ASTM D6903-07(2020)
(Test Method)Standard Test Method for Determination of Organic Biocide Release Rate From Antifouling Coatings in Substitute Ocean Water
Standard Test Method for Determination of Organic Biocide Release Rate From Antifouling Coatings in Substitute Ocean Water
SIGNIFICANCE AND USE
4.1 This test method is designed to provide a laboratory procedure to quantify and characterize changes in the release rate of organic biocide from antifouling coatings that occur during a period of immersion under specified laboratory conditions of constant temperature, pH, salinity, and hydrodynamics. Quantitative measurement of biocide release rate is necessary to help in selection of materials, providing quality control, and understanding the performance mechanism.
4.2 Results from this test method establish a pattern of biocide release from an antifouling coating over a minimum of 45 days exposure under controlled laboratory conditions. Biocide release rates of antifouling paints in-service vary over the life of the coating system depending on the formulation and on the physical and chemical properties of the environment. Factors such as differences in berthing locations, operating schedules, length of service, condition of paint film surface, temperature, pH, and salinity influence the actual release rate under environmental conditions. Results obtained using this test method do not reflect actual biocide release rates that will occur in service, but provide comparisons of the release rate characteristics of different antifouling formulations in substitute ocean water under the prescribed laboratory conditions.
4.3 By comparison with published copper and organotin release rate data4,5 obtained either by direct measurements from ship hulls or release rate measurements from harbor exposed panels, all data indicate that the results of this generic rotating-cylinder test method significantly overestimate the release rate of biocide when compared to release rates under in-service conditions. For example, published results demonstrate that this generic test method produces higher measurements of copper and organotin release rates than from direct in situ measurements for the same coating on in-service ship hulls and harbor-exposed panels. The difference betwee...
SCOPE
1.1 This test method covers the laboratory determination of the rate at which organic biocide is released from an antifouling coating exposed in substitute ocean water. The test is run entirely in the laboratory under controlled conditions of pH, temperature, salinity, and hydrodynamics. Analytical procedures are provided for the determination of the release rate of 4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), zinc and copper pyrithione (ZPT and CuPT), and N-cyclopropyl-N′-(1,1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine (CDMTD). At predetermined intervals, substitute ocean water samples are analyzed for leached biocide using a suitable analytical technique.
1.2 In cases in which the antifouling coating contains both an organic biocide and a copper-based biocide, the release rate of copper may optionally be concurrently determined according to the procedure found in Test Method D6442.
1.3 The procedure contains the preparation steps for the determination of the release rate of biocide in substitute ocean water from antifouling paints including apparatus, reagents, holding tank conditions, and sampling point details. The procedure calls for the accurate determination of organic biocide concentrations in substitute ocean water at the low μg L-1 (parts per billion, ppb) level. To detect and correct for reagent impurities and allow a suitable level of analytical precision to be achieved, the analytical method to be used for the determination of the concentration of organic biocide in substitute ocean water must meet the acceptability criteria given in Annex A2. Where Annex A2 specifies a limit of quantitation (LOQ), the procedure for determining the LOQ for the organic biocide in substitute ocean water by the analytical method presented in Annex A3 is to be followed.
1.4 Suitable analytical methods that use high-performance liquid chromatography (HPLC) for determining the concentration of DCOIT, ZP...
General Information
- Status
- Published
- Publication Date
- 31-Jul-2020
- Technical Committee
- D01 - Paint and Related Coatings, Materials, and Applications
- Drafting Committee
- D01.45 - Marine Coatings
Relations
- Effective Date
- 01-Aug-2020
- Effective Date
- 01-Aug-2020
- Effective Date
- 01-Jun-2020
- Effective Date
- 01-Jun-2012
- Effective Date
- 15-Jul-2008
- Effective Date
- 01-Nov-2007
- Effective Date
- 01-Jun-2006
- Effective Date
- 01-Mar-2006
- Effective Date
- 01-Jul-2005
- Effective Date
- 10-Aug-2003
- Effective Date
- 10-May-2003
- Effective Date
- 01-Jan-2001
- Effective Date
- 01-Jan-2001
- Effective Date
- 10-Dec-1999
- Effective Date
- 10-Feb-1999
Overview
ASTM D6903-07(2020) sets forth a standardized laboratory test method for determining the release rate of organic biocides from antifouling coatings in substitute ocean water. Developed by ASTM International, this standard is widely used in the marine coatings industry to evaluate the biocidal performance of antifouling paints under precisely controlled laboratory conditions. The procedure provides necessary data for the comparison and quality assurance of different antifouling formulations, guiding material selection and understanding of coating behavior over time.
Key Topics
- Test Environment: The method specifies controlled laboratory conditions for temperature, pH, salinity, and hydrodynamics, simulating a marine environment while ensuring reproducibility of results.
- Quantitative Analysis: Detailed analytical procedures are provided to accurately determine the release rates of key organic biocides: 4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), zinc pyrithione (ZPT), copper pyrithione (CuPT), and N-cyclopropyl-N'-(1,1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine (CDMTD).
- Substitute Ocean Water: The use of artificial seawater ensures consistent testing conditions and minimizes environmental variability.
- Measurement Techniques: High-performance liquid chromatography (HPLC) and related analytical methods are recommended for detecting low concentrations (parts per billion, ppb) of biocides with high precision.
- Sample Preparation and Handling: Instructions cover proper sample generation, handling, and analytical requirements to minimize contamination and ensure accuracy.
- Result Interpretation: While the method provides comparative data under laboratory conditions, it acknowledges that results may overestimate in-service release rates due to enhanced laboratory-controlled parameters.
Applications
- Antifouling Coating Development: R&D professionals use this standard to compare the biocide release characteristics of new and existing antifouling paint formulations.
- Quality Control: Manufacturers employ ASTM D6903-07(2020) as a quality assurance tool, verifying consistency and compliance in production batches.
- Regulatory Submission: Data generated from this test method supports environmental compliance, regulatory submissions, and product registration in the marine coatings sector.
- Material Selection: Coastal infrastructure installers and shipowners utilize release rate patterns to select coatings with optimal long-term performance based on anticipated service conditions.
- Performance Evaluation: By simulating immersion over 45 days, the test establishes biocide release profiles that help predict antifouling effectiveness during the initial and medium-term exposure periods.
Related Standards
- ASTM D6442: Test Method for Copper Release Rate from Antifouling Coatings in Substitute Ocean Water.
- ASTM D1141: Practice for Preparation of Substitute Ocean Water, essential for preparing accurate test solutions.
- ASTM D1005: Test Method for Measuring Dry-Film Thickness of Organic Coatings, referenced for accurate film thickness assessment.
- ASTM D1193: Specification for Reagent Water, ensuring purity for solution preparation and analytical procedures.
Practical Value
Adopting ASTM D6903-07(2020) streamlines the evaluation of organic biocide release rates from marine antifouling coatings, providing reliable, repeatable data critical to:
- Optimizing product formulation.
- Assessing performance prior to full-scale marine deployment.
- Improving quality control and product consistency.
- Facilitating compliance with international environmental and maritime regulatory standards.
By standardizing laboratory measurements, this test method plays an integral role in advancing marine coating technologies and supporting the global fight against biofouling.
Keywords: ASTM D6903, biocide release rate, antifouling coatings, organic biocide, substitute ocean water, marine coatings, quality control, performance evaluation, DCOIT, ZPT, CuPT, CDMTD.
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Frequently Asked Questions
ASTM D6903-07(2020) is a standard published by ASTM International. Its full title is "Standard Test Method for Determination of Organic Biocide Release Rate From Antifouling Coatings in Substitute Ocean Water". This standard covers: SIGNIFICANCE AND USE 4.1 This test method is designed to provide a laboratory procedure to quantify and characterize changes in the release rate of organic biocide from antifouling coatings that occur during a period of immersion under specified laboratory conditions of constant temperature, pH, salinity, and hydrodynamics. Quantitative measurement of biocide release rate is necessary to help in selection of materials, providing quality control, and understanding the performance mechanism. 4.2 Results from this test method establish a pattern of biocide release from an antifouling coating over a minimum of 45 days exposure under controlled laboratory conditions. Biocide release rates of antifouling paints in-service vary over the life of the coating system depending on the formulation and on the physical and chemical properties of the environment. Factors such as differences in berthing locations, operating schedules, length of service, condition of paint film surface, temperature, pH, and salinity influence the actual release rate under environmental conditions. Results obtained using this test method do not reflect actual biocide release rates that will occur in service, but provide comparisons of the release rate characteristics of different antifouling formulations in substitute ocean water under the prescribed laboratory conditions. 4.3 By comparison with published copper and organotin release rate data4,5 obtained either by direct measurements from ship hulls or release rate measurements from harbor exposed panels, all data indicate that the results of this generic rotating-cylinder test method significantly overestimate the release rate of biocide when compared to release rates under in-service conditions. For example, published results demonstrate that this generic test method produces higher measurements of copper and organotin release rates than from direct in situ measurements for the same coating on in-service ship hulls and harbor-exposed panels. The difference betwee... SCOPE 1.1 This test method covers the laboratory determination of the rate at which organic biocide is released from an antifouling coating exposed in substitute ocean water. The test is run entirely in the laboratory under controlled conditions of pH, temperature, salinity, and hydrodynamics. Analytical procedures are provided for the determination of the release rate of 4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), zinc and copper pyrithione (ZPT and CuPT), and N-cyclopropyl-N′-(1,1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine (CDMTD). At predetermined intervals, substitute ocean water samples are analyzed for leached biocide using a suitable analytical technique. 1.2 In cases in which the antifouling coating contains both an organic biocide and a copper-based biocide, the release rate of copper may optionally be concurrently determined according to the procedure found in Test Method D6442. 1.3 The procedure contains the preparation steps for the determination of the release rate of biocide in substitute ocean water from antifouling paints including apparatus, reagents, holding tank conditions, and sampling point details. The procedure calls for the accurate determination of organic biocide concentrations in substitute ocean water at the low μg L-1 (parts per billion, ppb) level. To detect and correct for reagent impurities and allow a suitable level of analytical precision to be achieved, the analytical method to be used for the determination of the concentration of organic biocide in substitute ocean water must meet the acceptability criteria given in Annex A2. Where Annex A2 specifies a limit of quantitation (LOQ), the procedure for determining the LOQ for the organic biocide in substitute ocean water by the analytical method presented in Annex A3 is to be followed. 1.4 Suitable analytical methods that use high-performance liquid chromatography (HPLC) for determining the concentration of DCOIT, ZP...
SIGNIFICANCE AND USE 4.1 This test method is designed to provide a laboratory procedure to quantify and characterize changes in the release rate of organic biocide from antifouling coatings that occur during a period of immersion under specified laboratory conditions of constant temperature, pH, salinity, and hydrodynamics. Quantitative measurement of biocide release rate is necessary to help in selection of materials, providing quality control, and understanding the performance mechanism. 4.2 Results from this test method establish a pattern of biocide release from an antifouling coating over a minimum of 45 days exposure under controlled laboratory conditions. Biocide release rates of antifouling paints in-service vary over the life of the coating system depending on the formulation and on the physical and chemical properties of the environment. Factors such as differences in berthing locations, operating schedules, length of service, condition of paint film surface, temperature, pH, and salinity influence the actual release rate under environmental conditions. Results obtained using this test method do not reflect actual biocide release rates that will occur in service, but provide comparisons of the release rate characteristics of different antifouling formulations in substitute ocean water under the prescribed laboratory conditions. 4.3 By comparison with published copper and organotin release rate data4,5 obtained either by direct measurements from ship hulls or release rate measurements from harbor exposed panels, all data indicate that the results of this generic rotating-cylinder test method significantly overestimate the release rate of biocide when compared to release rates under in-service conditions. For example, published results demonstrate that this generic test method produces higher measurements of copper and organotin release rates than from direct in situ measurements for the same coating on in-service ship hulls and harbor-exposed panels. The difference betwee... SCOPE 1.1 This test method covers the laboratory determination of the rate at which organic biocide is released from an antifouling coating exposed in substitute ocean water. The test is run entirely in the laboratory under controlled conditions of pH, temperature, salinity, and hydrodynamics. Analytical procedures are provided for the determination of the release rate of 4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), zinc and copper pyrithione (ZPT and CuPT), and N-cyclopropyl-N′-(1,1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine (CDMTD). At predetermined intervals, substitute ocean water samples are analyzed for leached biocide using a suitable analytical technique. 1.2 In cases in which the antifouling coating contains both an organic biocide and a copper-based biocide, the release rate of copper may optionally be concurrently determined according to the procedure found in Test Method D6442. 1.3 The procedure contains the preparation steps for the determination of the release rate of biocide in substitute ocean water from antifouling paints including apparatus, reagents, holding tank conditions, and sampling point details. The procedure calls for the accurate determination of organic biocide concentrations in substitute ocean water at the low μg L-1 (parts per billion, ppb) level. To detect and correct for reagent impurities and allow a suitable level of analytical precision to be achieved, the analytical method to be used for the determination of the concentration of organic biocide in substitute ocean water must meet the acceptability criteria given in Annex A2. Where Annex A2 specifies a limit of quantitation (LOQ), the procedure for determining the LOQ for the organic biocide in substitute ocean water by the analytical method presented in Annex A3 is to be followed. 1.4 Suitable analytical methods that use high-performance liquid chromatography (HPLC) for determining the concentration of DCOIT, ZP...
ASTM D6903-07(2020) is classified under the following ICS (International Classification for Standards) categories: 25.220.60 - Organic coatings. The ICS classification helps identify the subject area and facilitates finding related standards.
ASTM D6903-07(2020) has the following relationships with other standards: It is inter standard links to ASTM D6903-07(2013), ASTM D6442-06(2020), ASTM D1005-95(2020), ASTM D6442-06(2012), ASTM D1141-98(2008), ASTM D1005-95(2007), ASTM D6442-06, ASTM D1193-06, ASTM D6442-05, ASTM D1141-98(2003), ASTM D6442-03, ASTM D1005-95(2001), ASTM D1005-95, ASTM D6442-99, ASTM D1193-99e1. Understanding these relationships helps ensure you are using the most current and applicable version of the standard.
ASTM D6903-07(2020) is available in PDF format for immediate download after purchase. The document can be added to your cart and obtained through the secure checkout process. Digital delivery ensures instant access to the complete standard document.
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D6903 − 07 (Reapproved 2020)
Standard Test Method for
Determination of Organic Biocide Release Rate From
Antifouling Coatings in Substitute Ocean Water
This standard is issued under the fixed designation D6903; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope ocean water are given in Appendix X1 – Appendix X3,
respectively. Other methods may be used provided that they
1.1 This test method covers the laboratory determination of
meet the appropriate criteria given in Annex A2.
the rate at which organic biocide is released from an antifoul-
ing coating exposed in substitute ocean water. The test is run
1.5 Whenthereleaserateofahighlyphotosensitiveorganic
entirely in the laboratory under controlled conditions of pH,
biocide is being determined, steps must be taken to protect the
temperature, salinity, and hydrodynamics. Analytical proce-
apparatus and samples from exposure to natural and artificial
dures are provided for the determination of the release rate of
visible light sources. Any such requirement for these steps to
4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), zinc and
be taken for a particular biocide is indicated in Annex A2.
copper pyrithione (ZPT and CuPT), and N-cyclopropyl-N'-(1,
1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine 1.6 Thepracticallimitsforquantifyingbiocidereleaserates
-2 -1
(CDMTD).At predetermined intervals, substitute ocean water bythismethodarefrom4.5to500 µgcm d forDCOIT,0.36
-2 -1 -2 -1
samples are analyzed for leached biocide using a suitable
to 500 µgcm d for CuPT, 0.36 to 500 µgcm d for ZPT,
-2 -1
analytical technique.
and 2.7 to 500 µgcm d for CDMTD. These ranges may be
-2 -1
extended to 3.8 to 500 µgcm d for DCOIT, 0.16 to 500 µg
1.2 In cases in which the antifouling coating contains both
-2 -1 -2 -1
cm d for CuPT, 0.2 to 500 µgcm d for ZPT, and 2.2 to
an organic biocide and a copper-based biocide, the release rate
-2 -1
500 µgcm d for CDMTD if the procedures described in
of copper may optionally be concurrently determined accord-
Appendix X1 – Appendix X3 (as appropriate) are followed.
ing to the procedure found in Test Method D6442.
The quantitation of release rates lower than these ranges will
1.3 The procedure contains the preparation steps for the
require the use of analytical methods with lower limits of
determination of the release rate of biocide in substitute ocean
quantitation than those specified in Annex A2.
water from antifouling paints including apparatus, reagents,
holding tank conditions, and sampling point details. The
1.7 The results of this test method do not reflect environ-
procedure calls for the accurate determination of organic
mental biocide release rates for antifouling products, and are
biocide concentrations in substitute ocean water at the low µg
not suitable for direct use in the process of generating
-1
L (parts per billion, ppb) level. To detect and correct for
environmental risk assessments, environmental loading
reagent impurities and allow a suitable level of analytical
estimates, or for establishing release rate limits for regulatory
precision to be achieved, the analytical method to be used for
purposes. See also Section 4.
the determination of the concentration of organic biocide in
1.8 The values stated in SI units are to be regarded as the
substitute ocean water must meet the acceptability criteria
given in Annex A2. Where Annex A2 specifies a limit of standard. The values given in parentheses are for information
only.
quantitation(LOQ),theprocedurefordeterminingtheLOQfor
the organic biocide in substitute ocean water by the analytical
1.9 This standard does not purport to address all of the
method presented in Annex A3 is to be followed.
safety concerns, if any, associated with its use. It is the
1.4 Suitable analytical methods that use high-performance
responsibility of the user of this standard to establish appro-
liquid chromatography (HPLC) for determining the concentra-
priate safety, health, and environmental practices and deter-
tion of DCOIT, ZPT and CuPT, and CDMTD in substitute
mine the applicability of regulatory limitations prior to use.
1.10 This international standard was developed in accor-
1 dance with internationally recognized principles on standard-
This test method is under the jurisdiction of ASTM Committee D01 on Paint
andRelatedCoatings,Materials,andApplicationsandisthedirectresponsibilityof
ization established in the Decision on Principles for the
Subcommittee D01.45 on Marine Coatings.
Development of International Standards, Guides and Recom-
Current edition approved Aug. 1, 2020. Published August 2020. Originally
mendations issued by the World Trade Organization Technical
approved in 2007. Last previous edition approved in 2013 as D6903 – 07 (2013).
DOI: 10.1520/D6903-07R20. Barriers to Trade (TBT) Committee.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6903 − 07 (2020)
2. Referenced Documents temperature, pH, and salinity influence the actual release rate
2 under environmental conditions. Results obtained using this
2.1 ASTM Standards:
test method do not reflect actual biocide release rates that will
D1005Test Method for Measurement of Dry-Film Thick-
occur in service, but provide comparisons of the release rate
ness of Organic Coatings Using Micrometers
characteristics of different antifouling formulations in substi-
D1141Practice for the Preparation of Substitute Ocean
tute ocean water under the prescribed laboratory conditions.
Water
D1193Specification for Reagent Water 4.3 By comparison with published copper and organotin
4,5
D6442Test Method for Determination of Copper Release release rate data obtained either by direct measurements
Rate From Antifouling Coatings in Substitute Ocean from ship hulls or release rate measurements from harbor
Water exposed panels, all data indicate that the results of this generic
rotating-cylinder test method significantly overestimate the
2.2 U.S. Federal Standard:
release rate of biocide when compared to release rates under
40 CFR 136,Appendix B, revision 1.11
in-service conditions. For example, published results demon-
3. Summary of Test Method
strate that this generic test method produces higher measure-
mentsofcopperandorganotinreleaseratesthanfromdirectin
3.1 The candidate paint system is applied to the cylindrical
situmeasurementsforthesamecoatingonin-serviceshiphulls
test specimens. The coated specimens are placed in a tank of
and harbor-exposed panels. The difference between the results
substitute ocean water in which the levels of organic biocide
of this test method and the panel and ship studies was up to a
and copper (where the coating also contains a biocidal copper
-1
factorofabout30basedoncopperreleaseratedataforseveral
compound) are kept below 100 µgL by circulating the
4,6
commercial antifouling coatings. No direct release rate data
substitute ocean water through a suitable filtration system (see
from ship hulls or harbor-exposed panels have been generated
5.1.3).At specified intervals, each specimen is placed in 1500
to-date for the biocides covered by this method. However, the
mL of substitute ocean water (see Section 8 for details) and
expectation is that the results of this test method, when
rotatedat60rpmfor1h(orless,see8.7forfurtherexplanation
compared with the direct measurements from ship hulls and
and instruction). The rate of biocide release from the paint is
harbor-exposed panels, could follow the same trend. Realistic
determined by measuring concentrations of the biocide in the
estimates of the biocide release from a ship’s hull under
substitute ocean water in the individual measuring containers.
in-service conditions can only be obtained from this test
3.2 Annex A2 provides acceptance criteria for analytical
method where the difference between the results obtained by
procedures for measuring the concentration of specific organic
this test method and the release rate of an antifouling coating
biocides in substitute ocean water. Suitable methods are
in service is taken into account.
providedinAppendixX1–AppendixX3.Alternativemethods
4.4 Where the results of this test method are used in the
may be used provided that they meet the acceptance criteria
process of generating environmental risk assessments, for
given in Annex A2.
environmental loading estimates, or for regulatory purposes, it
is most strongly recommended that the relationship between
4. Significance and Use
laboratory release rates and actual environment inputs is taken
4.1 This test method is designed to provide a laboratory
into account to allow a more accurate approximation of the
procedure to quantify and characterize changes in the release
biocide release rate from antifouling coatings under real-life
rate of organic biocide from antifouling coatings that occur
conditions. This can be accomplished through the application
during a period of immersion under specified laboratory
of appropriate correction factors.
conditions of constant temperature, pH, salinity, and hydrody-
namics. Quantitative measurement of biocide release rate is
5. Apparatus
necessary to help in selection of materials, providing quality
5.1 Sample Generation—SeeAnnexA2forguidanceonany
control, and understanding the performance mechanism.
particular materials restriction and handling requirements re-
4.2 Results from this test method establish a pattern of
lating to each organic biocide.
biocidereleasefromanantifoulingcoatingoveraminimumof
5.1.1 Release Rate Measuring Container—A nominal 2-L
45 days exposure under controlled laboratory conditions.
( ⁄2-gal) container made of an inert material, approximately
Biocide release rates of antifouling paints in-service vary over
13.5 cm (5.3 in.) in diameter and 19 cm (7.5 in.) high, is fitted
thelifeofthecoatingsystemdependingontheformulationand
withthreerodsalsomadeofaninertmaterial,approximately6
on the physical and chemical properties of the environment.
mm (nominal ⁄4 in.) in diameter to serve as baffles. Rods shall
Factors such as differences in berthing locations, operating
be evenly spaced on the inside circumference of the container
schedules, length of service, condition of paint film surface,
to prevent swirling of the water with the test cylinder during
2 4
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Valkirs,A. O., Seligman, P. F., Haslbeck, E., and Caso, J. S., Marine Bulletin,
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Vol. 46 (2003), pp. 763–779.
Standards volume information, refer to the standard’s Document Summary page on Champ,M.A.andSeligman,P.F., Organotin: Environmental Fate and Effects,
theASTM website. Chapter 19 — Measurement and Significance of the Release Rate for Tributyltin,
AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments, (1996) Chapman and Hall, pp 383–403.
732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http:// Finnie,A.A.,ImprovedEstimatesofEnvironmentalCopperReleaseRateFrom
www.access.gpo.gov. Antifouling Coatings, Biofouling, Vol. 22 (2006), pp 279–291.
D6903 − 07 (2020)
rotation. The rods will be secured to the container walls using bottom-end can be used. Do not coat the lower 1 to 2 cm (0.39
an inert adhesive. The material of construction of the release to 0.79 in.) of the test cylinder. The test cylinder shall be of
rate measuring container and rods for use with any particular such height so that a rotating device can be attached to and
biocide shall be as specified in A2.3. When the release rate of rotatethecylinderwiththeupperendofthecylinderabovethe
a photosensitive material is to be determined, the container level of the test container immersion liquid to prevent entry of
shall be protected from light. The requirement to protect the theimmersionliquidintothetestcylinder(seeAnnexA1).The
release rate container from light for any particular organic material of construction of the test cylinder (including the
biocide is indicated in A2.4. bottomend-disk)forusewithanyparticularbiocideshallbeas
specified in A2.3. It is advisable to weight the cylinder by
NOTE1—Theresultsofthistestmethodwillbeadverselyaffectedifthe
filling with water so that the unit does not have buoyancy.
biocide is strongly adsorbed or absorbed by the release rate measuring
container or the test cylinder, or both. Where the release rates of two or
NOTE 2—When coating release rates are very high, it may be desirable
moredifferentbiocidesaretobeconcurrentlydeterminedfromasingleset 2 -1
to use a 5-cm band (100-cm paint area) to avoid exceeding 200 µgL
ofmeasurements,thereleaseratemeasuringcontainer,associatedrodsand
of organic biocide in the measuring containers (see 8.7.1).
the test cylinders must all be made of a material that is inert to all of the
biocides, otherwise repeat testing (different cylinders and measuring 5.1.6 Test Cylinder Rotating Device—The device shall be
containers) for each biocide will be required.
capable of rotating the test cylinder in the release rate measur-
-1
ing container at 60 6 5 rpm (0.2 6 0.02 m s , velocity of test
5.1.2 Constant Temperature Control—This control is a
cylinder surface). No part of the rotating device shall be
means of maintaining the release rate measuring containers at
immersed in substitute ocean water.
atemperatureof25 61°Cduringtherotationperiod(see8.7).
5.1.7 pH Meter, with a suitable electrode.
5.1.3 Holding Tank—This tank is an inert plastic container
5.1.8 Appropriate Hydrometer or Salinometer.
of such dimensions so as to permit immersion of four or more
test cylinders and must be equipped with a system to circulate
5.2 Analysis of Leachate—Suitable analytical procedures
the seawater continuously in the tank through an activated
are provided for the determination of the release rate of
carbon filter and, optionally, an absorbent filter. If an absor-
4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), zinc and
bent filter is used, regenerate the ion exchange resin following
copper pyrithione (ZPT and CuPT), and N-cyclopropyl-N'-(1,
the manufacturer’s instructions and wash the resin with sub-
1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine
stitute ocean water before use. The rate of water flow and the
(CDMTD). Refer to Appendix X1 – Appendix X3 for addi-
size of the filter shall be selected to maintain the concentration
tional apparatus requirements for the analysis of specific
-1
ofeachorganicbiocidebelow100 µgL (100ppb)and,when
organic biocides in which these analytical methods are to be
the coating contains a biocidal copper compound, the concen-
used.
-1
tration of copper below 100 µgL . Flow rates should be set to
obtaintwotoeightturnoversperhour.Whenthereleaserateof
6. Reagents and Materials
a photosensitive material is to be determined, the holding tank
6.1 Sample Generation:
shall be protected from light. The requirement to protect
6.1.1 Purity of Reagents—Reagent grade chemicals shall be
holding tank from light for any particular organic biocide is
used in all tests, unless otherwise indicated. It is intended that
indicated in A2.4.
all reagents conform to the specifications of the Committee on
5.1.4 The size and geometry of the tanks as well as the
Analytical Reagents of theAmerican Chemical Society where
positioning of the inflow and outflow ports for the water
such specifications are available. Other grades may be used,
circulation system shall be selected to obtain a slow, relatively
provided it is first ascertained that the reagent is of sufficiently
uniformflowofsubstituteoceanwaterpastalltestcylindersin
high purity to permit its use without lessening the accuracy of
the tank. Maintain the pH of the substitute ocean water
the determination.
between 7.9 and 8.1, the salinity between 33 and 34 parts per
6.1.2 Purity of Water—Distilled water conforming to Type
thousand (ppt), and the temperature at 25 6 1°C (77 6 2°F).
II of Specification D1193.
5.1.5 Test Cylinders—Approximately 6.4-cm (nominal 2 ⁄2-
6.1.3 Substitute Ocean Water—Artificial ocean water in
in.) outside diameter by 17.8-cm (nominal 7-in.) long pipe or
accordance with Practice D1141, section on Preparation of
equivalent cylindrical shapes made of an inert material and
Substitute Ocean Water, or a proprietary equivalent with a
coatedwitha10-cm(3.94-in.)bandofantifoulingpaintaround
salinity of 33 to 34 ppt and pH 7.9 to 8.1.
the exterior circumference of the test cylinder to provide 200
6.1.4 Extraction Media—Activatedcarbonand,optionally,a
cm ofpaintfilmthatcanbeimmersedandfreelyrotatedinthe
chelating ion-exchange resin, iminodiacetic (imminodiacetic)
releaseratemeasuringcontainer(seeNote1andNote2).Atop
acid exchange resin on a styrene support, nominal particle size
disk, fitted with a shaft of proper diameter for the rotating
range approximately 0.300 to 0.850 mm (20 to 50 mesh) (see
device, shall be sealed to the cylinder. Seal the bottom of the
5.1.3).
test cylinder so as to form a watertight joint. Alternatively,
prefabricated one-piece test cylinders with an integral sealed
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington,
A filter cartridge, containing a chelating iminodiacetic (alternative spelling – DC. For suggestions on the testing of reagents not listed by theAmerican Chemical
imminodiacetic)acidion-exchangeresinonastyrenesupport(nominalparticlesize Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
range approximately 0.300 to 0.850 mm (20 to 50 mesh)) of sufficient capacity to U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
require regeneration only once a month or less frequently, has been found suitable. copeial Convention, Inc. (USPC), Rockville, MD.
D6903 − 07 (2020)
6.1.5 Hydrochloric Acid (HCl)—10% v/v, aqueous solu- allow the paint to dry for 7 6 1 day at 25 6 2°C (77 6 36°F)
tion. and 30 to 80% relative humidity. Include application method
6.1.6 Sodium Hydroxide (NaOH)—1.0 N, aqueous solution. and coating thickness in report.
6.1.7 Sodium Chloride (NaCl)—5 M, aqueous solution.
8.4 Measure the initial dry film thickness using a suitable
6.2 Analysis of Leachate—Refer to Appendix X1 –
nondestructive procedure found in Test Method D1005 or
Appendix X3 for Reagents and Materials requirements for the
another suitable nondestructive method and report the method
analysis of specific organic biocides where these analytical
used. Remove masking promptly after paint is dry. At the
methods are to be followed.
conclusionofthetest,allowthetestcylinderstodryforatleast
12 h at ambient conditions and measure the film thickness
7. Hazards
again.
7.1 Warning—Antifouling paints may contain toxic mate-
8.5 After the drying period, place one or more sets of three
rials that could cause skin and eye irritation on contact and
replicate coated cylinders coated with test paint and one blank
adverse physiological effect if ingested or inhaled. See anti-
(unpainted) cylinder in a holding tank. The painted surface on
fouling coating supplier’s Material Safety Data Sheet.
the cylinders must be completely submerged. Cylinders must
7.2 In the preparation of test specimens and the application
be stationary and positioned so that substitute ocean water
of various types of paints, the use of appropriate protective
moving through the tank will flow around each cylinder.
clothing and equipment is required consistent with local, state,
8.6 Maintain the substitute ocean water within the pre-
and federal government regulations, and recognized industrial
scribed range (see 5.1.4) by monitoring and adjusting the pH,
and technical standards. Spills, overspray, and unused material
salinity, and temperature of the substitute ocean water in the
shall not be flushed down the drain, but should be disposed of
holding tank at least every third day from the start through to
as hazardous waste.
the end of the study (see Note 3). Monitor the pH and adjust if
7.3 Additional notes relating to the hazards associated with
necessary using either dilute NaOH or dilute HCl. Monitor the
theanalysesofspecificorganicbiocidesaregiveninAppendix
salinityandadjustifnecessarybyaddingdistilledwateror5 M
X1 – Appendix X3.
NaCl. Determine the organic biocide concentration in the
holding tank at each sampling point and, where the coating
8. Procedure
contains a biocidal copper compound, also determine the
8.1 Prepare the exposure surfaces of three replicate test
copper concentration as specified in Test Method D6442 (see
cylinderstoprovideasuitablesurfaceforadhesionofthepaint
Note 4). Replace or regenerate the extraction media before the
-1
system to be applied. The surface area to be painted shall be
concentrationoforganicbiocideexceeds100 µgL andbefore
lightly abraded with 200-grit sandpaper to promote adhesion. -1
the concentration of copper exceeds 100 µgL .
Before coating, wipe abraded area to remove dust. Mask the
NOTE 3—More frequent monitoring and adjustment of pH and salinity
surfacestoremainuncoated(includingthebottom1to2cmof
may be required to maintain the substitute ocean water within the
the exterior circumferential surface of the test cylinder).
prescribed range during the early stages of a study while the system
Identify each cylinder to agree with coating sample code or
equilibrates.
designation.
NOTE 4—This must be done even if the copper release rate is not being
concurrently determined.
8.2 Paints shall be manufactured a minimum of seven days
before testing. Also, test paints shall not be allowed to age
8.7 At 1, 3, 7, 10, 14, 21, 24, 28, 31, 35, 38, 42, and 45-day
beyond the manufacturer’s recommended shelf life. Provide
intervals, transfer all cylinders in a given set from the holding
typical storage conditions during aging, that is, sealed in a
tank(s) into individual measuring containers, each containing
container commonly used for sale and held at 20 to 30°C (68
1500 mL of substitute ocean water that, before use, has been
to 86°F).
passed through a filter containing the extraction media. The
substitute ocean water may additionally be passed through a
8.3 For each coating, apply antifouling paint to the exterior
0.2-µm filter if required to remove microbial contamination.
circumferential surface of a set of three replicate test cylinders
On each sampling day, randomly assign cylinders (blank and
to produce a continuous band of antifouling paint with an
painted) to measuring containers.When transferring cylinders,
exposure surface of 200 cm . Ensure surface is completely
liftthecylindersoutoftheholdingtank,allowsubstituteocean
covered with finished dry film coating thickness of 100 to 200
water to drain off, install the cylinder into the rotating device,
µm(0.004to0.008in.).If,duringthetest,thefilmthicknessis
and submerge the painted area into the substitute ocean water.
expected to fall below 50 µm, then a greater thickness of paint
Immediately start rotation of the cylinder at 60 6 5 rpm and
shall be applied. Alternative surface areas are allowed when
2 2
continue rotation for 1 h (see 8.7.1). When transferring the
200 cm is not appropriate; deviations from the 200-cm
cylinders do not touch, or in any way damage the paint film,
surface area shall be noted in the final report. Follow manu-
and do not allow the paint surface to dry. The transfer shall be
facturer’s instructions with respect to mixing and drying.At a
completedasquicklyaspossible(generallyinlessthan5min).
minimum, mechanically shake until the paint appears homo-
geneous.Applyusingabrush,spongepaintapplicator,orspray 8.7.1 If, when a measurement is taken, the organic biocide
as recommended by the manufacturer. If the paint is marketed concentration in the individual measuring container is deter-
-1
only in spray cans, then apply as a spray. If applied by brush, mined to be >200 µgL , the rotation period for the next
thefilmshallnotshowbrushmarks.Afterthefinalapplication, measurementshallbereducedtolessthan1h,withthegoalof
D6903 − 07 (2020)
ultimately building the rotation period back up to 1 h. The where:
amount by which the rotation period is reduced shall be
C = concentration of biocide in substitute ocean water,
biocide
-1
estimatedbasedonfamiliaritywiththecoatingbeingevaluated
µgL ,
and experience with the test method and shall take into
V = substitute ocean water volume in measuring
consideration the degree to which the measurement exceeded
container, L,
-1 -1
200 µgL . If the next measurement also exceeds 200 µgL , D = hours per day (24),
the period of rotation shall be further reduced until the result T = rotation period, h, and
-1
A = area of paint, cm .
falls below 200 µgL . Once a measurement has been taken
-1
that falls below 200 µgL , the period of rotation shall be
9.2.2 Calculate the mean release rate at each data point
incrementally readjusted to a maximum of1hatthe earliest
(sampling day) for each set of triplicate test cylinders.
possible point in the testing.
9.3 Calculation of Cumulative Biocide Release:
8.7.2 Any measurements taken in which the concentration
9.3.1 Calculate the cumulative release of biocide from the
of organic biocide in the individual measuring container was
start of the trial through Day 45 as follows:
-1
>200 µgL shall be used to calculate release rate and shall be
R 1R
~ !
recorded in the final report. i j
¯
R 5 R ~j 2 i! 5 ~j 2 i! (2)
0,45 ( i,j (
8.7.3 Any measurements taken in which the period of
rotation was less than 1 h shall be used to calculate the release
where:
rate and shall be recorded in the final report.
-2
R = cumulative release (µg of organic biocide cm )
0,45
8.8 Iftestingbeyondtheminimum45-dayperiodisdesired,
from the start of the trial through Day 45,
-2
¯
the study may be extended. During the extended test, remove R = mean release rate (µg of organic biocide cm
i,j
-1
the cylinders from the holding tank at least once every 7 days d ) between consecutive sampling Days i and j
to make a measurement of the release rate in accordance with for all data points between the start of the trial
the above procedure. and Day 45,
i and j = timeelapsed(days)sincethestartofthetrialfor
8.9 At the completion of the cylinder rotation, transfer the
eachpairofconsecutivedatapoints,specifically
cylinder back to the holding tank. Withdraw approximately a
0 and 1, 1 and 3, 3 and 7 days, and so forth,
100-mLsubsampleofthesubstituteoceanwaterandfollowthe
respectively, and
sample treatment and storage procedure detailed for each
-2
R and R = mean release rates (µg of organic biocide cm
i j
organic biocide in Annex A2. Withdraw a separate 100-mL
-1
d ) for each set of triplicate test cylinders for
subsample for each organic biocide to be quantified. If copper
each pair of consecutive data points from the
release rates are being simultaneously measured, withdraw an
start of the trial through Day 45, specifically
additional100-mLsubsampleandtreatinaccordancewithTest
Days 0 and 1, Days 1 and 3, Days 3 and 7, and
Method D6442.
so forth, respectively, and the release rate on
8.10 Sample Treatment—Store samples in accordance with
Day0(R ) is taken as 0 µg of organic biocide
-2 -1
the procedures found in Annex A2 as appropriate until ready
cm d .
for analysis. Determine the concentration of organic biocide in
9.3.2 The cumulative release of organic biocide for other
each subsample using an analytical method that satisfies the
periods of time may be calculated if required as follows:
acceptance criteria given in Table A2.1.
~R 1R !
i j
¯
R 5 R j 2 i 5 j 2 i (3)
~ ! ~ !
NOTE 5—It is important that the subsamples used for quantitation of
x,y ( i,j (
organic biocide release rates are not acidified unless specified in the
sample treatment for that biocide in Annex A2.
where:
-2
R = cumulative release (µg of organic biocide cm )
x,y
9. Calculation
from Day x through to Day y,
-2
¯
R = mean release rate (µg of organic biocide cm
9.1 Calculate the organic biocide concentration in each
i,j
-1
treated subsample (see 8.10) based on the instrument response d ) between consecutive sampling Days i and j
for all data points from Day x through Day y,
for samples and blanks.
i and j = timeelapsed(days)sincethestartofthetrialfor
NOTE 6—If organic biocide is detected in the substitute ocean water
each pair of consecutive data points, for
usedtofilltheindividualsamplingcontainers,thisshallbereflectedinthe
example, 0 and 1, 1 and 3, 3 and 7 days, and so
calculation.
forth, respectively, and
9.2 Calculation of the Release Rate at Each Data Point -2
R and R = mean release rates (µg of organic biocide cm
i j
(Sampling Day): -1
d ) for each set of triplicate test cylinders for
-2 -1
9.2.1 Calculate the release rate (µgcm d ) for each
each pair of consecutive data points from Day x
individual test cylinder.
through Day y, for example, on Days 0 and 1,
R 5 ~C 3 V 3 D!/~T 3 A! (1) Days 1 and 3, Days 3 and 7, and so forth,
cyl biocide
respectively, and where Day 0 is included, the
5 C 31.5 324 / 1 3200
~ ! ~ !
biocide
release rate on Day 0 (R ) is taken as 0 µgof
-2 -1
organic biocide cm d .
5C 30.18 for200 cm paint area
~ !
biocide
D6903 − 07 (2020)
-2
NOTE 7—Previous editions of Test Method D6442 calculated the
R and R = mean release rates (µg of organic biocide cm
i j
cumulative (copper) release as follows: R + 2(R ) + 4(R ) + 3(R )+
-1
1 3 7 10
d ), for each set of triplicate test cylinders for
4(R ) + 7(R ) + 3(R ) + 4(R ) + 3(R ) + 4(R ) + 3(R 8) + 4(R )
14 21 24 28 31 35 3 42
each pair of consecutive data points, for ex-
+ 3(R ), where R,R,R,R , and so forth are the release rates for
45 1 3 7 10
ampleDays21and24,Days24and28,Days28
sampling Days 1, 3, 7, 10, and so forth, respectively. The current data
treatment provides a more accurate calculation of the cumulative release.
and 31, and so forth, respectively.
However, the formulas presented in 9.3.1 and 9.3.2 are still simple
9.5.1 Forthepurposesofthistestmethod,a“pseudo-steady
representationsofcumulativereleaseandmaynotprovideafullyaccurate
state” is defined as being a period of at least 24 days and
estimation of cumulative release under the test conditions, particularly if
the rate of release is changing rapidly over the test period.
containing 4 or more data points in which the arithmetic mean
ofthereleaseratevaluesforeachsetoftriplicatetestcylinders
9.4 Mean Release Rate:
at each data point differs from the weighted mean release rate
9.4.1 Calculate the mean release rate (µg of organic biocide
overthecalculationperiodbynomorethan15%,andthefinal
-2 -1
cm d ) from Day 21 through the end of the trial as follows:
day of the pseudo-steady state is the final day of the trial.
~R 1R !
i j
j 2 i NOTE 9—Not all coatings will exhibit a pseudo-steady state. When a
~ !
¯
(
R j 2 i 2
~ !
i,j
(
¯
coatingdoesexhibitapseudo-steadystate,thedeterminedpseudo-steady-
R 5 5 (4)
21,end
j 2 i j 2 i
~ ! ~ ! state biocide release rate should not be assumed necessarily to reflect a
( (
true steady-state release rate under the conditions of the testastherelease
where:
rate of the coating may continue to change beyond the test period.
-2
¯
R = mean release rate (µg of organic biocide cm
21,end
-1
d ) between Day 21 and the last day of 10. Report
sampling,
10.1 Report the following information:
-2
¯
R = mean release rate (µg of organic biocide cm -1
i,j
10.1.1 Reporttheconcentrationin µgL oforganicbiocide
-1
d ) between consecutive sampling Days i and j
in the substitute ocean water of the holding tank and the
-2
for all data points from Day 21 through the last
measuringtankandtherateoforganicbiociderelease(µgcm
day of sampling, -1
d ) for each sampling point (give values for individual
i and j = timeelapsed(days)sincethestartofthetrialfor
replicates as well as the mean). Plot the rate of organic biocide
eachpairofconsecutivedatapoints,specifically
release as a function of time (use linear axes).
Days 21 and 24, 24 and 28, 28 and 31, and so
10.1.2 Report the cumulative release of organic biocide
forth, respectively, and
fromthestartofthetrialthroughDay45(9.3.1),andreportthe
-2
R and R = mean release rates (µg of organic biocide cm
i j
mean organic biocide release rate for Days 21 through the end
-1
d ) for each triplicate set of test cylinders for
of the study (9.4.1). Also, when calculated, report the cumu-
each pair of consecutive data points from Day
lative release over other periods (9.3.2), the mean release rate
21throughthelastdayofsampling,specifically
over other periods (9.4.2), and the pseudo-steady-state release
Days 21 and 24, Days 24 and 28, Days 28 and
rate (9.5).
31, and so forth, respectively.
10.1.3 Report samples where the concentration of biocide
NOTE 8—Eq 4 calculates the weighted mean release rate, taking into -1
exceeded200 µgL inthemeasuringcontainerandsamplesin
account any differences in time between data points, and is a more valid
which the period of rotation was less than 1 h.
treatmentofthedatathancalculationofthesimplearithmeticmeanofthe
10.1.4 When the coating contains a biocidal copper
data.Thecalculationmaybeconvenientlydoneusingasuitablecomputer-
generated spreadsheet.
compound, report samples where the concentration of copper
-1
exceeded 100 µgL in the holding tank.
9.4.2 Eq 4 may be modified to calculate the mean release
10.1.5 Report the limit of quantitation for the organic
rate over other periods if required.
biocide in substitute ocean water determined by the laboratory
9.5 If the coating exhibits a pseudo-steady state, calculate
performing the test method in accordance with Annex A3.
the pseudo-steady-state biocide release rate as follows:
10.1.6 Report the coating application method and initial
coating dry film thicknesses (8.3) and final coating dry film
R 1R
~ !
i j
~j 2 i!
¯ ( thickness (8.4).
R ~j 2 i! 2
( i,j
¯
R 5 5 (5)
PSS
10.1.7 Report the pH, temperature, and salinity in the
~j 2 i! ~j 2 i!
( (
holding tank at each monitoring point (8.6).
where:
10.1.8 Report any deviations from this test method or the
¯
R = meanorganicbiocidereleaserate(µgoforganic requirements of this test method.
PSS
-2 -1
biocide cm d ) over the pseudo-steady-state
period, Day x to Day y, 11. Precision and Bias
-2
¯
R = mean release rate (µg of organic biocide cm
i,j
11.1 Precision:
-1
d ) between consecutive sampling Days i and j
11.1.1 Repeatability:
for all data points from Day x through Day y,
11.1.1.1 DCOIT—The mean DCOITrelease rates from Day
i and j = timeelapsed(days)sincethestartofthetrialfor
21through45forthreeindividualtestcylindersusingthesame
each pair of consecutive data points, for
batch of paint and concurrently measured in the same labora-
example,Days21and24,24and28,28and31,
torybythesameoperatorsusingthesameequipmentwere10.9
and so forth , respectively, and
-2 -1 -2 -1 -2 -1
µgcm d , 11.3 µgcm d , and 10.4 µgcm d . Based on
D6903 − 07 (2020)
-2 -1 -2 -1 -2 -1
these results, the determined precision under repeatability were 4.31µgcm d , 4.90 µgcm d , and 5.15 µgcm d .
condition for this test method is 64.3% relative standard Based on these results, the determined precision under repeat-
deviation. ability condition for this test method is 68.9% relative
11.1.1.2 CuPT—The mean CuPT release rate from Day 21 standard deviation.
through 45 for three individual test cylinders using the same 11.1.2 Reproducibility—The reproducibility of the proce-
batch of paint and concurrently measured in the same labora- dure in this test method for measuring organic biocide release
torybythesameoperatorusingthesameequipmentwere1.46 rates from antifouling coating compositions is being deter-
-2 -1 -2 -1 -2 -1
µgcm d , 1.42 µgcm d , and 1.39 µgcm d . Based on mined.Participatinglaboratorieswillparticipateinacombined
these results, the determined precision under repeatability round robin effort on both this test method and Test Method
condition for this test method is 62.0% relative standard D6442 (copper release rate method). By doing this, participat-
deviation. ing laboratories will benefit from economy of effort, and the
11.1.1.3 ZPT—The mean ZPT release rate from Day 21 jointroundrobinwillresultinreproducibilitydataformultiple
through 45 for three individual test cylinders using the same test methods.
batch of paint and concurrently measured in the same labora-
11.2 Bias—Noinformationcanbepresentedonbiasforthis
tory by the same operator using the same equipment were
procedure for measuring the organic biocide release rate from
-2 -1 -2 -1 -2 -1
6.13 µgcm d ,6.06 µgcm d ,and6.12 µgcm d .Based
antifouling coatings because no material having an accepted
on these results, the determined precision under repeatability
reference value is available.
condition for this test method is 60.5% relative standard
11.3 Refer to Appendix X1 – Appendix X3 for information
deviation.ThereleaserateofZPTfromonepaintwastestedin
on the precision and bias of the given test methods for
one laboratory at two different times, and those tests were
quantitation of organic biocide in substitute ocean water.
separated by five years. In the first test, the Day 21 to 45 mean
-2 -1
release rate was calculated to be 6.5 6 0.9 µgcm d and in
12. Keywords
the second test, the Day 21 to 45 mean release rate was
-2 -1
calculated to be 6.1 6 0.4 µgcm d . 12.1 antifouling coating; copper pyrithione (CuPT);
11.1.1.4 CDMTD—The mean CDMTD release rate from N-cyclopropyl-N'-(1,1-dimethylethyl)-6-(methylthio)-1,3,5-
Day 21 through 45 for three individual test cylinders using the triazine-2,4-diamine (CDMTD); organic biocide; release rate;
same batch of paint and concurrently measured in the same zinc pyrithione (ZPT); 4,5-dichloro-2-n-octylisothiazolin-3-
laboratory by the same operators using the same equipment one (DCOIT)
ANNEXES
(Mandatory Information)
A1. DESCRIPTION OF PROPOSED TESTING APPARATUS
A1.1 A200-cm antifoulingpaintfilmofspecifiedthickness
isappliedtotheoutercurvedsurfaceofaninertcylinderclosed
at one end. This cylinder is suspended with its closed end
immersed within and concentric with a larger inert cylinder
holding substitute ocean water. The coated internal cylinder is
rotated about its axis at 60 6 5 rpm to produce a peripheral
-1
speed of about 0.2 m s (about 0.4 knots) (see Fig. A1.1 –
required baffles not shown).
FIG. A1.1 Test Cylinder in Release Rate Measuring Container (Re-
quired Baffles Not Shown)
D6903 − 07 (2020)
A2. THE ANALYSIS OF ORGANIC BIOCIDES IN SUBSTITUTE OCEAN WATER
A2.1 Scope concentrations of DCOIT, CuPT, ZPT, and CDMTD in substi-
tute ocean water test samples, which have been generated in
A2.1.1 The measurement of the release rate of an organic
accordance with this test method. These acceptance criteria
biocidefromanantifoulingcoatingbythistestmethodcallsfor
cover the limit of quantitation for the biocide in substitute
the quantitation of the biocide in substitute ocean water at low
ocean water by the analytical method, precision, recovery,
concentrations. The analytical method used to determine the
linearity, and other parameters as specified in Table A2.1.
biocide concentration must therefore meet certain acceptance
criteria to ensure that an appropriate level of precision and
A2.1.3 When a LOQ criterion is specified, the LOQ for the
accuracy is achieved.
biocide in substitute ocean water by the analytical method is
A2.1.2 This annex describes the acceptance criteria for determined in accordance with the procedure given in Annex
analytical methods to be used for the determination of the A3.
TABLE A2.1 Acceptance Criteria for Analytical Methods to be Used for the Quantitation of Biocide in Leachate Subsamples
Analytical Acceptance Criteria for
Parameter DCOIT ZPT CuPT CDMTD
Accuracy Spike recovery at the specified LOQ Spike recovery at the Spike recovery at specified Spike recovery at specified LOQ
-1 -1 -1 -1 -1 -1
(25µgL ) and 100 µg L DCOIT in specified LOQ (2.0 µg L ) LOQ (2.0 µg L ) and 20 µg (15µgL ) and 50 µg L of
-1 -1
substitute ocean water shall be and 20 µg L of ZPT in L of CuPT in substitute CDMTD in substitute ocean water
between 70 to 125 % of target. substitute ocean water shall ocean water shall be shall be between 70 to 125 % at
-1
be between 70 to 125 % at between 70 to 125 % at 2.0 15 µg L and 80 to 120 % at 50
-1 -1 -1
2.0µgL and 80 to 120 % µg L and 80 to 120 % at µg L .
-1
at 20 µg L . 20 µg.
Repeatability Repeatability for a minimum of five Repeatability for a minimum Repeatability for a Repeatability for a minimum of
replicate analyses of calibration of five replicate analyses of minimum of five replicate five replicate analyses of
standards shall show a relative calibration standards shall analyses of calibration calibration standards shall show a
standard deviation of ±15 % or less. show a relative standard standards shall show a relative standard deviation of
deviation of ±15 % or less. relative standard deviation ±15 % or less.
of ±15 % or less.
Reproducibility Analysis of the seven or more DCOIT Analysis of the seven or Analysis of the seven or Analysis of the seven or more
spikes used to determine the LOD in more ZPT spikes used to more CuPT spikes used to CDMTD spikes used to determine
accordance with Annex A3 shall show determine the LOD in determine the LOD in the LOD in accordance with
a relative standard deviation of ±15 % accordance with Annex A3 accordance with Annex A3 Annex A3 shall show a relative
or less. shall show a relative shall show a relative standard deviation of ±15 % or
standard deviation of 20 % standard deviation of less.
or less. ±20 % or less.
Specificity When chromatographic methods are When chromatographic When chromatographic When chromatographic methods
used, the retention time of the analyte methods are used, the methods are used, the are used, the retention time of
shall match that of a certified standard. retention time of the analyte retention time of the the analyte shall match that of a
shall match that of a analyte shall match that of certified standard.
certified standard. a certified standard.
Limit of The LOD for the quantitation of DCOIT The LOD for the The LOD for the The LOD for the quantitation of
Detection in substitute ocean water by the quantitation of ZPT in quantitation of CuPT in CDMTD in substitute ocean water
-1 -1
(LOD) method shall be 7.8 µg L or less, substitute ocean water by substitute ocean water by by the method shall be 3.5 µg L
determined in accordanc ewith Annex the method shall be 0.6 µg the method shall be 0.6 µg or less, determined in
-1 -1
A3. L or less, determined in L or less,determined in accordancewith Annex A3.
accordancewith Annex A3. accordancewith Annex A3.
Limit of The LOQ for the quantitation of DCOIT The LOQ for the The LOQ for the The LOQ for the quantitation of
Quantitation in substitute ocean water by the quantitation of ZPT in quantitation of CuPT in CDMTD in substitute ocean water
-1
(LOQ) method shall be 25.0 µg L or less, substitute ocean water by substitute ocean water by by the method shall be 15.0 µg
-1
determined in accordance with Annex the method shall be 2.0 µg the method shall be 2.0 µg L or less, determined in
-1 -1
A3. L or less, determined in L or less, determined in accordance with Annex A3.
accordance with Annex A3. accordance with Annex A3.
Linearity A minimum of five calibration standards A minimum of five A minimum of five A minimum of five calibration
covering the working range of the calibration standards calibration standards standards covering the working
method and analyzed in duplicate shall covering the working range covering the working range range of the method and
show a correlation coefficient (R )of of the method and analyzed of the method and analyzed in duplicate shall show
0.99 or higher. in duplicate shall show a analyzed in duplicate shall a correlation coefficient (R )of
correlation coefficient (R ) show a correlation 0.99 or higher.
of 0.99 or higher. coefficient (R )of0.99or
higher.
D6903 − 07 (2020)
A2.1.4 The results of this test method will be adversely blowing techniques or us
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