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

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

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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

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Nonylphenol Ethoxylates:

Aquatic Hazard, Exposure and Risk Existing Regulations, and Voluntary Initiatives Barbara Losey Director, AP&E Research Council

January 11, 2017

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NPEs – Aquatic Hazard, Occurrence and Risk

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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

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Biodegradation Pathways

  • f NPEs/NPEMs

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NP/NPE Aquatic Toxicity Modes of Action

  • NP has a weak binding affinity (activity) for

the nuclear estrogen receptor

  • 103- 106 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

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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

  • rganism studies
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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)

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

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US EPA WQC NP (2005)

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Media Type WQC (µg/L, ppb) WQC (ng/L, ppt) Water Freshwater , acute Freshwater, chronic Saltwater, acute Saltwater, chronic 28.0 µg/L 6.6 µg/L 7.0 µg/L 1.7 µg/L 28,000 ng/L 6,600 ng/L 7,000 ng/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”

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Canadian Environmental Quality Guidelines for NP/NPE (2002)

Type Value (TEQ Basis)

Water Freshwater Marine 1.0 µg/L (1,000 ng/L) 0.7 µg/L (700 ng/L) Sediment Freshwater Marine 1.4 mg/kg-dw * (1,400 ng/g-dw) 1.0 mg/kg* (1,000 ng/g-dw) * Calculated based on equilibrium partitioning for sediments containing 1% total organic carbon

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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.”

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Toxicity-Based Sediment PNECs for NP

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Environmental Media Type PNEC* Sediment Freshwater Marine 6,150 ng/g-dw 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)

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Assessing Risk of Mixtures of NPE/NPEM Relative to NP

Canadian Toxic Equivalence Factors (TEF)

Compound TEF NP 1 NP1,2EO 0.5 NP3-17EO 0.005

  • Based on aquatic toxicity of

NPEM relative to NP

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

  • This approach was further

examined and corroborated by Coady et al (2010)

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

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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

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NP and NPE TEF Equivalent Occurrence in US Freshwater vs. NP WQC (1990-2005)

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Percent Rank

20 40 60 80 100

NP Concentration (ug/L)

10 20 30 40 50 99th Centile USEPA Water Criterion (6.6 ug/L)

A

Percent Rank

20 40 60 80 100 120

NP Equivalent Concentration (ug/L)

10 20 30 40 50 60 USEPA Water Criteria (6.6 ug/L) 97th Centile

B

  • Klecka, et al (2007)

Exceedances associated with effluent dominated ( ~ 100%) waters

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Aggregate TEF based Concentrations of NP/NPEM (1990-2005)

  • United States

– >6000 samples – 67% < LOQ – 97% < US EPA WQC for NP * – Avg. = 0.8 µg/L – Max = 40 µg/L

  • California

– 45 samples – 73% < LOQ – 100 % < US EPA WQC for NP* – Avg = 0.2 µg/L – Max = 2.0 µg/L

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* US EPA chronic freshwater WQC

NP = 6.6 µg/L, chronic saltwater WQC NP = 1.7 µg/L

Klecka, 2007

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Kostich (2017) USEPA-USGS Reconnaissance Paper

RL N N<RL N>WQC HQ NP 1000 ng/L 21 21

  • Avg. , Med and

Max HQ =0.15

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  • Monitoring conducted 2010 to 2016 in

US surface water

  • Calculated Hazard Quotient (HQ)

based on measured exposures and US EPA WQC for NP

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CA monitoring vs. US EPA Saltwater WQC for NP

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0.001 0.01 0.1 1 10 2 4 6 8 10 NP concentration (ug/L) Rank

Recent concentrations of NP in California coastal waters

Diehl 2012: (1/2 DL) Diehl 2012: (>DL) Klosterhaus 2013 (<DL) Klosterhaus 2013: (>DL)

USEPA saltwater criteria (1.7 ug/L)

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Existing Regulations, Voluntary Programs and Alternative Assessments

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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.

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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

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US EPA Design for Environment

  • US EPA Design for Environment Safer

Chemical Choice Program

– Includes the support and encouragement of the

  • ngoing voluntary phase-out of NPEs in

consumer and industrial laundry detergents – Safer Detergent Stewardship Initiative (2007)

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CARB Consumer Product Categories in which APEs are Prohibited*

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Product Category Effective Date Sell Through Date General Purpose Cleaner (nonaerosol) 12/31/2012 12/31/2015 General Purpose Degreaser (nonaerosol) 12/31/2012 12/31/2015 Glass Cleaner (nonaerosol) 12/31/2012 12/31/2015 Heavy-duty Hand Cleaner

  • r Soap (nonaerosol)

12/31/2012 12/31/2015 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)

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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

  • n packaging by 2018 and work to find

alternatives.

  • Wal-Mart commitment to expand products

certified under EPA’s Safer Choice Program

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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

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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

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References

  • European Chemicals Bureau PBT Working Group (ECB PBT WG). (2003). Substance Information Sheets for

Nonylphenol (CAS 25154-52-3) and Phenol, 4-Nonyl, branched (CAS 84852-15-3).

  • Klecka, G., Zabik, J., Woodburn, K., Naylor, C., Staples, C., & Huntsman, B. (2007). Exposure analysis of C8- and

C9-alkylphenols, alkylphenol ethoxylates, and their metabolites in surface water systems within the United States. Human and Ecological Risk Assessment, 13 (4), 792-822.

  • Klosterhaus, S.L., Grace, R., Hamilton, M.C. , Yee, D. (2013). Method Validation and reconnaissance of

pharmaceuticals, personal care products, and alkylphenols in surface waters, sediments and mussels in an urban

  • estuary. Environment International. 54: 92-99
  • Kostich, M.S., Flick, R.W., Batt, A.L., Mash, H.E., Boone, J.S., Furlong, E.T., Kolpin, D.W., Glassmeyer, S.T.

(2017). Aquatic Concentrations of Chemical Analytes Compared to Ecotoxicity Estimates. Science of the Total Environment 579: 1649-1657

  • Staples, C.A., Coady, K. and Losey, B. (2010, Nov). Assessing the Effects and Potential Risk of Branched para-

Nonylphenol to Sediment Dwelling Organisms. Poster Presentation at Society of Environmental Toxicology and Chemistry, North American Annual Meeting, Portland, OR, USA

  • US Environmental Protection Agency (US EPA). (2005). Aquatic life ambient water quality criteria - nonylphenol.

Report 822-R-05-005. US Environmental Protection Agency, Washington, DC, USA. http://www.epa.gov/waterscience/criteria/nonylphenol/final-doc.pdf

  • US EPA (2007) Design for Environment Safer Detergent Stewardship Initiative

https://www.epa.gov/saferchoice/design-environment-safer-detergents-stewardship-initiative

  • US EPA (2012) Design for Environment Program Alternative Assessment for NPEs.

https://www.epa.gov/sites/production/files/2014-06/documents/npe_final.pdf

  • US EPA Office of Pollution Prevention and Toxics. (2014, Oct ). TSCA Work Plan for Chemical Assessments: 2014

Update.

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