1、Designation: D6903 07 (Reapproved 2013)Standard Test Method forDetermination of Organic Biocide Release Rate FromAntifouling Coatings in Substitute Ocean Water1This standard is issued under the fixed designation D6903; the number immediately following the designation indicates the year oforiginal ad
2、option or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the laboratory determination ofthe rate at whi
3、ch organic biocide is released from an antifoul-ing coating exposed in substitute ocean water. The test is runentirely in the laboratory under controlled conditions of pH,temperature, salinity, and hydrodynamics. Analytical proce-dures are provided for the determination of the release rate of4,5-dic
4、hloro-2-n-octylisothiazolin-3-one (DCOIT), zinc andcopper 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 watersamples are analyzed for leached biocide using a suitableanalytical techniq
5、ue.1.2 In cases in which the antifouling coating contains bothan organic biocide and a copper-based biocide, the release rateof copper may optionally be concurrently determined accord-ing to the procedure found in Test Method D6442.1.3 The procedure contains the preparation steps for thedeterminatio
6、n of the release rate of biocide in substitute oceanwater from antifouling paints including apparatus, reagents,holding tank conditions, and sampling point details. Theprocedure calls for the accurate determination of organicbiocide concentrations in substitute ocean water at the low gL-1(parts per
7、billion, ppb) level. To detect and correct forreagent impurities and allow a suitable level of analyticalprecision to be achieved, the analytical method to be used forthe determination of the concentration of organic biocide insubstitute ocean water must meet the acceptability criteriagiven in Annex
8、 A2. Where Annex A2 specifies a limit ofquantitation (LOQ), the procedure for determining the LOQ forthe organic biocide in substitute ocean water by the analyticalmethod presented in Annex A3 is to be followed.1.4 Suitable analytical methods that use high-performanceliquid chromatography (HPLC) for
9、 determining the concentra-tion of DCOIT, ZPT and CuPT, and CDMTD in substituteocean water are given in Appendix X1-Appendix X3, respec-tively. Other methods may be used provided that they meet theappropriate criteria given in Annex A2.1.5 When the release rate of a highly photosensitive organicbioc
10、ide is being determined, steps must be taken to protect theapparatus and samples from exposure to natural and artificialvisible light sources. Any such requirement for these steps tobe taken for a particular biocide is indicated in Annex A2.1.6 The practical limits for quantifying biocide release ra
11、tesby this method are from 4.5 to 500 gcm-2d-1for DCOIT, 0.36to 500 gcm-2d-1for CuPT, 0.36 to 500 gcm-2d-1for ZPT,and 2.7 to 500 gcm-2d-1for CDMTD. These ranges may beextended to 3.8 to 500 gcm-2d-1for DCOIT, 0.16 to 500 gcm-2d-1for CuPT, 0.2 to 500 gcm-2d-1for ZPT, and 2.2 to500 gcm-2d-1for CDMTD i
12、f the procedures described inAppendix X1-Appendix X3 (as appropriate) are followed. Thequantitation of release rates lower than these ranges willrequire the use of analytical methods with lower limits ofquantitation than those specified in Annex A2.1.7 The results of this test method do not reflect
13、environ-mental biocide release rates for antifouling products, and arenot suitable for direct use in the process of generatingenvironmental risk assessments, environmental loadingestimates, or for establishing release rate limits for regulatorypurposes. See also Section 4.1.8 The values stated in SI
14、 units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.9 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health
15、 practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:21This test method is under the jurisdiction of ASTM Committee D01 on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D0
16、1.45 on Marine Coatings.Current edition approved June 1, 2013. Published June 2013. Originallyapproved in 2007. Last previous edition approved in 2007 as D6903 07. DOI:10.1520/D6903-07R13.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at service
17、astm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1D1005 Test Method for Measurement of Dry-Film Thick-ness of
18、 Organic Coatings Using MicrometersD1141 Practice for the Preparation of Substitute OceanWaterD1193 Specification for Reagent WaterD6442 Test Method for Determination of Copper ReleaseRate From Antifouling Coatings in Substitute OceanWater2.2 U.S. Federal Standard:340 CFR 136, Appendix B, revision 1
19、.113. Summary of Test Method3.1 The candidate paint system is applied to the cylindricaltest specimens. The coated specimens are placed in a tank ofsubstitute ocean water in which the levels of organic biocideand copper (where the coating also contains a biocidal coppercompound) are kept below 100 g
20、L-1by circulating thesubstitute ocean water through a suitable filtration system (see5.1.3). At specified intervals, each specimen is placed in 1500mL of substitute ocean water (see Section 8 for details) androtated at 60 rpm for 1 h (or less, see 8.7 for further explanationand instruction). The rat
21、e of biocide release from the paint isdetermined by measuring concentrations of the biocide in thesubstitute ocean water in the individual measuring containers.3.2 Annex A2 provides acceptance criteria for analyticalprocedures for measuring the concentration of specific organicbiocides in substitute
22、 ocean water. Suitable methods areprovided in Appendix X1-Appendix X3. Alternative methodsmay be used provided that they meet the acceptance criteriagiven in Annex A2.4. Significance and Use4.1 This test method is designed to provide a laboratoryprocedure to quantify and characterize changes in the
23、releaserate of organic biocide from antifouling coatings that occurduring a period of immersion under specified laboratoryconditions of constant temperature, pH, salinity, and hydrody-namics. Quantitative measurement of biocide release rate isnecessary to help in selection of materials, providing qu
24、alitycontrol, and understanding the performance mechanism.4.2 Results from this test method establish a pattern ofbiocide release from an antifouling coating over a minimum of45 days exposure under controlled laboratory conditions.Biocide release rates of antifouling paints in-service vary overthe l
25、ife of the coating system depending on the formulation andon the physical and chemical properties of the environment.Factors such as differences in berthing locations, operatingschedules, length of service, condition of paint film surface,temperature, pH, and salinity influence the actual release ra
26、teunder environmental conditions. Results obtained using thistest method do not reflect actual biocide release rates that willoccur in service, but provide comparisons of the release ratecharacteristics of different antifouling formulations in substi-tute ocean water under the prescribed laboratory
27、conditions.4.3 By comparison with published copper and organotinrelease rate data4,5obtained either by direct measurementsfrom ship hulls or release rate measurements from harborexposed panels, all data indicate that the results of this genericrotating-cylinder test method significantly overestimate
28、 therelease rate of biocide when compared to release rates underin-service conditions. For example, published results demon-strate that this generic test method produces higher measure-ments of copper and organotin release rates than from direct insitu measurements for the same coating on in-service
29、 ship hullsand harbor-exposed panels. The difference between the resultsof this test method and the panel and ship studies was up to afactor of about 30 based on copper release rate data for severalcommercial antifouling coatings.4,6No direct release rate datafrom ship hulls or harbor-exposed panels
30、 have been generatedto-date for the biocides covered by this method. However, theexpectation is that the results of this test method, whencompared with the direct measurements from ship hulls andharbor-exposed panels, could follow the same trend. Realisticestimates of the biocide release from a ship
31、s hull underin-service conditions can only be obtained from this testmethod where the difference between the results obtained bythis test method and the release rate of an antifouling coatingin service is taken into account.4.4 Where the results of this test method are used in theprocess of generati
32、ng environmental risk assessments, forenvironmental loading estimates, or for regulatory purposes, itis most strongly recommended that the relationship betweenlaboratory release rates and actual environment inputs is takeninto account to allow a more accurate approximation of thebiocide release rate
33、 from antifouling coatings under real-lifeconditions. This can be accomplished through the applicationof appropriate correction factors.65. Apparatus5.1 Sample GenerationSee AnnexA2 for guidance on anyparticular materials restriction and handling requirements re-lating to each organic biocide.5.1.1
34、Release Rate Measuring ContainerA nominal 2-L(12-gal) container made of an inert material, approximately13.5 cm (5.3 in.) in diameter and 19 cm (7.5 in.) high, is fittedwith three rods also made of an inert material, approximately 6mm (nominal14 in.) in diameter to serve as baffles. Rods shallbe eve
35、nly spaced on the inside circumference of the containerto prevent swirling of the water with the test cylinder duringrotation. The rods will be secured to the container walls usingan inert adhesive. The material of construction of the releaserate measuring container and rods for use with any particu
36、larbiocide shall be as specified in A2.3. When the release rate ofa photosensitive material is to be determined, the containershall be protected from light. The requirement to protect the3Available from U.S. Government Printing Office Superintendent of Documents,732 N. Capitol St., NW, Mail Stop: SD
37、E, Washington, DC 20401, http:/www.access.gpo.gov.4Valkirs, A. O., Seligman, P. F., Haslbeck, E., and Caso, J. S., Marine Bulletin,Vol. 46 (2003), pp. 763779.5Champ, M. A. and Seligman, P. F., Organotin: Environmental Fate and Effects,Chapter 19 Measurement and Significance of the Release Rate for T
38、ributyltin,(1996) Chapman and Hall, pp 383403.6Finnie,A.A., Improved Estimates of Environmental Copper Release Rate FromAntifouling Coatings, Biofouling, Vol. 22 (2006), pp 279291.D6903 07 (2013)2release rate container from light for any particular organicbiocide is indicated in A2.4.NOTE 1The resul
39、ts of this test method will be adversely affected if thebiocide is strongly adsorbed or absorbed by the release rate measuringcontainer or the test cylinder, or both. Where the release rates of two ormore different biocides are to be concurrently determined from a single setof measurements, the rele
40、ase rate measuring container, associated rods andthe test cylinders must all be made of a material that is inert to all of thebiocides, otherwise repeat testing (different cylinders and measuringcontainers) for each biocide will be required.5.1.2 Constant Temperature ControlThis control is ameans of
41、 maintaining the release rate measuring containers ata temperature of 25 6 1C during the rotation period (see 8.7).5.1.3 Holding TankThis tank is an inert plastic containerof such dimensions so as to permit immersion of four or moretest cylinders and must be equipped with a system to circulatethe se
42、awater continuously in the tank through an activatedcarbon filter and, optionally, an absorbent filter.7If an absor-bent filter is used, regenerate the ion exchange resin followingthe manufacturers instructions and wash the resin with sub-stitute ocean water before use. The rate of water flow and th
43、esize of the filter shall be selected to maintain the concentrationof each organic biocide below 100 gL-1(100 ppb) and, whenthe coating contains a biocidal copper compound, the concen-tration of copper below 100 gL-1. Flow rates should be set toobtain two to eight turnovers per hour. When the releas
44、e rate ofa photosensitive material is to be determined, the holding tankshall be protected from light. The requirement to protectholding tank from light for any particular organic biocide isindicated in A2.4.5.1.4 The size and geometry of the tanks as well as thepositioning of the inflow and outflow
45、 ports for the watercirculation system shall be selected to obtain a slow, relativelyuniform flow of substitute ocean water past all test cylinders inthe tank. Maintain the pH of the substitute ocean waterbetween 7.9 and 8.1, the salinity between 33 and 34 parts perthousand (ppt), and the temperatur
46、e at 25 6 1C (77 6 2F).5.1.5 Test CylindersApproximately 6.4-cm (nominal 212-in.) outside diameter by 17.8-cm (nominal 7-in.) long pipe orequivalent cylindrical shapes made of an inert material andcoated with a 10-cm (3.94-in.) band of antifouling paint aroundthe exterior circumference of the test c
47、ylinder to provide 200cm2of paint film that can be immersed and freely rotated in therelease rate measuring container (see Note 1 and Note 2).Atopdisk, fitted with a shaft of proper diameter for the rotatingdevice, shall be sealed to the cylinder. Seal the bottom of thetest cylinder so as to form a
48、watertight joint. Alternatively,prefabricated one-piece test cylinders with an integral sealedbottom-end can be used. Do not coat the lower 1 to 2 cm (0.39to 0.79 in.) of the test cylinder. The test cylinder shall be ofsuch height so that a rotating device can be attached to androtate the cylinder w
49、ith the upper end of the cylinder above thelevel of the test container immersion liquid to prevent entry ofthe immersion liquid into the test cylinder (see AnnexA1). Thematerial of construction of the test cylinder (including thebottom end-disk) for use with any particular biocide shall be asspecified in A2.3. It is advisable to weight the cylinder byfilling with water so that the unit does not have buoyancy.NOTE 2When coating release rates are very high, it may be desirableto use a 5-cm band (100-cm2paint area) to avoid exceeding 200 gL-1of organ
