July 2004
Environmental Technology
Verification Report


AANDERAA INSTRUMENTS, INC.
RCMMKllWITH
OPTODE 3830 MULTI-PARAMETER
WATER QUALITY PROBE/SONDE
                Prepared by
                 Battelle

                Banene
              Uw Business o/ Innovation

             In cooperation with the
      National Oceanic and Atmospheric Administration
                  _T^^y*

                   ^^ -
                  ''v^H ^^r*
          Under a cooperative agreement with


          U.S. Environmental Protection Agency

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                                         July 2004
 Environmental Technology Verification
                  Report

   ETV Advanced Monitoring Systems Center

       AANDERAA Instruments, Inc.
       ROM MkllwithOptode3830
Multi-Parameter Water Quality Probe/Sonde
                     by
                  Jeffrey Myers
                   Amy Dindal
                 Zachary Willenberg
                   Karen Riggs
                    Battelle
                Columbus, Ohio 43201

                     and

                  Paul Pennington
                  Michael Fulton
                  Geoffrey Scott

                  NOAA CCEHBR
              Charleston, South Carolina 29412

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                                       Notice
The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development, has financially supported and collaborated in the extramural program described
here. This document has been peer reviewed by the Agency and recommended for public release.
Mention of trade names or commercial products does not constitute endorsement or
recommendation by the EPA for use.

The National Oceanic and Atmospheric Administration (NOAA) does not approve, recommend,
or endorse any proprietary product or material mentioned in this publication. No reference shall
be made to NOAA in any advertising or sales promotion which would indicate or imply that
NOAA approves, recommends, or endorses any proprietary product or proprietary material
mentioned herein.
                                          11

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                                      Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the
nation's air, water, and land resources. Under a mandate of national environmental laws, the
Agency strives to formulate and implement actions leading to a compatible balance between
human activities and the ability of natural systems to support and nurture life. To meet this
mandate, the EPA's  Office of Research and Development provides data and science support that
can be used to solve environmental problems and to build the scientific knowledge base needed
to manage our ecological resources wisely, to understand how pollutants affect our health, and to
prevent or reduce environmental risks.

The Environmental Technology Verification (ETV) Program has been established by the EPA to
verify the performance characteristics of innovative environmental technology across all media
and to report this objective information to permitters, buyers, and users of the technology, thus
substantially accelerating the entrance of new environmental technologies into the marketplace.
Verification organizations oversee and report verification activities based on testing and quality
assurance protocols  developed with input from major stakeholders and customer groups
associated with the technology  area. ETV consists of seven environmental technology centers.
Information about each of these centers can be found on the Internet at http://www.epa.gov/etv/.

Effective verifications of monitoring technologies are needed to assess environmental quality
and to supply cost and performance data to select the most appropriate technology for that
assessment. Under a cooperative agreement, Battelle has received EPA funding to plan,
coordinate, and conduct such verification tests for "Advanced Monitoring Systems for Air,
Water, and  Soil"  and report the results to the community at large. Information concerning this
specific environmental technology area can be found on the Internet at
http ://www. epa.gov/etv/centers/center 1 .html.
                                           in

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                                 Acknowledgments
The authors wish to acknowledge the support of all those who helped plan and conduct the
verification test, analyze the data, and prepare this report. We would like to thank the National
Oceanic and Atmospheric Administration's (NOAA) National Ocean Service, National Centers
for Coastal Ocean Science staff at the Center for Coastal Environmental Health and
Biomolecular Research. In addition, NOAA's Coastal Service Center is acknowledged for
providing access to dock facilities on a tributary of Charleston Harbor for the saltwater testing,
as well as the South Carolina Department of Natural Resources for the use of its land and pier.
We also acknowledge the assistance of the ETV Advanced Monitoring Systems Center
stakeholders Christine Kolbe of the Texas Commission on Environmental Quality and
Paul Pennington and Geoff Scott of NOAA,  as well as James O'Dell and Linda Sheldon of the
U.S. Environmental Protection Agency.
                                          IV

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                                       Contents
                                                                                   Page


Notice	ii

Foreword 	 iii

Acknowledgments 	 iv

List of Abbreviations  	 viii

1 Background  	 1

2 Technology Description 	2

3 Test Design and Procedures  	3
       3.1  Introduction	3
       3.2 Test Site Characteristics 	3
       3.3  Test Design  	4
            3.3.1 Saltwater Testing 	7
            3.3.2 Freshwater Testing	 8
            3.3.3 Mesocosm Testing	9
       3.4  Reference Measurements	9

4 Quality Assurance/Quality Control	 11
       4.1  Instrument Calibration	 11
       4.2  Field Quality Control	 11
       4.3  Sample Custody	 11
       4.4  Audits 	 12
            4.4.1 Performance Evaluation Audit	 12
            4.4.2 Technical Systems Audit 	 12
            4.4.3 Audit of Data Quality	 13
       4.5  QA/QC Reporting  	 13
       4.6  Data Review 	 13

5 Statistical Methods	 15
       5.1  Calibration Check Accuracy  	 15
       5.2  Relative Bias 	 15
       5.3  Precision  	 16
       5.4  Linearity   	 16
       5.5  Inter-UnitReproducibility	 16

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6 Test Results	  17
      6.1  Calibration Check Accuracy  	20
      6.2  Relative Bias  	20
      6.3  Precision  	24
      6.4  Linearity  	25
      6.5  Inter-Unit Reproducibility	29
      6.6  Other Factors	39
            6.6.1 Ease of Use  	39
            6.6.2 Data Completeness	39

7 Performance Summary	40

8 References  	41

Appendix A Sample Printout, Data Reading Program 5059 	A-l
                                        Figures

Figure 2-1.   AANDERAA Oxygen Optode 3830	2
Figure 3-1.   Saltwater Site 	 5
Figure 3-2.   Freshwater Site	 5
Figure 3-3.   Mesocosm Tank  	6
Figure 3-4.   Saltwater Deployment	7
Figure 6-1.   Mk n with Optode 3830 Prior to Deployment  	 17
Figure 6-2.   Mk H with Optode 3830 After Saltwater Deployment 	 18
Figure 6-3.   Cleaned and Reconditioned Mk n with Optode 3830s in Storage Tank Used
             Between Deployments	 19
Figure 6-4.   Mkllwith Optode 3830 After Freshwater Deployment  	 19
Figure 6-5a.  Relative Bias Data for DO (Saltwater)  	21
Figure 6-5b.  Relative Bias Data for DO (Mesocosm)	21
Figure 6-5c.  Relative Bias Data for Temperature (Saltwater)  	22
Figure 6-5d.  Relative Bias Data for Temperature (Mesocosm)	22
Figure 6-5e.  Relative Bias Data for Turbidity (Saltwater)  	23
Figure 6-5f.  Relative Bias Data for Turbidity (Mesocosm)	23
Figure 6-6a.  Linearity Data for DO (Saltwater)	26
Figure 6-6b.  Linearity Data for DO (Mesocosm)  	  26
Figure 6-6c.  Linearity Data for Temperature (Saltwater)	27
Figure 6-6d.  Linearity Data for Temperature (Mesocosm)  	27
Figure 6-6e.  Linearity Data for Turbidity (Saltwater)	28
Figure 6-6f.  Linearity Data for Turbidity (Mesocosm)	28
Figure 6-7a.  Inter-Unit Reproducibility Data for DO During Saltwater Tests	30
Figure 6-7b.  Inter-Unit Reproducibility Data for DO During Freshwater Tests	31
Figure 6-7c.  Inter-Unit Reproducibility Data for DO During Mesocosm Tests	32
Figure 6-8a.  Inter-Unit Reproducibility Data for Temperature During Saltwater Tests	33
Figure 6-8b.  Inter-Unit Reproducibility Data for Temperature During Freshwater Tests .... 34
                                          VI

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Figure 6-8c.  Inter-Unit Reproducibility Data for Temperature During Mesocosm Tests .... 35
Figure 6-9a.  Inter-Unit Reproducibility Data for Turbidity During Saltwater Tests  	36
Figure 6-9b.  Inter-Unit Reproducibility Data for Turbidity During Freshwater Tests	37
Figure 6-9c.  Inter-Unit Reproducibility Data for Turbidity During Mesocosm Tests 	38
                                        Tables

Table 2-1.   Mk n with Optode 3830 Range, Resolution, and Accuracy
            as Provided by the Vendor	2
Table 3-1.   Water Characteristics at the Test Sites	4
Table 3-2.   Verification Test Schedule	6
Table 3-3.   Schedule for Saltwater Sample Collection—Tributary of Charleston Harbor  ....  8
Table 3-4.   Schedule for Freshwater Sample Collection—Rollings Wetlands 	  8
Table 3-5.   Schedule for Mesocosm Sample Collection	9
Table 3-6.   Maximum Sample Holding Times	  10
Table 4-1.   Replicate Analysis QC Criteria  	  12
Table 4-2.   Expected Values for Field Blanks  	  12
Table 4-3.   Summary of Performance Evaluation Audits	  12
Table 4-4.   Summary of Data Recording Process	  14
Table 6-1.   Calibration Check Accuracy  	20
Table 6-2.   Average Relative Bias Results for 1103 and 1104	24
Table 6-3.   Measurements and Percent Relative  Standard Deviations for
            1103 and 1104 During Stable Mesocosm Operation 	24
Table 6-4.   Average Absolute Difference Between 1103 and 1104 Readings for
            Each Parameter at Each Deployment Location  	29
Table 6-5.   Installation, Operation, and Maintenance Activities 	39
Table 7-1.   Summary of Performance	40
                                          vn

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                              List of Abbreviations
AMS
CCEHBR
DAS
DO
DSU
EPA
ETV
L
mg
mm
NIST
NOAA
NTU
PE
QA
QA/QC
QMP
RSD
ISA
Advanced Monitoring Systems
Center for Coastal Environmental Health and Biomolecular Research
data acquisition system
dissolved oxygen
data storage unit
U.S. Environmental Protection Agency
Environmental Technology Verification
liter
microMolar
milligram
millimeter
National Institute of Standards and Technology
National Oceanic and Atmospheric Administration
nephelometric turbidity unit
performance evaluation
quality assurance
quality assurance/quality control
Quality Management Plan
relative standard deviation
technical systems audit
                                        Vlll

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                                     Chapter 1
                                     Background
The U.S. Environmental Protection Agency (EPA) has created the Environmental Technology
Verification (ETV) Program to facilitate the deployment of innovative environmental tech-
nologies through performance verification and dissemination of information. The goal of the
ETV Program is to further environmental protection by substantially accelerating the acceptance
and use of improved and cost-effective technologies. ETV seeks to achieve this goal by provid-
ing high-quality, peer-reviewed data on technology performance to those involved in the design,
distribution, financing, permitting, purchase, and use of environmental technologies.

ETV works in partnership with recognized testing organizations; with stakeholder groups
consisting of buyers, vendor organizations, and permitters; and with the full participation of
individual technology developers. The program evaluates the performance of innovative tech-
nologies by developing test plans that are responsive to the needs of stakeholders, conducting
field or laboratory tests (as appropriate), collecting and analyzing data, and preparing peer-
reviewed reports. All  evaluations are conducted in accordance with rigorous quality assurance
(QA) protocols to ensure that data of known and adequate quality are generated and that the
results are defensible.

The EPA's National Exposure Research Laboratory and its verification organization partner,
Battelle, operate the Advanced Monitoring Systems (AMS) Center under ETV. The AMS Center
recently evaluated the performance of the AANDERAA Instruments,  Inc. RCM Mk n, housing
theOptode3830.

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                                         Chapter 2
                                  Technology Description
    The objective of the ETV AMS Center is to verify the performance characteristics of
    environmental monitoring technologies for air, water, and soil. This verification report provides
    results for the verification testing of the Mk n with Optode 3830 by AANDERAA Instruments,
    Inc. Following is a description of the Optode 3830, based on information provided by the
                           vendor. The information provided below was not verified in this test.
                           The Optode 3830 (Figure 2-1) uses a platinum porphyrin complex as a
                           dynamic fluorescence quencher to monitor oxygen in water. The
                           porphyrin complex is embedded in a gas-permeable foil that is
                           exposed to the surrounding water. A black optical isolation coating
                           protects the complex from sunlight and fluorescent particles in the
                           water. This sensing foil is attached to a sapphire window, providing
                           optical access for the measuring system from inside a watertight
                           titanium housing. The foil is excited by modulated blue light, and the
                           phase of a returned red light is measured. By linearizing and
                           temperature compensating with an incorporated temperature sensor,
                           the absolute oxygen concentration can be determined. The diameter of
                           the Optode 3830 is 36 millimeters (mm) (1.42 inches). It is  86 mm
                           (3.39 inches) long and weighs 0.23 kilograms (8.11 ounces). Pricing
                           information is available from the vendor.
                           The Mk n with Optode 3830 was verified for temperature, dissolved
Figure 2-1. AANDERAA   oxygen (DO), and turbidity.  The range, resolution, and accuracy, as
Oxygen Optode 3830       indicated by the vendor, for those parameters are listed below.

    Table 2-1. Mk II with Optode 3830 Range, Resolution, and Accuracy as Provided by the
    Vendor
Parameter
Air saturation
Oxygen
concentration
Temperature
Turbidity
Range
Oto 120%
0 to 500 ^Molar (nM)
-2.7 to 36.6°C
0 to 20 nephelometric
turbidity units (NTU)

Resolution

Accuracy

<0.4% <5%
<
0.
0.
1 (iM
1 % of range
1% of full scale
<8 nM or
±0.05°C
2% of full
5%, whichever

scale
is greater



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                                     Chapter 3
                            Test Design and Procedures
3.1 Introduction
This verification test was conducted according to procedures specified in the Test/QA Plan for
Long-Term Deployment of Multi-Parameter Water Quality Probes/Sondesm The purpose of the
verification test was to evaluate the performance of the Mk n with Optode 3830 under realistic
operating conditions. The Mk n with Optode 3830 was evaluated by determining calibration
check accuracy and by comparing Mk n with  Optode 3830 measurements with standard
reference measurements and measurements from handheld calibrated probes. Two Mk n with
Optode 3830s were deployed in saltwater, freshwater, and laboratory environments near
Charleston, South Carolina, during a 3  /^-month verification test. Water quality parameters were
measured both by the Mk n with Optode 3830 and by reference methods consisting of
collocated field-portable instrumentation and analyses of collected water samples. During each
phase,  performance was assessed  in terms of calibration check accuracy, relative bias, precision,
linearity, and inter-unit reproducibility.

The performance of the Mk n with Optode 3830 was verified in terms of the following
parameters:

•   DO
•   Temperature
•   Turbidity.
3.2 Test Site Characteristics

The three test sites used for this verification were selected in an attempt to expose the Mk n with
Optode 3830 to the widest possible range of conditions while conducting an efficient test. The
three sites included one saltwater, one freshwater, and one controlled location. Approximate
ranges for the target parameters at each of the test sites as determined by reference
measurements are given in Table 3-1.

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Table 3-1.  Water Characteristics at the Test Sites
Saltwater
Parameter
DO
Temperature
Turbidity
Low
3 milligrams/
liter (mg/L)
20°C
8NTU
High
6 mg/L
28°C
37NTU
Freshwater
Low
6.8 mg/L
ire
1.7NTU
High
11. 2 mg/L
27°C
3.6NTU
Mesocosm
Low
9.3 mg/L
9°C
0.4NTU
High
12.1 mg/L
16°C
15NTU
3.3 Test Design

The verification test was designed to assess the performance of multi-parameter water probes
and was closely coordinated with the National Oceanic and Atmospheric Administration
(NOAA) through the Center for Coastal Environmental Health and Biomolecular Research
(CCEHBR). The test was conducted in three phases at a saltwater site in a tributary of
Charleston Harbor; a freshwater site at the Hollings wetland on the CCEHBR campus; and a
controlled site at the CCEHBR mesocosm facility in Charleston, South Carolina. At each test
site, two Mk n with Optode 3830s were deployed as close to each other as possible to assess
inter-unit reproducibility. The first phase of the test was conducted at the saltwater site (Figure
3-1). The CCEHBR campus has access to the tributary of Charleston Harbor site, which is a
predominantly tidal body of water that receives some riverine input; its salinities range from 20
to 35 parts per thousand. The second phase of the test was conducted at the freshwater site
(Figure 3-2). The freshwater site was a wetlands area near the Hollings Marine Research
Laboratory, located on the CCHEBR campus. The third phase was conducted at the CCEHBR's
mesocosm facility (Figure 3-3). This facility contains modular mesocosms that can be classified
as "tidal" or "estuarine." The mesocosm phase included both saltwater and freshwater
conditions.

The precision measurements were performed before the Mk n with Optode 3830 was deployed
into the  saltwater environment. The Mk n with Optode 3830 was placed in a tank of saline water
inside the NOAA laboratory. While in this stable environment, the Mk n with Optode 3830
sampled at a rate of once per minute for approximately 30 minutes to collect data used in the
percent relative standard deviation (RSD).

The schedule for the various testing  activities is given in Table 3-2.

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Figure 3-1.  Saltwater Site
Figure 3-2. Freshwater Site

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           Figure 3-3. Mesocosm Tank
Table 3-2. Verification Test Schedule
                    Activity
      Date
 Vendor setup for saltwater phase
 Begin saltwater phase
 End saltwater phase
 Set up freshwater phase
 Begin freshwater phase
 End freshwater phase
 Vendor setup for mesocosm phase
 Begin mesocosm phase
 End mesocosm phase
 Return all equipment	
  October 1, 2003
  October 2, 2003
 October 30, 2003
 October 31,2003
November 4, 2003
December 8, 2003
December 9, 2003
December 10, 2003
  January 5, 2004
  January 8, 2004

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3.3.1  Saltwater Testing

The saltwater phase lasted for 28 days, during which time the Mk n with Optode 3830
monitored the naturally occurring range of the target parameters 24 hours per day at 10-minute
measurement intervals. Dockside reference measurements were made for DO and temperature,
while reference samples for turbidity were collected and returned to the laboratory for analysis.
Figure 3-4 shows the Mk n with Optode 3830s at the pier. The Mk n with Optode 3830s were
mounted on iron posts that were driven into the river bed. The Mk n with Optode 3830s were
approximately 0.5 meters apart in the shallows of the tidal river. Reference samples were
collected throughout the day during the test. For the duration of this phase, the Mk n with
Optode 3830s were deployed at depths between approximately one and 10 feet, varying
according to the tide. Table 3-3 shows the times and numbers of samples taken throughout the
saltwater test phase.
                  Figure 3-4. Saltwater Deployment

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Table 3-3.  Schedule for Saltwater Sample Collection—Tributary of Charleston Harbor
Test Day
1
7
8
14
15
22
26
27
28
29
Date
10/2/2003
10/8/2003
10/9/2003
10/15/2003
10/16/2003
10/23/2003
10/27/2003
10/28/2003
10/29/2003
10/30/2003
# Reference Samples

2
4
4
4
6
9
6
6

Activities
Deploy Mk II with Optode 3830s








Retrieve Mk II with Optode 3830s
3.3.2  Freshwater Testing

Freshwater testing was conducted at the wetlands on the CCEHBR campus and lasted 35 days.
As in the saltwater portion of the verification test, the Mk n with Optode 3830 monitored the
naturally occurring target parameters 24 hours per day, while reference measurements were
made and turbidity reference samples collected, again rotating among collection times. Table 3-4
shows the sampling times and number of samples collected throughout the freshwater test phase.
The Mk n with Optode 3830s were hung from a large post suspended several feet from the
bottom of the pond.

During this portion of the deployment, the salinity and stratification of the freshwater pond
increased. Natural weather and extreme tidal events caused the freshwater pond to become
brackish and highly stratified. Reference measurements taken at varying depths along the water
column during the first week of December showed significant stratification between the top and
bottom of the freshwater pond. As a result, the freshwater phase at the Rollings wetlands was
discontinued on December 8. The mesocosm deployment (Section 3.3.3) was extended to collect
data using a freshwater deployment.

Table 3-4. Schedule for Freshwater Sample Collection—Hollings Wetlands
Test Day
1
2
o
J
4
17
30
36
Date
11/4/2003
11/5/2003
11/6/2003
11/7/2003
11/20/2003
12/03/2003
12/08/2003
# Reference Samples

6
9
6
9
9
16
Activities
Deploy Mk II with Optode 3830s





Retrieve Mk II with Optode 3830s

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3.3.3 Mesocosm Testing
Mesocosm testing was performed over 27 days according to the schedule shown in Table 3-5.
Reference measurements were made and water samples were collected during each test day
throughout the normal operating hours of the facility (nominally 6 a.m. to 6 p.m.). During this
phase, the mesocosm was manipulated to introduce variations in the measured parameters. The
turbidity of the system was varied by operating a pump near the sediment trays to suspend
additional solids in the water. During the last three weeks of testing, saltwater was drained and
replaced with freshwater. These activities are detailed in Table 3-5.
Table 3-5. Schedule for Mesocosm Sample Collection
   Test Day
  Date
# Reference Samples
               Activities
      1
      4
      6
      9
     24
     27
12/10/2003
12/12/2003

12/13/2003
12/15/2003

12/16/2003
12/17/2003
12/18/2003
 1/2/2004
 1/5/2004
        4
        6
Deploy Mk II with Optode 3830s in saltwater
10:00 - Transition to freshwater (to change
conductivity)
Begin freshwater portion of deployment
11:05 - Turn off air bubblers and turn off
circulation pump
10:40 - Turn on circulation pump
10:50 - Add mud slurry (to change turbidity)
13:00 - Add additional mud slurry
15:11 - Turn off circulation pump
                   10:20 - Turn on air bubblers (to change DO)
                   Retrieve Mk II with Optode 3830s	
Variations in temperature and DO were driven by natural forces. Parameters over the ranges
specified in Table 3-1 were monitored by the Mk n with Optode 3830. Samples were collected
and analyzed using a reference method for comparison.
3.4 Reference Measurements
The reference measurements made in this verification test and the equipment used for these
measurements were as follows:
•   DO—National Institute of Standards and Technology (NIST)-traceable, commercially
    available probe (Orion 830A)
•   Temperature—NIST-traceable, handheld thermocouple and readout (Orion 830A)
•   Turbidity—Hach Ratio XR turbidity meter (Hach 43900).

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Reagents were distilled deionized water (for field blanks) and a Hach Ratio XR turbidity
standard from Advanced Polymer Systems. Sampling equipment consisted of 0.5- to 1.0-L glass
bottles, a Niskin sampling device provided by CCEHBR, and provisions for sample storage. The
maximum sample holding times are given in Table 3-6. All sample holding time requirements
were met.

Table 3-6.  Maximum Sample Holding Times

               Parameter                                Holding Time
   DO                                                      none(a)
   Temperature                                              none
   Turbidity	24 hours	
(^  "None" indicates that the sample analyses must be performed immediately after sample collection or in the water
   column at the site.
                                          10

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                                     Chapter 4
                        Quality Assurance/Quality Control
Quality assurance/quality control (QA/QC) procedures were performed in accordance with the
quality management plan (QMP) for the AMS Center(2) and the test/QA plan for this verification
test.(1)
4.1 Instrument Calibration

Both the portable and laboratory reference instruments were calibrated by CCEHBR according
to the procedures and schedules in place at the test facility, and documentation was provided to
Battelle.
4.2 Field Quality Control

Replicate samples were taken during field sampling for assessment of the reference methods.
The replicate samples were collected once each week during a regular sampling period by
splitting field samples into two separate samples (containers) and analyzing both by the same
laboratory reference methods. The results from the replicate analysis and the field blanks met the
criteria listed in Tables 4-1 and 4-2, respectively. A container of deionized water (field blank)
was taken to the field, brought back to the laboratory, and analyzed in the same manner as the
collected samples.
4.3 Sample Custody

Samples collected at the saltwater, freshwater, and mesocosm sites were transported by the
scientist performing the sampling at CCEHBR to the laboratory in an ice-filled cooler and
analyzed immediately; therefore, no chain-of-custody forms were required.
                                          11

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Table 4-1. Replicate Analysis QC Criteria
   Parameter
     Observed Agreement
   DO
   Temperature
   Turbidity
            ±5%
            ±1°C
           ±5NTU
Table 4-2. Expected Values for Field Blanks
   Parameter
Observed Maximum Difference
   Turbidity
            1NTU
4.4 Audits

4.4.1 Performance Evaluation Audit

A performance evaluation (PE) audit was conducted by the Battelle Test Coordinator once
during the verification test to assess the quality of the reference measurements. For the PE audit,
independent standards were used. Table 4-3 shows the procedures used for the PE audit and
associated results.

Table 4-3.  Summary of Performance Evaluation Audits
Audited
Parameter
DO
Temperature
Turbidity
Audit Procedure
Oakton 100 monitor
Orion 230 thermometer
Advanced Polymer Systems
turbidity standard
Acceptable
Tolerance
±5%
±rc
±10%
Actual
Difference
1.1%
0.0 °C
0.72%
Passed
Audit
Yes
Yes
Yes
The DO measurement made by the Orion 830A was compared with that from a handheld DO
Oakton 100 monitor. Agreement within 1.1% was achieved. The comparison was made with a
sample of collected water, and agreement was within 0.0°C. A NIST-traceable Orion 230
thermometer was used for the temperature performance audit. The Hach turbidity meter
measurements were compared with an independent turbidity standard. Agreement within 0.72%
was observed.

4.4.2  Technical Systems Audit

The Battelle Quality Manager conducted a technical systems audit (TSA) on October 28, 2003,
to ensure that the verification test was performed in accordance with the test/QA plan(1) and the
AMS Center QMP(2) As part of the audit, the Battelle Quality Manager reviewed the reference
                                         12

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methods used, compared actual test procedures to those specified in the test/QA plan, and
reviewed data acquisition and handling procedures. Observations and findings from this audit
were documented and submitted to the Battelle Verification Test Coordinator for response. The
records concerning the TSA are permanently stored with the Battelle Quality Manager.

During the verification test, two deviations from the test/QA plan were necessary. The first
occurred when natural weather events caused the freshwater pond to become brackish and
highly stratified, resulting in reference measurements that were not representative of the water
the Mk n with 3830 measured. An extended freshwater period, beginning on December 13,
2003, was added to the end of mesocosm deployment to provide data from a freshwater
deployment. Therefore, relative bias and linearity data were not collected at the freshwater site.
The data were collected from the mesocosm extension instead.  The second deviation occurred
when a problem with the Niskin sampler developed. The sampler broke after several uses at the
beginning of the saltwater period and was replaced as soon as possible. However, this
malfunction resulted in fewer  reference samples. The deviations had no impact on the results of
the test.

4.4.3  Audit of Data Quality

At least 10% of the data acquired during the verification test was audited. Battelle's Quality
Manager traced the data from  the initial acquisition, through reduction and statistical analysis,
to final reporting, to ensure the integrity of the reported results. All calculations performed on
the data undergoing the audit were checked.
4.5 QA/QC Reporting

Each assessment and audit was documented in accordance with Sections 3.3.4 and 3.3.5 of the
QMP for the ETV AMS Center.(2) Once the assessment report was prepared, the Verification
Test Coordinator ensured that a response was provided for each adverse finding or potential
problem and implemented any necessary follow-up corrective action. The Battelle Quality
Manager ensured that follow-up corrective action was taken. The results of the TSA were sent to
the EPA.
4.6 Data Review

Records generated in the verification test were reviewed within two weeks of generation before
these records were used to calculate, evaluate, or report verification results. Table 4-4 sum-
marizes the types of data recorded. The review was performed by a Battelle technical staff
member involved in the verification test, but not the staff member who originally generated the
record. The person performing the review added his/her initials and the date to a hard copy of
the record being reviewed.
                                           13

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Table 4-4.  Summary of Data Recording Process
     Data to be
     Recorded
 Responsible
    Party
  Where Recorded
     How Often
     Recorded
  Disposition of Data(a)
 Dates, times of test   CCEHBR
 events
 Test parameters
Battelle/
CCEHBR
 Mk II with Optode
 3830 data           CCEHBR
  - digital display     CCEHBR
  - electronic
    output
 Reference monitor    CCEHBR
 readings/reference
 analytical results
 Reference
 calibration data
 PE audit results
CCEHBR
 Battelle
               Laboratory record
               books/data sheets
Laboratory record
books/data sheets
Data sheets
Probe data acquisition
system (DAS); data
stored on probe down-
loaded to personal
computer

Laboratory record
book/data sheets or
data management
system, as appropriate
Laboratory record
books/data sheets/DAS
Laboratory record
books/data sheets/DAS
                       Start/end of test; at
                       each change of a test
                       parameter; at sample
                       collection
Each sample
collection
                                       Continuous
                                       10-minute sampling;
                                       data downloaded to
                                       personal computer
After each batch
sample collection;
data recorded after
reference method
performed

Whenever zero and
calibration checks are
done


At times of PE audits
Used to organize/check
test results; manually
incorporated data into
spreadsheets - stored in
test binder

Used to organize/check
test results; manually
incorporated data into
spreadsheets - stored in
test binder

Used to organize/check
test results; incorporated
data into electronic
spreadsheets - stored in
test binder
Used to organize/check
test results; manually
incorporated data into
spreadsheets - stored in
test binder

Documented correct
performance of reference
methods - stored in test
binder

Test reference methods
with independent
standards/measurements -
stored in test binder
 1 All activities subsequent to data recording were carried out by Battelle.
                                                   14

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                                     Chapter 5
                                 Statistical Methods
The statistical methods presented in this chapter were used to verify the performance parameters
listed in Section 3.1.
5.1 Calibration Check Accuracy

The Mk n with Optode 3830 was calibrated for each measured parameter at the beginning and
end of each deployment period according to the vendor's instruction manual. The results from
the calibration checks were summarized, and accuracy was determined each time the calibration
check was conducted. Calibration check accuracy (A) is reported as a percentage, calculated
using the following equation:

                                 A=l-(Cs-Cp)/CsxWO                               (1)

where Cs is the value of the reference standard, and Cp is the value measured by the Mk n with
Optode 3830. The closer^ is to 100, the more consistent the calibration check accuracy.
5.2 Relative Bias

Water samples were analyzed by both the reference method and the Mk n with Optode 3830,
and the results were compared. The results for each sample were recorded, and the accuracy was
expressed in terms of the average relative bias (B), as calculated from the following equation:
where CP is a measurement taken from the Mk n with Optode 3830 being verified at the same
time as the reference measurement was taken, and CR is the reference measurement. This
calculation was performed for each reference sample analysis for each of the three target water
parameters. In addition, relative bias was assessed independently for each Mk n with Optode
3830 to determine inter-unit reproducibility.
                                          15

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5.3 Precision

The standard deviation (S) of the measurements made during a period of stable operation at the
mesocosm was calculated and used as a measure of probe precision:
                          S =
                              n-1
(Ck-C)2
  k    '
                                                  1/2
(3)
where n is the number of replicate measurements, Ck is the concentration reported for the kth
measurement, and C is the average concentration of the replicate measurements.

Precision was calculated for each of the three target water parameters. Probe precision was
reported in terms of the percent RSD of the series of measurements.

                                           S
                                 %RSD =  =xlOO                                   (4)
                                           C                                         y '

5.4 Linearity

For target water parameters, linearity was assessed by linear regression, with the analyte
concentration measured by the reference method as an independent variable and the reading
from the analyzer verified as a dependent variable. Linearity is expressed in terms of the slope,
intercept, and coefficient of determination (R2). Linearity was assessed separately for each Mk n
with Optode 3830.
5.5 Inter-Unit Reproducibility

The results obtained from the two Mk n with Optode 3830s were compiled independently and
compared to assess inter-unit reproducibility. Inter-unit reproducibility was determined by
calculating the average absolute difference between the two Mk n with Optode 3830s. In
addition, the two Mk n with  Optode 3830s were compared by evaluating the relative bias of
each.
                                           16

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                                      Chapter 6
                                     Test Results
The results of the verification of the two Mk n with Optode 3830s (identified as 1103 and 1104
in this report) are presented in this section. The Mk n with Optode 3830 data were recorded at
10-minute intervals throughout the verification test. First, a visual record of the condition of the
Mk n with Optode 3830s pre- and post-deployment is discussed, then the statistical comparisons
are made. Finally, a record of the activities involved in servicing and maintenance of the Mk n
with Optode 3830s is presented.

Prior to the initial saltwater deployment, the Mk n with Optode 3830s were in "like-new"
condition. That is, they arrived from the vendor crated and ready for installation. Figure 6-1
shows one of the two Mk n with Optode 3830s in its pre-deployment condition. As deployed,
the end where the individual  probes are placed is exposed and oriented on top of the probe.
           (5)
                             (4)
       Figure 6-1. Mk II with Optode 3830 Prior to Deployment. Starting at the top
       center and proceeding clockwise: (1) close-up of clean Mk n with housing
       removed, (2) close-up of Optode 3830, (3) clean turbidity probe, (4) data storage
       unit, (5) Mk n dock with housing and protective side bars.
                                           17

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Following the saltwater deployment, the Mk n with Optode 3830s were retrieved from the water
and immediately returned to the laboratory to record the post-deployment condition.  Figure 6-2
shows the post-deployment condition of the Mk n with Optode 3830s. The Mk n with Optode
3830s were covered with a combination of green algae, silt, and some shell growth.
     Figure 6-2. Mk II with Optode 3830 After Saltwater Deployment. Both Mk H
     with Optode 3830s after being removed from the saltwater deployment (top), with
     close-ups of Mk n with Optode 3830 (left) and turbidity probe (right).
Prior to redeployment at the freshwater location, the Mk n with Optode 3830s were cleaned.
This consisted of gently rubbing the optical windows of the turbidity and oxygen probes with a
towel and 10% acetic acid solution. Then the Mk n with Optode 3830s were placed overnight in
a tank of oxygen-saturated water before deployment. Figure 6-3 shows the cleaned and
reconditioned Mk n with Optode 3830s in this tank.
                                          18

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              Figure 6-3. Cleaned and Reconditioned Mk II with
              Optode 3830 in Storage Tank Used Between Deployments

Finally, the condition of the Mk n with Optode 3830s after the freshwater deployment was
recorded and is shown in Figure 6-4. As can be seen from the photos, the Mk n with Optode
3830s appeared more fouled after the saltwater deployment than after the freshwater
deployment, both from biofouling and small marine life.
              Figure 6-4.  Mk II with Optode 3830 After Freshwater
              Deployment, with Close-up of Mk n with Optode 3830 (right)
                                         19

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6.1 Calibration Check Accuracy

The Mk n with Optode 3830s were calibrated only at the beginning of the test. The calibrations
were checked at the end of each deployment as instructed by the vendor. No check was
performed for temperature. Table 6-1 shows the results from these calibration checks for the
saltwater, freshwater, and mesocosm tests.

Table 6-1.  Calibration Check Accuracy

Deployment
Location Date
Saltwater 10/29/2003
Freshwater 12/9/2003
Mesocosm 1/13/2004
Calibration Check Accuracy (%)
1103
DO
98.9
98.9
99.7
Turbidity
30
1,500
NA(a)
1104
DO
97.3
95.6
83.9
Turbidity
18
800
520
^ Saturated; no data reported.

The accuracy shown in Table 6-1 is the comparison of how well the Mk n with Optode 3830s
held their calibration throughout the verification test. The Mk n with Optode 3830s were factory
calibrated; and, therefore, no adjustments to the calibrations were made during the verification
test. As shown in the table, the turbidity calibration check did not correlate well with the initial
calibration values. The Mk n with Optode 3830, as tested, used a turbidity probe that had a
maximum range of 20 NTU, which is designed for the most common use of these probes—open
ocean waters.

The calibration check accuracy for DO was consistently greater than 98.9% for the 1103. The
1104 measurements were consistently lower than the 1103 from the first day of deployment and
had a calibration check accuracy ranging from 83.9 to 97.3%.
6.2 Relative Bias

Relative bias (the percent difference between the Mk n with Optode 3830 measurements and the
reference measurements) was assessed by comparing the reference measurements with the 1103
and 1104 readings. The Mk n with Optode 3830 reading that was closest in time to the reference
sample was used. Plots of the 1103 and 1104 data, along with the corresponding reference
measurements that were used for the relative bias calculations, are shown in Figures 6-5a-f

No data are reported for the freshwater period because of the stratification that occurred. The
relative bias results are summarized in Table 6-2. The temperature measurements resulted in a
relative bias that was below 2% throughout the test. The oxygen relative accuracy was below
20% throughout the saltwater deployment and below 10% throughout the mesocosm
deployment. During saltwater deployment, the turbidity probe exhibited higher bias  because the
deployment conditions sometimes exceeded the Mk n with Optode 3830 range. These results
                                          20

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        « Reference
         1103
                                               Saltwater
                                                                                a  |  t
                                                                                n  &
 10/6/20030:00
                  10/11/20030:00
                                   10/16/20030:00        10/21/20030:00
                                            Date and Time
                                                                      10/26/20030:00
                                                                                       10/31/20030:00
Figure 6-5a.  Relative Bias Data for DO (Saltwater)
 £ 10
      * Reference
      • 1104
      41103
         I
                    5
                                              Mesocosm
12/10/20030:00    12/15/20030:00    12/20/20030:00
                                           12/25/20030:00
                                           Date and Time
                                                          12/30/20030:00     1/4/20040:00      1/9/20040:00
Figure 6-5b.  Relative Bias Data for DO (Mesocosm)
                                              21

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       • Reference
        1103
       a 1104
                                         Saltwater
 10/6/2003 0:00
                 10/11/20030:00       10/16/20030:00       10/21/20030:00
                                           Date and Time
                                                                  10/26/20030:00
                                                                                   10/31/20030:00
Figure 6-5c. Relative Bias Data for Temperature (Saltwater)
       * Reference
        1104
       A 1103
                                         Mesocosm
  12/10/20030:00    12/15/20030:00    12/20/20030:00    12/25/20030:00     12/30/20030:00
                                           Date and Time
                                                                      1/4/20040:00     1/9/20040:00
Figure 6-5d. Relative Bias Data for Temperature (Mesocosm)
                                            22

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        * Reference
        • 1103
        A1104
                                              Saltwater
  10/6/20030:00       10/11/20030:00       10/16/20030:00       10/21/20030:00
                                            Date and Time
                                                                     10/26/20030:00
                                                                                      10/31/20030:00
Figure 6-5e.  Relative Bias Data for Turbidity (Saltwater)
       • Reference
         1104
       41103
            n
            n
            £
                       A 9
                                              Mesocosm
 12/10/20030:00    12/15/20030:00    12/20/20030:00
                                           12/25/20030:00
                                           Date and Time
Figure 6-5f. Relative Bias Data for Turbidity (Mesocosm)
                                                         12/30/20030:00     1/4/20040:00     1/9/20040:00
                                              23

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Table 6-2. Average Relative Bias Results for 1103 and 1104

Parameter
DO
Temperature
Turbidity
Saltwater
1103 (%) 1104 (%)
-19.7 -13.8
-0.99 -1.76
54.2 69.0
Mesocosm
1103 (%)
-6.79
-1.76
-521
1104 (%)
6.61
-1.51
-452
occurred during deployments where the parameter being measured changed throughout the day.
Since the Mkn with Optode 3830 recorded at intervals of 10 minutes, there could have been as
much as 5 minutes' difference between the time of the reference sample and the nearest recorded
Mk n with Optode 3830 data. Because of this temporal effect, between 1% and 3% of the
relative bias calculations may be attributable to the differences seen between the two
measurements. In addition, when combined with the manufacturer's specifications for the
accuracy of the reference measurements of 2%, a total of up to 5% difference may be due to the
combined temporal effects and inherent accuracy of the reference measurements.
6.3 Precision

Table 6-3 shows the results of calculations taken from measurements performed before the
saltwater deployment. The precision, reported as %RSD, was less than 3% for temperature and
DO. Data from turbidity resulted in higher %RSDs (24.4 and 26.8) possibly as a result of the
fact that measurements were near the zero point and particles moving into the detector's view
would cause a measurement to spike, despite all attempts to keep the test conditions constant.
Table 6-3. Measurements and Percent Relative Standard Deviations for 1103 and 1104
During Stable Mesocosm Operation



Maximum
Minimum
Standard
Deviation
Average
%RSD
1103
DO
(mg/L)
308
294

3.99
303
1.32
Temperature
(°C)
17.8
16.4

0.377
17.1
2.20
Turbidity
(NTU)
2.3
0.387

0.38
1.41
26.8
1104
DO
(mg/L)
314
305

2.32
311
0.73
Temperature
(°C)
17.7
16.2

0.474
16.9
2.80
Turbidity
(NTU)
2.5
0.387

0.35
1.45
24.4
                                          24

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6.4 Linearity

Linearity was assessed by comparing probe readings against the reference values for each of the
parameters at each deployment location. Figures 6-6a-f give the results of this comparison by
showing the slope, intercept, and coefficient of determination (R2) for each parameter. Linearity
and regression coefficients indicated the best agreement between the Mk n with Optode 3830
readings and reference values for temperature. During the saltwater deployment, the DO
measurements resulted in slopes between 0.70 and 0.74 and regression coefficients between 0.76
and 0.79 over a range of 3 to 6 mg/L. During the mesocosm deployment, the Mk n with Optode
3830 demonstrated less linear behavior, with the slopes and regression coefficients both
decreasing for DO. Finally, when the turbidity sensor was within its working range and not
obstructed (as was 1103 during the mesocosm deployment), the measurements resulted in a
slope of 0.99 and a regression coefficient of 0.93 over a range of 0.4 to 15 NTU.
                                          25

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                                       Reference DO (mg/L)
    Figure 6-6a.  Linearity Data for DO (Saltwater)
               1103 Linear Regression
  _ 18
                y=0.3634x +7.0959
                   R2 = 0.2757

              1104 Linear Regression
                y= 1.2668X + 2.1114
                  R2 = 0.0663
                                     D      10.5      1
                                      Reference DO (mg/L)
Figure 6-6b.  Linearity Data for DO (Mesocosm)
                                           26

-------
          •  1103
          A  1104
         	1103
          - - 1104
1103 Linear Regression
 y= 1.0459X-0.7295
    R2 = 0.9809
                  1104 Linear Regression
                   y= 1.0368X-0.3761
                      R2 = 0.9787
                               22           24
                                    Reference Temperature (C)
 Figure 6-6c.  Linearity Data for Temperature (Saltwater)
                                   Reference Temperature (C)
Figure 6-6d. Linearity Data for Temperature (Mesocosm)
                                            27

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                   1103 Linear Regression
                    y=0.5485x-2.2404
                       R2 = 0.6367
  5. 15
                   1104 Linear Regression
                    y=0.4721x-3.5261
                       R2 = 0.5378
                              15          20          25           30
                                       Reference Turbidity (NTU)
Figure 6-6e.  Linearity Data for Turbidity (Saltwater)
                     1103 Linear Regression
                      y=0.5485x-2.2404
                         R2 = 0.6367
                     1104 Linear Regression
                       y=0.4721x-3.5261
                         R2 = 0.5378
                               15         20         25
                                        Reference Turbidity (NTU)
    Figure 6-6f. Linearity Data for Turbidity (Mesocosm)
                                                 28

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6.5 Inter-Unit Reproducibility

Inter-unit reproducibility was assessed both by comparing the relative bias of the two Mk n with
Optode 3830s (Section 6.2) and by comparing the average absolute differences between the two
Mk n with Optode 3830 readings for each parameter at each deployment location. Freshwater
results are included because the two  Mk n with Optode 3830s were deployed to the same depth.
Figures 6-7 through 6-9 show the data used for these calculations. These calculations were made
for the readings where there was an analogous reference measurement only. The results of
average difference comparisons are shown in Table 6-4, where "n" is the number of
measurements.

Table 6-4.  Average Absolute Difference Between 1103 and 1104 Readings for Each
Parameter at Each Deployment Location


Location
Saltwater
Freshwater
Mesocosm
Average
Average
DO
(mg/L)
1.02
1.42
1.78
1.41


3,
5,
3,

Absolute Difference Between 1103

n
328
188
888

Temperature
TO
0.16
0.04
0.03
0.08


4,
5,
3,


n
192
188
888

and 1104 Readings
Turbidity
(NTU)
3.12
10.9
7.26
7.08


4,
5,
3,


n
192
188
888

The DO difference between the two Mk n with Optode 3830s tested averaged 1.41 mg/L
(Figures 6-7a-c). The average difference in temperature readings was 0.08°C. The average
difference in turbidity readings was 7.08 NTU.

The magnitude of the inter-unit reproducibility results for turbidity was affected by the apparent
saturation of the 1103 sensor during the freshwater test.
                                          29

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  B>



  O
  Q
    9/26/2003     10/1/2003     10/6/2003     10/11/2003    10/16/2003    10/21/2003    10/26/2003     10/31/2003    11/5/2003

    12:00 AM     12:00 AM     12:00 AM     12:00 AM     12:00 AM      12:00 AM      12:00 AM     12:00 AM     12:00 AM

                                                    Date and Time



Figure 6-7a. Inter-Unit Reproducibility Data for DO During Saltwater Tests (Between October 20 and October

26, 2003, extremely low tides caused the equipment to come out of the water.)

-------
    14
    12
   10/26/2003    10/31/2003    11/5/2003     11/10/2003
   12:00 AM     12:00 AM     12:00 AM     12:00 AM
11/15/2003
 12:00 AM
11/20/2003
 12:00 AM
11/25/2003   11/30/2003    12/5/2003     12/10/2003
 12:00 AM     12:00 AM     12:00 AM     12:00 AM
                                                         Date and Time
Figure 6-7b.  Inter-Unit Reproducibility Data for DO During Freshwater Tests

-------
to
               12/5/200312:00  12/10/200312:00 12/15/200312:00  12/20/200312:00  12/25/200312:00  12/30/200312:00  1/4/200412:00   1/9/200412:00
                    AM             AM            AM            AM            AM             AM             AM            AM
                                                                    Date and Time
             Figure 6-7c. Inter-Unit Reproducibility Data for DO During Mesocosm Tests

-------
    9/26/2003
    12:00 AM
10/1/2003
12:00 AM
10/6/2003
12:00 AM
10/11/2003
 12:00 AM
 10/16/2003
  12:00 AM
Date and Time
10/21/2003
 12:00 AM
10/26/2003
 12:00 AM
10/31/2003
 12:00 AM
11/5/2003
12:00 AM
Figure 6-8a. Inter-Unit Reproducibility Data for Temperature During Saltwater Tests

-------
    26.0
    24.0
    12.0
    10/26/2003   10/31/2003    11/5/2003
     12:00 AM     12:00 AM    12:00 AM
11/10/2003    11/15/2003   11/20/2003   11/25/2003   11/30/2003
 12:00 AM    12:00 AM     12:00 AM     12:00 AM     12:00 AM
                Date and Time
12/5/2003    12/10/2003
12:00 AM     12:00 AM
Figure 6-8b. Inter-Unit Reproducibility Data for Temperature During Freshwater Tests

-------
  12/5/200312:00  12/10/200312:00 12/15/200312:00  12/20/200312:00 12/25/200312:00 12/30/200312:00   1/4/200412:00   1/9/200412:00
      AM           AM            AM            AM           AM           AM            AM           AM
                                                   Date and Time
Figure 6-8c. Inter-Unit Reproducibility Data for Temperature During Mesocosm Tests

-------
       40
               -1103
               1104
       35 -H  • Reference
       30
                                                                              klkllllIllkl
      9/26/2003     10/1/2003     10/6/2003     10/11/2003    10/16/2003     10/21/2003     10/26/2003    10/31/2003     11/5/2003
      12:00 AM     12:00 AM     12:00 AM      12:00 AM      12:00 AM     12:00 AM      12:00 AM      12:00 AM      12:00 AM
                                                        Date and Time
Figure 6-9a. Inter-Unit Reproducibility Data for Turbidity During Saltwater Tests

-------
     25 -i
     20
    10/26/2003    10/31/2003    11/5/2003    11/10/2003   11/15/2003    11/20/2003    11/25/2003    11/30/2003     12/5/2003     1
    12:00 AM     12:00 AM     12:00 AM     12:00 AM     12:00 AM     12:00 AM     12:00 AM     12:00 AM     12:00 AM
                                                           Date and Time

Figure 6-9b.  Inter-Unit Reproducibility Data for Turbidity During Freshwater Tests

-------
oo
               12/5/200312:00  12/10/200312:00 12/15/200312:00  12/20/200312:00 12/25/200312:00  12/30/200312:00  1/4/200412:00   1/9/200412:00
                    AM            AM            AM            AM             AM            AM             AM            AM
                                                                   Date and Time

           Figure 6-9c. Inter-Unit Reproducibility Data for Turbidity During Mesocosm Tests

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6.6 Other Factors

6.6.1  Ease of Use

The Mk n with Optode 3830 was installed and deployed by CCHEBR staff with the oversight of
AAKDERAA during installation and Battelle during deployment. Once the Mk n with Optode
3830s were deployed, the vendor adopted a "hands off' approach for the remainder of the test.
No maintenance was required. Data were collected to a personal computer by removing the data
storage unit (DSU) from the Mk n with Optode 3830 and plugging it into a serial cable supplied
by the vendor. AANDERAA-supplied software (Data Reading Program 5059, Version 1.00
build 84) was used to communicate with the DSU, which performed without a problem. The
software allowed the data to be converted to ASCII format for inclusion in external data
processing software. A sample printout from the software is shown in Appendix A. The Mk n
with Optode 3830 required minimal interaction by operators during the test. Those interactions
that did occur are described in Table 6-5.

Table 6-5. Installation, Operation, and Maintenance Activities
Date
10/1/2003
10/2/2003
10/30/2003
10/31/2003
11/4/2003
12/8/2003
12/8/2003
12/10/2003
1/5/2004
1/5/2004
1/5/2004
Total
Service Time Activity
— Vendor representatives arrived on site.
— Mk II with Optode 3830 deployed.
— Mk II with Optode 3830 collected.
60 minutes Data downloaded.
— Mk II with Optode 3830 deployed.
— Mk II with Optode 3830 collected.
60 minutes Data downloaded.
— Mk II with Optode 3830 deployed.
— Mk II with Optode 3830 collected.
15 minutes Data downloaded.
— End of test.
135 minutes
6.6.2  Data Completeness

All of the required data were recorded during this verification. The two Mk n with Optode
3830s submitted for this test collected data at 10-minute intervals from October 1, 2003, until
January 5, 2004, without any interruption in data collection. One hundred percent of the
required data was collected by the Mk n with Optode 3830.
                                          39

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                                     Chapter 7
                              Performance Summary
Two Mk n with Optode 3830s were evaluated in saltwater, freshwater, and mesocosm
environments between October 2, 2003, and January 5, 2004. These Mk U with Optode 3830s
measured DO, temperature, and turbidity in water at 10-minute intervals throughout these
deployments. Table 7-1 summarizes the performance of the Mk U with Optode 3830s.

Table 7-1. Summary of Performance
Statistical
Measure
Calibration
check
accuracy1-3'
Average relative
bias(c)
Average
precision
Parameter
DO (%)
Turbidity (%)
DO (%)
Temperature (%)
Turbidity (%)
DO (%RSD)
Temperature
(%RSD)
Turbidity (%RSD)
Linearity
Inter-unit
reproducibility
DO (mg/L)
Temperature (°C)
Turbidity (NTU)
1103
Saltwater Freshwater Mesocosm
98.9 98.9 99.7
30 1,500 NA®
-19.7 -(d) -6.79
-0.99 -(d) -1.76
54.2 -(d) -521
1103
1.32
2.20
26.8
1104
Saltwater Freshwater Mesocosm
97.3 95.6 83.9
18 800 520
-13.8 -(d) 6.61
-1.76 -(d) -1.51
69.0 -(d) -452
1104
0.73
2.80
24.4
Best agreement between readings and reference values was for temperature.
During the saltwater deployment, the DO measurements resulted in slopes
between 0.70 and 0.74 and regression coefficients between 0.76 and 0.79 over
a range of 3 to 6 mg/L. During the mesocosm deployment, slopes and
regression coefficients both decreased. Finally, when the Mk II was within its
range, the turbidity measurements resulted in a slope of 0.99 and a regression
coefficient of 0.93 over a range of 0.4 to 15 NTU.
Average Difference Between 1103 and 1104 Readings
Saltwater Freshwater Mesocosm
1.02 1.42 1.78
0.16 0.04 0.03
3.12 10.9 7.26
B' The closer the percentage is to 100, the better.
^ Saturated; no data reported.
^ The closer the percentage is to zero, the better
^ Stratification; no data reported.
                                          40

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                             Chapter 8
                             References
Test/QA Plan for Long-Term Deployment of Multi-Parameter Water Quality
Probes/Sondes, Battelle, Columbus, Ohio, Version 1.0, May 2002.

Quality Management Plan (QMP) for the ETV Advanced Monitoring Systems Center.,
Version 4.0, U.S. EPA Environmental Technology Verification Program, Battelle,
Columbus, Ohio, December 2002.
                                  41

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      Appendix A
     Sample Printout
Data Reading Program 5059
           A-l

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Fife  Edit  Library  View  Window  Help
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S Raw Data List [III Engineering List |
Record iDate&Time j 1. Reference | :. Current Speed
D 01.
01,
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01.
01,

01,
01.
01,
01,
0 01,
1 01,
2 01,
3 01,
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9 01,
20 01,
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0 01,
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46 01,
47 01,
48 01.
49 01,
50 01,
51 01,
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53 01.
54 01,
55 01.
56 01.
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58 01.
0.200307:27... 42
0.200=107:37... 42
0.200307:47... 42
U..200-3 07:57.., 42
0.200:i 03:07... 42
0.200308:17... 42
0.200308:27... 42
0,200308:37... 42
0.200308:47... 42
0.200308:57... 42
0.200309:07... 42
0.2003 09! 17... 42
0.200309:27... 42
0.200309:37... 42
Li. 200309:47.., 42
0.200309:57... 42
0.2003
0.2003
0.200:;
Q.2Q03
0.2003
0.2003
0.2003
0.2003
0.200-3
0.2003
0.2003
0.2003
9.2003
0.2003
0.2003
0.2003
0.2003
0.200-3
0.200-3
0.2003
0.2003
0.2003
0.2003
0.2003
0.2003
0.2003
0.2003
0.200-::
0.2003
0.2003
0.2003
0.200-3
0.2003
0.2003
0.200-3
0.2003
0.2003
0.2003
0.2003
0.2003
0.2003
0.200-3
0.2003
0:07... 42
0(17... 42
0:27... 42
0:37... 42
0:47... 42
0:57... 42
H07... 42
1:17... 42
1:27... 42
1:37... 42
1(47... 42
1:57... 42
2;07.,, 42
2:17... 42
2:27... 42
2:37... 42
2:47... 42
2:57... 42
3:07... 42
3;17... 42
3i27... 42
3:37... 42
3:47... 42
3:57,. , 42
4:07... 42
4:17... 42
4:27... 42
4:37... 42
4:47... 42
4:57... 42
5:07.,, 42
5:17... 42
5:27... 42
5;37.,, 42
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5:57... 42
6:07.., 42
6:17... 42
6:27... 42
6:37... 42
6:47... 42
6:57... 42
7:07... 42
0
12.0253
2.0531
13.4918
27.5702
J. Current Direct, ,, | 4. Temperature 5. Conduct rvstv 1 6, Oxygen | 7, Turbidity 8. Signal strenqht 1 9. Tilt J *]
21,1926 0 269.053 0.344464 0 0
58.984 21.4837 0 267,1 1,89015 -39.9993 44...,
47.029 20.1941 0 268.565 1,36102 -39.9993 38...,
04.425 19,7132 0 271,495 1,30789 -39.9993 39...,
20,453 19.2017 0 273.448 22,4703 -39.8:32 36.,,,
19.9444 93.5256 18.9783 0 274,913 22,4703 -39.9993 36....
6.4525
5,866
9.9722
12.9052
14.3717
14.9583
14.9583
17.3047
16,7181
18.7712
18.7712
21.1176
22.5841
26.6903
27.2769
28.7434
27.8635
28.1568
26.9836
24.9305
24.0506
21.9975
21.9975
22.2908
22.2903
26.9836
23.7573
19.0645
13.4913
7.9191
7.3325
3.8129
1.7598
1,7598
4.6928
7,0392
8.799
8,799
7.0392
7.9191
6,4526
9.3856
11.1454
7.9191
11.732
10.5588
12.9052
15.8382
17.3047
20.531
24,9305
29.0367
32.5563
06.389 13.2778 U 84,9642 22.5013 -24.4766 4.0...
43,513 18,5323 0 92,2387 22,5013
44.92 18.7233 0 89,8472 22,5013
53.006 18.7552 0 91 ,8004 22.5013
50.545 13.7552 0 96,6834 19,939
49,49 18.8826 0 03,031 16,9213
47.381 18.9783 0 08,403 16,7003
48.084 19.1697 0 14,751 7,4216
47,732 19,4573 0 22,563 9,7925
44.216 19.7773 0 28,911 8,6076
43.513 20.0337 0 35,747 9,4718
45,974 20.2584 0 42,095 8,7506
47,381 20.419 0 49,42 8,522
54.413 20.5799 0 57,721 8,2093
50.194 20.7409 0 63.5S1 8.2093
55,116 20,8375 0 68,464 9,9097
51.952 20.9665 0 70,905 9,7633
56.171 20.9665 0 74.811 20.5294
50.194 20.9343 0 32.136 20,7373
J45.271 2 .1926 0 91,902 20,2924
47.029 2 .3866 0 200,203 21,7634
43.513 2 .516 0 200,691 22,5323
347,381 2 .5608 0 200,691 22,5323
38.591 2 .8078 0 203,621 22,5323
42.107 2 .7105 0 208.504 22,5323
55,116 2 .9377 0 209,969 22,5633
J58.28 22,1002 0 2 4,364 22,5633
56.171 22.1978 0 2 6.317 22,5633
51.248 22.3606 0 2 8,27 22.5633
37.688 22.5563 0 2 7,293 22.5633
40,349 22.6216 0 2 6,317 22,5633
1.9544 22.6869 0 2 4,364 22.5633
9.772 22,7196 0 201 ,668 22,5633
73.339 22.7196 0 187,019 18,2376
77.206 22.0352 0 209,969 13.714
31.35 22.3002 0 206,551 12,3822
46.375 22.491 0 220,223 1 1 ,0173
33.608 22.5563 0 222,665 0,4551
44.156 22.5889 0 222,665 0,9917
45,562 22.5869 0 223, 153 0,0221
31.85 22.5563 0 220,712 ,74237
46.617 22.5889 0 221 ,688 ,5133
35.718 22.6216 0 223,641 ,56457
52,946 22.6542 0 226,083 0,3276
47.32 22.6542 0 227,06 ,81861
45.914 22.6542 0 229,013 ,48842
25.521 22,6216 0 228,036 0,787
40.288 22.5563 0 228,036 0,6338
39.234 22.5563 0 227,548 1 ,5813
31,35 22.5237 0 226,571 12,1492
32.202 22.491 0 224,618 13,793
31,85 22.491 0 223,641 15,1228
32.905 22.5237 0 221 .683 16.4254
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