Revision History for U.S. Geological Survey Open-File Report 2014–1028 By Richard J. Wagner, Patrick W. Moran, Steven D. Zaugg, Jennifer M. Sevigny, and Jody M. Pope Contaminants of Emerging Concern in the Lower Stillaguamish River Basin, Washington, 2008–11 ----------------------------------------------------- Posted online March 3, 2014 ----------------------------------------------------- Revised and reposted June 3, 2016 The chemical names in all text and tables has been changed to conform with guidelines described in the USGS Office of Water Quality Water-Quality Information Note 2015.05 "NWIS Parameter Code Names: Special Characters and Italics (http://water.usgs.gov/usgs/owq/WaQI/index.html)and (http://water.usgs.gov/usgs/owq/pcode/names.html). Datums CHANGE FROM: North American Vertical Datum of 1929 (NGVD 29) and North American Datum of 1927 (NAD 27). CHANGED TO: North American Vertical Datum of 1988 (NAVD 88) and North American Datum of 1983 (NAD 83). ADDED: "Quality Assurance" section. ADDED: following terms to the "Abbreviations and Acronyms": BNR biological nutrient removal QC quality control GC gas chromatography HPLC high performance liquid chromatograph/mass spectrometry LC liquid chromatography LRL laboratory reporting level LT-MDL long-term method detection level CHANGES: All text to reflect the laboratory method used to analyze pharmaceutical compounds analyzed by multiple methods. P.4 - Changed the words "collecction methods" to "analytical methods" in "Purpose and Scope". p.4 -Addded Appendix table A5 to show enivronmental samples collected. p.4 - Added the phrase biological nutrient removal (BNR) to the phrase describing the Arlington WWTP upgrade in "Wastewater Treatment Plants" section. p.5 - Changed from: for analysis of human-health pharmaceuticals by NWQL schedule 2080, and wastewater compounds were analyzed by NWQL schedule 1433. To: for analysis of human-health pharmaceuticals by NWQL schedule 2080; pharmaceutical and other compounds by NWQL custom method 8058; and wastewater compounds by NWQL schedule 1433. p.5 - Changed reference from A1 to A1-a and A1-b p.5 - In Reconnaissance Sites section, change from: for analysis of human-health pharmaceuticals by NWQL schedule 2080, and wastewater compounds were analyzed by NWQL schedule 1433. To: for analysis of human-health pharmaceuticals by NWQL schedule 2080; pharmaceutical and other compounds by NWQL custom method 8058; and wastewater compounds by NWQL schedule 1433. p.5 - In "Wastewater Treatment Plants" section, changed: Subsamples were filtered through a 0.7 micrometer glass-fiber filter and submitted to the NWQL for analyses of waste-indicator chemicals, pesticides, human-health pharmaceuticals, and in 2010 also analysis of steroidal hormones; the analyses were completed using NWQL custom method 2434. To: Subsamples were filtered through a 0.7 micrometer glass-fiber filter and submitted to the NWQL for analyses of waste-indicator chemicals and related compounds, pesticides, human-health pharmaceuticals, and in 2010 also analysis of steroidal hormones; the analyses were completed using NWQL custom method 2434. p.6 - Changed the first sentence from: Samples were analyzed for human-health pharmaceutical compounds using NWQL schedule 2080, for wastewater compounds using NWQL schedule 1433, for hormone samples using NWQL custom method 2434, and for halogenated organic compounds in solids using NWQL custom method 8093. To: Samples were analyzed for human-health pharmaceutical compounds using NWQL schedule 2080; for wastewater compounds using NWQL schedule 1433,and additional pharmaceuticals and organic compounds by NWQL custom methods 8058 and 8144; for hormone samples using NWQL custom method 2434; and for halogenated organic compounds in solids using NWQL custom method 8093. p.6 - Changed the sentence "In addition, eight pharmaceutical compounds also were analyzed by custom methods that are modifications to the method described by Zaugg and others (2006)." To: In addition, pharmaceutical compounds also were analyzed by custom methods that are modifications to the method described by Zaugg and others (2006), as further described by Phillips and others (2010) and Zaugg and others (2014). p.6 - Moved the following two sentences to the end of the first paragraph: The method, using these modifications, has not been completely evaluated by the USGS, and no publication can be cited at this time that describes the custom method used. Hence, the results for these compounds are for screening purposes only and are not available from the National Water Information System (NWIS) database. p.6 - Removed the number "eight" from the above sentence. REFERENCES: Changed: Childress, C. J.O., Foreman, W.T., Connor, B. F., and Maloney, T.J., 1999, New reporting procedures based on long-term method detection levels and some considerations for interpretations of water-quality data provided by the U.S. Geological Survey National Water Quality Laboratory: Open-File Report 99-193, 19. To: Oblinger Childress, C. J., Foreman, W.T., Connor, B. F., and Maloney, T.J., 1999, New reporting procedures based on long-term method detection levels and some considerations for interpretations of water-quality data provided by the U.S. Geological Survey National Water Quality Laboratory: Open-File Report 99-193, accessed March 1, 2015 at http://pubs.er.usgs.gov/publication/ofr99193. Changed: Washington State Department of Ecology, 2013, River and stream flow monitoring—Stillaguamish R. nr Silvana: Washington State Department of Ecology Web site, accessed September 5, 2013, at https://fortress.wa.gov/ecy/wrx/wrx/flows/station.asp?wria=05. To: Washington State Department of Ecology, 2013, River and stream flow monitoring—Stillaguamish R. nr Silvana: Washington State Department of Ecology Web site, accessed January 22,2015 at//fortress.wa.gov/ecy/eap/flows/station.asp?wria=05&historical=true ADDED: Maloney, T.J., ed., 2005, Quality management system, U.S. Geological Survey National Water Quality Laboratory: U.S. Geological Survey Open-File Report 2005-1263, version 1.3, 9 November 2005, chapters and appendixes variously paged, accessed January 22, 2015 at http://pubs.usgs.gov/of/2005/1263/. Burrows, H., Weir, R., and Stohner, J., ed., 1979, Pure and Applied Chemistry, Volume 51, Issue 11, Pages 2243–2250, ISSN (Online) 1365-3075, ISSN (Print) 0033-4545, DOI: 10.1351/pac197951112243, accessed February 23, 2015 at http://goldbook.iupac.org/src_PAC1979512243.html Phillips, P.J., Smith, S.G., Kolpin, D.W., Zaugg, S.D., Buxton, H.T., and Furlong, E.T., 2010, Method Description, Quality Assurance, Environmental Data, and other Information for Analysis of Pharmaceuticals in Wastewater-Treatment-Plant Effluents, Streamwater, and Reservoirs, 2004-2009: U.S. Geological Survey Open-File Report 2010-1102, 36 p., accessed January 21, 2016 at http://pubs.usgs.gov/of/2010/1102/. Shoemaker, J.A., and Bassett M. V., 2005, Measurement of chloroacetanilide and other acetamide herbicide degradates in drinking water by solid phase extraction and liquid chromatography/tandem mass spectrometry (LC/MS/MS), Method 535, v. 1.1, April 2005, EPA Document #: EPA/600/R-05/053 Stevenson, D.L., ed., 2013, Quality management system, U.S. Geological Survey National Water Quality Laboratory: unpublished U.S. Geological Survey Report, version 2.1, 28 May 2013, chapters variously paged. Stevenson, D.L., and Barnard, A.R., eds., 2013, U.S. Geological Survey National Water Quality Laboratory quality assurance and quality control: unpublished U.S. Geological Survey Report, version 1.0, 26 March 2013, viii + 75 p. Zaugg, S.D., Phillips, P.J., and Smith, S.G., 2014, Analysis of pharmaceutical and other organic wastewater compounds in filtered and unfiltered water samples by gas chromatography/mass spectrometry: U.S. Geological Survey Open-File Report 2013–1297, 24 p., accessed March 10, 2015 at http://dx.doi.org/10.3133/ofr20131297. TABLES The chemical names in all text and tables have been changed to conform to guidelines described in the USGS Office of Water Quality Water-Quality Information Note 2015.05 "NWIS Parameter Code Names: Special Characters and Italics. Dashes in all tables changed to "em dashes". All tables were re-formatted to provide borders in the cell column headers and extraneous trailing zeroes were removed from concentration values in all tables (if applicable). Tables 4,7, and Appendix tables A2 were revised to correct an incorrect parameter code and name used for a laboratory surrogate compound used in National Water Quality Laboratory (NWQL) schedule 1433. All instances of Caffeine-C13 (99584) were changed to Caffeine-d9 (91741), as described in USGS NWQL Rapi-Note 15-19 (http://wwwnwql.cr.usgs.gov/rapi-note-index.shtml). Table 1 Datums changed from North American Vertical Datum of 1929 (NGVD 29) and North American Datum of 1927 (NAD 27). TO: North American Vertical Datum of 1988 (NAVD 88) and North American Datum of 1983 (NAD 83). Table 2 Corrected station name of 12170050 from Stillaguamish River near Thule Road near Stanwood, WA to: Stillaguamish River near Thomle Road near Stanwood, WA Table 3 Changed title from Table 3.--Concentrations of human-health pharmaceutical compounds in samples from streams in the Stillaguamish River Basin, Washington, September 2008. To: Table 3.—Concentrations of human-health pharmaceutical compounds analyzed by USGS National Water Quality Laboratory Schedule 2080 in samples from streams in the Stillaguamish River Basin, Washington, September 2008. Changed headnotes from: [<, less than; E, estimated; National Water Information System (NWIS) codes in parentheses] To: [<, less than; E, estimated; RM, river miles; National Water Information System (NWIS) codes in parentheses. Caffeine (50305) and cotinine (62005) are also analyzed by National Water Quality Laboratory (NWQL) schedule 1433. Preferred method for caffeine is NWQL schedule 1433 and NWQL schedule 2080 for cotinine]. Added RM abbreviation to headnotes for river miles. Corrected station name of 12170050 from Stillaguamish River near Thule Road near Stanwood, WA to: Stillaguamish River near Thomle Road near Stanwood, WA Table 4 Changed title from: Table 4.--Concentrations of wastewater indicator compounds in samples from streams in the Stillaguamish River Basin, Washington, September 2008. To: Table 4.—Concentrations of wastewater indicator compounds analyzed by USGS National Water Quality Laboratory Schedule 1433 in samples from streams in the Stillaguamish River Basin, Washington, September 2008. Eliminated space between < and first number in concentration values for Benzophenone (62067) and ß-Sitosterol (62068). Changed headnotes from [<, less than; E, estimated; National Water Information System (NWIS) codes in parentheses] To: [<, less than; E, estimated; RM, river mile; National Water Information System (NWIS) codes in parentheses. Caffeine (50305) and cotinine (62005) are also analyzed by National Water Quality Laboratory (NWQL) schedule 2080. Preferred method for caffeine is NWQL schedule 1433 and NWQL schedule 2080 for cotinine.] Corrected station name of 12170050 from Stillaguamish River near Thule Road near Stanwood, WA to: Stillaguamish River near Thomle Road near Stanwood, WA Added RM abbreviation to headnotes for river miles. Table 5 Changed title from: Table 5.-- Concentrations of human-health pharmaceutical compounds analyzed by research methods in samples from streams in the Stillaguamish River Basin, Washington, September 2008. To:Table 5.—Concentrations of pharmaceutical compounds analyzed by USGS National Water Quality Laboratory custom method 8058 in samples from streams in the Stillaguamish River Basin, Washington, September 2008. Changed headnotes from: [<, less than; National Water Information System (NWIS) codes in parentheses] To:[--, no data; <, less than; RM, river mile; National Water Information System (NWIS) codes in parentheses. Codeine (62003) is also analyzed by National Water Quality Laboratory (NWQL) schedule 2080. Preferred method for analysis of codeine is NWQL schedule 2080. Surrogate data are in Table 4.] Added footnote to explain missing data for Armstrong Creek sample September 23 (Sample broken in transit). Added surrogate data for Schedule 2080: (90797) and (99571). Added RM abbreviation to headnotes for river miles. Table 6 Changed title from:Table 6.-- Physical properties and concentrations of human-health pharmaceutical compounds in samples from influent and effluent of wastewater treatment plants in the lower Stillaguamish River Basin, Washington, 2009-11. To: Table 6.—Physical properties and concentrations of human-health pharmaceutical compounds analyzed by USGS National Water Quality Laboratory schedule 2080 in samples from influent and effluent of wastewater treatment plants in the lower Stillaguamish River Basin, Washington, 2009-11. Changed headnotes from: [--, no data; <, less than; A, average; E, estimated; National Water Information System (NWIS) codes in parentheses] To:[--, no data; <, less than; A, average; E, estimated; National Water Information System (NWIS) codes in parentheses. Caffeine (50305) and cotinine (62005) are also analyzed by National Water Quality Laboratory (NWQL) schedule 1433. Preferred method for caffeine is NWQL schedule 1433 and NWQL schedule 2080 for cotinine.] Table 7 Changed title from: Table 7.--Concentrations of wastewater indicator compounds in samples of influent and effluent from wastewater treatment plants in the lower Stillaguamish River Basin, Washington, 2009-11. To:Table 7.—Concentrations of wastewater indicator compounds analyzed by USGS National Water Quality Laboratory Schedule 1433 in samples from influent and effluent of wastewater treatment plants in the Stillaguamish River Basin, Washington, 2009-11. and headnotes from: [--, no data; <, less than; E, estimated; National Water Information System (NWIS) codes in parentheses] To: [--, no data; <, less than; E, estimated; U, deleted because of matrix interference. National Water Information System (NWIS) codes in parentheses. Caffeine (50305) and cotinine (62005) are also analyzed by National Water Quality Laboratory (NWQL) schedule 2080. Preferred method for caffeine is NWQL schedule 1433 and NWQL schedule 2080 for cotinine] Addded U code for compounds deleted because of matrix interference Table 8 Changed title from:Table 8.--Concentrations of human-health pharmaceutical compounds analyzed by research methods in samples from influent and effluent from wastewater treatment plants in the lower Stillaguamish River Basin, Washington, 2009-11. To: Table 8.—Concentrations of pharmaceutical and other organic compounds analyzed by USGS National Water Quality Laboratory custom methods 8058 and 8144 in samples from influent and effluent of wastewater treatment plants in the lower Stillaguamish River Basin, Washington, 2009-11. Changed headnotes from: [--, no data, <, less than; E, estimated; National Water Information System (NWIS) codes in parentheses] To: [--, no data, <, less than; E, estimated; U, deleted because of matrix interference; National Water Information System (NWIS) codes in parentheses. Acetaminophen (62000), carbamazepine (62793), codeine (62003), diltiazem (62008), and diphenhydramine (62796) are also analyzed by Schedule 2080 (the preferred method). Surrogate data available in Table 7.] Added columns for Sample volume (99587)and Butalbital (63768). Added U codes for compounds deleted because of matrix interference Table 9 Changed title from: Table 9.--Concentrations of steroidal hormones and related compounds in samples of effluent from selected wastewater treatment plants in the lower Stillaguamish River Basin, September 2010. To: Table 9.—Concentrations of steroidal hormones and related compounds analyzed by USGS National Water Quality Laboratory custom schedule 2434 in samples from effluent of selected wastewater treatment plants in the lower Stillaguamish River Basin, Washington, September 2010. Removed spaces between < and 2 in cells AD6, AD7, and AB7 Table 10 Changed title from: Table 10.--Concentrations of halogenated organic compounds in solids and sediments from selected wastewater treatment plants in the lower Stillaguamish River Basin, Washington, 2009-11. To: Table 10.—Concentrations of halogenated organic compounds analyzed by USGS National Water Quality Laboratory custom method 8093 in solids and sediments from selected wastewater treatment plants in the lower Stillaguamish River Basin, Washington, 2009-11. Changed headnotes from: [<, less than; E, estimated; U, unable to analyze due to interference. Samples from Arlington in 2009 are in mass only (in micrograms). All other samples are concentrations in micrograms per kilogram. National Water Information System (NWIS) codes in parentheses] To: [<, less than; E, estimated; U, unable to analyze because of matrix interference. Samples from Arlington in 2009 are in mass only (in micrograms). All other samples are concentrations in micrograms per kilogram. National Water Information System (NWIS) codes in parentheses.] Changed footnote from: Note - results are in mass (in micrograms) only To: Note - results for shaded shells are in mass (in micrograms) only Changed definition of U code from: unable to analyze due to interference To: U, deleted because of matrix interference Table A1 Split into Table A1 and A2: Changed title from: Table A1. Parameter codes, parameter names, alternative or common names, typical uses, Chemical Abstracts Service (CAS) Registry Numbers, and minimum reporting limits for human-health pharmaceutical compounds analyzed at the USGS National Water Quality Laboratory for samples from the Stillaguamish River Basin, Washington, 2008-11. To: Table A1.—Parameter codes, parameter names, alternative or common names, typical uses, Chemical Abstracts Service (CAS) Registry Numbers, and reporting levels for human-health pharmaceutical compounds analyzed by USGS National Water Quality Laboratory Schedule 2080 for samples from the Stillaguamish River Basin, Washington, 2008-11. Table A2.—Parameter codes, parameter names, alternative or common names, typical uses, Chemical Abstracts Service (CAS) Registry Numbers, and reporting levels for pharmaceutical and other organic compounds analyzed by USGS National Water Quality Laboratory custom methods 8058 and 8144 for samples from the Stillaguamish River Basin, Washington, 2008-11. Table A2 Renamed Table A3 Changed title from: Table A2. Parameter codes, parameter names, typical uses or sources, Chemical Abstracts Service (CAS) Registry Numbers, and minimum reporting limits for wastewater indicator compounds analyzed at the USGS National Water Quality Laboratory for samples from the Stillaguamish River Basin, Washington, 2008-11. To: Table A3.—Parameter codes, parameter names, typical uses or sources, Chemical Abstracts Service (CAS) Registry Numbers, and reporting levels for wastewater indicator compounds analyzed by USGS National Water Quality Laboratory Schedule 1433 in samples from the Stillaguamish River Basin, Washington, 2008-11. Added metolachlor to list of compounds Corrected alphabetized version of compounds Table A3 Renamed Table A4 Changed title from: Table A3.--Parameter codes, parameter names, typical uses or sources, Chemical Abstracts Service (CAS) Registry Numbers, and minimum reporting limits for steroidal hormones and related compounds analyzed at the USGS National Water Quality Laboratory (NWQL) by custom method 2434 for samples from the Stillaguamish River Basin, Washington, September 2010. To: Table A4.—Parameter codes, parameter names, typical uses or sources, Chemical Abstracts Service (CAS) Registry Numbers, and reporting levels for steroidal hormones and related compounds analyzed by USGS National Water Quality Laboratory custom method 2434 in samples from the Stillaguamish River Basin, Washington, September 2010. Table A4 Renamed Table A5 Changed title from: Table A4. --Parameter codes, parameter names, Chemical Abstracts Service (CAS) Registry Numbers, and minimum reporting limits for halogenated organic compounds in solids and sediments analyzed at the USGS National Water Quality Laboratory by custom method LC8093 for samples from the Stillaguamish River Basin, Washington, 2008-11. To: Table A5.—Parameter codes, parameter names, Chemical Abstracts Service (CAS) Registry Numbers, and reporting levels for halogenated organic compounds in solids and sediments analyzed by USGS National Water Quality Laboratory custom method 8093 for samples from the Stillaguamish River Basin, Washington, 2009-11. Changed column from: Minimum reporting limit To: Reporting level Changed line 68 from: Surrogates to: Surrogates (in percent) ADDED: Table A6.—Types and numbers of environmental samples processed for streams and wastewater treatment plants in the Stillaguamish River Basin, Washington, 2008-11. ADDED: Table B1.—Types and numbers of quality-control samples processed for streams and wastewater treatment plants in the Stillaguamish River Basin, Washington, 2008-11. Table B2.—Percent recovery of surrogate compounds and concentrations of organic compounds in field blanks processed in the Stillaguamish River Basin, Washington, 2008-11. Table B3.—Field matrix spike recoveries in quality-control samples analyzed by USGS National Water Quality Laboratory schedule 1433 in samples from the Stillaguamish River Basin, Washington, 2008-11. Table B4.—Laboratory matrix spike recoveries in quality-control samples analyzed by USGS National Water Quality Laboratory schedule 2080 and custom schedule 2434 in samples from the Stillaguamish River Basin, Washington, 2009-11. Table B5.—Parameter code, parameter name, and field matrix spike recoveries that are outside the acceptance criteria for quality-control samples of wastewater indicator compounds in samples from the Stillaguamish River basin, 2008-11. Table B6.—Concentrations and relative percent difference in replicates analyzed by National Water Quality Laboratory Schedule 2080 and custom methods 8058 and 8144 in samples from the Stillaguamish River Basin, Washington, 2008-11.