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Occurrence of bisphenol A diglycidyl ethers (BADGEs) and novolac glycidyl ethers (NOGEs) in archived biosolids from the U.S. EPA’s Targeted National Sewage Sludge Survey Jingchuan Xue, Arjun K. Venkatesan, Qian Wu, Rolf U Halden, and Kurunthachalam Kannan Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.5b01115 • Publication Date (Web): 29 Apr 2015 Downloaded from http://pubs.acs.org on May 12, 2015
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Environmental Science & Technology
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Occurrence of bisphenol A diglycidyl ethers (BADGEs) and novolac
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glycidyl ethers (NOGEs) in archived biosolids from the U.S. EPA’s
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Targeted National Sewage Sludge Survey
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Jingchuan Xue1; Arjun K. Venkatesan2, Qian Wu1, Rolf U. Halden2, Kurunthachalam Kannan1,3,*
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Wadsworth Center, New York State Department of Health, and Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Albany, NY 12201, United States
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Center for Environmental Security, The Biodesign Institute, Arizona State University, Tempe, AZ 85287, United States
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Biochemistry Department, Faculty of Science and Experimental Biochemistry Unit, King Fahd Medical Research Center, King Abdulaziz University, Jeddah, Saudi Arabia
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*Corresponding author: K. Kannan,
[email protected] 18
Wadsworth Center
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Empire State Plaza, P.O. Box 509
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Albany, NY 12201-0509
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Tel: +1-518-474-0015
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Fax: +1-518-473-2895
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E-mail:
[email protected] 24 25 26
Submission to: ES&T
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Abstract
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Epoxy resins incorporating bisphenol A diglycidyl ether (BADGE) and novolac glycidyl
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ether (NOGE) are used in a wide range of applications, including adhesives, structural and
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electrical laminates. However, little is known about the occurrence of BADGE, NOGE, and
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their derivatives in the environment. Using liquid chromatography-tandem mass spectrometry,
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BADGE, bisphenol F glycidyl ether (BFDGE), 3-ring NOGE, and eight of their derivatives
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(BADGE‧2 H2O, BADGE‧H2O, BADGE‧HCl‧H2O, BADGE‧2 HCl, BADGE‧HCl,
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BFDGE‧2 H2O, and BFDGE‧2 HCl) were determined in archived biosolid samples collected
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from 68 wastewater treatment plants (WWTPs) from the northeastern, midwestern, western,
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and southern regions of the USA. BADGE‧2 H2O was the most frequently detected
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(DR=99%) and the most abundant compound found (median: 93.6 ng/g dry weight [dw]) in
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this family. The highest total concentrations of target chemicals, ranging from 83.6 to 2490 2 ACS Paragon Plus Environment
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ng/g dw, were found in biosolids collected from the northeastern United States. The sum of
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geometric mean (GM) concentration of BADGE, NOGE and their derivatives in biosolids
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increased with the treatment capacity of WWTPs. Based on the measured concentrations in
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biosolids and predicted mass in wastewater, it was estimated that approximately 3.5% of the
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total production of BADGEs was emitted through WWTP discharges.
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Key words: biosolids; sewage sludge; BADGE; BFDGE; NOGE; epoxy resins
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Introduction
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Bisphenol A diglycidyl ether [BADGE or 2,2-bis(4-(2,3-epoxypropyl)phenyl) propane] is a
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synthetic industrial compound obtained by a condensation reaction between 2 moles of
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epichlorohydrin and 1 mole of 2, 2-bis(4-hydroxyphenol) propane (bisphenol A or BPA) in
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the presence of sodium hydroxide.1 BADGE-based epoxy resins account for 90-95% of
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epoxy resin production in the USA.2 Similarly, novolac glycidyl ether (NOGE)-based resin, a
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complex mixture containing compounds with more than two aromatic rings and glycidyl
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groups, is produced from the reaction between novolac and epichlorohydrin.3 The two-ring
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(2R-) product of NOGE is referred to as bisphenol F diglycidyl ether (BFDGE). Other NOGE
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analogues with 3R- to 8R- products are also used in commerce.3 Similarly, formulations
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containing mixtures of more than one type of epoxy resins (e.g., blends of BADGE and
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BFDGE resins) are also available in commerce.1
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BADGE and NOGE are categorized as “high production volume (HPV) chemicals”
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by the United States Environmental Protection Agency (EPA). The combined production and
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import volume of BADGE based epoxy resin (CAS No. 25068-38-6) was in the range of 1 to
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10 million pounds, and that of BFDGE based epoxy resin (CAS No. 28064-14-4) was
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~500,000 pounds in the USA in 2006.4 Polymers based on BADGE and NOGE are the
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dominant type of epoxy resins used in internal coatings of food and beverage cans, lids of
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glass jars, wine storage vats, and water pipes.5-7 BADGE and NOGE are also used as
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additives for the elimination of surplus hydrochloric acid in the production of polyvinyl
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chloride (PVC) organosols.3, 8 In addition, epoxy resins are widely used in electrical,
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electronic, automotive and construction industries, among others.1 BADGE has a low water solubility (10. Method LOQs were
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determined in the same manner with the post-matrix spiked (nine- to eleven-point) calibration
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curves. As a check for instrumentation drift in response factors, a midpoint calibration
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standard was injected after every 6 samples. To check for carryover of target chemicals from
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sample to sample, a pure solvent (methanol) was injected after every 6 samples.
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Several procedural blanks were analyzed with each batch of samples to determine the
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contamination arising from laboratory materials and solvents. Throughout the analysis, six
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sludge samples were selected randomly for pre-extraction matrix spike (MS) (two for every
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25 samples) by spiking 40 ng of target analytes and passing them through the entire analytical
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procedure.
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Data Analysis
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For the calculation of geometric mean (GM), arithmetic mean, and median of study results,
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concentrations below the LOQ were substituted with a value equal to half the LOQ. Data
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were acquired with Analyst software version 1.4.1 (Applied Biosystems, Foster City, CA).
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The concentrations in biosolids are presented on a dry weight (dw) basis, unless stated
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otherwise. Microsoft Excel 2007 was used for the statistical analysis. The statistics software
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R v.3.1.0 was employed for Spearman correlation analysis. Statistical significance was set at
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p
