c/EPA
United States
Environmental Protection
Agency
Office of Water    EPA 800-B-14-001
Washington DC 20460  September 2014
www.eoa.aov.nodes   Final Report
                    VESSEL DISCHARGE
                SAMPLE COLLECTION &
            ANALYTICAL MONITORING
             A How-To Reference for EPA's
               2013 Vessel General Permit
                                   (VGP)

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                                                                        Table of Contents
                                Table of Contents

SUMMARY OF KEY POINTS	1

SECTION 1 GETTING STARTED	5
    1.1    Finding A Sampling Service Provider and/or an Analytical Laboratory	5
    1.2    Questions to Ask When Identifying a Laboratory or Sampling Service
          Provider	7

SECTION 2 MONITORING REQUIREMENTS FOR EACH DISCHARGE	11
    2.1    Bilgewater/Oily Water Separator Effluent	11
    2.2    Graywater	14
      2.2.1   Additional Considerations for Field Tests (pH and Total Residual
             Chlorine)	15
      2.2.2   Additional Considerations for Multiple Graywater Discharge Points	15
    2.3    Exhaust Gas Scrubber Washwater	18
      2.3.1   Additional Considerations for Field Tests (pH and Total Residual
             Chlorine)	20
    2.4    Ballast Water	21
      2.4.1   Biological Monitoring	21
      2.4.2   Additional Considerations for Field Tests (Total Residual Chlorine)	23
      2.4.3   Residual Biocides from Ballast Water Treatment	23
      2.4.4   Other Ballast Water Sampling Approaches	24

SECTION 3 SAMPLING	27
    3.1    List of Sampling Equipment	27
    3.2    Sample Collection Steps	28
    3.3    Dissolved Metals Filtration	31
    3.4    Sample Packing and Shipping	33
    3.5    Bottle Labels and Chain of Custody (COC) Forms	37
                                         in

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                                                                              List of Tables
                                    List of Tables
Table 2-1. Bilgewater Analytical Method Details	13
Table 2-2. Graywater Analytical Method Details	15
Table 2-3. Analytes for Exhaust Gas Scrubber Washwater	18
Table 2-4. Exhaust Gas Scrubber Washwater Analytical Method Details	19
Table 2-5. Indicator Organism Monitoring Parameters*	22
Table 2-6. Example Ballast Water Indicator Organism Sample Collection and
       Preservation Techniques	22
Table 2-7. Monitoring  Schedule for Residual Biocides or Derivatives of the
       Residual Biocide	23
Table 2-8. Residual Biocides and Biocide Derivative Monitoring Requirements	25
                                           IV

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                                                                           List of Figures
                                   List of Figures
Figure 2-1. A Comparison of the Bilgewater Samples Taken Before and
      After Bilgewater Treatment	12
Figure 2-2. Sampling of Bilgewater from a Bilgewater Treatment System	13
Figure 2-3. Examples of Oil Content Meter and Monitoring System	14
Figure 2-4. Composite Sample of Treated Mixed Graywater/Sewage Effluent	16
Figure 2-5. Two Examples of Sample Collection Points for Graywater Discharge	17
Figure 2-6. The EcoSilencer® Scrubber Installed on the Pride of Kent	20
Figure 2-7. Sampling Tap At the Pump of a Ballast Water Treatment System	23
Figure 3-1. Vessel Discharge Being Collected in a Labeled Sample Bottle	27
Figure 3-2. Example of Various Types of Sample Bottles and Various Preservation
      Chemicals in Dropper Bottles	28
Figure 3-3. Typical Field Measurement Meters and Strips for Chlorine and pH	29
Figure 3-4. Sample Collectors Conducting Field Measurements	29
Figure 3-5. Sodium Thiosulfate	29
Figure 3-6. Sample Collection	30
Figure 3-7. Filled Sample Bottles Preserved on Ice	31
Figure 3-8. Samplers Performing Dissolved Metals Filtration	32
Figure 3-9. A Typical Peristaltic Pump	32
Figure 3-10. Disposable Filter Cartridges and Tubing	33
Figure 3-11. Packing Glass and Plastic Bottles	34
Figure 3-12. Garbage Bags Used to Line a Cooler	34
Figure 3-13. Individually Packed Samples in a Cooler	35
Figure 3-14. Samples in a Sealed Bag and Bags of Ice to Keep the Samples Cold During
      Shipping	35
Figure 3-15. Place the Chain of Custody in a Plastic Bag to Keep it Dry	36
Figure 3-16. A Packed Cooler Showing the  Custody  Seal and Strapping Tape	36

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                VI

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Sampling How-Tofor the 2013 Vessel General Permit
SUMMARY OF KEY POINTS
       The purpose of this document is to provide vessel owners/operators with tips and tools
for meeting the sample collection and analysis monitoring requirements in the 2013 VGP. The
document is written primarily to better educate vessel owners/operators who intend to conduct
some or all of the sampling themselves rather than contracting these sampling activities to
experienced third-party sampling service providers.  However, EPA expects many vessel
owners/operators will look to sampling service providers and laboratories to perform these
activities for them and this document should serve as a resource for them as well.

       Many NPDES permittees hire full-service "turnkey" operations to sample and analyze
their discharges in lieu of building these capabilities in-house. Such service providers are
currently available in many ports and EPA is aware that additional entities are considering
offering similar services soon.  When an owner/operator is not interested or unable to perform
these sampling activities, use of a full-service provider is a viable alternative.

       This summary of key points provides the most crucial information on the following
aspects of sampling collection:

       •   Finding a Sampling Service Provider and/or an Analytical Laboratory
       •   Sample Preparation
       •   Collecting and Handling Samples
       •   Shipping Samples to a Laboratory.

       Refer to the detailed sections of this document for information on the types of discharges
required to be sampled as well as more comprehensive information on how to ensure sampling
activities provide results consistent with the VGP requirements.

How DO I FIND A SAMPLING SERVICE PROVIDER OR AN ANALYTICAL LABORATORY?

       Since different laboratories offer different services, a vessel owner/operator will need to
find an analytical laboratory  capable of meeting the monitoring requirements specified in the
permit before conducting the actual sample collection. In addition to analyzing the samples (or
arranging to have them analyzed), some services will provide prepared sampling bottles and
sampling gear, conduct the actual sampling,  and complete any necessary paperwork and forms.
Conversely, some laboratory services only include analysis of a sample delivered to their lab.
Finding the right sampling service provider and laboratory is similar to finding any other
specialty service contractor in that you need  to find entities that are capable of meeting all of
your needs. Most commercial laboratories have websites that list their services and can be found
through internet searches or word of mouth.  The National Environmental Laboratory
Accreditation Program (NELAP) maintains a list of about 1,500 laboratories here: http://nelac-
institute.org/lams/search. NELAP also maintains a list of laboratories accredited through each of
the 50 states; however, about 20 percent of states only list laboratories accredited for drinking
water testing. See http://www.nelac-institute.org/abdb.php for details on state programs. The
American Council of Independent Laboratories  (ACIL) website also has a search function to find
environmental laboratories by location. See https://m360.acil.org/frontend/search.aspx?cs=1018.

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Sampling How-Tofor the 2013 Vessel General Permit
Also, while most of the laboratories identified from these sources are in the United States, vessel
owners/operators are not required to use laboratories located in the United States so long as the
lab meets the requirements of each test methods. Note that EPA does not endorse these
laboratories and does not require use of a NELAP lab, but is providing this information as a
resource. EPA does not require use of a "certified" or "accredited" laboratory for sampling and
analytical analysis to comply with the VGP's monitoring conditions.

       Since some samples have short holding times between sample collection and analysis
(i.e., less than a day in many instances), vessel owners/operators will need to consider the timing
of sample collection to allow sufficient time for transport to the laboratory for analysis.
Therefore, the physical location of the laboratory may be important because of the ability to
arrange for sample pickup by laboratory personnel or a courier service.

WHAT QUESTIONS SHOULD I ASK WHEN IDENTIFYING A SAMPLING SERVICE PROVIDER
AND/OR LABORATORY?

    •   Is the laboratory capable of providing the analyses for every pollutant parameter for
       each of the discharges that the permit requires? Will the laboratory's reported results
       meet all the requirements of the approved analytical methods of the 2013 VGP?
          In some cases, a single laboratory cannot be identified that can provide all of the
          vessels' analytical needs. In these situations, multiple laboratories may be needed to
          perform the range of analyses. Discuss  each of the required analyses and explain to
          the laboratory the  characteristics/source of the samples.

    •   Can the laboratory or sampling service provider offer a complete service which would
       include sample collection and transport.  In the event they cannot offer such service (or
       you are not interested in such a service), can the laboratory provide bottles or other
       supplemental equipment for sampling such as bottles pre-labeled with your specific
       information, bottles with preservation chemicals already added, extra bottles in case of
       breakage and coolers/shipping materials?
          If laboratories do not currently offer these services, ask if an exception can be made.
          Otherwise the vessel owner/operator will need to acquire these materials separately
          and ensure that they meet the method requirements.

    •   Can the laboratory provide or arrange for courier services to pick up the samples
       directly from the vessel and all necessary paperwork? If not, how will the samples be
       delivered to the laboratory? What are the holding times for each sample and are there
       any other logistical and sampling limitations to consider?
       -   If you are seeking courier service from the laboratory, ensure they have escorted or
          unescorted access to the  dock from which the sample will need to be picked up.

    •   How and when will the results be reported back to the vessel? What will the data
       package contain?

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Sampling How-Tofor the 2013 Vessel General Permit
       -   You need to be certain that the sample service provider is able to complete sampling
          and analysis and provide any necessary documentation and in time for you to be able
          to meet the VGP reporting requirements for the results of that monitoring.

COLLECTING SAMPLES AND SHIPPING

       This section lists equipment commonly used for vessel sampling, steps for sampling
collection, and procedures for sample packing and shipping.  Note that you may not need all
equipment listed or may omit certain steps depending on which samples you must collect.

If I collect the samples myself, what equipment will I need?
         Sampling Pole                              •  Bubble Wrap/Bubble Bags
         Sample Bottles                              •  Shipping Paperwork/Traffic
         Field Test Equipment                           Reports
         Buckets and Disposable Bucket Liners         *  Garbage Bags
         Bottle Labels                                •  Clear and Strapping Tape
         Pens                                       •  Ice/Refrigeration/Coolers
         Disposable Gloves                           *  Zipper storage bags
         Preservation Chemicals                      *  Chain of Custody Forms
         Zip Ties                                    •  Custody Seals
         Log Book                                  •  Coolers
How does my crew Collect, Pack, and Ship Samples?

       1.     Assemble all the necessary sampling equipment, materials, and supplies onsite.
       2.     Ensure that bottles are appropriately labeled (waterproof labels are best as they
             remain intact and legible).
       3.     Collect a discharge sample aliquot to perform any necessary field measurements
             (e.g., pH, free residual chlorine). Refer to the user manuals for the field test
             instruments to ensure proper use and maintenance of these meters.
       4.     Determine whether sodium thiosulfate (^28203) is needed for preservation due
             to the presence of chlorine in the sample and add to the sample bottles as
             appropriate.
       5.     Fill the sample bottles with the appropriate discharge samples.
       6.     If necessary, filter the sample for dissolved metals. See instructions for sample
             filtering in Section 3.3 below.
       7.     If the laboratory was unable to add preservation chemicals to each bottle, add any
             appropriate preservation chemicals at this point and test the pH or chlorine to
             ensure that the enough has been added.

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Sampling How-Tofor the 2013 Vessel General Permit
       8.      Cool the samples on ice as dictated by the analytical methods. If the discharge
              water is hot to the touch, consider the need to allow samples to cool for a few
              minutes prior to placing in ice water to prevent shattering of the sample container
              or loss of the lid liner into the sample.
       9.      Repeat steps 2 through 9 if more than one discharge needs to be sampled.
       10.     Complete chain of custody forms.
       11.     Wrap glass sample bottles with "bubble wrap" and place all bottles (glass and
              plastic) in individually sealed zipper storage bag to contain liquids and
              preservation chemicals in case of shattering, punctures, or leaks.
       12.     Line the  cooler with a large garbage bag to further ensure nothing leaks from the
              cooler.
       13.     Place sample bottles and a temperature blank upright in the garbage bag in the
              cooler and close bag with twist-tie.
       14.     Arrange  sealed plastic freezer bags  filled with ice (or chemical ice) on top of the
              sample bottles (if sample cooling is required for preservation) to maintain
              preservation temperature during shipping.
       15.     Place the completed chain of custody form in the cooler (retain a copy for your
              records).
       16.     Close cooler and  secure with strapping tape to ensure that the lid will remain
              closed if the latch is accidentally released or damaged. Also tape the cooler drain
              plug closed so it will not open during shipment.
       17.     Place a custody seal on the cooler to verify the cooler has not been opened or
              tampered with during shipment and secure with clear tape to  prevent loss during
              transport.
       The following is an example of a bottle label:
         Sample Number:                      000001
         Sampling Port:                        Miami, Florida
         Vessel Name/Number:                 Container Vessel 123
         Sampling Point Description:           Exhaust Gas Scrubber Inlet Water
         Day and Time of Sample Collection:    8/8/2013 4:30 PM EST
         Analysis to be Performed:              Total Metals
         Sample Bottle Type:                   500-mL Plastic Bottle
         Preservation Used:                    HNO3 to pH<2
      V  Sampler Initials:                      FH and GW

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Sampling Ho-w-To for the 2013 Vessel General Permit                                             Section 1


 SECTION 1
 GETTING STARTED	

Purpose of this Document: To provide tips and tools for complying with the sample collection
and analysis monitoring requirements in the 2013 VGP.

Target Audience: Anyone (vessel owners/operators, crew, service providers, and laboratories)
collecting or analyzing samples of discharges from vessels as required under the 2013 VGP.

Vessel Required to Collect and Analyze Samples under the 2013 VGP:

      •  Any vessel discharging bilgewater to waters subject to the VGP constructed on or
          after December 19, 2013 and greater than 400 gross tons (see Part 2.2.2 of the VGP)
      •  Any large cruise ship discharging graywater to waters subject to the VGP within 3
          nautical miles of shore (see Part 5.1  of the VGP)
      •  Any medium cruise ship discharging graywater to waters  subject to the VGP within 1
          nautical mile of shore (see Part 5.2 of the VGP)
      •  Any vessel constructed on or after December 19, 2013, having a maximum crew
          capacity of at least 15 crew, and providing  overnight accommodation to those crew,
          and discharging graywater to waters subject to the VGP (see Part 2.2.15 of the VGP)
      •  Any vessel operating on the Great Lakes, that is not a "commercial vessel," and
          discharging graywater to waters subject to the VGP  (see Part 2.2.15 of the VGP)
      •  Any vessel discharging exhaust gas scrubber washwater to waters subject to the VGP
          (see Part 2.2.26 of the VGP)
      •  Any vessel operating a ballast water treatment system and discharging ballast water to
          waters subject to the VGP (see Part 2.2.3 of the VGP).

      Results of monitoring are required to be reported to the EPA as part of the annual
reporting requirements of the 2013 VGP. See Part 4 of that permit for specific reporting and
recordkeeping requirements.  Also, visit EPA's electronic (eNOI) system, accessible at:
http://water.epa.gov/polwaste/npdes/vessels/, for specifics on how monitoring results are to be
reported to EPA.

1.1   FINDING A SAMPLING SERVICE PROVIDER AND/OR AN ANALYTICAL LABORATORY

      Once it is determined  that a vessel is required to collect samples of bilgewater, graywater,
exhaust  gas scrubber wastewater, and/or ballast water  discharges, the owner/operator of the
vessel will have to determine how those samples will be collected, handled, analyzed, and
reported, and what documentation is necessary to be retained. In many instances, these activities
will require the owner/operator to find a sampling service provider and/or an analytical
laboratory capable of meeting the monitoring requirements specified in the permit. Finding the
right sampling service provider or analytical laboratory is similar to finding any other specialty
service contractor. Most service providers and commercial laboratories have websites that list
their services and can be found through internet searches or word of mouth. The National
Environmental Laboratory Accreditation Program (NELAP) maintains a list of about 1,500

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Sampling Ho-w-To for the 2013 Vessel General Permit                                             Section 1
laboratories (there are about 6,000 to 10,000 laboratories in the US) that are accredited through
their program organized by analytical method, which may also be useful in identifying a
qualified laboratory. See http://nelac-institute.org/latns/search. NELAP also maintains a list of
laboratories accredited through each of the 50 states; however, about 20% of states only list
laboratories accredited for drinking water testing. See http://www.nelac-institute.org/abdb.php
for details on state programs. American Council of Independent Laboratories (ACIL) is  the trade
association representing about 100 independent, commercial scientific and engineering firms
across the U.S. Their website also has a search function to find environmental laboratories by
location. See https://m360.acil.org/frontend/search.aspx?cs=1018. Note that EPA does not
endorse these laboratories, but is providing this information as a resource. Also, while most of the
laboratories identified from these sources are in the United States, vessel owners/operators are
not required to use laboratories located in the United States to meet the requirements of the 2013
VGP. However, EPA notes that any non-U.S. laboratory must use appropriate quality assurance
and quality control procedures to ensure that sample results are accurate.

       Section 2 of this  document contains a summary of VGP monitoring requirements and can
be used as the starting point for the types of services needed from a service provider and/or
laboratory. This section will help in determing answers to the following questions, which will be
important to understand  before contacting a service provider or laboratory:

       •  Which vessels and vessel discharges require sampling?
       •  Are vessel sampling points accessible (can the sample be collected easily from either
          a pre-installed tap or discharge point)? If not, what arrangements need to be made to
          collect the sample?
       •  What analyses are required of each discharge?
       •  What is the timeframe and frequency of sampling?
       •  What is the anticipated vessel location/condition during sampling?
       •  Who is the point of contact for sampling, follow-up questions, etc? Is that a  contact
          in your headquarters operation, a vessel agent, a member of your crew, or someone
          else?

       Also,  since some samples have short allowable holding times between sample collection
and analysis,  vessel owners/operators will need to consider both the timing of sample  collection
and the time for transport to the laboratory for analysis when selecting the appropriate sampling
service provider and/or laboratory.  Therefore, the physical location of the laboratory and the
ability of the  service provider to gain access to the vessel to collect samples while a discharge is
occurring may be important to ensure that samples can be analyzed within the appropriate
holding times required to demonstrate compliance with permit requirements (see allowable
holding times in Title 40 Code of Federal Regulations Part 136).  For example, the ability to
arrange for sample pickup by laboratory personnel or a courier service (which can a few minutes
to a few hours) instead of shipping the samples through a commercial parcel delivery  service like
DHL, FedEx, or UPS (which can take a day or more).

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Sampling Ho-w-To for the 2013 Vessel General Permit                                            Section 1


       When contacting potential sampling service providers or laboratories, be sure to discuss
the details of the planned sample collection and analysis with them. Below are some questions to
ask and the types of services that should be considered.

1.2    QUESTIONS TO ASK WHEN IDENTIFYING A LABORATORY OR SAMPLING SERVICE
       PROVIDER

       1.     Although not required, is the laboratory NELAC (National Environmental
             Laboratory Accreditation Conference) certified to perform all of the analyses
             for each of the discharges that the vessel requires? If not, what other
             indications do you have that the laboratory can and will perform the monitoring
             consistant with the methods specified in 40 CFR Part 136 or other methods
             specifically allowed in the permit?
             If a single laboratory cannot be identified that can provide all of the vessels'
             analytical needs, multiple laboratories may be needed to provide the full range of
             required analyses. Discuss each of the required analyses and explain to the
             laboratory the characteristics/source of the  samples and any associated allowable
             holding times for those sample parameters.
       2.     What experience does the laboratory or sampling service provider have with
             sampling and analyzing samples consistent with the analytical methods
             required for your discharge?
             Sampling service providers and laboratory  personnel may have additional insights
             and tips for avoiding sampling and  analysis problems. Consider the volume of
             sample needed, range of analytical results,  preservation requirements, sample
             collection schedule/timing,  etc.
       3.     Can the laboratory or sampling service provider offer a complete "turnkey"
             service which would include sample collection and transport?
             This is often  the best way to ensure that samples are collected, handled, and
             analyzed properly and avoids the vessel owner/operator from having to learn all
             the details of proper sample collection and  handling techniques. Some
             laboratories and sampling service providers offer a full range of services, which
             can include actual sample collection, transport, analysis, and preparation of all
             required recordkeeping documents. In these instances, you should be certain that
             the service provider is able  to board your vessel at the appropriate time and
             location (e.g., appropriate access to the port).
       4.     If collecting  samples  on your own, check to see if the laboratory can provide
             bottles or other supplemental equipment for sampling? Are the bottles pre-
             labeledwith  vessel-specific information? Will there be extra bottles available in
             case of breakage? Does the laboratory provide sample bottles with the
             preservation chemicals already added?
             If the laboratory does not typically offer  these services, ask if an exception can be
             made. Often  these laboratories are willing to perform such services, that being
             when they will  collect the samples, transport the samples to the laboratory,
             analyze the samples, and prepare any necessary reports with the sampling results.

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Sampling Ho-w-To for the 2013 Vessel General Permit                                             Section 1


              Otherwise, the vessel owner/operator will need to acquire appropriate laboratory-
              grade bottles and preservation chemicals from a laboratory equipment supplier.
              See an example bottle label in Section 3.5. If these services are available, discuss
              the logistics of receiving the needed equipment.
              If the sampling service provider or laboratory does not provide sample bottles
              with  the preservation chemicals already added, the appropriate preservation
              chemicals will need to be purchased separately. In addition, the amount of
              preservation chemicals required will need to be calculated based on the pH of the
              discharge. Generally speaking, a few milliliters of preservation chemicals are
              needed to appropriately preserve 500 mL of wastewater at a pH of 7.  If the
              laboratory is able to provide this service, the pH of the discharge will need to be
              provided to the laboratory so they can estimate the amount of preservation
              chemical to add to each bottle (details of the type of preservation needed by
              discharge is provided in tables in Section 2).
       5.      Will  the sampling service provider and/or laboratory be able to provide filters
              and other supplies to perform any necessary filtering in the field?
              See Section 3.3 for more information regarding dissolved metals filtering
              equipment and procedures.
       6.      Can  the sampling service provider or laboratory provide or arrange for courier
              services to pick up the samples directly from the vessel? If not, how will the
              samples be delivered to the laboratory?  Will the samples meet their holding
              times in consideration of any logistical and sampling limitations?
              Generally speaking, a sample with a 5-day holding time or greater could be
              shipped over-night to the laboratory, but a sample with less than a 5-day holding
              time  will require a faster shipping method (i.e.  courier service). Additional time
              considerations for packaging and shipping, coordination, weekend schedules, etc.
              must be considered. If samples will be shipped using a commercial delivery
              service, see the section on "Sample Packing and Shipping" in Section 3.4 below.
       7.      If shipping samples is necessary, will the laboratory provide the shipping
              coolers and packaging materials?
              See the "List of Sampling Equipment" in Section 3.1 below.
       8.      Will  the laboratory provide all necessary paperwork for the samples such as
              bottle labels, field logs,  chain of custody forms, sample custody seals, etc?
              See an example of a standard chain of custody form in Section 3.5 of this
              document.
       9.      How and when will the results be reported back to the vessel? What will the
              data package contain?
              A standard laboratory data package may include the following items:
                 •  Narrative Report: including a cover page containing the following
                    information: laboratory name, episode number, sample numbers, method
                    number and date, and a list of laboratory analysis ID numbers. The

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Sampling Ho-w-To for the 2013 Vessel General Permit                                             Section 1


                    narrative should include any difficulties encountered in the production of
                    the analytical and QA/QC data, resolution of those difficulties, deviations
                    from the methods, any comments on the method performance, and any
                    problems associated with the analysis of specific samples (including
                    reasons and recommendations).
                 •  Summary Report Forms: including forms summarizing all sample,
                    instrument, and method QC results, including calibration and calibration
                    verification information as well as percent recovery information.
                 •  Miscellaneous Data: including sample and standard preparation
                    logbooks, and the current Method Detection Limit/ Initial Precision and
                    Recovery (MDL/IPR).
       10.     What other sampling logistics should be considered to ensure accurate and high
              quality data are attained, while minimizing your burden and specialized
              training needed for your crew?
              For example, can sampling be accomplished during a vessel's annual  survey or in
              locations with established sampling infrastructure (e.g., in areas where services
              exist which conduct actual sampling for you)? Alternatively, will you designate a
              dedicated crew member to be responsible for sampling obligations?

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Sampling Ho-w-To for the 2013 Vessel General Permit                                                        Section 1
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Sampling How-Tofor the 2013 Vessel General Permit                                              Section 2


 SECTION 2
 MONITORING REQUIREMENTS FOR EACH DISCHARGE	

       This section provides an overview of monitoring required under the 2013 VGP.

       Consistent with Part 4.2 of the 2013 VGP, records of all monitoring information,
including all calibration and maintenance records, continuous monitoring instrumentation
records (including strip chart recordings if applicable), sampling and testing results, and
laboratory quality assurance (QA) documentation, must be retained onboard or kept
electronically for a period of 3 years and must include:

       •   The date, exact place, and time  of sampling or measurements;
       •   The individual(s) who performed  the sampling or measurements;
       •   The individual(s) who performed  the analyses and any meter recalibration;
       •   The techniques or methods used for sample analyses; and
       •   The results of such analyses and oil content meter (OCM) readings.

       Consistent with Part 4 of the 2013 VGP, monitoring  data must be submitted
electronically (or on paper if EPA grants a  waiver) at least once per calendar year no later than
February 28 of the year after the data are collected. EPA has developed an electronic reporting
system accessible from EPA's 2013 VGP homepage at
http://water.epa.gov/polwaste/npdes/vessels/Vessel-General-Permit.cfm.  Data must be
submitted on the applicable VGP discharge monitoring reports (DMRs) as shown in Appendix H
of the 2013 VGP (which have been incorporated into the electronic reporting system) and are to
be submitted as part of the vessel's annual  report (except for initial cruise ship graywater
monitoring that may be due before the annual report). As appropriate, you must also report any
waivers or other documentation on your annual report.

       As described in Section 1, owners/operators required to monitor will have to contact one
or more sampling service providers or contract laboratories to coordinate logistics to collect and
or analyze the samples.  Owners/operators  should be certain to communicate the documentation
requirements of the  permit to these service providers and laboratories as summarized above.

2.1     BlLGEWATER/OlLY WATER SEPARATOR EFFLUENT

       Part 2.2.2 of the 2013 VGP requires owners/operators of new build vessels constructed
on or after December 19, 2013 and greater than 400 gross tons that may discharge bilgewater
into U.S. waters, to  collect a sample of bilgewater effluent (discharge from the vessel after
bilgewater treatment system) annually1  for analysis of oil and grease content by one of the
following methods:
1 Part 2.2.2.1 of the 2013 VGP provides a monitoring waiver provision after two years of monitoring provided certain conditions
are met. Applicable vessel owners/operators may cease conducting analytical monitoring if:
  •The analytical monitoring results are below 5 parts per million (ppm) oil and grease for two consecutive years of permit
    coverage;

                                            n

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
       •  EPA Method 1664; or
       •  ISO 9377-2 (2000) Water Quality-Determination of Hydrocarbon Oil Index-Part 2:
          Method Using Solvent Extraction and Gas Chromatography (incorporation by
          reference, see 46 CFR §162.050-4).
       In addition, the 2013 VGP requires that a reading of the OCM be recorded at the time of
sample collection so that the oil content measured by the laboratory can be compared to that
measured by the OCM.
          Figure 2-1. A Comparison of the Bilgewater Samples Taken Before and
                               After Bilgewater Treatment

       EPA Method 1664 measures oil and grease content as Hexane Extractable Material
(HEM), and also measures Silica Gel Treated N-Hexane Extractable Material (SGT-HEM).
Both HEM and SGT-HEM samples are extracted using hexane, but for the SGT-HEM samples,
the hexane extract undergos an additional silica gel treatment process  to remove polar material,
and therefore, measurements include only nonpolar material. The weight of extracted oil and
grease after the solvent is evaporated is then reported.  EPA Method 1664 is approved by EPA at
40 CFR Part  136 (http://www.epa.gov/region9/qa/pdfs/40cfr 13603.pdf) for measuring oil and
grease under the Clean Water Act; therefore, EPA Method 1664 is routinely offered by
commercial analytical laboratories in the United States.

       Alternatively, ISO Method 9377-2 runs a portion of the dried solvent extract through a
gas chromatography instrument (reported as oil index).The ISO 9377-2 (2000) method is that
   •The vessel has an oil water separator that has been type approved by any flag administration to be capable of meeting a 5
   ppm standard or has an alarm and overboard discharge control unit which prevents the discharge of any bilgewater with an
   oil content of greater than 5 ppm oil and grease;
   •The vessel owner/operator calibrates the OCM annually; and
   •The vessel's OCM never reads above 5 ppm during discharges into U.S. waters.
                                            12

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
specified by the US Coast Guard at 46 CFR 162.050-39 for measuring oil content in samples
taken in approval testing of bilgewater separators, monitors, and alarms; this method is not
commonly offered by US commercial analytical laboratories. There is a disparity in costs
between the two methods with ISO 9377-2 (2000) potentially costing five to ten times more than
EPA Method 1664. However, the hydrocarbon oil index method may be more likely to produce
results consistent with type approval testing.  The vessel owner/operator can choose which
method they wish to employ. Table 2-1 summarizes sample collection and analysis procedures
for bilgewater monitoring.

                    Table 2-1. Bilgewater Analytical Method Details

Analyte
HEM


Hydrocarbon
Oil Index


Method
EPA-1664A


ISO 9377-
2:2000


MRL
5


0.1



Unit
mg/L


mg/L



Container
Any Color
Wide-mouth
Glass Bottles
Amber Glass
Bottles with
Teflon® lid
Sample
Volume
Two 1 -Liter
Bottles

Two 1 -Liter
Bottles


Preservation
Cool to <6°C, HC1 or
H2SO4 to pH <2

Cool to <6°C


Holding
Time
28 days


4 days


MRL = Method Reporting Limit.
         Figure 2-2. Sampling of Bilgewater from a Bilgewater Treatment System
                                          13

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
             Figure 2-3. Examples of Oil Content Meter and Monitoring System

2.2    GRAYWATER

       Part 2.2.15.2 of the 2013 VGP specifies that new build vessels constructed on or after
December 19, 2013 and with a maximum crew capacity greater than or equal to 15,  and
providing overnight accommodations to those crew are required to collect samples of graywater
discharge for analysis.2 For these vessels, the 2013 VGP requires two samples a year3 to be
collected, at least 14 days apart, and analyzed for the following:

       •   Biological Oxygen Demand (BOD)
       •   Fecal Coliform or E. coll
       •   Total suspended solids
       •   pH
       •   Total residual chlorine

       The analyses must be conducted according to 40 CFR Part 136 methods and the results
must be reported in the vessel's Annual Report. Samples for fecal coliform or E. coli may be
collected and analyzed only once per year if the owner/operator is having difficulties meeting the
short holding times. Table 2-2 summarizes sample collection and analysis procedures for
graywater monitoring.
2 Large and medium cruise ships discharging graywater to waters subject to this permit have additional graywater monitoring
requirements. See Parts 5.1.2 and 5.2.2 of the VGP for gray water monitoring requirements for large and medium cruise ships,
respectively. Additionally, vessels operating on the Great Lakes that are not "commercial vessels" that discharge graywater are
also required to monitor that graywater. See part 2.2.15.1.
3 Monitoring is not required in any calendar year that the vessel does not enter waters subject to this permit; however, the vessel's
Annual Report must clearly state that the vessel did not enter waters subject to this permit.
                                               14

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
                     Table 2-2. Graywater Analytical Method Details

Analyte
BOD
Fecal
Coliform

E. coli


Total
Suspended
Solids
pH
Total
Residual
Chlorine

Method*
SM5210B
SM 9222D or
9221E

EPA 1603


SM 2540 D
SM 4500-H B
SM 4500-C1
G


MRL
2
1

1


3

Unit
mg/L
CPU or
MPN/100 mL

CPU or
MPN/100 mL

mg/L

Container
1 Plastic Bottle
1 Plastic Bottle

1 Plastic Bottle


1 Plastic Bottle

Sample
Volume
500-mL
120-mL

120-mL


1 -Liter

Preservation
Cool, <6°C
Cool, <10°C,
Na2S2O3 if
Chlorine
Present
Cool, <10°C,
Na2S2O3 if
Chlorine
Present
Cool, <6°C
Maximum
Holding
Time
48 hours
8 hours

8 hours


7 days
Field Tests

MRL = Method Reporting Limit.
* Sampling and testing shall be conducted according to 40 CFR Part 136.The listed methods are suggested methods
but EPA will also accept sufficiently sensitive methods that are considered equivalent.

 2.2.1  Additional Considerations for Field Tests (pH and Total Residual Chlorine)

       Note that pH and total residual chlorine need to be measured within 15 minutes of sample
collection and therefore need to be measured and recorded at the time of sample collection rather
than at a commercial laboratory. This monitoring is performed using test meters equipped with
the appropriate sensors designed to meet the analytical method listed. Generally, a 1-liter sample
container jar is filled during  sample collection for use in performing these measurements.
Typically, samples for field measurements are collected first, because if total residual chlorine is
detected, sodium thiosulfate (^28203) will need to be added as a preservative for the fecal
coliform or E. coli samples. (ASTM D7365-09a specifies preservation options for samples
containing chlorine.) Vessel owners/operators should calibrate all equipment used for field
measurements using the applicable calibration procedures specified by the instrument
manufacturer.

 2.2.2  Additional Considerations for Multiple Graywater Discharge Points

       For vessels with multiple graywater discharge points (e.g., sinks, laundry facilities,
showers, galley kitchens, etc), consider collecting a sample of each  of the  discharge points and
compositing them together for a representative sample of the vessel's entire graywater discharge,
or sampling from an existing combined graywater collection tank.  Compositing protocols should
consider the relative discharge volumes of the various graywater sources. Regardless of where
                                            15

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
graywater is sampled, the sampling point must be reported to EPA when you submit your
monitoring data.
       Figure 2-4. Composite Sample of Treated Mixed Graywater/Sewage Effluent

       All records of the graywater sampling must identify the proportions of waste streams
being sampled (such as mixed graywater, mixed graywater and blackwater, and galley). If actual
amounts are not available, then estimated proportions should be provided.
                                          16

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
      Figure 2-5. Two Examples of Sample Collection Points for Graywater Discharge
                                            17

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
2.3    EXHAUST GAS SCRUBBER WASHWATER

       Part 2.2.26 of the 2013 VGP specifies that twice during the first year of permit coverage
or system operation, whichever is later, each vessel operating a wet exhaust gas scrubber system
must collect and analyze exhaust gas scrubber related samples.4 One of those samples may be
conducted as part of a vessel's annual or other survey, and during the first year of system operation,
one of those sampling events may be conducted as part of system installation to ensure it is
functioning properly. The two samples must be collected at least 14 days apart. After the first
year, samples must be collected at least once per calendar year and may be collected as part of
the vessel's annual survey as appropriate.

       For each sampling event,  samples must be collected of each of the following:

       •  Exhaust gas scrubber inlet water (for background),
       •  Untreated water leaving the scrubber (but before any treatment system), and
       •  The discharged water (after any treatment).

       The 2013 VGP requires these exhaust gas scrubber related samples to be analyzed for the
analytes listed in Table 2-3.

                Table 2-3. Analytes for Exhaust Gas Scrubber Washwater
Analytical Group




Dissolved Metals







Total Metals




Polycyclic Aromatic Hydrocarbons (PAHs)
Specific Compounds
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Thallium
Vanadium
Zinc
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Thallium
Vanadium
Zinc
Acenaphthylene
Acenaphthene
Anthracene
B enz [a] anthracene
Benzo[ghi]perylene
1 These monitoring conditions do not apply to inert gas scrubbers used as part of a safety system in a vessel tank.
                                           18

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
                  Table 2-3. Analytes for Exhaust Gas Scrubber Washwater
Analytical Group











Nitrate/Nitrite
pH
Specific Compounds
Benzo[a]pyrene
Benzo [b]fluoranthene
Benzo [kjfluoranthene
Chrysene
Dibenz [a,h] anthracene
Fluoranthene
Fluorene
Indeno [ 1 ,2,3 -cd]pyrene
Naphthalene
Phenanthrene
Pyrene


        Table 2-4 summarizes sample collection and procedures for analyzing exhaust gas
scrubber washwater samples.
            Table 2-4. Exhaust Gas Scrubber Washwater Analytical Method Details

Analyte
Dissolved
Metalsd
Total Metals

Nitrate/Nitrite

PAHs




pH
Total Residual

Chlorine"

Method*
EPA-200.8 or
EPA-200.93
EPA-200.8 or
EPA-200.93
EPA 353. 2

EPA-550.1,EPA-
610, EPA-625,
EPA-8100,EPA-
8270corEPA-
8310
SM 4500-H B

SM 4500-C1 G


MRL
1-5

1-5

0.01

5





Unit
ug/L

ug/L

mg/L

ug/L





Container
One Plastic
Bottle
One Plastic
Bottle
One Plastic
Bottle
One Amber
Glass Bottle
with
Teflon® Lid

Sample
Volume
500-mL

500-mL

1 -Liter

1 -Liter





Preservation
0.45 urn filterb,
HNO3 to pH<2
HNO3 to pH<2

Cool, <6°C,
H2SO4 to pH <2
Cool, <6°C,
Na2S2O3 if
chlorine present



Holding Time
6 Months

6 Months

28 Days

Extraction
within 7 days;
Analysis of
extract within
40 days

Field Tests


MRL = Method Reporting Limit.
* The listed methods are suggested methods but EPA will also accept sufficiently EPA Part 136 methods that are
considered equivalent.
a Because matrix interference is a known issue for arsenic and selenium in saltwater samples, EPA strongly
recommends using Octopole Reaction Cell ICP-MS, Dynamic Reaction Cell ICP-MS, hydride generation with a
graphite furnace, or other appropriate approach consistent with 200.8 or 200.9 to minimize this interference.
b These samples will need to be filtered immediately after collection. See the Dissolved Metals Filtration section of
this document.
0 Collected to determine PAHs sample preservation requirements.
d Vessel owner/operators may want to consider seeking laboratories that can conduct metal filtration of the samples
at the lab. This will simplify onboard sampling and processing requirements.

                                                19

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
           Figure 2-6. The EcoSilencer" Scrubber Installed on the Pride of Kent5

 2.3.1  Additional Considerations for Field Tests (pH and Total Residual Chlorine)

       Note that pH and total residual chlorine need to be measured within 15 minutes of sample
collection and therefore need to be measured and recorded at the time of sample collection rather
than at a commercial laboratory. Also, while total residual chlorine is not identified in the permit
as a required analyte, it is needed to determine if preservation is needed for PAHs samples.  This
monitoring is performed using test meters equipped with the appropriate sensors designed to
meet the analytical method listed. Generally, a 1-liter sample container is filled during sample
collection for use in performing these field measurements. If total residual chlorine is detected,
sodium thiosulfate (^28203) will need to be added as a preservative for any PAHs sample.
(ASTM D7365-09a specifies treatment options for samples containing chlorine.) Vessel
owners/operators should ensure that all equipment used for field measurements are calibrated
following applicable calibration procedures specified by the instrument manufacturer.
5 Source: Entec. 2005. European Commission Directorate General Environment, Service Contract on Ship
Emissions: Assignment, Abatement and Market-based Instruments, Task 2c - SO2 Abatement Final Report. August
2005. Entec UK Limited.
                                            20

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Sampling How-Tofor the 2013 Vessel General Permit                                              Section 2


2.4    BALLAST WATER

 2.4.1  Biological Monitoring

       The 2013 VGP specifies that vessels using a ballast water treatment system (i.e., those
subject to Part 2.2.3.5.1.1.1 of the 2013 VGP) must sample and analyze ballast water discharges
for the following biological indicators:

       •  Total heterotrophic bacteria,
       •  E. coli, and
       •  Enterococci.

       The vessel's ballast water system must be provided with sampling ports arranged in order
to collect representative  samples of the vessel's ballast water. In addition to the sampling ports
designed and installed in accordance with the specifications in the ETV Protocol
(http://nepis.epa.gov/Adobe/PDF/P10097A4.pdf). Sampling ports must be located:

       •  As close as practicable to the ballast water management system prior to treatment to
          determine concentrations of living organisms upon uptake; and
       •  As close as practicable to the ballast water management system overboard outlet prior
          to the discharge point to determine concentrations of living organisms prior to
          discharge.6

       Sampling of ballast water discharges for these vessels must be conducted two times
during the first year the system is installed or used for vessels with devices for which high
quality data are available (See Part 2.2.3.5.1.1.4 of the 2013 VGP for definition of high quality
data). For vessels with high quality data, if sampling results are below permit limits for two
consecutive events, the vessel owner/operator may reduce monitoring to one time per year after
the first year. However, if the vessel owner/operator exceeds a permit limit on any sampling
event, they must return to monitoring two times per year until they have two additional results
below  permit limits.

       For vessels required to perform ballast water monitoring for which high quality data are
not available, monitoring must be conducted four times per year.

       For all vessels required to perform ballast water monitoring, one of the samples may be
conducted as part a vessel's annual or other survey, and during the first year, one of those
sampling events may be conducted as part of the installation of the system to ensure it is
functioning properly.

       Table 2-5 summarizes applicable analytical methods that can be used for ballast water
monitoring for indicator organisms.  Table 2-6 provides a few examples of ballast water
indicator organism sample collection and preservation technniques for some of the most common
analytical methods.
6 See 46 CFR 162.060-28
                                           21

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
                   Table 2-5. Indicator Organism Monitoring Parameters1'
Measurement
Total
Heterotrophic
Bacteria
E. coli
Enterococci
Instrument or
Analysis
Plate Counts
Selective
Substrate
Selective
Substrate
EPA Method

EPA Method
1103. land
1603
EPA Method
1106. land
1600
Standard
Method
SM9215
SM 9223B
SM 9230C
ASTM
ASTMD5465
ASTMD5392-
93
ASTMD5259-
92(2006)
ISO
ISO 6222: 1999
ISO 9308-
1:2000
ISO 7899-
2:2000
Other

Colilert®
Enterolert®
 Sampling and testing shall be conducted according to 40 CFR Part 136.The listed methods are suggested methods,
but EPA will also accept Part 136 methods that are considered equivalent.
 Table 2-6. Example Ballast Water Indicator Organism Sample Collection and Preservation
                                          Techniques
Analyte
Total
Heterotrophic
Bacteria
E. coli
Enterococci
Total Residual
Chlorine3
Method
SM9215
EPA 1603 or
Colilert®
EPA 1600 or
Enterolert®
SM 4500-C1 G
MRL
1
1
1
Unit
CPU or
MPN/100 mL
CPU or
MPN/100 mL
CPU or
MPN/100 mL
Container
Plastic Bottle
Plastic Bottle
Plastic Bottle
Sample
Volume
120-mL
120-mL
120-mL
Preservation
Cool, <4°C,
Na2S2O3 if Chlorine
Present
Cool, <10°C,
Na2S2O3 if Chlorine
Present
Cool, <10°C,
Na2S2O3 if Chlorine
Present
Holding
Time
8 hours
8 hours
8 hours
Field Test
MRL = Method Reporting Limit.
a Collected to determine sample preservation requirements and not for compliance monitoring.
                                              22

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
       Figure 2-7. Sampling Tap At the Pump of a Ballast Water Treatment System

 2.4.2  Additional Considerations for Field Tests (Total Residual Chlorine)

       Note that total residual chlorine needs to be measured in the field to determine the type of
preservation needed for the three biological indicators samples. This monitoring is performed
using test meters equipped with the appropriate sensors designed to meet the analytical method
listed. Generally, a 1-liter sample container is filled during sample collection for use in
performing field measurements. If total residual chlorine is detected, sodium thiosulfate
(Na2S2O3) will need to be added as a preservative for any biological indicators samples. (ASTM
D7365-09a specifies treatment options for samples containing chlorine.) Vessel owners/operators
should ensure that all equipment used for field measurements are calibrated following applicable
calibration procedures specified by the instrument manufacturer.

 2.4.3  Residual Biocides from Ballast Water Treatment

       Vessels subject to Part 2.2.3.5.1.1.1 of the 2013 VGP must conduct monitoring of the
ballast water discharge for any residual biocides or derivatives used in the treatment process to
demonstrate that residual biocides or derivatives are in compliance with this permit. Table 2-7
below summarizes required sampling frequency based on ballast water treatment type and
available data. Table 2-8 summarizes sample collection and analysis procedures for ballast water
monitoring for residual biocides.
         Table 2-7. Monitoring Schedule for Residual Biocides or Derivatives of the
                                    Residual Biocide7
Type of Monitoring
Initial Monitoring
Maintenance Monitoring
Devices for Which High Quality Type
Approval Data Are Available
3 times in the first 10 discharge events (not
to exceed a 180 day period).
2 times per year.
Devices for Which High Quality
Data Are Not Available
5 times in the first 10 discharge events
(not to exceed a 180 day period).
4 times per year.
7 See Section 2.2.3.5.1.1.5.2 of the 2013 VGP for definition of high quality data.
                                           23

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Sampling How-Tofor the 2013 Vessel General Permit                                             Section 2
 2.4.4  Other Ballast Water Sampling Approaches

       The VGP's ballast water sampling requirements are not as extensive as living organism
sampling currently being contemplated in other forums, including by the International Maritime
Organization (IMO), or under other efforts, including EPA and US Coast Guard's development
of shipboard based sampling protocols for under the ETV program. Those approaches help to
better understand ballast water treatment system performance for both type approval testing and
onboard compliance.  For example, the EPA ETV protocols are used by the U.S. Coast Guard to
define methods required for the land-based portion of U.S. type approval (see
http://nepis.epa.gov/Adobe/PDF/P10097A4.pdffor a copy of the ETV ballast water protocol).
Likewise, numerous test facilities have been established in Asia, Europe, and North America to
characterize ballast water treatment system performance in the context of land-based testing
using the G8 guidelines and/or the ETV protocols.  EPA will continue to track the development
of testing methodologies, and may modify future permit monitoring conditions as  appropriate to
maximize consistency with other approaches and produce better monitoring information.
                                          24

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
                        Table 2-8. Residual Biocides and Biocide Derivative Monitoring Requirements
Biocide
Alkylamines
Chlorine or
Chlorine
dioxide
Menadione
Ozone
Peracetic
Acid
Analyte
Alkylamines
Chlorine Dioxide
Total Residual
Oxidizers (TRO) as
C12
Chlorite*
Chlorate*
Total
Trihalomethanes3
Haloacetic Acidsb*
Menadione
Total Residual
Oxidizers (TRO) as
C12
Bromate*
Bromoform*
Total
Trihalomethanes3
Haloacetic Acidsb*
pH
Analytical Methods
EPA Method 8360B and 8270D
EPA Method 327.0-1; SM 4500
C1O2E
SM 4500-C1 G; ISO 7393/2
EPA Method 300.1
EPA Method 300.1
EPA Method 8260
EPA Method 552.2
NA
SM 4500-C1 G; ISO 7393/2
EPA Method 3 17; EPA
Method 300.1; ASTMD 6581-
00
EPA Method 8260
EPA Method 8260
EPA Method 552.2
SM 4500 H+
Minimum
Volume
25mL
(8260B)
16mL
(327.0-1)
50mL
250 mL
250 mL
25mL
40mL

50mL
250 mL
25mL
25mL
40mL
25mL
Sample Holding
Time
14 days (8260B)
4 hours (327.0-1); As
soon as possible (SM)
15 minutes
14 days
28 days
14 days
14 days

15 minutes
28 days (3 17; 300.1)
14 days
14 days
14 days
As soon as possible
MDL
Varies by
compound (8260D);
10 ug/L (8270C)
Varies (327.0-1); 10
to 100 mg/L (SM)
10 ug/L, under ideal
conditions
Varies
Varies
Varies
Varies by
compound

10 ug/L, under ideal
conditions
Varies (3 17; 300.1)
Varies
Varies
Varies by
compound

Effluent
Limit or
Action
Report
200 ug/L
100 ug/L
Report
Report
Report
Report
Report
100 ug/L
Report
Report
Report
Report
6.5-9s.u.
Limit Type
NA
Instantaneous
Maximum
Instantaneous
Maximum
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Instantaneous
Maximum
                                                              25

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Sampling How-Tofor the 2013 Vessel General Permit
Section 2
                          Table 2-8. Residual Biocides and Biocide Derivative Monitoring Requirements
Biocide

Analyte
Peracetic Acid
Hydrogen Peroxide
Analytical Methods
Photometric analysis
(Pinkernell, 1997; EMD
Chemicals, 2011; CHEMetrics
2010)
Titimetric analysis (JIS K
1463:2007; EMD Chemicals,
2011; CHEMetrics 2010))
Minimum
Volume
25 mL
25 mL
Sample Holding
Time
As soon as possible
As soon as possible
MDL
500 ug/L
500 ug/L
Effluent
Limit or
Action
Report
Report
Limit Type
NA
NA
* Potential byproduct or derivative.
MDL - Method Detection Limit.
NA - Not applicable.
a Total trihalomethanes is the sum of the concentrations of chloroform, bromodichloromethane, dibromochloromethane, and bromoform.
b Haloacetic acids is the sum of the concentrations of mono-, di-, and trichloroacetic acids and mono- and dibromoacetic acids.
                                                                   26

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Sampling How-Tofor the 2013 Vessel General Permit
Section 3
 SECTION 3
 SAMPLING
       This section lists equipment commonly used for vessel sampling, steps for sample
collection, and procedures for sample packing and shipping. These tips are provided as a way to
get started.  Sampling procedures may have to be customized or adjusted to suit the specific
requirements of each vessel.
         Figure 3-1. Vessel Discharge Being Collected in a Labeled Sample Bottle
3.1    LIST OF SAMPLING EQUIPMENT
       The following is a list of sampling equipment, materials, and supplies that may be needed
for proper sampling, depending on both the sample type being collected and the sampling
location.
       •   Sampling Pole (to access sample ports in hard to reach locations)
       •   Sample Bottles (plastic, glass, etc.) (to collect samples)
       •   Field Test Equipment (for pH, chlorine)
       •   Buckets and Disposable Bucket Liners (if taking a large volume of sample)
       •   Bottle Labels
       •   Pens
       •   Disposable Gloves
       •   Preservation Chemicals
       •   Zip Ties
                                          27

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Sampling How-Tofor the 2013 Vessel General Permit
Section 3
          Log Book
          Bubble Wrap/Bubble Bags (to protect the samples during shipping)
          Shipping Paperwork/Traffic Reports
          Garbage Bags (to wrap the samples in shipping)
          Clear and Strapping Tape
          0.45 |im Filters and Other Filtering Equipment (if needed for dissolved metals)
          Ice/Refrigeration/Coolers (some samples need to be chilled until reaching the lab)
          Zipper Storage Bags
          Chain of Custody Forms
          Peristaltic Pump/Tubing (if needed)
          Custody Seals
               Figure 3-2. Example of Various Types of Sample Bottles and
                   Various Preservation Chemicals in Dropper Bottles
3.2    SAMPLE COLLECTION STEPS
       The following are the general steps for sample collection.
       1.     Assemble all the necessary sampling equipment, materials, and supplies onsite.
       2.     Ensure that bottles are appropriately labeled (waterproof labels are best as they
             remain intact and legible). See example bottle label in Section 3.5.
       3.     Ensure that the vessel discharge system is fully operational and has adequate
             flow.
       4.     Collect a discharge sample aliquot to perform any necessary field measurements
             (e.g., pH, free residual chlorine). Refer the user manuals for the field test
             instruments to ensure proper use and maintenance of these meters.
                                           28

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Sampling How-Tofor the 2013 Vessel General Permit
                                                                   Section 3
      Figure 3-3. Typical Field Measurement Meters and Strips for Chlorine and pH.
       5.
Figure 3-4. Sample Collectors Conducting Field Measurements

Determine whether sodium thiosulfate (Na2S2O3) is needed for preservation due
to the presence of chlorine in the sample and add to the sample bottles as
appropriate. See in Section 2 to determine the samples and the conditions in
which sodium thiosulfate needs to be added.
                             Figure 3-5. Sodium Thiosulfate
                                          29

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Sampling How-Tofor the 2013 Vessel General Permit
                                                                     Section 3
       6.
Fill the sample bottles with the appropriate discharge samples. Wear disposable
gloves and use clean equipment to avoid contaminating and cross-contaminating
samples.
       8.
       9.
                Figure 3-6. Sample Collection

If necessary, filter the sample for dissolved metals. See instructions for sample
filtering in Section 3.3 below.

If the laboratory was unable to add preservation chemicals to each bottle, add any
appropriate preservation chemicals at this point and test the pH or chlorine, if
need be to ensure that the enough has been added.
Cool the  samples on ice as dictated by the analytica methods. If the discharge
water is hot to the touch, consider the need to allow samples to cool for a few
minutes prior to placing in ice water to prevent shattering of the sample container
or loss of the lid liner into the sample. To avoid contamination, avoid submerging
sample containers in ice water.
                                            30

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Sampling How-Tofor the 2013 Vessel General Permit
                                                                          Section 3
       10.
       11.

       12.
             Figure 3-7. Filled Sample Bottles Preserved on Ice

       Repeat steps 2 through 9 if more than one discharge needs to be sampled.
       Complete chain of custody forms. See example chain of custody form in Section
       3.5.
3.3
       Once the samples have been cooled to their appropriate preservation temperature,
       pack the samples for transport to the laboratory. If air or overnight shipping is
       necessary, see the section on "Sample Packing and Shipping" in Section 3.4
       below. Otherwise pack the samples in the coolers to avoid breakage.
13.    Transfer custody of the samples to the laboratory  and retain a copy of the chain of
       custody form for your records.
DISSOLVED METALS FILTRATION
       Note: Some labs will filter metals once the sample is shipped/delivered to the laboratory.
This may be preferable to avoid on-site sample filtration (as described below).

       Equipment Needed:

       •  Peristaltic pump;
       •  Approximately 3 feet of New 3/8" Inner Diameter (ID.) pump silicone tubing;
       •  0.45 um cartridge filter with 3/8" Outer Diameter (O.D.) push barbs; and
       •  A 1-liter plastic sample bottle to collect the filtrate (sample).
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Sampling How-Tofor the 2013 Vessel General Permit
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               Figure 3-8. Samplers Performing Dissolved Metals Filtration
       Filtration Procedure:
       1.
       4.
Place new silicone tubing in the peristaltic pump to prevent cross contamination
from previous samples. Allow approximately 2 feet of tubing to extend from both
sides (suction and discharge) of the pump head.
Place a 0.45 um disposable cartridge filter on the discharge end of the pump
tubing. Verify the direction of flow through the cartridge filter (direction of the
flow arrow indicated on the filter housing).
Start the peristaltic pump and place the suction end of the pump tubing into the
unfiltered sample.
            Figure 3-9. A Typical Peristaltic Pump

Fill the 1-liter plastic sample bottle to approximately 3/4 full by collecting the
discharge from the cartridge filter directly into the sample bottle.  Change filter
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Sampling How-Tofor the 2013 Vessel General Permit
                                                                     Section 3
       5.
between samples to prevent contamination of samples or when the flow out of the
filter decreases significantly indicating filter is clogged.

Add nitric acid into the filtered sample for preservation to pH <2.
                  Figure 3-10. Disposable Filter Cartridges and Tubing

3.4    SAMPLE PACKING AND SHIPPING

       When samples must be shipped, all samples must be packaged and shipped in accordance
with Department of Transportation (DOT) or International Air Transport Association (IATA)
regulations. Below are a few tips to ensure the integrity of the samples is maintained through
receipt at the laboratory, that the coolers meet the shipping requirements, and that the samples
and coolers do not leak. Note that a leaking package will not be delivered.

       1.      Ensure all bottles are tightly closed and have a waterproof label.
       2.      Wrap each glass sample bottle with "bubble wrap" and place all bottles in
              individually sealed zipper storage bags to contain liquids and preservation
              chemicals in case of shattering, punctures, or leaks. Place plastic bottles in
              individual zipper storage bags as well to contain any leaks.
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Sampling How-Tofor the 2013 Vessel General Permit
                                                                      Section 3
       3.
         Figure 3-11. Packing Glass and Plastic Bottles

Line the cooler with a large garbage bag to further ensure nothing leaks from the
cooler.
                     Figure 3-12. Garbage Bags Used to Line a Cooler

       4.     Place sample bottles and a temperature blank upright in the garbage bag in the
              cooler and close bag with twist-tie.
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Sampling How-Tofor the 2013 Vessel General Permit
Section 3
                  Figure 3-13. Individually Packed Samples in a Cooler
       5.      Arrange sealed plastic freezer bags filled with ice (or chemical ice) on top of the
              sample bottles (if sample cooling is required for preservation). This will ensure
              that the preservation temperature of the samples is maintained through receipt at
              the laboratory, which may take several days.
  Figure 3-14. Samples in a Sealed Bag and Bags of Ice to Keep the Samples Cold During
                                        Shipping
       6.      Place the completed chain of custody form in the cooler (retain a copy for your
              records).
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Sampling How-Tofor the 2013 Vessel General Permit
Section 3
          Figure 3-15. Place the Chain of Custody in a Plastic Bag to Keep it Dry.
       7.      Close cooler and secure with strapping tape to ensure that the lid will remain
              closed if the latch is accidentally released or damaged.  Also tape the cooler drain
              plug closed so it will not open during shipment.
       Figure 3-16. A Packed Cooler Showing the Custody Seal and Strapping Tape
                                           36

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Sampling How-Tofor the 2013 Vessel General Permit                                            Section 3


       8.     Place a completed address label on the lid of the cooler including name, address,
             and telephone number of the receiving laboratory and the return address and
             telephone number of the shipper.
       9.     Place a custody seal on the cooler in a manner that will allow the laboratory to
             verify the cooler has not been opened or tampered with during shipment. Place
             clear tape over the custody seal to ensure the custody seal remains on the cooler
             during transport to the laboratory.
3.5    BOTTLE LABELS AND CHAIN OF CUSTODY (COC) FORMS

       Each sample container should have a label that clearly provides information identifying
and describing the sample. Ideally, sample container labels should provide the following
information:

       •  Site name
       •  Sample identification number
       •  Date and time the sample was collected
       •  Sampling location (e.g., site name or address)
       •  Container size
       •  Container type
       •  Type of sample (grab or composite)
       •  Analysis
       •  Preservatives added, if applicable
       •  Name or initials of sample  collector(s)

       All of the information on the sample label should be identical  to the information on the
COC form. The sample collector should be able to extrapolate based on field notes, bottle labels,
and COCs where and when the samples were taken in case additional sampling or analysis is
necessary.

       To facilitate sample collection  activities and ensure proper labeling, sample containers
should be pre-labeled as much as is practical prior to sample collection. Sample labels should be
completed with waterproof ink and securely affixed to each sample container to identify each
sample clearly. If waterproof ink is not used, it is recommended that the sampler cover the
label(s) with clear packaging tape after writing the sampling information onto the label.

       The COC form should include  any available information regarding the potential hazards
associated with the sample, handling procedures required for the samples, sample identification
number, sample concentration, if known, sampling location, sample date and time, sample
matrix, names and signatures of the samplers, and signatures of all individuals who had custody
of the samples. A COC form should remain with the samples from collection to laboratory
receipt.  If samples are split into two or more shipping containers, copies of the COC form should
be placed with each container and directly indicate the contents.
                                           37

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Sampling How-Tofor the 2013 Vessel General Permit                                             Section 3
       A COC form creates an accurate written record that can be used to trace the creation,
possession, and handling of the sample from the moment it is collected through analysis. A COC
form is used and required, without exception, for the tracking and recording of on-site or off-site
sample collection, transport and analysis. A COC form accompanies each sample or group of
samples as custody of the sample(s) is transferred from one custodian to another. One copy of
the form is retained by the original sample collector, and the original is obtained by the receiving
laboratory. If multiple laboratories are receiving a sample, individual COC forms should be
submitted; each COC form represents the contents of the sample shipment. Each laboratory or
facility representative who accepts an incoming sample shipment signs and dates the COC form.
It is typically the laboratory or facility's responsibility to maintain internal logbooks and custody
records throughout sample preparation and analysis. Sample custodians are typically responsible
for initiating, maintaining, and completing COC tracking. A sample custodian is the person
responsible for the custody of a sample or samples at a particular time, until custody is
transferred to another person (and so documented), who then becomes the new custodian. A
sample is under a person's custody if:

       •  It is in that person's possession,
       •  It is in that person's view, after being in that person's physical possession,
       •  It was in that person's physical possession and then he/she locked it up to prevent
          tampering, or
       •  It was in that person's physical possession and then he/she placed it in a designated
          and identified secure area.

       Handling of COC forms during sample transportation depends on the method of
transport. If the laboratory is  within driving distance, the sample containers can be couriered to
the laboratory. In this case, then the courier should sign off on the COC. It is important to note
that common commercial carriers will not usually accept responsibility for handling and
completing COC forms. This often necessitates packing the COC form in the shipping container
(enclosed with other documentation in a plastic zipper-type bag). As long as COC forms are
sealed inside the shipping or  transport container and the container's custody seals are intact,
commercial carriers are not required to sign the COC form. Using a computer and the Web, the
tracking information generated by a common carrier can be obtained if complete COC tracking is
required. This  documentation is attached to the COC form to show that the sample container was
in the possession of the carrier during the missing COC time. This time period should be noted as
"common  carrier" on the COC form between the final custodian at the sample site location and
laboratory receipt.

       Although COC forms vary in style, format, and detail, the forms  should contain the same
minimal information required to identify the sample. Procedures for filling out other styles of
COC forms will be very similar. It is best for the samplers to fill out the  COC form provided by
the party receiving the samples. Sample screening can influence the strategy used for sample
analysis. Consult with the laboratory service to see if they have existing  COC templates and
whether they can prefill  some of the known information. The following information should be
provided and the following steps  should be followed to complete COC forms:

       •  General information (sample owners, contact information, site name)
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Sampling How-Tofor the 2013 Vessel General Permit
                                   Section 3
       •   Sample specific information for each sample that will be traveling in the same
          cooler/transport container (i.e., sample identification number, sample type [matrix],
          grab or composite, number and type of sample containers, and date and time sample
          was collected)
       •   Sign, date, and enter the time under "Relinquished by" entry. Have the person
          receiving the sample sign the "Received by" entry. If shipping samples by a common
          carrier, print the carrier to be used in this space (e.g., Federal Express, UPS).
       •   If a common carrier is used,  a copy of the airbill is to be kept for recording purposes
          by both the sender and recipient.
       •   Place the original signed copy of the COC form in a plastic zipper-type bag or other
          appropriate waterproof sample shipping package. Retain a copy with the field
          records.
       •   Complete carrier-required shipping papers.
       •   If possible, fax or scan and email a copy of the COC form and field report to the party
          receiving the samples.

       The following is an example of a bottle label:
     f Sample Number:
       Sampling Port:
       Vessel Name/Number:
       Sampling Point Description:
       Day and Time of Sample Collection:
       Analysis to be Performed:
       Sample Bottle Type:
       Preservation Used:
       Sampler Initials:
000001
Miami, Florida
Container Vessel 123
Exhaust Gas Scrubber Inlet Water
8/8/2013 4:30 PMEST
Total Metals
500-mL Plastic Bottle
HNO3 to pH<2
FH and GW
                                          39

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Sampling How-Tofor the 2013 Vessel General Permit
                                     Section 3
       The following is a sample Chain of Custody form:
Name of Lab
Lab Address
and contact information
Location:
Sampling Contact:
Email Address:
Phone:
Shipped by:
Received by:
CHAIN
OF
CUSTODY
Comments:
Ship To:
ATTN:
Garner:
Airbill:
Ship Date:
Received Date:
Sample Point Description
Sample
Number










Date
and
Time










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•8
JK
*o
o










Vessel
or
Amb lent
Source










Discharge
Type










Additional Sample
Description










Preservation (y/h)










£
£>
§
••a
•R
£










^
•5?
_>,
5










Salt Water (y/n)










I
Analysis













































































T emp erature b lank — Ship:
Temperature blank —Receipt:
                                              40

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