Clean all glassware with conc. nitric acid
and rinse thoroughly in distilled water
before use.
SPECIAL PRECAUTIONS: All perchloric acid digestions are required to be done in a perchloric acid
hood. When working with concentrated acids, wear protective clothing and gloves.
SAMPLING:
1. Calibrate each personal sampling pump with a representative sampler in line.
2. Sample at an accurately known flow rate between 1 and 4 L/min for a total sample size of 200 to 2000
L (see Table 1) for TWA measurements. Do not exceed a filter loading of approximately 2 mg total dust.
SAMPLE PREPARATION:
3. Open the cassette filter holders and transfer the samples and blanks to clean beakers.
4. Add 5 mL ashing acid. Cover with a watchglass. Let stand 30 min at room temperature.
NOTE: Start a reagent blank at this step.
5. Heat on hotplate (120 °C) until ca. 0.5 mL remains.
NOTE 1: Recovery of lead from some paint matrices may require other digestion techniques. See
Method 7082 (Lead by Flame AAS) for an alternative hotplate digestion procedure or Method
7302 for a microwave digestion procedure.
NOTE 2: Some species of Al, Be, Co, Cr, Li, Mn, Mo, V, and Zr will not be completely solubilized by this
procedure. Alternative solubilization techniques for most of these elements can be found
elsewhere [5-10]. For example, aqua regia may be needed for Mn [6,12].
6. Add 2 mL ashing acid and repeat step 5. Repeat this step until the solution is clear.
7. Remove watchglass and rinse into the beaker with distilled water.
8. Increase the temperature to 150 °C and take the sample to near dryness (ca. 0.5 mL).
9. Dissolve the residue in 2 to 3 mL dilution acid.
10. Transfer the solutions quantitatively to 25-mL volumetric flasks.
11. Dilute to volume with dilution acid.
NOTE: If more sensitivity is required, the final sample volume may be held to 10 mL.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
ELEMENTS (ICP): METHOD 7300, Issue 3, dated 15 March 2003 - Page 3 of 8
CALIBRATION AND QUALITY CONTROL:
12. Calibrate the spectrometer according to the manufacturers recommendations.
NOTE: Typically, an acid blank and 1.0 |jg/mL multielement working standards are used. The following
multielement combinations are chemically compatible in 4% HN03/1% HCI04:
a. Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, La, In, Na
b. Ag, K, Li, Mg, Mn, Ni, P, Pb, Se, Sr, Tl, V, Y, Zn, Sc
c. Mo, Sb, Sn, Te, Ti, W, Zr
d. Acid blank
13. Analyze a standard for every ten samples.
14. Check recoveries with at least two spiked blank filters per ten samples.
MEASUREMENT:
15. Set spectrometer to conditions specified by manufacturer.
16. Analyze standards and samples.
NOTE: If the values for the samples are above the range of the standards, dilute the solutions with
dilution acid, reanalyze and apply the appropriate dilution factor in the calculations.
CALCULATIONS:
17. Obtain the solution concentrations for the sample, Cs(pg/mL), and the average media blank, Cb(|jg/mL),
from the instrument.
18. Using the solution volumes of sample, Vs (mL), and media blank, Vb (mL), calculate the concentration,
C (mg/m3), of each element in the air volume sampled, V (L):
CsVs- CbVb , ,
C = ,mgim
NOTE: (jg/L = mg/m3
EVALUATION OF METHOD:
Issues 1 and 2
Method, 7300 was originally evaluated in 1981 [2,3]. The precision and recovery data were determined at 2.5
and 1000 |jg of each element per sample on spiked filters. The measurements used for the method evaluation
in Issues 1 and 2 were determined with a Jarrell-Ash Model 1160 Inductively Coupled Plasma Spectrometer
operated according to manufacturer's instructions.
Issue 3
In this update of NIOSH Method 7300, the precision and recovery data were determined at approximately 3x
and 10x the instrumental detection limits on commercially prepared spiked filters [12] using 25.0 mL as the
final sample volume. Tables 3 and 4 list the precision and recovery data, instrumental detection limits, and
analytical wavelengths for mixed cellulose ester (MCE) and polyvinyl chloride (PVC) filters. PVC Filters which
can be used fortotal dust measurements and then digested for metals measurements were tested and found
to give good results. The values in Tables 3 and 4 were determined with a Spectro Analytical Instruments
Model End On Plasma (EOP)(axial) operated according to manufacturer's instructions.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
ELEMENTS (ICP): METHOD 7300, Issue 3, dated 15 March 2003 - Page 4 of 8
REFERENCES:
[1] Millson M, Andrews R [2002]. Backup data report, Method 7300, unpublished report, NIOSH/DART.
[2] Hull RD [1981]. Multielement Analysisoflndustrial Hygiene Samples, NIOSH Internal Report, presented
at the American Industrial Hygiene Conference, Portland, Oregon.
[3] NIOSH [1982], NIOSH Manual of Analytical Methods, 2nd ed„ V. 7, P&CAM 351 (Elements by ICP),
U.S. Department of Health and Human Services, Publ. (NIOSH) 82-100.
[4] NIOSH [1994]. Elements by ICP: Method 7300, Issue 2. In: Eller PM, Cassinelli ME, eds., NIOSH
Manual of Analytical Methods, 4th ed. Cincinnati, OH: U.S. Department of Health and Human Services,
Centers for Disease Control and Prevention, National Institute forOccupational Safety and Health, DHHS
(NIOSH) Publication No. 94-113.
[5] NIOSH [1994], Lead by FAAS: Method 7082. In: Eller PM, Cassinelli ME, eds., NIOSH Manual of
Analytical Methods, 4th ed. Cincinnati, OH: U.S. Department of Health and Human Services, Centers
for Disease Control and Prevention, National Institute for Occupational Safety and Health, DHHS
(NIOSH) Publication No. 94-113.
[6] NIOSH [1977]. NIOSH Manual of Analytical Methods, 2nd ed., V. 2, S5 (Manganese), U.S. Department
of Health, Education, and Welfare, Publ. (NIOSH) 77-157-B.
[7] NIOSH [1994]. Tungsten, soluble/insoluble: Method 7074. In: Eller PM, Cassinelli ME, eds., NIOSH
Manual of Analytical Methods, 4th ed. Cincinnati, OH: U.S. Department of Health and Human Services,
Centers for Disease Control and Prevention, National Institute for Occupational Safety and Health, DHHS
(NIOSH) Publication No. 94-113.
[8] NIOSH [1979], NIOSH Manual of Analytical Methods, 2nd ed., V. 5, P&CAM 173 (Metals by Atomic
Absorption), U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 79-141.
[9] NIOSH [1977], NIOSH Manual of Analytical Methods, 2nd ed., V. 3, S183 (Tin), S185 (Zirconium), and
S376 (Molybdenum), U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-C.
[10] ISO [2001]. Workplace air - Determination of metals and metalloids in airborne particulate matter by
inductively coupled plasma atomic emission spectrometry - Part 2: Sample preparation. International
Organization for Standardization. ISO 15202-2:2001(E).
[11] ASTM [1985]. 1985 Annual Book of ASTM Standards, Vol. 11.01; Standard Specification for Reagent
Water; ASTM, Philadelphia, PA, D1193-77 (1985).
[12] Certification Inorganic Ventures for spikes.
METHOD REVISED BY:
Mark Millson and Ronnee Andrews, NIOSH/DART.
Method originallywritten by Mark Millson, NIOSH/DART, and R. DeLon Hull, Ph.D., NIOSH/DSHEFS, James
B. Perkins, David L. Wheeler, and Keith Nicholson, DataChem Labortories, Salt Lake City, UT.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
ELEMENTS (ICP): METHOD 7300, Issue 3, dated 15 March 2003 - Page 6 of 8
TABLE 2. EXPOSURE LIMITS, CAS #, RTECS
Element Exposure Limits, mg/m3 (Ca = carcinogen)
(Symbol) CAS# RTECS OSHA NIOSH ACGIH
Silver (Ag)
7440-22-4
VW3500000
0.01 (dust, fume, metal)
0.01 (metal, soluble)
0.1 (metal)
0.01 (soluble)
Aluminum (Al)
7429-90-5
BD0330000
15 (total dust)
5 (respirable)
10 (total dust)
5 (respirable fume)
2 (salts, alkyls)
10 (dust)
5 (powders, fume)
2 (salts, alkyls)
Arsenic (As)
7440-38-2
CG0525000
varies
C 0.002, Ca
0.01, Ca
Barium (Ba)
7440-39-3
CQ8370000
0.5
0.5
0.5
Beryllium (Be)
7440-41-7
DS1750000
0.002, C 0.005
0.0005, Ca
0.002, Ca
Calcium (Ca)
7440-70-2
-
varies
varies
varies
Cadmium (Cd)
7440-43-9
EU9800000
0.005
lowest feasible, Ca
0.01 (total), Ca
0.002 (respir.), Ca
Cobalt (Co)
7440-48-4
GF8750000
0.1
0.05 (dust, fume)
0.02 (dust, fume)
Chromium (Cr)
7440-47-3
GB4200000
0.5
0.5
0.5
Copper (Cu)
7440-50-8
GL5325000
1 (dust, mists)
0.1 (fume)
1 (dust)
0.1 (fume)
1 (dust, mists)
0.2 (fume)
Iron (Fe)
7439-89-6
N04565500
10 (dust, fume)
5 (dust, fume)
5 (fume)
Potassium (K)
7440-09-7
TS6460000
-
-
-
Lanthanum
7439-91-0
-
-
-
--
Lithium (Li)
7439-93-2
-
-
-
--
Magnesium (Mg)
7439-95-4
OM2100000
15 (dust) as oxide
5 (respirable)
10 (fume) as oxide
10 (fume) as oxide
Manganese (Mn)
7439-96-5
009275000
C 5
1; STEL 3
5 (dust)
1; STEL 3 (fume)
Molybdenum (Mo)
7439-98-7
QA4680000
5 (soluble)
15 (total insoluble)
5 (soluble)
10 (insoluble)
5 (soluble)
10 (insoluble)
Nickel (Ni)
7440-02-0
QR5950000
1
0.015, Ca
0.1 (soluble)
1 (insoluble, metal)
Phosphorus (P)
7723-14-0
TH3500000
0.1
0.1
0.1
Lead (Pb)
7439-92-1
OF7525000
0.05
0.05
0.05
Antimony (Sb)
7440-36-0
CC4025000
0.5
0.5
0.5
Selenium (Se)
7782-49-2
VS7700000
0.2
0.2
0.2
Tin (Sn)
7440-31-5
XP7320000
2
2
2
Strontium (Sr)
7440-24-6
-
-
-
-
Tellurium (Te)
13494-80-9
WY2625000
0.1
0.1
0.1
Titanium (Ti)
7440-32-6
XR1700000
-
-
-
Thallium (TI)
7440-28-0
XG3425000
0.1 (skin) (soluble)
0.1 (skin) (soluble)
0.1 (skin)
Vanadium (V)
7440-62-2
YW240000
-
C 0.05
-
Tungsten
7440-33-7
-
5
5
10 (STEL)
5
10 (STEL)
Yttrium (Y)
7440-65-5
ZG2980000
1
N/A
1
Zinc (Zn)
7440-66-6
ZG8600000
-
--
-
Zirconium (Zr)
7440-67-7
ZH7070000
5
5, STEL 10
5, STEL 10
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
ELEMENTS (ICP): METHOD 7300, Issue 3, dated 15 March 2003 - Page 7 of 8
TABLE 3. MEASUREMENT PROCEDURES AND DATA [1].
Mixed Cellulose Ester Filters (0.45 jim)
wavelength
Est. LOD
LOD
Certified % Recovery
Percent
Certified
%
Percent
Element
nm
mq/
ng/mL
3x LOD
(C)
RSD
10x LOD
Recovery
RSD
(a)
Filter
(b)
(N=25)
(b)
(c)
(N=25)
Ag
328
0.042
1.7
0.77
102.9
2.64
3.21
98.3
1.53
Al
167
0.115
4.6
1.54
105.4
11.5
6.40
101.5
1.98
As
189
0.140
5.6
3.08
94.9
2.28
12.9
93.9
1.30
Ba
455
0.005
0.2
0.31
101.8
1.72
1.29
97.7
0.69
Be
313
0.005
0.2
0.31
100.0
1.44
1.29
98.4
0.75
Ca
317
0.908
36.3
15.4
98.7
6.65
64.0
100.2
1.30
Cd
226
0.0075
0.3
0.31
99.8
1.99
1.29
97.5
0.88
Co
228
0.012
0.5
0.31
100.8
1.97
1.29
98.4
0.90
Cr
267
0.020
0.8
0.31
93.4
16.3
1.29
101.2
2.79
Cu
324
0.068
2.7
1.54
102.8
1.47
6.40
100.6
0.92
Fe
259
0.095
3.8
1.54
103.3
5.46
6.40
98.0
0.95
K
766
1.73
69.3
23.0
90.8
1.51
96.4
97.6
0.80
La
408
0.048
1.9
0.77
102.8
2.23
3.21
100.1
0.92
Li
670
0.010
0.4
0.31
110.0
1.91
1.29
97.7
0.81
Mg
279
0.098
3.9
1.54
101.1
8.35
6.40
98.0
1.53
Mn
257
0.005
0.2
0.31
101.0
1.77
1.29
94.7
0.73
Mo
202
0.020
0.8
0.31
105.3
2.47
1.29
98.6
1.09
Ni
231
0.020
0.8
0.31
109.6
3.54
1.29
101.2
1.38
P
178
0.092
3.7
1.54
84.4
6.19
6.40
82.5
4.75
Pb
168
0.062
2.5
1.54
109.4
2.41
6.40
101.7
0.88
Sb
206
0.192
7.7
3.08
90.2
11.4
12.9
41.3
32.58
Se
196
0.135
5.4
2.3
87.6
11.6
9.64
84.9
4.78
Sn
189
0.040
1.6
0.77
90.2
18.0
3.21
49
21.79
Sr
407
0.005
0.2
0.31
101.0
1.55
1.29
97.3
0.65
Te
214
0.078
3.1
1.54
102.0
2.67
6.40
97.4
1.24
Ti
334
0.050
2.0
0.77
98.4
2.04
3.21
93.4
1.08
Tl
190
0.092
3.7
1.54
100.9
2.48
6.40
99.1
0.80
V
292
0.028
1.1
0.77
103.2
1.92
3.21
98.3
0.84
w
207
0.075
3.0
1.54
72.2
10.1
6.40
57.6
14.72
Y
371
0.012
0.5
0.31
100.5
1.80
1.29
97.4
0.75
Zn
213
0.310
12.4
4.60
102.2
1.87
19.3
95.3
0.90
Zr
339
0.022
0.9
0.31
88.0
19.4
1.29
25
57.87
(a) Bold values are qualitative only because of low recovery.
(b) Values are certified by Inorganic Ventures INC. at 3x and 10x the approximate instrumental LOD
(c) Values reported were obtained with a Spectro Analytical Instruments EOP ICP; performance may vary with
instrument and should be independently verified.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
-------
ELEMENTS (ICP): METHOD 7300, Issue 3, dated 15 March 2003 - Page 8 of 8
TABLE 4. MEASUREMENT PROCEDURES AND DATA [1],
Polyvinyl Chloride Filter (5.0 pm)
wavelength
Est. LOD
LOD
Certified
%
Percent
Certified17
%
Percent
Element
nm
M9 per
ng/mL
3x LOD
Recovery
RSD
10x LOD
Recovery
RSD
(c)
filter
(b)
(a)
(N=25)
(b)
(a)
(N=25)
Ag
328
0.042
1.7
0.78
104.2
8.20
3.18
81.8
18.9
Al
167
0.115
4.6
1.56
77.4
115.24
6.40
92.9
20.9
As
189
0.140
5.6
3.10
100.7
5.13
12.70
96.9
3.2
Ba
455
0.005
0.2
0.31
102.4
3.89
1.270
99.8
2.0
Be
313
0.005
0.2
0.31
106.8
3.53
1.270
102.8
2.1
Ca
317
0.908
36.3
15.6
68.1
12.66
64.00
96.8
5.3
Cd
226
0.0075
0.3
0.31
105.2
5.57
1.27
101.9
2.8
Co
228
0.012
0.5
0.31
109.3
4.67
1.27
102.8
2.8
Cr
267
0.020
0.8
0.31
109.4
5.31
1.27
103.4
4.1
Cu
324
0.068
2.7
1.56
104.9
5.18
6.40
101.8
2.4
Fe
259
0.095
3.8
1.56
88.7
46.82
6.40
99.1
9.7
K
766
1.73
69.3
23.4
96.4
4.70
95.00
99.2
2.2
La
408
0.048
1.9
0.78
45.5
4.19
3.18
98.8
2.6
Li
670
0.010
0.4
0.31
107.7
4.80
1.27
110.4
2.7
Mg
279
0.098
3.9
1.56
54.8
20.59
6.40
64.5
5.7
Mn
257
0.005
0.2
0.31
101.9
4.18
1.27
99.3
2.4
Mo
202
0.020
0.8
0.31
106.6
5.82
1.27
98.1
3.8
Ni
231
0.020
0.8
0.31
111.0
5.89
1.27
103.6
3.2
P
178
0.092
3.7
1.56
101.9
17.82
6.40
86.5
10.4
Pb
168
0.062
2.5
1.56
109.6
6.12
6.40
103.2
2.9
Sb
206
0.192
7.7
3.10
64.6
22.54
12.70
38.1
30.5
Se
196
0.135
5.4
2.30
83.1
26.23
9.50
76.0
17.2
Sn
189
0.040
1.6
0.78
85.7
27.29
3.18
52.0
29.4
Sr
407
0.005
0.2
0.31
71.8
4.09
1.27
81.2
2.7
Te
214
0.078
3.1
1.56
109.6
7.49
6.40
97.3
3.8
Ti
334
0.050
2.0
0.78
101.0
9.46
3.18
92.4
5.5
Tl
190
0.092
3.7
1.56
110.3
4.04
6.40
101.9
2.0
V
292
0.028
1.1
0.78
108.3
3.94
3.18
102.5
2.6
w
207
0.075
3.0
1.56
74.9
15.79
6.40
44.7
19.6
Y
371
0.012
0.5
0.31
101.5
3.63
1.27
101.4
2.5
Zn
213
0.310
12.4
4.70
91.0
68.69
19.1
101.0
9.6
Zr
339
0.022
0.9
0.31
70.7
54.20
1.27
40.4
42.1
(a) Values reported were obtained with a Spectro Analytical Instruments EOP ICP; performance may vary with
instrument and should be independently verified.
(b) Values are certified by Inorganic Ventures INC. at 3x and 10x the approximate instrumental LOD [12].
(c) Bold values are qualitative only because of low recovery. Other digestion techniques may be more
appropriate for these elements and their compounds.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
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Center for Toxicology and Environmental Health, L.L.C.
5120 N. Shore Drive, North Little Rock, AR 72118 Phone: 501.801.8500 www.cteh.com
Appendix 2
Quality Assurance Project Plan
Enbridge Pipeline Crude Release
July 29, 2010
Prepared For:
Incident Command
Prepared By:
Center for Toxicology and Environmental Health, L.L.C.
5120 North Shore Drive
North Little Rock, AR 72118
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Table of Contents
1. Purpose 3
2. SCOPE AND OBJECTIVES 3
3. Project Organization and Responsibility 3
3.1. Project Organization 4
3.2. Responsibility for Quality Assurance and Quality Control 4
3.3. Qualified Individual (QI) 4
3.4. Pro j ect Manager 4
3.5. Laboratory Subcontractors 5
3.6. DATA QUALITY OBJECTIVES 5
3.7. Intended Data Use and Objectives 5
3.8. Data Quality/Measurement Objectives 5
3.9. Representativeness 6
3.10. Completeness 6
3.11. Comparability 6
3.12. Analytical Methods and DQOs 6
4. SAMPLING PROCEDURES AND FIELD MEASUREMENTS 7
5. SAMPLE HANDLING, DOCUMENTATION, AND CUSTODY 7
6. QUALITY ASSURANCE PROCEDURES FOR LABORATORY ACTIVITIES 7
7. QUALITY ASSURANCE PROCEDURES FOR FIELD ACTIVITIES 8
7.1. Internal Quality Control 8
7.2. Equipment 8
7.3. Sampling Equipment Decontamination 9
7.4. Calibration, Operation and Maintenance 9
7.5. Field Documentation 9
7.6. Procedures to Assess Precision, Accuracy, Completeness and Comparability. 9
7.7. Corrective Action 9
8. DATA REDUCTION, ASSESSMENT AND VALIDATION 9
8.1. Laboratory Data 9
8.2. Field Measurement Data 10
8.3. Data Management 10
8.4. Data Validations 10
9. AUDITS 10
9.1. Field Systems Audit 10
9.2. Laboratory Audit 11
10. CORRECTIVE ACTION 11
10.1. Immediate Corrective Action 11
10.2. Long-Term Corrective Action 11
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1. Purpose
This Quality Assurance Project Plan ("QAPP") has been prepared to provide assurance
that community air monitoring and sampling activities conducted as part of the
response to the Enbridge Pipeline crude oil release meet performance goals. In
addition, the methods and procedures described herein were developed in general
accordance with conventionally-accepted Quality Assurance and Quality Control
(QA/QC) objectives.
2. SCOPE AND OBJECTIVES
This QAPP represents the foundation of QA/QC that will be utilized to assess and
verify that sampling, testing, and analysis activities are executed in a manner
consistent with applicable guidance and conventional QA/QC objectives. The
procedures described in the QAPP are intended to assess the data generated in terms
of representativeness, precision, accuracy, completeness and comparability.
Details about the sampling methodologies can be found in the individual work plans
prepared for each activity type. Much of the field sampling QA/QC methodology and
rationale is described in the individual work plans and, for conciseness, is not
reproduced herein. Rather, this QAPP presents the following:
Project Organization and Responsibility
Data Quality Objectives
Sampling Procedures and Field Measurements
- Sample Handling, Documentation and Custody
- Quality Assurance Procedures for Laboratory Activities
Quality Assurance Procedures for Field Activities
- Data Reduction, Assessment and Validation
- Audits
Corrective Action
This QAPP is applicable to the work plans approved as of the date of this document.
To the extent that other work plans are written and approved that this QAPP is
applicable to, those activities will be incorporated by reference to the scope of the
QAPP herein.
3. Project Organization and Responsibility
This section describes the project organization and specifies personnel
responsibilities. The project organization presented in this section has been
developed to guide and assess the quality of sampling and testing procedures for
obtaining reliable data, and to facilitate effective communication and decision-making
during the project.
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3.1. Project Organization
The principal entities relevant to this QAPP that are involved in activities related to
the -Enbridge Pipeline Crude Release, and their respective roles, include the
following:
- Enbridge Energy - Responsible Party
- Unified Command Health and Environmental Representatives - review and
approval for procedures and deliverables
- Center for Toxicology and Environmental Health (CTEH] - complete all site
investigation work, including data validation.
- Sampling Manager - CTEH project manager responsible for sampling activities
3.2. Responsibility for Quality Assurance and Quality Control
The responsibilities of key members of the project team are summarized in the
following subsections.
3.3. Qualified Individual (Ql)
Enbridge Energy and their representatives will have full authority to direct, supervise,
and coordinate the project team, and to commit resources as deemed necessary. One
or more Enbridge Energy designates will be the focal point of communications for
contractual matters with the Project Managers and all subcontractors. The QI will
oversee all project planning and will review and approve project specifications, plans,
and procedures. The QI will have ultimate project responsibility for assuring that the
project is completed according to plan.
3.4. Project Manager
CTEH Sampling Managers will be responsible for the preparation of project plans,
specifications, and reports within their defined scope of work. The PMs will attend
meetings and conferences between Unified Command and any other project
participants. They will ensure that the necessary equipment, facilities, and staffing are
available to implement their portion of the project.
Sampling Managers are responsible for maintaining the schedule of the work and will
regularly advise the QI of the progress of the project. Each PM will provide direction
to the field staff and subcontractors involved in field sampling activities within his
scope so that the project is completed in accordance with the Work Plans and QAPP.
The PM will consult with any subcontractors to discuss compliance with the relevant
Work Plans and QAPP, and to evaluate corrective measures if problems occur.
The PM will also be responsible for the development and execution of QA/QC
activities in all phases of the project, including plan design, execution, data reduction,
and reporting for the scope of work. Each PM will serve as an in-house consultant to
the QI in the development of a project-specific internal QC system, as well as
providing an independent review of the project approach, methods and design.
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3.5. Laboratory Subcontractors
Integrated air samples will be sent to Galson Laboratories and, if resource limitations
require, Pace Analytical Services, Inc. and Air Toxics Ltd located in Syracuse. NY,
Minneapolis, MN, and Folsom, CA, respectively. Galson Laboratories is AIHA
Accredited, and Pace and Air Toxics are NELAP certified.
3.6. DATA QUALITY OBJECTIVES
This section on Data Quality Objectives (DQOs) presents the intended data usage and
QA objectives for the sampling and analysis that will be performed during the project.
The overarching DQO is to generate validated data that is suitable for its intended use.
3.7. Intended Data Use and Objectives
The data collected during field activities will be used to characterize the chemical
properties of media collected during the response. The data collected during field
activities will be used to characterize potential exposures of members of the public to
constituents potentially related to the release of oil from the Enbridge Energy
pipeline, by reporting on chemical constituents found in the environment at the time
and location of sample collection. The data may also be used to inform decisions
related to appropriate protective actions necessary to ensure health and safety of
members of the community.
3.8. Data Quality/Measurement Objectives
The purpose of DQOs is to establish a target level that can be measured against
whether data that is collected (through the sampling and analysis program) are of
appropriate quality to produce documented, consistent, and technically defensible
results. These results ultimately will define the characteristics and chemical
constituent concentrations present at the Site.
The quality of measurements made and the data generated will be evaluated in terms
of the following characteristics:
1. Representativeness
2. Precision and Accuracy
3. Completeness
4. Comparability
Specific objectives for each characteristic are established to develop sampling
protocols and identify applicable documentation, sample handling procedures, and
measurement system procedures. These objectives are established based on Site
conditions, objectives of the project, and knowledge of available measurement
systems. In addition, the following criteria for chemical sample handling and analysis
will help attain the DQOs:
- Standard chain-of-custody procedures
- Analytical testing will be performed according to approved laboratory
methods with data packages prepared that are consistent with Level 2 protocol
(a Level 3 and 4 CLP protocol may be required in some instances].
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3.9. Representativeness
Measurements will be made so that analytical results are as representative as
practical of the actual field conditions. Sampling protocols will be utilized to help
assure that samples collected are reasonably representative of the media present in
the field. Appropriate sample handling protocols, including such tasks as storage,
transportation, and preservation, will be used to protect the representativeness of the
samples gathered during the project. Proper documentation in the field and the
laboratory will verify whether protocols have been followed, and whether sample
identification and integrity have been preserved.
Representativeness will be assessed also by comparing the results of co-located
samples to determine the spread in the analytical results. The results of QC blanks
will be examined for evidence of contamination unrelated to the Site on sampling
activities. Such contamination may be cause for invalidation or qualification of
affected samples. Sample analytical data classified as "questionable" or "qualitative"
by any of the above criteria may be invalidated.
It is also anticipated that CTEH sampling activities in some instances may be
conducted in cooperation with EPA or other agency personnel. If available, results of
co-located samples may be evaluated to address representativeness of samples.
3.10. Completeness
The characteristic of completeness is a measure of the amount of valid data (or
samples) obtained as compared with the amount that was specified to be obtained
under normal conditions. The objective for completeness is to provide enough valid
data to ensure the goals of the field investigation are met. Completeness will be
evaluated for each sampling event specified relative to each activity on an individual
basis.
3.11. Comparability
The characteristic of comparability expresses the confidence that one set of analytical
data may be compared with another. Data sets that can be used for comparison
include results of studies conducted previously in the area. Comparability is
maintained by use of standard analytical methods, and units consistent with those
used in previous studies. Also, the personnel involved in data acquisition and
reduction must operate measurement systems within the calibrated range of the
particular instrument as well as utilize analytical methodologies that produce
comparable results. The comparability of field investigation tasks will be maintained
by following the applicable EPA Technical Guidance documents, and/or the applicable
Work Plan.
3.12. Analytical Methods and DQOs
Analytical testing will be performed according to the methods outlined in the
approved Work Plans.
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4. SAMPLING PROCEDURES AND FIELD MEASUREMENTS
The objectives of air sampling procedures and field measurements are to obtain
samples and measurements that are representative of the environment being
investigated. Through the use of proper sampling tools, sampling techniques, and
equipment decontamination procedures, the potential for cross contamination due to
trace levels of chemicals will be reduced. These procedures are described further in
the individual Work Plans.
5. SAMPLE HANDLING, DOCUMENTATION, AND CUSTODY
The purpose of specific procedures for sample handling, documentation and custody
is to maintain the integrity of samples during collection, transportation, analysis and
reporting. These procedures are necessary to validate the history of sample data,
from collection through reporting, by providing adequate documentation. The
sampling handling, documentation and custody procedures are provided in the
individual Work Plans. QA/QC checks will be performed during the field activities to
assess whether the procedures elaborated in the Work Plans are followed. An
appointed representative will perform the QA/QC check prior to packaging the
samples and transportation to the designated laboratory.
6. QUALITY ASSURANCE PROCEDURES FOR LABORATORY
ACTIVITIES
Qualified laboratories will perform chemical sample analyses of samples collected
under the direction of CTEH. Each laboratory maintains an internal Quality Assurance
Plan. These plans include the respective laboratory's internal QA/QC procedures that
cover all aspects of QA/QC during implementation of laboratory procedures. The
technical quality systems that are described in the Quality Assurance Plans include the
following:
Personnel Qualifications and Training
- Demonstration of Capability
Standard Operating Procedures
Documentation and Record-Keeping
- Analytical Test Methods and Procedures
Method Detection Limits
Method Quantitation Limits and Reporting Limits
- Traceability, Preparation of Standards, and Reference Materials
- Measurement Process
- QC Samples
- Control Charting
Performance Evaluation
- Corrective Action
- Preventative Maintenance
- Sample Handling and Management
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In addition, the plan includes the following information that will be utilized for this
project:
Test Procedures and Standard Operating Procedures Performed
Data Quality Acceptance Criteria
Calibration and QC Requirements
- Containers, Preservation, and Holding Times
Instrumentation, Software, and Applications
- Preventative Maintenance Schedule
- Training Certification Statements
QAPPs for each laboratory are attached.
7. QUALITY ASSURANCE PROCEDURES FOR FIELD ACTIVITIES
This section describes the general QA/QC procedures related to field activities during
the collection, handling, labeling, packaging, preservation, and custody of samples for
chemical analysis. Specific procedures for field activities are described in the
individual Work Plans. Field QA/QC samples will be used to verify that the sample
collection and handling process has not affected the quality of samples that will be
subjected to chemical analyses. This section discusses the preparation and collection
frequency of field QA/QC samples constituting of blanks and duplicates. This section
also provides a general guidance on maintaining QA/QC on the subsequent activities
to ensure the goals of the field activities are met.
7.1. Internal Quality Control
Field QA/QC samples will follow the procedures set forth below and in accordance
with the individual Work Plans. The required analyses and the amount of sample
needed to complete the analyses will be evaluated prior to the initiation of the
sampling event. The required quantity of sample matrix to perform all the analyses
will be collected.
Co-located Samples - True duplicates of many media types are not typically possible
because chemical constituents are rarely distributed uniformly in the media, even
within small volumes. For this reason, duplicate samples collected during this project
will be referred to as co-located samples. They are samples that are collected at the
same time and place.
Co-located samples will be collected for each media type at a rate of approximately
10% of samples collected or at least 1 duplicate sample per day per media type,
whichever is greater. USEPA region 5 has been invited to shadow field operations and
will collect co-located samples at a rate that they determine necessary.
7.2. Equipment
Appropriate tools and equipment will be utilized for collecting samples during the
field investigations. Using the correct equipment for sampling is important in meeting
the objectives of QA/QC. Laboratory supplied equipment such as sample containers
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are generally uncontaminated. However, a simple visual QA/QC check of any
containers in cases that were opened may identify certain potential issues. Sample
labels will be clearly printed in waterproof, indelible ink and placed directly on the
sample container^].
7.3. Sampling Equipment Decontamination
No sample equipment decontamination procedures are anticipated for this project.
7.4. Calibration, Operation and Maintenance
Instruments and equipment utilized for field measurements will be calibrated in
accordance with the frequency requirements and instrument manufacturer's
instructions. More frequent calibration may be performed if deemed appropriate.
Appropriate methods and calibration material (gases, etc.] will be used and the
procedures documented in the field records. The field measurement instruments will
be operated and maintained in accordance with the manufacturer's instructions and
industry standard specifications/procedures in order to maintain the consistency and
reliance of the measurement capacity of each instrument.
7.5. Field Documentation
Field logs, documentation forms, and calculation work sheets utilized during the field
investigations will be maintained accurately and in accordance with the requirements
of the individual Work Plans. Field logs and form may be collected in electronic
format, if deemed appropriate. Copies of paper field logs will be included in the
project reports as appropriate.
7.6. Procedures to Assess Precision, Accuracy, Completeness and
Comparability
No quantitative levels for precision and accuracy have been specified for field
measurements. However, proper maintenance and operation of instruments will be
followed to ensure instrument accuracy so that reliable results will be obtained.
Multiple readings and analysis of duplicate samples will be performed to measure the
precision of field measurements.
7.7. Corrective Action
If QA audits of data result in identification of unacceptable data, the field sampling
project manager will be responsible for developing and initiating corrective action.
Corrective action for sampling procedures may include evaluating and amending
sampling procedures or re-sampling.
8. DATA REDUCTION, ASSESSMENT AND VALIDATION
8.1. Laboratory Data
Reduction of laboratory measurements and laboratory reporting of analytical
parameters will be in accordance with the procedures specified for each analytical
method (i.e., perform laboratory calculations in accordance with the method-specified
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procedure). Upon receipt of the laboratory data, the data will be processed according
to the Data Management Plan (DMP) included as Appendix B.
8.2. Field Measurement Data
Project data personnel will perform assessment of field measurement data. Data
assessment will be performed (as appropriate) by checking calibration procedures
utilized in the field, evaluating duplicate and control sample analyses, and by
comparing the data to previous measurements obtained at the specific location. Large
variations, depending on matrix type, will be examined in association with changes in
local conditions and general trends. In some instances, instrument drift or
malfunction may be detected. If this is apparent, the data may be disregarded, but a
record of the evaluation will be maintained in the project records. If variations in data
cannot be explained, the data will be qualified and will be used for appropriate
purposes.
8.3. Data Management
Upon successful completion of the data assessment process, the data generated for
the investigations will be stored in a central location and/or database. Data
summaries and results will be submitted in accordance with the DMP. Further data
management details are provided in the DMP.
8.4. Data Validations
All data packages will receive a data package completion check from the
corresponding laboratory generating the data package to ensure that the deliverable
requirements specified for this project have been satisfied. A Level II data validation
will be performed on all sample delivery groups prior to release of the data. Third
party data reviews will be conducted on all data as the data are received to assess
whether the QC criteria established for the associated analytical methods established
for this project have been met. In addition, third party data Level IV validation will be
conducted on a minimum of 10 percent of the data packages generated. Further
details about data validation are included in the DMP.
9. AUDITS
Quality assurance audits will be performed to assess whether the QA/QC measures
are being utilized to provide data of acceptable quality. Further, audits will be
completed to verify that subsequent calculation, interpretation, and other project
outputs are checked and validated.
9.1. Field Systems Audit
Field auditors will visit field sampling teams periodically to observe the designated
control procedures that are set forth in this document and in the individual Work
Plans. These audits will address whether field tools, analytical instruments, and
reporting processes are selected and used to meet the requirements specified by the
project objectives stated in this plan and other project Work Plans. Equipment and
facilities provided for personnel health and safety will also be evaluated. Calibration
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and documentation procedures for instruments used in the field will receive special
attention. Field documentation and sample custody records will be reviewed. During
the audit, the sampling manager will review data handling procedures with the
appropriate personnel. Accuracy, consistency, documentation, and appropriate
selection of methodologies will be discussed.
9.2. Laboratory Audit
Laboratory audit procedures are described in the DMP.
10. CORRECTIVE ACTION
Corrective or preventive action is required when potential or existing conditions are
identified that may have an adverse impact on data quality. Corrective action can be
immediate or long term. In general, any member of the project staff who identifies a
condition adversely affecting quality can initiate corrective action by notifying in
writing their supervisor or the sampling manager. The written communication will
identify the condition and explain how it may affect data quality.
Corrective action in the field is the responsibility of the on-site staff. This includes
reviewing the procedures to be followed prior to sampling events and checking the
procedures taking place after the sampling event is completed. Corrective action with
regard to laboratory analyses is the responsibility of the selected laboratory.
10.1. Immediate Corrective Action
This type of corrective action is usually applied to spontaneous, nonrecurring
problems, such as instrument malfunction. The individual who detects or suspects
nonconformance to previously established criteria or protocol in equipment,
instruments, data, methods, etc., will immediately notify his/her supervisor. The
supervisor and the appropriate task leader will then investigate the extent of the
problem, if any, and take necessary corrective steps.
If a large quantity of data is affected, the sampling manager must prepare a
memorandum to the QI. These individuals will collectively decide on a course of
action to correct the deficiencies while the project continues to proceed. If the
problem is limited in scope, the task leaders will decide on a corrective action
measure, document the solution, and notify the sampling manager.
10.2. Long-Term Corrective Action
Long-term corrective action procedures are devised and implemented to reduce the
potential for the recurrence of a potentially serious problem. The sampling manager
and the QI will be notified of the problem and will conduct an investigation to
determine the severity and extent of the problem. Corrective actions may be initiated
as a result of other activities such as audits.
The sampling manager will be responsible for documenting all notification,
recommendations, final decisions, and notifying project staff and implementing the
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agreed upon course of action. The development and implementation of preventive
and corrective actions will be timed, to the extent possible, to minimize any adverse
impact on project schedules and subsequent data generation/processing activities.
However, scheduling delays will not override the decision to correct the data
collection deficiencies before proceeding with additional data collection. The
sampling manager also will be responsible for developing and implementing routine
program controls to minimize the need for corrective action.
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Enbridge Line 6B MP 608 Pipeline Release
Marshall, Michigan
Supplement to Sampling and Analysis Monitoring Plan
Ceresco Dam River Dredging
Enbridge Energy
Revised: October 7, 2010
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Table of Contents
1.0 Background .1
2.0 Purpose ...1
3.0 Water Sampling 1
4.0 Water Quality Monitoring 2
5.0 Analysis 3
Appendix A Manta 2 Multiprobe Calibration Procedures
Figures and Tables
Figure 1: Equipment Areas Map Attached
Figure 2: Equipment Areas Map .Attached
Figure 3: Sample and Dredge Locations Map Attached
Table 1: Water Quality Parameters and Proposed Action Values 2
Table 2: Analysis Parameters and Methods..................... ...3
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1.0 BACKGROUND
Region 5 EPA directed Enbridge Energy to dredge the Kalamazoo River in the area directly upstream of
the Ceresco Dam where submerged crude oil was identified on the stream bed. Dredging of the river bed
to remove submerged oil collected in river bed sediment will be performed. The collected sediment will
be pumped to a nearby de-watering bed and stored in a water permeable membrane. Water collected from
the sediment will be analyzed for benzene, toluene, ethyl benzene, and xylenes (BTEX). When analysis
of the water documents BTEX concentrations are below NPDES permit levels, the water will be
discharged back into the Kalamazoo River.
The Work Plan for Permanent Recovery of Submerged Oil and Oil-Contaminated Sediments at Priority
Locations and Ceresco Dam Dredging submitted as Attachment to the Supplemental Modification of the
Response Plan for Downstream Impact Area and the Source Area Response Plan dated October 3, 2010
describes the method for dredging including equipment to be used for this effort. Figures 1 and 2
attached to this document show equipment areas.
Sampling requirements for NPDES permit compliance is as follows:
Minimum
Maximum
Parameter
Limits for
Quality and
Concentration
Limits for
Quality and
Concentration
Frequency of
Analysis
Sample
Type
Intermediate Total BTEX
-
(report)
Weekly
Grab
Final Effluent BTEX
-
20 ug/L
Weekly
Grab
Total Lead
-
(report)
Weekly
Grab
Dissolved Oxygen
4.0 mg/1
-
Weekly
Grab
PH
6.5
9.0
Weekly
Grab
Equipment and Outfall
Inspections
-
(report)
3X Weekly
Visual
These test parameters are in accordance with, the NPDES Wastewater Discharge General Permit for
Petroleum Contaminated Wastewater Permit Certificate of Coverage Number MIG081158.
2.0 PURPOSE
This supplement to the Sampling and Analysis Plan (SAP) approved on August 2, 2010, and revised
August 17, 2010, serves to document the surface water sampling associated with the dredging operations.
Surface water samples will be collected upstream of the dredging operation, near the operations, and
downstream of the operation to assess water quality associated with the clean up operation. Samples will
be submitted for analysis at the end of each operational day as a batch. Analysis will be conducted by
Trace Analytical of Muskegon, Michigan. Identified sampling locations are included in Figure 3 attached
to this document.
3.0 WATER SAMPLING
Surface water samples will be collected in laboratory supplied certified clean glassware with method
appropriate preservatives as needed. Sample time, location, and conditions are recorded according to the
approved Sampling and Analysis Plan. Each sample is given a unique identification number using the
nomenclature outlined in the sampling plan.
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A toal of three samples locations will include one sample 500 feet upstream of dredging operations, one
sampledownstream of operations but upstream of the dam and one sample downstream of the dam just
west of the final containment measures. Samples will be collected at stream mid-depth from boat or other
means amenable to collection.
Samples will be collected at mid-operational shift during days 1 through 7 while active dredging activities
are occurring. Analytical results turn around time (TAT) will be next day. Sampling frequency after
seven (7) consecutive days will be determined by EPA OSC in consult with Enbridge..
Sample IDs and information are recorded on a Chain of Custody and sample custody is relinquished to
the laboratory for analysis.
4.0 WATER QUALITY MONITORING
Water quality parameters (pH, dissolved oxygen, specific conductivity, and temperature) will also be
measured and recorded during collection of each sample as prescribed in the Sampling and Analysis Plan.
Parameters will be collected from the same depth and at the same time as each surface water sample
during dredging operations and subject to the actionable values describe in Table 1. Oil sheen observed
during surface water collection will be documented. In addition, oil sheen observed being generated from
dredging operations will be immediately reported to Enbridge and Tetra Tech, who will determine the
necessary actions to prevent further release of sheen from the dredge area.
In addition to the water quality parameters collected with each sample, water quality parameters will also
be collected at one established location, downstream of dredging operations using a Eureka
Environmental Manta 2 Multiprobe (Manta) or similar device. It is expected that a Manta will be
deployed from a downstream location. Deployment locations and monitoring depth (shallow/surface,
mid-depth, or deep) will be determined with input from Company personnel and state and federal
agencies. The Manta will electronically log the water quality parameters at 15 minute intervals, 24 hours a
day, and deliver the data through cellular telemetry to a web-based database accessible to the interested
parties. The Manta will be calibrated in accordance with manufacturer's specifications and in accordance
with the calibration SOP (included in Appendix A) and can be set to alert (via text and/or email)
appropriate individuals should surface water quality parameters fall outside specified ranges established
by state and federal agencies (i.e., "actionable" values). The proposed actionable background turbidity
will be obtained daily from the upstream dredging operations.
Water quality parameters and proposed actionable values are presented in Table 1
Table 1
Water Quality Parameters and Proposed Actionable Values
Parameter
Proposed Actionable Value
Units
Temperature
NA1
°C
pH
6.5 < x > 9.0
Specific Conductivity
NA1
L S/cm
Dissolved Oxygen
4.0
mg/L
Turbidity
2x background levels
NTU
'NA-Not Applicable
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Dredging areas are identified in Figure 3 attached to this document.
5.0 ANALYSIS
Trace Analytical will analyze each sample using EPA and Standard Methods listed in Table 2.
Table 2: Analysis Parameters and Methods
Parameter
Method
Volatile Organic Compounds (VOCs)
SW846 8260
Semi-Volatile Organic Compounds (SVOCs)
SW846 8270
Gasoline Range Organics (GRO)
SW846 8015
Diesel Range Organcis (DRO)
SW846 8015
Oil Range Organics (ORO)
SW846 8015
Polychlorinated Biphenyls (PCBs)
SW846 8280
Michigan Metals and Titanium
SW846 6010, 7470
Total Organic Carbon (TOC)
SM5310
Hardness
SM2340
Total Suspended Solids (TSS)
SM2540
Laboratory instrument calibration will be maintained in conformance with EPA standards with
commercially produced standards.
Appropriate quality control samples will be periodically analyzed in accordance with the approved Data
Quality Management plan to ensure data defensibility.
-------
Appendix A
Manta 2 Multiprobe Calibration Procedures
-------
Sensor Specific Calibrations
pH
Use a two-point calibration using two (2) buffers, 7.00 and 10.0.
1. Rinse the sensors in DI water, discarding rinse into the decon bucket.
2. Rinses sensors with the first buffer (7.00).
3. Fill cup with the 7.00 buffer and upright the probe to immerse the sensors.
4. Follow the calibration instructions and discard the used solution into the decon
bucket.
5. Rinse the sensors with DI water. Discard rinse into decon bucket.
6. Rinse sensors with the second buffer (10.0).
7. Fill calibration cup with 10.0 buffer and upright probe to immerse the sensors.
8. Follow the calibration instructions on the instrument calibration screen and discard
the used solution into the decon bucket.
Specific Conductivity
Use a one (1) point calibration.
1. Rinse the sensors with DI water, discarding rinse into decon bucket.
2. Fill the calibration cup with the standard (appropriate to waters being sample). For
our purposes, 12,586 S/cm is the standard to be used.
3. Follow the calibration instructions on the instrument calibration screen and discard
the used solution into the decon bucket.
Turbidity
Use a two-point calibration, a zero and an approximate standard dependent upon water(s)
to be tested. For our purposes, we will use a standard solution of 400 NTU.
To Zero;
1. Rinse sensors twice with deionized water. Partially fill the calibrations cup with DI
water, close and shake vigorously. Discard rinse into decon bucket.
2. Fill the calibration cup with the zero turbidity standard, replace lid and upright the
Multiprobe to immerse the sensor in the solution.
3. Follow the calibration instructions on the instrument calibration screen and discard
the used solution into the decon bucket. .
To set the second point, repeat the steps above using a 400 NTU standard solution.
Discard used solutions into your decon bucket.
Dissolved Oxygen (DO)
Calibrate by setting the sensor's saturation point. Be sure to set the local Barometric
Pressure before calibrating DO.
1. Take a 1-liter jar and fill halfway with distilled water, screw on cap, and shake
vigorously for one (1) minute.
2. Remove cap and let jar stand for one (1) minute. This lets the tiny air bubbles float
out of the top.
3. Fill the calibration cup until the sensor is immersed in the aerated water, cap and
upright.
4. Wait a few minutes for the temperature and reading to equilibrate.
-------
5. Follow the calibration instructions on the instrument calibration screen and discard
the used solution into the decon bucket.
Fluorometer CDOM
Use a two-point calibration.
To Zero;
1. Rinse sensors twice with deionized water. Partially fill the calibrations cup with DI
water, close and shake vigorously. Discard rinse into decon bucket.
2. Fill the calibration cup with the zero standard, replace lid and upright the Multiprobe
to immerse the sensor in the solution.
3. Follow the calibration instructions on the instrument calibration screen and discard
the used solution into the decon bucket.
To set the second point, repeat the steps above using a relative standard solution. Discard
used solutions into your decon bucket.
-------
Figure 1: Equipment Areas Map
-------
¦
360'
f\)
O
o
27.5' TYP.
PROPOSED LAYDOWN AREA
SCMX-.
U
i
27.5' TYP"""
,,3'
iM-
rTrYTrYTTTYTl
Is.5' TYP
f
360'
f
SECTION A-A
Mf 10 SCME
7.5„
36.3'
200'
2 5
SUMP
30
6.5 TYP.
"4
SECTION B-B
N01 TO sc*e
V i
B5 su $
9 „ 1
H H
"I i|
xi» k. ii
¦ ¦ ¦!*
if
*«
»
,1
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o
¦fej
0
o
4)
N
O
<0
a
CO
*
CO
S
oo
fr.
0C9CNCO 8V
tJATl
AW
9/10
Gtum 8*
OAT]
AW
9/10
ococeo 8y
MK
C0>t
SOMX
I " =
!6
OUAWKi
1 1
n.ot
fWOJCCI K-Zoo
R.ver
4
«t( no.
-------
Figure 2: Equipment Areas Map
-------
-------
Figure 3: Sample and Dredge Locations Map
-------
urfaee^fl/ater
5.63 - South Area 37
Significant soft sediment with large amounts of submerged
"T—" oil (sheen and globules after agitation). .. ,
Surface Water/Mania
- . 1**1 W ' r
*fe
r-
^ 5.75 Nort^;
Large amounts of submerged oil (shee|n and globules after
agitation) but less soft sediment than south side, especially
^ near shore. Buoys dropped during polii^g to delineate
channel-side edge of submerged oil.
5.55 - North
Significant surface sheen made .submerged oil more difficult
to isolate, but similar setting to oppos'ite^side of channel.
Buoys dropped during poling to delineateNctTannel-side
edge of submerged oil. Upstream extent variable over
multiple';Visits. /
Surface Water/Manta
400 Feet
—I
1 inch =150 feet
Leaend
Observed Sheen/Globules After Poling
i _ i Priority Areas
O None Observed
Priority Area Approximate Containment (if known)
O Slight
Division Quarter Mile Grid
O Moderate
# Heavy
0 Air Sample Locations
@ Observed But Quantity Not Noted
O Surface Water
O Surface Water/Manta
Coordinate System: Michigan State Plane South
Horizontal Datum: NAD83
Vertical Datum: NAVD88
Units: International Feel
Aerial Phototyaphy from August 26. 2010
SAMPLING ANALYSIS PLAN
FIGURE 3 DREDGE AND SAMPLE LOCATIONS
Ceresco Dam
SUBMERGED OIL TASK FORCE
KALAMAZOO AND CALHOUN COUNTIES
MICHIGAN
Oct 3, 2010
TETRATECH
10/03/10 - K, Bellrichard/D. Lutz
E:\ArcMap Project Rles\ReportFigures\SAP_Figure3.mxd
-------
?
\ UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
August 16, 2011
Enbridge Energy, Limited Partnership
c/o Mr. Rich Adams
Vice President, Operations
Superior City Centre
Second Floor
1409 Hammond Ave.
Superior, Wisconsin 54880
Re: U.S. EPA Authorization to Discontinue Weekly Surface Water and Bi-Weekly
Sediment Sampling Requirement pursuant to the Administrative Order issued by U.S.
EPA on July 27, 2010, pursuant to §311(c) of the Clean Water Act (Docket No. CWA 1321-
5-10-001) and Supplement to the Administrative Order issued by U.S. EPA on September
23,2010
Dear Mr. Adams:
The United States Environmental Protection Agency (U.S. EPA) has directed Enbridge Energy,
Limited Partnership, Enbridge Pipelines (Lakehead) L.L.C., Enbridge Pipelines (Wisconsin), and
Enbridge Energy Partners, L.P. (herein collectively referred to as "Enbridge") to perform surface
water and sediment sampling during the response and recovery of oil released from Enbridge
Line 6B. U.S. EPA approved the requirements for surface water and sediment sampling in the
Enbridge Sampling and Analysis Plan, August 18, 2010.
On October 22, 2010, U.S. EPA and MDEQ agreed that reductions in the surface water and
sediment sampling may be appropriate (See Attachment 1) and that MDEQ should enter into a
long-term surface water and sediment sampling program with Enbridge.
On Thursday, August 4, 2011 U.S. EPA determined that the State of Michigan and Enbridge
have not yet agreed to a Sampling and Analysis Plan or a Surface Water and Sediment sampling
program. Therefore, Enbridge has continued to conduct the surface water and sediment sampling
pursuant to the U.S. EPA Order.
After review of the results obtained to date and the data objectives, Enbridge may discontinue the
surface water and sediment sampling currently being conducted as outlined in Attachment 1.
By way of a copy of this letter, U.S. EPA will inform MDEQ of this decision and if MDEQ
would like Enbridge to continue a surface water and sediment sampling program, MDEQ will
direct you accordingly.
If you have any questions regarding this letter, please contact me immediately at (231) 301-0559.
-------
Sincerely,
Ralph Dollhopf
Federal On-Scene Coordinator and Incident Commander
U.S. EPA, Region 5
Attachment
n L. Kirby-Miles, U.S. EPA, ORC
J. Cahn. U.S. EPA, ORC
J. Kimble, U.S. EPA
M. Durno, U.S. EPA
T. Edwards, U.S. EPA
S. Wolfe. U.S.EPA
Records Center, U.S. EPA, Reg. ¥
M. Duehamie, MDEQ
ML Alexander. MDEQ
2
-------
Attachment 1
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
MEMORANDUM
October 22, 2010
'Thru:
To:
From:
Ralph Doilhopf, U.S. EPA Incident Coir
Steve Wolfe, U.S. Ef A Monitoring Brar
Brian Schlieger. U.S. EPA Monitoring B
Brian Kelly, Operations Section Chief
Recommendation for reduction in Surface Water and Sediment Sampling for the
Enbridge Pipeline Release, Marshall, Calhoun County, Michigan
RE:
After review of the surface water (see attached pages for surface water summaries) and
sediment sampling results and under consultation with the Michigan Department of Natural
Resources and Environment (MDNRE), Water Resources Division, the following
recommendations are made concerning surface water and sediment sampling (effective
immediately):
SURFACE WATER SAMPLING DOWNSTREAM MORROW LAKE
On a weekly basis, Enbridge shall collect 1 surface water sample at the point nearest the
Morrow Lake Dam (location SW-126). If oil-related compounds are detected, the next sampling
event will include a sample from SW-126 and the next downstream location (SW-Q10),
This sample is being collected to show that oil from the Enbridge pipeline release has not gone
past Morrow Darn,
SURFACE WATER SAMPLING MORROW LAKE
The every other day sampling of the former U.S. EPA "Mud Puppy" locations will be
discontinued (locations ML-1 through ML-10).
Weekly sampling of 20 other locations within Morrow Lake are sufficient coverage for the Lake.
The Daily Mud Puppy sample results have not shown any changes over time during the course
of 3 months of sampling. Enbridge has chosen 20 locations throughout Morrow Lake that will
be sampled and provides ample coverage as discussed with MDNRE. All of the chosen
locations (which includes the 10 former Mudpuppy locations) have historical data associated
with them to show trends over time.
Weekly sampling of 11 locations co-located with the collection/containment structures related to
O&M will replace the current 23 sampling locations. The samples will be collected immediately
downriver of the collection/containment points.
SURFACE-WATER SAMPLING KALAMMTORjVER
Page 1 of 3
-------
0^'-'a"v>v
A
? J UNITED' STATES ENVIRONMENTAL PROTECTION AGENCY
MEMORANDUM
' H >1
Co-locating the sample points with the O&M structures were chosen as these areas have
petroleum contamination still associated with them and pose the greatest chance of ongoing
petroleum releases into the environment.
SEDIMENT SAMPLING MORROW LAKE
The former U.S. EPA "Mud Puppy" locations will be discontinued {locations ML-1 through ML-
10). Bi-weekly sampling of two locations will be sufficient coverage for Morrow Lake. The two
locations will be one at the entrance to the lake from the Kalamazoo River and one near the
• Lake Morrow Dam from the deeper part of the lake.
These locations are recommended by MDNRE as the most likely to have deposition.
SEDlMNISMjPLlNG KALAMAZOO RIVER
Sediment samples will be collected on a Bi-weekly basis along the Kalamazoo River. The
sediment samples will be co-located with the 11 new surface water sampling locations.
The sediment sample locations were co-located with the surface water sampling locations in
order to continue to monitor for submerged oil effects due to containing petroleum in discreet
areas.
Enbridge will provide a map annotating all of the new sampling locations.
ANALYTES
All samples will be analyzed for the following analytes:
TPH- DRO, GRO, ORO
Benzene
o- xylene
Naphthalene
1,2,3-Trimethylbenzene
Cycloheaxane
n-propylbenzene
Phenanthrene
1,2,4-Trimethylbenzene
Ethylbenzene
p-tsopropyl toluene
Mercury
1,3,5 Trimethyl benzene
Isopropylbenzene
Sec-Butyibenzene
Beryllium
2-Methylnaphthalene
m & p Xylene
Toluene
Iron
Molybdenum
Nickel
Titanium
Vanadium
Page 2 of 3
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
MEMORANDUM
DURATION
This recommendation is being made with the understanding that Enbridge will enter into a long-
term surface water and sediment sampling/monitoring program with MDNRE. New sampling
plans for surface water and sediment sampling developed by Enbridge and approved by
MDNRE will replace these recommendations.
NOTE: These recommendations do not affect any additional sampling that is being performed
for the dredging project, aeration projects, or any other submerged oi! project.
Page 3 of 3
-------
Surface Wafer Sampling Detections and Screening Summary
Monitoring Program Sample Locations
Enbridge Energy Pipeline 6B
Marshall, Ml
Geographic Zone
Sample
Location
Date
Sample ID
Amalyte
Result
p,g/L
Source of Lowest
Screening
Criterion
Lowest
Screening
Crtierion ^g/L
iDowiiitiintrofMoiTow Late 1
SW-205
07-Aug-10
WSQ8Q71541GP61
Lead
28
HNV-DW 14
SW-201
16-Aug-10
W508161122GAH1
Mercury
0,15 J
GSI . 0.0013
SW-009
17-A«g-10
W5Q8171225KW1
Mercury
0.281
GSI • 0.0013
SW-202
: ' • iep-10
WSF09111037JLS1
SIm. urmifr >««
rwercury
0.18.J
GSI 0.0013
SW-201
11-Sep-10
WSF09111314JLS1
Mercwy
0,047! i l
GSI : 0.0013
SW-131
13-Sep-10
WSF09131055RTV1
Mercury
0.13! J
0013
SW-205
13-Sep-10
WSF09131204RRD1
Mercury
0.028I
J
GSI i 0.0013
SW-200
21-Sep-10
WSF09211245JPN1
Mercury
0.01
J
I GSI |
; 0.0013 |
SW200
25-Sep-10
WSF09251015SDD1
Mercury
0,009;
J
GSI i 0.0013
sw-ooe
27-Sep-10
WSFQ9270930RTV1
Mercury
0.012;
J
GS! ! 0.0013
SW-131
2T-S®p-10
WSF09271035RTV1
Mercury
0,022!
J
GSI i 0.0013
SW-205
27-Sep-tO
WSF09271205RRD1
Mercury
0.016iJ
;i i 0.0013
SW-206
27-Sep-tO
WSF09271310RRD1
Bercuiy
0.011 iJ
' 0013
SW~2«
27-Sep-1G
WSF09271335RRD1
Mercury
0.011J
GSI ! 0.0013
Zone Total Number of
Exceedances ¦ 14 1
| Morrow Late 1
SW-111
0
1
5
WS08012000PDS1
Vanadium
98
12
SW-111
02-Aug-10
WS08021S50PDS1
Vanadiym
37
ESES3I
12
SW-111
17-Aug-tO
WS08170728RCM1
Mercury
0.079 J
GSI
0.00:
ML-1
Q1-5ep-10
WSE090103SOFML1
Mercury
0.06 J
GSI
0.0013
SW933
05-Sep-tO
W5E09050915MHS1
Mercwy
8,064 j
GSI
0.0013
SW-934
I
©
WSE0907102QJRP1
Mercury
0.022 J
GSI
0.00:
SW-933
10-Sep-10
WSE09101433RCM1
Mercury
0.43
GSI
0 0013
SW-938
1S-Sep-10
WSE0915143SJRP1
Lead
15
HNV-DW
14
SW-935
22-S«p-10
WSE09220833RCM1
Mercury
0.096 J
GSI
0.0013
SW-934
25-Sep-10
WSE0925093GARM1
Mercury
0.14 J
GSI
0.0013
SW937
27-Sep-10
WSE09271Q48RCM1
Mercury
0,025 J
GSI
0.0013
Zone Total Number of
!&c©edsuc'':"'; ¦= V;; j
Monitoring Sumirmy of Surface Wmr D«toeB mil Bceevkneesjtlax
-------
Surface Water Sampling Detections and Screening Summary
Monitoring Program Sample Locations
Enbridge Energy Pipeline 6B
Marshall, Mi
Geographic Zone
Sample
Location
Date
Sample ID
Analyte
Result
Pflli
fi ¦
| i
> i j
V *.
T.iii-i:.f.
:.;W-107 I 27»Sep-16 j Vte0092Tl 10 ••••.-• ¦ V-.- wy : 0.0ft- . 013
^Zmef^NumSv^Mmmdarms ®f
Ut'-.lr .sir. ?.'< :v,o: '• ,.'m-
SW-001
27-JuMO
WS07270938TJV1
Benzene
7
HNV-OW
>
SW-O02
27-JuMO
WS0727i(MOT,JV1
• . tzene
39
HNV-DW
¦¦¦¦
SW-003
27-JuHO
WS07271030TJV1
Benzene
32
BNV-DW
¦
SW-004
27-JtiHQ
WS0727110OTJV1
Beaten®
23
HNV-DW
SW-100
28-JuHO
WSO7282O40TED1
Phnnarithrerw
2.4
FCV
SW-116
03-Aug-t0
WS08031510PDS1
Vanadium
24
FCV/GSI
SW-115
03-AU8-10
'wsoiflQiiooPDii
Vanadium
140
FCV/GS1
12
SW-108
17-AUS-10
WS0B1714S5JRP1
Mercury
0,063 J
GSI
0,00 ¦
SW-103
25-SW-10
WSB09251121JLS2
Mercury
0.023 J
GSI
0.0013
SW-104
27-Sep-10
WS809271230PMB1
Mercury
0.009 J
GSI
0.0013
SW-002
02-Sep-10
WSC09021505JLS3
Mercury
0,2
GSI
0.0013
SWO03
17-Sep-IO
WSC08171616TDF1
Mercury
0.092 J
GSI
0.0013
SW-0Q3
27-S«p-10
WSC09271351JLS1
Mercury
0.01 J
GSI
0.0013
SW-108
VVSE0903060SSWA1
Mercury
0,017 J
GSI
0,0013
Zone Total Number of ExesBdanees =«
Notes;
UglL » micrograms per Iter
GSI = Groundwater Surface Water Interfiles Criterion {Table 2 of Attachment I of the RRDOp Memo No, 1»January 2009),
FCV " final Cronic Value Criterion {Rule S? Water Quality Values, December 2009),
HNV-ow » Human Noncancer Value Drtning Water Criterion (Rule 5? Water Quality Values, Decaniber 2009),
NA - criterion or value is not available, or riot applicable
Monitoring Summary of Sulfas® Water Detects and Excsedances-xlsx
2 of 3
-------
Surface Water Sampling Detections and Screening Summary
Monitoring Program Sample Locations
Enbridge Energy Pipeline 68
Marshall, Ml
Compound
Analysis Summary
Scaemirtf Summary
3
E1
1 S
12
5 ®
5 Q
"S
3> J3
f 1
3 ®
Z Q
15
® <®
ja S
E 3
3 l
140
Xylenes, Total
4.3
3?
1402
GSI
35
Semi-Volatile Organic* {pg/L);
2-Methy]naphthaIene
4,4
8
1546
FCV
19
Naphthalene
2.1
7
1S4S
FCV
__
Phenanthrene
24
5
1546
FCV
1.4
1
28-JuMQ
Upstream of Morrc
Matata fpfl/LJ;
Beryllium
1.7
88
1329
GSI
33
iron
11000
1300
1329
NA
_
Lead
h__
943
1167
HNV-DW
14
2
9/15/2010
Morrow Lake
Mercury
0.-53
29
1329
GSI
0.0013
" 29
9/27/2010
Morrow Lake
Molybdem
8.7
484
1010
HNV-DW
__
Nickel
72
__
1021
1513
FCV
125
Vanadium
749
1513
FCV/GSI
12
4
8/3/2010
Upstream of Porte
Notes:
ng/t - micrograms par liter
GSI = Groundwater Surface Water Interface Criterion (Table 2 of Attachment 1 of the RRD Op Memo No. 1, January 2008),
FCV = Final Cranio Value Criterion (Rule 57 Water Quality Values, December 2009).
HNV-DW = Human Moncancer Value Drilling Water Criterion (Rule 67 Water Quality Values, December 200S}.
NA - criterion or value is not available, or not applicable
Monttoring Summary of Surface WW»r Qelsefe and Exmeimmmxtm
1 of 1
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