Critical applications of SW 846 US EPA methods to evaluation of marine samples quality

Silvério, Patrícia Ferreira; Gonçalves, Cristina; Taniguchi, Satie; Lima, Sylvia Niemeyer Pinheiro

Abstracts

Technical evaluation of analytical data is of extreme relevance considering it can be used for comparisons with environmental quality standards and decision-making as related to the management of disposal of dredged sediments and the evaluation of salt and brackish water quality in accordance with CONAMA 357/05 Resolution. It is, therefore, essential that the project manager discusses the environmental agency's technical requirements with the laboratory contracted for the follow-up of the analysis underway and even with a view to possible re-analysis when anomalous data are identified. The main technical requirements are: (1) method quantitation limits (QLs) should fall below environmental standards; (2) analyses should be carried out in laboratories whose analytical scope is accredited by the National Institute of Metrology (INMETRO) or qualified or accepted by a licensing agency; (3) chain of custody should be provided in order to ensure sample traceability; (4) control charts should be provided to prove method performance; (5) certified reference material analysis or, if that is not available, matrix spike analysis, should be undertaken and (6) chromatograms should be included in the analytical report. Within this context and with a view to helping environmental managers in analytical report evaluation, this work has as objectives the discussion of the limitations of the application of SW 846 US EPA methods to marine samples, the consequences of having data based on method detection limits (MDL) and not sample quantitation limits (SQL), and present possible modifications of the principal method applied by laboratories in order to comply with environmental quality standards.

sediment; SW 846 methods; Quantitation limit; Salt and brackish water; interferences

Avaliação técnica do resultado analítico é de extrema relevância, pois o mesmo será utilizado para comparação com legislações e tomadas de decisão, tais como, disposição adequada de sedimento dragado e avaliação da qualidade de água superficial salobra e salina frente à classificação da Resolução CONAMA 357/05. É fundamental que o gestor ambiental discuta com o laboratório contratado as recomendações e exigências técnicas da legislação em questão e do órgão ambiental, acompanhe o andamento das análises e solicite re-análise, quando há suspeita de resultados anômalos. As principais recomendações técnicas são: (1) limites de quantificação do método (LQs) inferiores aos padrões ambientais; (2) análises realizadas em laboratórios cujo escopo analítico esteja acreditado pelo Instituto Nacional de Metrologia (INMETRO) ou qualificado ou aceito pelo órgão ambiental licenciador; (3) cadeia-de-custódia para rastreabilidade das amostras; (4) cartas-controle para evidência de desempenho do método analítico empregado pelo laboratório; (5) análise com material de referência certificado ou, em sua ausência, ensaios realizados por adição padrão ou adição de reforço e (6) apresentação de cromatogramas para as análises realizadas por cromatografia. Dentro deste contexto, visando auxiliar o gestor ambiental na avaliação dos relatórios de ensaio, este trabalho tem como objetivo discutir as aplicações dos métodos SW 846 da US EPA usados para as matrizes marinhas, as implicações de basear os estudos em limites de detecção (LDM) e não nos de quantificação da amostra (LQA) e discutir modificações de metodologia propostas para atendimento aos padrões de qualidade.

Sedimento; Métodos SW 846; Limite de quantificação; Água salgada e salobra; Interferências

CONAMA (Conselho Nacional do Meio Ambiente). 2009a. Resolução no. 344, 25 de março de 2004. Available at <www.mma.gov.br/port/CONAMA/res/res04/res34404.xml> accessed February, 2009.
CONAMA (Conselho Nacional do Meio Ambiente). 2009b. Resolução no. 357, 17 de março de 2005. Available at <www.mma.gov.br/port/conama/res/res05/res35705.pdf> accessed in February, 2009.
GONÇALVES, C; YAMAMOTO, C. R.; TURQUIA, S.; SILVÉRIO, P.; NIEMEYER, S. Aplicação de correção interelementar por ICP-OES a material dragado em ambientes marinhos. In: CONGRESO IBEROAMERICANO DE FÍSICA Y QUÍMICA AMBIENTAL, 5., 2008 Libro de Resumenes Mar del Plata, Argentina. Sociedad Iberoamericana de Física y Química Ambiental, España. 2008.
NORLOCK, F. M.; JANG J.; ZOU Q.; SCHOONOVER T.M; LI A. J. Large-Volume injection PTV-GC-MS Analysis of Polycyclic Aromatic Hydrocarbons in air and sediment samples. Air & Waste Mange.Assoc, v. 52, p. 19-26, 2002.
SCHOLZ, T. G.; FLORY, D. A. Clearing up the confusion. Environ. Protect, v. 10, p. 37-41, 1999. 1999.
TAYLOR, J. K. Quality assurance of chemical measurements 1^st ed. Lewis Publishers. Boca Raton, Fla.: CRC Press, 1987. 328 p.
US CFR. Code of Federal Regulations Title 40: Protection of Environment, Part 136 – Guidelines establishing test procedures for the analyses of pollutants, Appendix B to Part 136 – definition and procedure for the determination of Method Detection Limit rev. 1.11. Available at <http://ecfr.gpoaccess.gov> accessed in February, 2009.
US EPA. Tier I Data Validation Manual for the Ohio EPA Division of Hazardous Waste Management, February 7, 2006, Revision 4.0, 2009a. 124 p. Available at <www.epa.state.oh.us/dhwm/pdf/TierIDVManual.pdf> accessed in February, 2009.
US EPA Office of Emergency and remedial response, Washington DC. 2009. Risk Assessment guidance for superfund – V. I: Human Health Evaluation Manual (Part A) – Chapter 5, EPA/540/1-89/002, 1999. Available at <www.epa.gov/oswer/riskassessment/ragsa/ch5.pdf> accessed in February, 2009.
US EPA. Method 7000B – Flame Atomic Absorption Spectrometry, Feb. 2007, rev.02, 72 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/7000b.pdf> accessed in February, 2009c.
US EPA. Method 6010C – Inductively coupled plasma – Atomic emission spectrometry, Feb. 2007, rev.03, 72 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/6010c.pdf> accessed in February, 2009d.
US EPA. Method 8270D – Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS), Feb. 2007, rev.04, 72 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8270d.pdf> accessed in February, 2009e.
US EPA. Method 8310 – Polynuclear Aromatic Hydrocarbons, Sep. 1986, rev.00, 13 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8310.pdf> accessed in February, 2009f.
US EPA. Method 8100 – Polynuclear Aromatic Hydrocarbons, Sep.. 1986, rev.00, 10 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8100.pdf> accessed in February, 2009g.
US EPA. Method 8082A – Polychlorinated Biphenyls (PCBs) by Gas Chromatography, Feb. 2007, rev.01, 56 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8082a.pdf> accessed g February, 2009h.
US EPA. Method 8081B – Organochlorine Pesticides by Gas Chromatography, Feb. 2007, rev.02, 57 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8081b.pdf> accessed in February, 2009i.
US EPA. Superfund Analytical Services/Contract Laboratory Program (CLP), Multi-Media, Multi-Concentration Organics Analysis, SOM01.2, Exhibit D - Analytical Method for the Analysis of Semivolatile Organic Compounds, May, 2005 Available at <http://nsdi.epa.gov/superfund/programs/clp/som1.htm#pdf> accessed in February, 2009j.
US EPA. Method 8000C – Determinative Chromatographic Separations, March 2003, rev.03, 66 p. Available at <www.epa.gov/epawaste/hazard/testmethods/sw846/new_meth.htm#8000C> accessed in February, 2009k.
US EPA. 3630C – Silica gel Cleanup, Dec 1996, rev.03, 15 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/3630c.pdf> accessed in February, 2009l.
US EPA. Method 3620C – Florisil Cleanup, Feb 2007, rev. 03, 27 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/3620c.pdf> accessed in February, 2009m.
US EPA. Method 3665A – Sulfuric acid/Permanganate Cleanup, Dec 1996, rev.01, 5 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/3665a.pdf> accessed February, 2009n.
US EPA. Method 3660B – Sulfur Cleanup, Dec 1996, rev. 02, 6 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/3660b.pdf> accessed February, 2009o.
US EPA. Method 7470A – Mercury in liquid waste (manual cold-vapor technique), September 1994, rev.01, 6 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/7470a.pdf> accessed February, 2009p.
US EPA. Method 7471B – Mercury in solid or semisolid waste (manual cold-vapor technique), February 2007, rev.02, 11 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/7471b.pdf> accessed February, 2009q.
WSDA (Washington State Department of Agriculture) and WSDE (Washington State Department of Ecology). Ecology Publication no. 04-03-048 - Surface Water Monitoring Program for Pesticides in Salmonid-Bearing Streams, April to December, 2003 – Nov. 2004. 2009. 110 p. Available at <www.ecy.wa.gov/biblio/0403048.html> accessed in February, 2009.

Publication Dates

Publication in this collection
31 Aug 2010
Date of issue
June 2010

History

Received
02 Mar 2009
Reviewed
28 Sept 2009
Accepted
03 Mar 2010

This work is licensed under a Creative Commons Attribution 4.0 International License.

[1] CONAMA (Conselho Nacional do Meio Ambiente). 2009a. Resolução no. 344, 25 de março de 2004. Available at <www.mma.gov.br/port/CONAMA/res/res04/res34404.xml> accessed February, 2009.

[2] CONAMA (Conselho Nacional do Meio Ambiente). 2009b. Resolução no. 357, 17 de março de 2005. Available at <www.mma.gov.br/port/conama/res/res05/res35705.pdf> accessed in February, 2009.

[3] GONÇALVES, C; YAMAMOTO, C. R.; TURQUIA, S.; SILVÉRIO, P.; NIEMEYER, S. Aplicação de correção interelementar por ICP-OES a material dragado em ambientes marinhos. In: CONGRESO IBEROAMERICANO DE FÍSICA Y QUÍMICA AMBIENTAL, 5., 2008 Libro de Resumenes Mar del Plata, Argentina. Sociedad Iberoamericana de Física y Química Ambiental, España. 2008.

[4] NORLOCK, F. M.; JANG J.; ZOU Q.; SCHOONOVER T.M; LI A. J. Large-Volume injection PTV-GC-MS Analysis of Polycyclic Aromatic Hydrocarbons in air and sediment samples. Air & Waste Mange.Assoc, v. 52, p. 19-26, 2002.

[5] SCHOLZ, T. G.; FLORY, D. A. Clearing up the confusion. Environ. Protect, v. 10, p. 37-41, 1999. 1999.

[6] TAYLOR, J. K. Quality assurance of chemical measurements 1^st ed. Lewis Publishers. Boca Raton, Fla.: CRC Press, 1987. 328 p.

[7] US CFR. Code of Federal Regulations Title 40: Protection of Environment, Part 136 – Guidelines establishing test procedures for the analyses of pollutants, Appendix B to Part 136 – definition and procedure for the determination of Method Detection Limit rev. 1.11. Available at <http://ecfr.gpoaccess.gov> accessed in February, 2009.

[8] US EPA. Tier I Data Validation Manual for the Ohio EPA Division of Hazardous Waste Management, February 7, 2006, Revision 4.0, 2009a. 124 p. Available at <www.epa.state.oh.us/dhwm/pdf/TierIDVManual.pdf> accessed in February, 2009.

[9] US EPA Office of Emergency and remedial response, Washington DC. 2009. Risk Assessment guidance for superfund – V. I: Human Health Evaluation Manual (Part A) – Chapter 5, EPA/540/1-89/002, 1999. Available at <www.epa.gov/oswer/riskassessment/ragsa/ch5.pdf> accessed in February, 2009.

[10] US EPA. Method 7000B – Flame Atomic Absorption Spectrometry, Feb. 2007, rev.02, 72 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/7000b.pdf> accessed in February, 2009c.

[11] US EPA. Method 6010C – Inductively coupled plasma – Atomic emission spectrometry, Feb. 2007, rev.03, 72 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/6010c.pdf> accessed in February, 2009d.

[12] US EPA. Method 8270D – Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS), Feb. 2007, rev.04, 72 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8270d.pdf> accessed in February, 2009e.

[13] US EPA. Method 8310 – Polynuclear Aromatic Hydrocarbons, Sep. 1986, rev.00, 13 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8310.pdf> accessed in February, 2009f.

[14] US EPA. Method 8100 – Polynuclear Aromatic Hydrocarbons, Sep.. 1986, rev.00, 10 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8100.pdf> accessed in February, 2009g.

[15] US EPA. Method 8082A – Polychlorinated Biphenyls (PCBs) by Gas Chromatography, Feb. 2007, rev.01, 56 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8082a.pdf> accessed g February, 2009h.

[16] US EPA. Method 8081B – Organochlorine Pesticides by Gas Chromatography, Feb. 2007, rev.02, 57 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/8081b.pdf> accessed in February, 2009i.

[17] US EPA. Superfund Analytical Services/Contract Laboratory Program (CLP), Multi-Media, Multi-Concentration Organics Analysis, SOM01.2, Exhibit D - Analytical Method for the Analysis of Semivolatile Organic Compounds, May, 2005 Available at <http://nsdi.epa.gov/superfund/programs/clp/som1.htm#pdf> accessed in February, 2009j.

[18] US EPA. Method 8000C – Determinative Chromatographic Separations, March 2003, rev.03, 66 p. Available at <www.epa.gov/epawaste/hazard/testmethods/sw846/new_meth.htm#8000C> accessed in February, 2009k.

[19] US EPA. 3630C – Silica gel Cleanup, Dec 1996, rev.03, 15 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/3630c.pdf> accessed in February, 2009l.

[20] US EPA. Method 3620C – Florisil Cleanup, Feb 2007, rev. 03, 27 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/3620c.pdf> accessed in February, 2009m.

[21] US EPA. Method 3665A – Sulfuric acid/Permanganate Cleanup, Dec 1996, rev.01, 5 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/3665a.pdf> accessed February, 2009n.

[22] US EPA. Method 3660B – Sulfur Cleanup, Dec 1996, rev. 02, 6 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/3660b.pdf> accessed February, 2009o.

[23] US EPA. Method 7470A – Mercury in liquid waste (manual cold-vapor technique), September 1994, rev.01, 6 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/7470a.pdf> accessed February, 2009p.

[24] US EPA. Method 7471B – Mercury in solid or semisolid waste (manual cold-vapor technique), February 2007, rev.02, 11 p. Available at <www.epa.gov/epaoswer/hazwaste/test/pdfs/7471b.pdf> accessed February, 2009q.

[25] WSDA (Washington State Department of Agriculture) and WSDE (Washington State Department of Ecology). Ecology Publication no. 04-03-048 - Surface Water Monitoring Program for Pesticides in Salmonid-Bearing Streams, April to December, 2003 – Nov. 2004. 2009. 110 p. Available at <www.ecy.wa.gov/biblio/0403048.html> accessed in February, 2009.

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Critical applications of SW 846 US EPA methods to evaluation of marine samples quality

Abstracts

Publication Dates

History