Nonylphenol Ethoxylates: Aquatic Hazard, Exposure and Risk Existing - PowerPoint PPT Presentation

Nonylphenol Ethoxylates: Aquatic Hazard, Exposure and Risk Existing Regulations, and Voluntary Initiatives Barbara Losey Director, AP&E Research Council January 11, 2017 1

NPEs – Aquatic Hazard, Occurrence and Risk 2

NP/NPEs not Persistent or Bioaccumulative • NPEs and their degradation intermediates, including NP, are not persistent or bioaccumulative by any international, national or state definition – Environment Canada, 2006 – ECB PBT Workgroup, 2003 – -Washington State, Dept of Ecology, 2006 – US EPA TSCA Work Plan, 2014 – Klecka, 2008 3

Biodegradation Pathways of NPEs/NPEMs 4

NP/NPE Aquatic Toxicity Modes of Action • NP has a weak binding affinity (activity) for the nuclear estrogen receptor o 10 3 - 10 6 fold less potent than endogenous estradiol (E2) • NPE metabolites NP1EO, NP2EO • Weakly estrogenic in some screening tests, less potent than NP • ≥ NP4EO have no estrogenic activity 5

NP/NPE Aquatic Toxicity Modes of Action • Adverse effects of NP in ecotoxicity studies are due to multiple modes of action that occur within the same exposure concentrations . • Lines of evidence include: – Gene array tests; – Comparing Acute to Chronic ratios for NP vs. EE2; – Critical/adverse effects in in vivo , whole organism studies

NP/NPE Aquatic Toxicity Modes of Action • Robust aquatic toxicity database for NP • Adverse effects observed in in vivo toxicity studies (i.e. effects on survival, growth and development, and reproduction) – represent integration of several MoAs – characterize population level effects – used for deriving Water Quality Criteria (WQC) and Predicted No Effect Concentrations (PNEC) 7

Water Quality Criteria (WQC) and Predicted No Effect Concentrations (PNECs) for NP in Water and Sediment 8

US EPA WQC NP (2005) Media Type WQC WQC (µg/L, ppb) (ng/L, ppt) Water Freshwater , acute 28.0 µg/L 28,000 ng/L Freshwater, chronic 6.6 µg/L 6,600 ng/L Saltwater, acute 7.0 µg/L 7,000 ng/L Saltwater, chronic 1.7 µg/L 1,700 ng/L US EPA WQC “ represent the concentration in water at which aquatic life are protected from acute and chronic adverse effects” 9

Canadian Environmental Quality Guidelines for NP/NPE (2002) Type Value (TEQ Basis) Water Freshwater 1.0 µg/L (1,000 ng/L) Marine 0.7 µg/L (700 ng/L) Sediment Freshwater 1.4 mg/kg-dw * (1,400 ng/g-dw) Marine 1.0 mg/kg* (1,000 ng/g-dw) * Calculated based on equilibrium partitioning for sediments containing 1% total organic carbon 10

Canadian EQGs for NP/NPE • “ It appears that the concentrations of NP required to elicit oestrogenic effects are comparable to concentrations at which other chronic toxic effects are observed.” 11

Toxicity-Based Sediment PNECs for NP Environmental Type PNEC* Media Sediment Freshwater 6,150 ng/g-dw Marine 1,230 ng/g-dw * Toxicity-based PNECs for benthic organisms based on studies with sediment-dosed concentrations of NP according to EU Guidance and similar to US EPA Guidance (Staples, 2010) 12

Assessing Risk of Mixtures of NPE/NPEM Relative to NP Canadian Toxic Equivalence Factors (TEF) • Based on aquatic toxicity of Compound TEF NPEM relative to NP NP 1 • This approach was further NP1,2EO 0.5 examined and corroborated by NP3-17EO 0.005 Coady et al (2010) Example: If concentrations for a surface water sample are NP 0.1 µg/L, NP1EO 0.1 µg/L, NP1EC 0.1 µg/L then aggregated concentration = ∑ (0.1 x 1) + (0.1 x 0.5) + (0.1 x 0.005) = 0.1505 µg/L

NP/NPEs – Occurrence and Risk in US and California Aquatic Environment 14

Klecka (2007) National Surveys of US Surface Water • National survey of US surface water – Sampling conducted in 1990 - 2005 – > 6000 samples from published literature, raw data provided by primary authors – Data primarily from US EPA and USGS studies – Compared TEF-based concentrations NP/NPEM to US WQC for NP 15

NP and NPE TEF Equivalent Occurrence in US Freshwater vs. NP WQC (1990-2005) 50 NP Equivalent Concentration (ug/L) 60 99th Centile A B 97th Centile 50 NP Concentration (ug/L) 40 40 30 30 20 20 10 USEPA Water Criterion (6.6 ug/L) USEPA Water Criteria (6.6 ug/L) 10 0 0 0 20 40 60 80 100 0 20 40 60 80 100 120 Percent Rank Percent Rank Exceedances associated with effluent dominated ( ~ 100%) waters - Klecka, et al (2007) 16

Aggregate TEF based Concentrations of NP/NPEM (1990-2005) • United States • California – >6000 samples – 45 samples – 67% < LOQ – 73% < LOQ – 97% < US EPA WQC – 100 % < US EPA for NP * WQC for NP* – Avg. = 0.8 µg/L – Avg = 0.2 µg/L – Max = 40 µg/L – Max = 2.0 µg/L Klecka, 2007 * US EPA chronic freshwater WQC NP = 6.6 µg/L, chronic saltwater 17 WQC NP = 1.7 µg/L

Kostich (2017) USEPA-USGS Reconnaissance Paper • Monitoring conducted 2010 to 2016 in US surface water • Calculated Hazard Quotient (HQ) based on measured exposures and US EPA WQC for NP RL N N<RL N>WQC HQ NP 1000 21 21 0 Avg. , Med and ng/L Max HQ =0.15 18

CA monitoring vs. US EPA Saltwater WQC for NP Recent concentrations of NP in California coastal waters 10 USEPA saltwater criteria (1.7 ug/L) NP concentration (ug/L) 1 Diehl 2012: (1/2 DL) 0.1 Diehl 2012: (>DL) Klosterhaus 2013 (<DL) Klosterhaus 2013: (>DL) 0.01 0.001 0 2 4 6 8 10 Rank 19

Existing Regulations, Voluntary Programs and Alternative Assessments 20

U.S. Clean Water Act • US EPA WQC for NP (2005) – See slide 9 for details – Clean Water Act provides states ability to generate Water Quality Standards to assess and regulate locations that might be found to exceed the US EPA WQC for NP and sources that contribute to them. 21

U.S. Emergency Planning and Community Right-to-Know Act • Added NP to the Toxics Release Inventory (2014) • Proposal to Add NPE to Toxics Release Inventory (Nov. 2016) – Currently out for public comments 22

US EPA Design for Environment • US EPA Design for Environment Safer Chemical Choice Program – Includes the support and encouragement of the ongoing voluntary phase-out of NPEs in consumer and industrial laundry detergents – Safer Detergent Stewardship Initiative (2007) 23

CARB Consumer Product Categories in which APEs are Prohibited* Product Category Effective Date Sell Through Date General Purpose Cleaner 12/31/2012 12/31/2015 (nonaerosol) General Purpose 12/31/2012 12/31/2015 Degreaser (nonaerosol) Glass Cleaner 12/31/2012 12/31/2015 (nonaerosol) Heavy-duty Hand Cleaner 12/31/2012 12/31/2015 or Soap (nonaerosol) Oven or Grill Cleaner 12/31/2012 12/31/2015 * Reference CARB Regulation for Reducing Emissions from Consumer Products, § 94509. Standards for Consumer Products (m)(3) -Table 94509(m)(3) 24

Wal-Mart • Wal-Mart Restricted use of NPEs - 2006 • NPEs Listed among others as Wal-Mart High Priority Chemicals – July 2016 – Requires manufacturers to list these ingredients on packaging by 2018 and work to find alternatives. • Wal-Mart commitment to expand products certified under EPA’s Safer Choice Program 25

Alternative Assessments • US EPA (2012) Design for Environment Program Alternative Assessment on NPE • BizNGO (2013) Model Alternative Assessment on NPE in All Purpose Cleaners – Conducted as Model for Alternative Assessment under CA Safer Consumer Products 26

References • BizNGO (2013, Nov). Model Alternative Assessment: Nonylphenol Ethoxylates in All-Purpose Cleaners. http://www.bizngo.org/static/ee_images/uploads/resources/NPE_FAA.pdf • Coady, K., Staples, C. Losey, B., and Klecka, G. (2010). A Hazard Assessment of Aggregate Exposure to Nonylphenol and Nonylphenol Mono- and Di-ethoxylates in the Aquatic Environment. Human and Ecological Risk Assessment: An International Journal. Volume 16, Issue 5, pgs 1066- 1094 • Coady, K. (2016, Nov) Advantages and Challenges for Determining Mode of Action of Industrial Chemicals: A Case Study with Alkylphenol and Alkylphenol Ethoxylates. Poster Presentation at Society of Environmental Toxicology and Chemistry (SETAC), North American Annual Meeting, Orlando, FL, USA • Diehl, J., Johnson, S.E., Xia, K. West, A. , Tomanek, L. (2012). The Distribution of 4-nonylphenol in marine organisms of North American Pacific Coast estuaries. Chemosphere 87 (2012) 490–497. • Environment Canada, National Guidelines and Standards Office (2001, April). Canadian Environmental Quality Guidelines for Nonylphenol and Its Ethoxylates. Scientific Supporting Document (Water, Sediment and Soil) • Environment Canada (EC). (2006). Ecological categorization of substances on the Domestic Substance List; Categorization Decisions. http://www.ec.gc.ca/substances/ese/eng/dsl/cat_index.cfm. • Environment Canada and Health Canada (EC and HC). (2001). Priority substances list assessment report for nonylphenol and its ethoxylates. ISBN: 0-662-29248-0. http://www.hc-sc.gc.ca/ewh- semt/pubs/contaminants/psl2-lsp2/nonylphenol/index-eng.php. 27