## A quatic Life Water Quality Standards

Technical Support Document for Nonylphenol and Ethoxylates
Triennial Water Quality Standard Amendm ents to Minn. R. chs. 7050 and 7052

DRAFT For External Review, October 14, 2010

TBD 2010

### Minnesota Pollution Control Agency

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This report is available in alternative formats upon request, and online at www.pca.state.mn.us

Document number: wq-s6-16 Authors Phil Monson, M.S.

Contributors / acknowledgements Angela Preimesberger, M.S.

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chlorine or chlorine derivatives.3Technical Support Document for 2008- 2012 Triennial Rule Amendments

TECHNICAL SUPPORT DOCUMENT FOR NONY LPHENOL AND NONYLPHENOL ETHOXYLATES



## Contents

Abstract

.............................................................................................................................. ..................................... 5

INTRODUCTION

.............................................................................................................................. ......................... 6

Nonylphenol ethoxylates in the environment ........................................................................................................ 6

HOW AND WHY WATER QUALITY STANDARDS ARE DEVELOPED .......................................................................... 6

U.S. EPA National Clean Water Act 304(a) Aquatic Life Criteria ................................................................... 6

Development of aquatic life criter ia for nonylphenol ethoxylates ............................................................... 7

Endocrine-active endpoints for nonylphenol ethoxylates ............................................................................ 8

Draft Water Quality Standards fo r Nonylphenol and Ethoxylates ......................................................................... 9

Minnesota aquatic life WQSs for nonylphenol ethoxylates ......................................................................... 9

Considerations of Human heal th in aquatic life criteria ............................................................................. 10

Implementation

.............................................................................................................................. ............ 10

References 19

4Abstract

From the Minnesota State Register , Volume 33 (35), March 2, 2009:

Nonylphenol (NP) is an industrial chemical used primarily as an intermediary compound in the development of
numerous commercial non-ionic surfactants. These surfact ants are ingredients of detergents and emulsifyers found in household, industrial, agricultural, and other app lications. The chemical makeup of the surfactants is largely in the form of nonylphenol and octylphenol ethoxylates, more broadly referred to as alkylphenol ethoxylates (APEs). Concentrations of these APEs prim arily consist of nonylpheno l ethoxylates (NPE) and have been reported from water samples collected from studies of the Mississippi River, smaller Minnesota streams,
and wastewater effluents. Sources of NPEs to the environment include point and nonpoint discharges to
surface waters. Under anaerobic condi tions NPEs breakdown to NP.

Nonylphenol is toxic to aquatic organisms demonstra ted, in part, through re cent national criteria established by the EPA (AWQC– Nony lphenol 2007( EPA822R05005)). The need to develop national criteria was based both on concerns of NP toxicity and its presen ce in surface waters throughout the nation. The capacity of NP as an endocrine-disrupting compound is al so documented in the EPA criteria document and in numerous reports in the scientific literature. Endocrine-disrupting ch emicals (EDCs) are those compounds [human-made compounds or natural compounds at unnatural concentrations due to human activity] that exert an adverse effect through interactio n with the endocrine system of mammals, birds, fish, amphibians and many invertebrates [from the MPCA’s Legislative report on
EDCs www.pca.state.mn.us/publicatio ns/reports/lrp-ei-1sy08.pdf ].

The Minnesota Pollution Control Agency (MPCA) has revi ewed the EPA AWQC and rece nt literature to develop draft numeric acute and chronic water quality criteria as the basis for future proposed Water Quality Standards (WQSs). Based on the available data on NP a nd NPEO, MPCA ‘s acute (FAV and MS) and chronic (CS)
criteria were developed to be tota l NPE concentrations (NP plus two short chain ethoxylates, NP1E0 and NP2EO). MPCA reviewed EPA’s conclusions on the EDC studi es that suggest while the draft chronic criteria are not based specifically on EDC –mediated effects, would be protective of chronic adverse effects observed in aquatic species studies that impact aquatic communities.

5

## Introduction

Nonylphenol (NP) is a mixture of isomers of branched and substituted structures within a nonyl (9 carbon) group formed in the process of petroleum distillation. Nonylphenol is produced in large quantities in the United States with estimates of over 200 million pounds produced per year. Commercial production limits the number of isomers to a few primar y products dominated by the chem ical 4(para)-nonylphenol (4-NP). Nonylphenol alone has limited use, but is an ingredient in the manufacture of a wide variety of alkylated products broadly described as nony lphenol ethoxylates (NPEO). These co mpounds have a primary use as nonionic surfactants in commercial and household cleaning products, industrial materials processing, and additives to pesticide formulations and industrial lubricants. The focus of this discussion will be placed on 4-NP and two short-chain ethoxylates: nonylphenol mono -ethoxylate (NP1EO) and nonylphenol di-ethoxylate (NP2EO). For purposes of this document, the term nonyl phenol ethoxylate (NPEO) will be used inclusive of the chemicals 4-NP (CAS #: 84852-15-3, NP1EO (CA S #: 27986-36-3) and NP 2EO (CAS#: 20427-84-3).

Nonylphenol ethoxylates in the environment

Nonylphenol ethoxylates are often cons tituents of municipal or industrial wastes in effluent discharges to surface waters. In Minnesota, NPEO has been found in surface waters and sediments from around the state (Lee et al. 2004; Lee et al. 2008; MPCA 2009). Regular mo nitoring for NPEOs in Minnesota surface waters is
limited due to lack of standardized analytical procedures and regulato ry necessity. Nonylphenol ethoxylates inputs to surface waters and associated treatment facilities are a various mix of 1-20 carbon chain polyethoxylates. The short-chain (1 or 2 carbon) ethoxy lates and 4-NP tend to be the most toxic to aquatic organisms (Servos 1999; Bistodeau et al. 2006), and are the most persistent forms in wastewater. Initial degradation of longer (3- 20) chain ethoxylates occurs through natural processes resulting in their breakdown to the less water soluble NP1EO, NP2EO and 4-NP (Soares 2008) . The two short chain intermediate compounds (NP1EO, NP2EO) may degrad e further to 4-NP, but all three te nd to resist degradation and are often found in sediments, wastewater sludge, and wastewater effluents.



## HOW AND WHY WATER QUALITY STANDARDS ARE DEVELOPED

U.S. EPA National Clean Water Act 304(a) Aquatic Life Criteria

The MPCA is required by federal law to assess and revise its rules that protect the designated, beneficial uses of state surface water and groundwater. Mandates under the Clean Water Act maintain a state’s requirement to develop water quality standards (WQSs) for the protection of aquatic lif e communities. The U.S. Environmental Protection Agency (EPA) is responsible for developing these 304(a) Ambient Water Quality
Criteria (AWQC) on a national basis, and it is up to the stat e to use or modify criteria based on more local and scientifically defensible data that are still as protective as national criteria. Concern for the protection of aquatic life prompted the to develop national aquati c life AWQC for nonylphenol, centering on the compound 4-nonylphenol (EPA 2005). The national criteria for freshwater aquatic life are based on evaluation of toxicity endpoints of nonylphenol to aquatic organisms. Th is document pursues the development of numeric
standards derived for the combined concentrations of the three most toxic and persistent nonylphenol ethoxylate compounds, 4-NP, NP1EO and NP2EO as the basis for draft acute and chronic WQSs.

6

### Development of aquatic life crit eria for nonylphenol ethoxylates

Toxicity data for NPEO used to develop a numeric standa rd was evaluated through national guidance provided by the EPA (USEPA 1985) and requirements in Minn. R. ch s. 7050 and 7052. Briefly, st udies from the scientific literature are assembled, acceptable toxicity endpoint s and taxonomic categories are compiled, and a species sensitivity distribution is calculated that assumes prot ection of about 95% of aquatic communities. Effects of NPEO on aquatic organisms were assessed for survival e ndpoints reported from shor t-term (acute) laboratory exposures. The primary mode of acti on of NPEO on the whole organism is generally considered a narcotic effect. Toxicity tests are described as the lethal or effect concentration of 50% of the (test) population, referred to as LC50 or EC50, respec tively. These endpoints serve as th e basis for developing the species sensitivity distribution as described in the EPA guidance.

Scientific studies were evaluated fo r acceptable data based primarily on information provided in the 1985 EPA Guidelines and ASTM methodologies (A STM, 2009). Toxicity information used for development of this numeric standard included those data published in the EPA na tional AWQC document augmented with additional reports from studies published over the past ten years. Development of a numeric standard combined toxicity results of the three related nonyl phenol compounds: 4-NP, NP1EO and NP2E O. Most toxicity information is based on tests using the compound 4-NP. Additional liter ature includes studies that reported results for six aquatic species in exposures to NP1EO and NP2EO (Table 1). Results of three of these studies could not be used as two were from species of a non-native frog, and one used a mixture of unreported nonylphenol ethoxylates (NPEO).

Studies with acceptable NPEO data provided values used to calculate a numeric standard for 23 freshwater genera comprising 28 species from 81 acute toxicity endpoints. Data sources for these endpoints were combined from sources of the existing EPA AWQC docu ment and the open literature (Table 2). Species acute sensitivity to NPEO ranged from 55.72 micrograms/liter (μg/l) for Hyalella to 4108.6 μg/L for Xenopus . Use of Xenopus extends the convention of developing an aquatic li fe standard from toxicity test using only native species. However, Xenopus is an accepted laboratory test species demonstrated, in part, through its use in toxicity testing using FETAX methods (ASTM 2004) and methods employed by the EPA to examine endocrine disrupting compounds. A comparison of reported endpoin ts between NPEO and 4-NP tend to show that the short chain ethoxlylates are slightly less toxic than 4- NP for the species tested. This observation has been reported from other sources (EPA 20 05; Servos 1999). Studies reporting toxicity endpoints for short-chain ethoxylates are few, and these toxicity values are dis bursed throughout the range of endpoints for all NPEO. As such, values reported for toxicity endpoints of 4- NP, NP1EO and NP2EO are considered together as equally toxic and deemed appropriate for inclusion in deriving the numeric standards. Additional information on the combined toxicity of NP, NP1EO and NP2EO to aquatic life may be available following actions of rulemaking recently proposed by the EPA (Federal Register 2009).

Table 3 provides a summary of the Minnesota Pollution Control Agency’s (MPCA) draft WQSs. The calculated Final Acute Value (FAV) of 59.78 μg/L for NPEO compares to the national criterion FAV for freshwater of 55.49 μg/L for 4-NP. This difference can be explained in part as both the total number of geometric mean acute values (GMAV) and the GMAVs for the four lowest taxa are slightly higher in development of this numeric standard compared to the national criteria. Developing numeric standards that includes effects of NPEO is reasonable because: 1) short-chain et hoxylates are expected to be the mo st common form of NPEO in surface waters. They are the most recalcitrant form in the etho xylated chain degradation, and are most likely to be a

7component of effluent discharges, 2) These short-ch ain NP ethoxlylates degrade further to 4-NP under anaerobic conditions found in many aquatic sediments. A numeric standard for NP EO serves to reduce the total amounts of 4-NP present in the environment by also reducing the potential release of the short-chain ethoxylates.

Calculation of chronic standard (CS) values can be ac hieved in one of two ways. Given sufficient chronic toxicity data to fulfill the Tier I taxonomic categories, a chronic value can be calculated in the same manner as the acute value. With insufficient chronic toxicity da ta, an acute to chronic ratio can be used. The latter method was used to compute the acute to chronic ratios (ACR) available for three freshwater species. National

freshwater AWQC are based on an ACR for an estuarine species, which was not used for this numeric standard development. National guidelines suggest that choice of an ACR be determined using either 1) the geometric mean of three or more ACRs if there is no apparent tr end between ACR values and ac ute toxicity values, or 2) the ACR for the study pair that had a GMAV closest to th e calculated FAV. The former method was selected as no apparent trend could be discerned from the data. It wa s observed that fish appear to have large differences
between their acute and chro nic endpoints, so it was important that the one ACR available for fish (rainbow trout) be included in the calculations of the final ACR (8.023). Also, as fish appear to have greater chronic sensitivity and rainbow trout are an important aquatic sp ecies in Minnesota, a chronic standard for cold-water (class 2A) uses was calculated using the ACR (28.11) for rainbow trout. The chronic standard for all other class 2 waters was calculated using the geometric mean ACR for the three species shown in Table 2. Studies have reported chronic effects of NPEO on aquatic organisms using conventional endpoints that represent effects on populations of aquatic animals (i.e., survival and growth), but were not sufficient for Tier 1 assessment. The national AWQC document provides an examination of chronic effects reported from the literature through 2005.



### Endocrine-active endpoints for nonylphenol ethoxylates
Nonylphenol is documented as an endocrine active co mpound (EAC) described in part through its estrogenic activity in aquatic organisms, particularly vertebra tes (EPA 2005). Endocrine Acti ve Compounds are broadly
described as chemicals that exert effects attributed to disruption of the endocrine system, which regulates critical growth, developmental and repr oductive aspects of an organism’s life cycle. These sorts of compounds are also referred to as endocrine disrupting compounds , but the term EAC serves to better describe the activity of these compounds in biological systems. Cu rrent understanding of EACs characterize them through both activational (e.g., vitellogenin production) and organizational (e.g., intersex) endpoints, and a variety of measured responses through histologic al, physiological, molecular (i.e., pr otein, gene) and other observations. This document, however, will not be developing aquati c life WQSs based on endocrine-active endpoints. The challenge with developing numeric standards based on EAC endpoints is the scientific information gap, specific to NPEOs, that precludes a connection of thes e endpoints to effects at the population level 1

.

Research with NPEO has documented effects of estrog enic exposure in organism s to responses measured through chemical reproductive proteins (e.g., vitelloge nin induction) and their cellular precursors (e.g., m-RNA induction) (Vazquez-Duhalt 2005). These chemical biomarkers also have been associated with internal effects (e.g., gonadal deformities), external effects (anatomica l deformities, secondary sex characteristics), and some limited reproductive (fecundity, hatchi ng success), behavioral (spawning success) and other effects (growth,

8 1 Other environmental pollutants that have re levant ecological effects data for evalua ting population level effect are discussed in the MPCA’s 2008 Legislative Report, Endocrine Disrupting Compounds (at http://www.pca.state.mn.us/publications/reports/lrp-ei1sy08.pdf ).survival). Absolute outcomes of toxicity tests using NPEO, however, have yet to report definitive doseresponse and endpoint calculations that are critical to development of numeric standards for aquatic life. As NPEO comes from entirely anthro pogenic sources, surveys of wastew ater effluents and ambient waters have detected these compounds in a number of sites in Minnesota (Lee et al. 2004 and 2008). In conjunction with this analysis, laboratory studies have examined organism responses to ex posures of whole effluent dilutions and aqueous solutions spiked with releva nt concentrations of nonylphenols ( Bistodeau et al. 2006,
Schoenfuss et al. 2002). Outcomes from these tests did not pro duce any absolute connections to reproductive effects. Recently, Schoenfuss (2008) showed that chro nic exposures of fathead minnow to nonylphenols in wastewater effluent affected spawning behavior of ma les. Results of these tests do not include conclusive dose-response characteristics, but serve to provide addi tional information of possible population-level effects in connection with wastewater effluents containing measurable amounts of NPEO. Numerous studies have examined behavioral and reproductive-related effects following exposure to whole effluents, mixtures and treatments containing nonylphenol and octylphenol etho xylates. Dr. Scheonfuss is currently engaged with the agency in efforts that include assessing repro ductive effects in female fathead minnows.

The intent of this standards development is to ensu re additional protection to aquatic organisms from exposure to the broader suite of nonylphenol ethoxy lates through attempting to keep the most toxic compounds (4-NP, NP1EO and NP2EO) from entering the environment. A cursory examination of the recent literature (i.e., ECOTOX database search) suggest that many studies reporting chroni c effects of NPEO focused more on assessing endocrine active e ndpoints. These too were reported in the national criteria document as other endpoints (US EPA 2005; Table 6). From these (T able 6) data, a species sensitivity distribution was created (Figure A) that offers a rela tive comparison between this range of endpoints and the chronic value of NPEO developed for the draft CSs. The species sens itivity distribution was plotted using the online EPA program CADDIS (US EPA 2000). This exercise was not meant to prescribe any definitive measure of effect on the aquatic community, but it may serve to provide some insight toward the relative protection offered by the draft Minnesota chronic standard to aquatic life.



## Draft Water Quality Standards for Nonylphenol and Ethoxylates

Minnesota aquatic life WQSs for nonylphenol ethoxylates

The MPCA has decided to adopt criteria values for no nylphenol ethoxylates best described as 4-nonylphenol (CAS number 84852-15-3), NP1EO (CAS number 104– 35–8) and NP2EO (CAS number 27176– 93–8). Development of a state standard for this suite of NPEO serves both as a means to adopt water quality standards that fulfill the Clean Water Act mandate and provide better protection for aquatic life uses in the state. Adopting these standards for NPEO versus standard s for 4-NP alone is better suited because the realistic environmental exposure to aquatic organisms is not restricted to a single chemical.

Sources used to gather information needed for the deve lopment of aquatic life criteria were retrieved from a
search of academic databases. Primary databases were Scirus ( www.scirus.com ), Google Scholar (scholar.google.com), University of Minnesota library, MPCA library resources, U. S. EPA ECOTOX and other sources. The national criteria document (US EPA 2005) prov ided the majority of the toxicity data used for the Minnesota criteria development.

9The Aquatic Life Summary Sheets (Table 3) presents the technical detail for the Class 2 Final Acute Value (FAV) and Chronic Standard (CS) value of 59.78 μg/L, rounded to 60 μg/L, and 7.4 μg/L, re spectively. Additionally, a separate chronic value for cold water uses (Class 2A) of2.4 μg/L was developed for the protection of coldwater fish. Development of these Minnesota standards considered additional data from the scientific literature that expanded upon studies using 4-NP, NP1EO and NP2EO. Results of those tests did not show 4- NP to be considerably more toxic th an NP1EO or NP2EO, and the addition of toxicity test endpoints for more species serves to better reflect a broader aquatic co mmunity response. Inclusion of one study using the amphibian Xenopus , though not particularly sensitive, offers a broader perspective of surrogate test species.
Minnesota standard calculations also a dded to the calculation of an acute to chronic ratio (ACR). In efforts to

better reflect the freshwater focus of Minnesota criter ia, the national ACR using a saltwater species was not included in the final ACR used for deriving a chronic value.



### Considerations of Human health in aquatic life criteria

The national AWQC for nonylphenol (US EPA 2005) only developed aquatic life acute and chronic standards
and did not include a review of human health-based chro nic criterion. EPA has also not published toxicological values for use in risk assessment in the Integrated Ri sk Information System (IRIS). Developing water quality

standards also include review of available data to ev aluate the beneficial uses of drinking water, fish consumption, and recreational primary contact. MPCA works closely with the Minnesota Department of Health (MDH) on toxicological evaluations and had re quested a human health review to ensure that the chronic standard being developed will be protective for both aquatic communities and human health (MDH 2009). MDH provides toxicological data reviews used by MPCA since the 1990 adoption of human healthbased methods and standards. Prior to recommending to xicological values for use by MPCA, the dataset has to meet their criteria for sufficient and acceptable da ta (e.g. MDH HBV level- refe rence doses and appropriate drinking water intake rates). At this time, MDH did not develop a final reference dose or provide human health risk assessment advice (RAA) for nonylphenol. However, a survey of available secondary literature revealed sources of information about the mammalian toxicity of nonylphenol to suggest that the human health-based WQS would not be as stringent as the chronic standard developed to protect aquatic life. As a review of primary information sources was not possible, the presen tation of these results could not be used in the development of NPE standards. MPCA will continue to evaluate the availability of final toxicological assessments by EPA’s IRIS and MDH for future consideration in WQSs.



### Implementation
WQSs are expected to be assessed and updated every thr ee years according to provis ions in the Clean Water Act. The MPCA has the responsibility for assessing ex isting water quality standards and for considering any new or existing national criteria for surface wate rs to develop WQSs. Develo ping Minnesota WQSs for nonylphenol ethoxylates is based on lack of existing criteria or WQSs for these chemicals and availability of National AWQC to provide guidance only for 4-nony lphenol. Based on additional research data, MPCA augmented the National criteria values by adding the two short-chain ethoxylates (NP1EO, NP2EO) when developing protective values for the three most toxic nonylphenol ethoxylates. A study of selected surface waters in Minnesota found nonylphe nol ethoxylates present in many la kes and streams, and not always associated with wastewater sources (Lee et al. 2009). Setti ng values protective of aquatic life for NPEOs offers a better assurance that these anthropogenic chemicals are less likely to be released to the environment.

10Methods for chemical analysis of nonylphenol ethoxylate s are available through sele ct laboratory procedures and draft guidance documents under review by the Am erican Society for Testing and Materials (ASTM). A standard method for the analysis of surface water a nd wastewater is anticipated to be complete by 2012. Current practices of sample analysis are on a proj ect basis (see Zaugg et al. 2006), which provide for quantifying concentrations of to tal NPEO1, NPEO2 and 4- NP.

Table 1. Acute toxicity values considered in development of numeric aquatic life standards . Notes: n – not used for standard development: (marin e) – marine species; (short test) – test length unaccept able; (chemical) – exposure chemical not reported or unacceptable; (non-native) – not native species; (methods) – unacceptable methods used. ACR – data used to calculate acute to chronic ratio.

Species Scientific Name Endpoint Conc. (ug/L) Chemical

exposure Author Notes

Acipenser oxyrhynchus 80 4 - NP Dwyer et al. 2000 n (marine) Acipenser oxyrhynchus 80 4 - NP Dwyer et al. 2000 n (marine) Alosa sapidissima 50 4 - NP Dwyer et al. 2000 n (short test)
Bufo boreas 120 4 - NP Dwyer et al. 1999 y Ceriodaphnia 210 NPEO Isidori et al. 2006 y; ACR Ceriodaphnia 220 NPEO Isidori et al. 2006 y; ACR Ceriodaphnia 70 NPEO Isidori et al. 2006 n (chemical) Ceriodaphnia 92.4 NPEO TenEcyck and Markee 2007 y Ceriodaphnia 328 NPEO TenEcyck and Markee 2007 y Ceriodaphnia 716 NPEO TenEcyck and Markee 2007 y Chironomus 160 4 -NP England 1993 y Crinia insignifera 6400 NPEO Mann and Bidwell 2000 n (non-native) Crinia insignifera 4500 NPEO Mann and Bidwell 2000 n (non-native) Daphnia magna 104 4 - NP Brooke 1993 y; ACR Daphnia magna 190 4 - NP Comber 1993 y; ACR Daphnia magna 180 4 -NP Hirano et al. 2004 y Etheostoma 190 4 - NP Dwyer 1999 y Etheostoma 110 4 - NP Dwyer 1999 y Etheostoma lepidum 220 4 - NP Dwyer et al. 1999 y Etheostoma lepidum 200 4 - NP Dwyer et al. 1999 y Etheostoma lepidum 190 4 - NP Dwyer et al. 1999 y Etheostoma rubrum 110 4 - NP Dwyer et al. 1999 y Etheostoma rubrum 170 4 - NP Dwyer et al. 1999 y Etheostoma rubrum 130 4 - NP Dwyer et al. 1999 y Gila elegans 310 4 - NP Dwyer 1995 y Gila elegans 270 4 - NP Dwyer 1995 y Gila elegans 290 Sappington et al. 2001 y Hyallela 20.7 4 - NP Brooke 1993 y Hyallela 150 4 -NP England 1995 y L. variegatus 342 4 - NP Brooke 1993 y Lampsilis cardium 1190 4 -NP Milam et al. 2005 n (methods) Lampsilis siliquoidea 490 4 -NP Milam et al. 2005 n (methods) Lepomis 209 4 - NP Brooke 1993 y Leptodea fragilis 570 4 -NP Milam et al. 2005 n (methods)

11Ligumia subrostrata 1040 4 -NP Milam et al. 2005 n (methods)

Litoria adelaidensis 9200 NPEO Mann and Bidwell 2000 n (non-native)

Litoria adelaidensis 8800 NPEO Mann and Bidwell 2000 n (non-native)

Litoria adelaidensis 8800 NPEO Mann and Bidwell 2000 n (non-native) Megalonaias nervosa 560 4 -NP Milam et al. 2005 n (methods) Onchorhynchus 221 4 - NP Brooke 1993 y; ACR Onchorhynchus 190 4 - NP Dwyer 1995 y Onchorhynchus 260 4 - NP Dwyer 1995 y Onchorhynchus 140 4 - NP Dwyer 1995 y Onchorhynchus 270 4 - NP Dwyer 1995 y

Species Scientific Name Endpoint Conc. (ug/L) Chemical

exposure Author Notes

Onchorhynchus 180 4 - NP Dwyer 1995 y Onchorhynchus 180 4 - NP Dwyer 1995 y Onchorhynchus 160 4 - NP Dwyer 1995 y Onchorhynchus 150 4 - NP Dwyer 1995 y Onchorhynchus 140 4 - NP Dwyer 1995 y Onchorhynchus 220 4 - NP Dwyer 1995 y Oncorhynchus clarkii stomias 150 Sappington et al. 2001 y Oncorhynchus gilae apache 170 Sappington et al. 2001 y Oncorhynchus mykiss 190 Sappington et al. 2001 y Ophiogomphus 596 4 - NP Brooke 1993 y Oryzias latipes 870 4 - NP Kashiwada et al. 2002 n (test spp.) Oryzias latipes 850 4 - NP Kashiwada et al. 2002 n (test spp.) Oryzias latipes 130 4 - NP Kashiwada et al. 2002 n (test spp.) Oryzias latipes 850 4 - NP Kashiwada et al. 2002 n (test spp.) Physella 774 4 - NP Brooke 1993 y Pimephales promelas 128 4 - NP Brooke 1993 y Pimephales promelas 210 4 - NP Dwyer 1995 y Pimephales promelas 360 4 - NP Dwyer 1995 y Pimephales promelas 310 4 - NP Dwyer 1995 y Pimephales promelas 330 4 - NP Dwyer 1995 y Pimephales promelas 170 4 - NP Dwyer 1995 y Pimephales promelas 290 4 - NP Dwyer 1995 y Pimephales promelas 140 4 -NP Holcombe et al. 1984 y Pimephales promelas 270 Sappington et al. 2001 y Pimephales promelas 323 NPEO TenEcyck and Markee 2007 y Pimephales promelas 136 NPEO TenEcyck and Markee 2007 y Pimephales promelas 218 NPEO TenEcyck and Markee 2007 y Poeciliopsis occidentalis 250 4 - NP Dwyer et al. 1999 y Poeciliopsis occidentalis 250 4 - NP Dwyer et al. 1999 y Poeciliopsis occidentalis 230 4 - NP Dwyer et al. 1999 y Ptychocheilus lucius 270 4 - NP Dwyer 1995 y Ptychocheilus lucius 240 4 - NP Dwyer 1995 y Ptychocheilus lucius 260 Sappington et al. 2001 y Rana sphenocephala 340 4- NP Bridges et al. 2002 y Scaphirhynchus platorynchus 200 4 - NP Dwyer et al. 1999 n (short test) Scaphirhynchus platorynchus 130 4 - NP Dwyer et al. 1999 n (short test) Scaphirhynchus platorynchus 130 4 - NP Dwyer et al. 1999 y Thamnocephalus platyurus 4.82 NP form Brausch and Smith 2007 n (chemical) Thamnocephalus platyurus 2.6 NP form Brausch and Smith 2007 n (chemical) Thamnocephalus platyurus 3.68 NP form Brausch and Smith 2007 n (chemical)
Utterbackia imbecilis 770 4 -NP Milam et al. 2005 y

12Xenopus laevis 5400 NPEO Mann and Bidwell 2000 y Xenopus laevis 2800 NPEO Mann and Bidwell 2000 y Xenopus laevis 3300 NPEO Mann and Bidwell 2000 y Xenopus laevis 4600 NPEO Mann and Bidwell 2000 y Xenopus laevis 3900 NPEO Mann and Bidwell 2000 y Xenopus laevis 4600 NPEO Mann and Bidwell 2000 y Xenopus laevis 4800 NPEO Mann and Bidwell 2000 y Xiphophorus helleri 205.98 Kwak et al. 2001 y Xyrauchen texanus 190 4 - NP Dwyer 1995 y Xyrauchen texanus 160 4 - NP Dwyer 1995 y Xyrauchen texanus 170 Sappington et al. 2001 y

13Table 2. Calculations of aquatic life num eric standard for 4- NP, NP1EO and NP2EO

.

Genus name GMAV Rank P ACR

Xenopus 4108.6 18 Physella 774.0 17 Ophiogomphus 596.0 16

Lumbriculus 342.0 15

Rana 340.0 14

Gila 289.5 13 Ptychocheilus 256.4 12 Ceriodaphnia 251.3 11 9.08 Pimephales 225.9 10 Lepomis 209.0 9 Onchorhynchus 181.4 8 28.11 Xyrauchen 172.9 7

Chironomus 160.0 6

Etheostoma 159.8 5 0.26 Daphnia 152.6 4 0.21 2.02 Scaphirhynchus 130.0 3 0.16

Bufo 120.0 2 0.11 Hyallela 55.7 1 0.05

GMAV P ln GMAV (ln GMAV) Sq Rt P

Daphnia magna 152.6 0.21 5.0281 25.2820 0.4588 Scaphirhynchus plato 130.0 0.16 4.8675 23.6929 0.3974

Bufo boreas 120.0 0.11 4.7875 22.9201 0.3244 Hyallela azteca 55.7 0.05 4.0204 16.1635 0.2294

Genus ACR

s2 Num 0.6029 Ceriodaphnia 9.08

s2 Denom 0.0293 Onchorhynchus 28.11
S2 20.6093 Daphnia 2.02 Sqrt S2 4.5397 Mysis 8.40

L 3

. 0 7 5 6

A 4

. 0 9 0 7

FAV 59.7808

GeoMean CC: Chronic Calc(Mysis) 7.1 ACR (Mysis; EPA Crit.) 8.40
CC: Chronic Calc #1 7.5 ACR (RBT, D.m., C.d., Mysis): 7.95 CC (2A Salmonid): 2.1 ACR (2A salmonid): 28.11 CC (FW ACR): 7.5 ACR FW (RBT, C.d., D.m.) 8.02

14MINNESOTA POLLUTION CONTROL AGENCY DRAFT AQUATIC LIFE NUMERIC STANDARD SUMMARY SHEETS

Table 3 Draft Water Quality Standards

A. Chemical: Nonylphenol ethoxylates CAS# Date January 2010

B. Minnesota Criterion: ug/l (unless noted otherwise)

Water Class Use CS MS FAV Basis 2

1,2A DW, Salmonid 2.4 30 59.78 PCAT1
1,2Bd DW, NonSalmonid 7.4 30 59.78 PCAT1
2B, 2C, 2D NonSalmonid 7.4 30 59.78 PCAT1

Other Round to 60

Are Minnesota numeric standards modified from existing EPA criteria? Yes Is toxicity related to wate r quality characteristic?: No If yes, above standard values determined for: Slope: Acute:
Chronic:
Formulas: MPCA EPA

CS:

MS:

FAV:

Notes: Chronic criteria lowered for 2A waters to protect Rainbow Trout

C. EPA Criterion: ug/l

Date: Dec 2005 CCC: 6.6 Basis: EPA T1 (4- nonylphenol)

MC: 28 Basis: EPA T1 (4- nonylphenol)

FAV: 55.49 Basis: EPA T1 (4- nonylphenol) D. Other Criteria ug/l Source E. Notes: U.S. EPA Aquatic Li fe for Nonylphenol available at: www.epa.gov/waterscience /criteria/nonylphenol

2 Criteria basis codes for part B:
EPA = From EPA criterion PCA = Criterion developed by Minneso ta Pollution Control Agency staff T1 = Direct aquatic life toxicity, EPA national criteria procedures used T2 = Direct aquatic life toxicity , EPA advisory procedures used Hs = Human health systemic effects Hc = Human health carcinogenic effects R = Tissue residue (bioaccumulation)

W = Wildlife effects O = Organoleptic (taste and odor) Other = Criterion based on other end point

15MINNESOTA POLLUTION CONTROL AGENCY DRAFT AQUATIC LIFE NUMERIC STANDARD
Determination of Numeric Standard from Aquatic Life Toxicity Values

A. Chemical: Nonylphenol ethoxylates CAS# Date January 2010

B. EPA National Method

1. Data requirements: Salmonid (2A water only): Onchorhynchus

Osteichthyes (fish): Scaphirhynchus, Pimephales Chordata (fish, amphibian): Bufo, Rana.

Planktonic crustacean: Daphnia, Ceriodaphnia

Benthic crustacean: Hyalella azteca Aquatic insect: Chironomus, Ophiogomphus. Phylum other than Arthropoda or
Chordata: Physella

Second insect or phylum not already rep.: Lumbriculus

2. GMAVs Lowest 4(2A): 152.65 (Daphnia magna) Lowest 4(2B,2C, 2D): same ug/l 130.0 (Scaphirhynchus platorynchus) same
N: 23 120. 0 (Bufo boreas) N: same 55.7 (Hyalella azteca) same
3. FAV: 2A: 59.78 2B, 2C, 2D: 59.78 4. Adjustments to FAVs: None

5. Chronic data: No. Species:

mean values

6. ACR Measured: Acute value Chronic value ACR Ceriodaphnia 214.94 23.66 9.083 Onchorhynchus 221 7.861 28.11 Daphnia (Geomean) 140.57 69.50 2.023

GeoMean ACR: 7.795 Note: Onchorhynchus ACR (28.11) used

for class 2A chronic criterion
calculation.

7. Final Plant Value: Not Determined

C. EPA Advisory Method Not Determined

D. Notes: Nonyphenol ethoxylates are descri bed as combined aqueous concen trations of 4-nonylphenol, nonylphenol mono-ethoxylate (NP1EO) a nd nonylphenol di-ethoxylate (NP2EO).

16MINNESOTA POLLUTION CONTROL AGENCY DRAFT AQUATIC LIFE NUMERIC STANDARD
HUMAN HEALTH – To Be Determined

A. Chemical: Nonylphenol ethoxylates CAS# Date 30 June 2009

B. EPA Human Health Criterion: DW and fish : none fish only: none DW only: none ug/l ADI/Ref.dose: mg/kg/day Cancer Potency Slope: (mg/kg-d) -1

Final BCF: %lipid:

RSC:

C. Minnesota Human Health Criterion 1. Ref.dose: mg/kg/day Source:

RSC: Source: 2. Cancer Potency Slope: (mg/kg-d) -1 Source: 3. Measured BAFs: Species/Tissue BAF %lipid Norm BAF

1.

2.

Geo mean: 4. Measured BCFs: Species/Tissue BCF %lipid Norm. BCF

1.

2.

Geo mean: 5. Edible portion BAF or BCF BAF BCF Cold water: 6.0 % lipid Warm water: 1.5 % lipid 6. Geo mean unadjusted for lipid:

7. log Kow: adjust. for % lipid: meas. QSAR: Est. BCF:

8. Parachor: 9. Food Chain Multiplier:

10. Final BAF: 2A: 2B,2C, 2D: 11. Criteria: ug/l 2A: 2Bd: 2B/2C, 2D: HRL/HBV:

D. Organoleptic: ug/l Source:

E. Notes: Sufficiently reviewed human health toxi cological values were not available from U.S. EPA’s Integrated Risk Information System or Minnesota De partment of Health (MDH 2009) to develop a human health-based CS. EPA’s 304 (a) AWQC also did not pr ovide final recommended national bioaccumulation
factors.

17Figure A. Data summarized from US EPA (2005), Table 6 as plotted using a species sensitivity distribution performed by CADDIS (US EPA 2000).

Atl. Salmon D. galeata

Clawed frog zooplankton/
benthic macs

D. magna Duckweed Bluegill Platyfish moss

Swordtail FHM Carp RBT

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

1

0.10 1.00 10.00 100.00 1000.00 10000.00Proportion of species affected

Micrograms NPEO per liter Represents 5% or less of reported chronic values for aquatic species.

Taxa Micrograms NPEO per
liter Standard
Deviation Proportion
Taxa Number of
Observations

Swordtail 0.20 4% 1

FHM 2.88 0.17 11% 4 Carp 10.00 18% 2

RBT 18.80 0.73 25% 18

Atl. Salmon 20.00 32% 1 D. galeata 22.40 39% 1 Clawed frog 27.87 0.15 46% 2 zooplankton 41.80 54% 1

benthmacs 41.80 54% 1 D. magna 54.14 0.11 68% 3

Duckweed 125.00 75% 1 Bluegill 135.90 82% 1 Platyfish 960.00 89% 1

moss 2500.00 96% 1

Plotted data summarized from EPA 2005, Tabl e 6.

18

### References

American Society for Testing and Materials (ASTM). Au gust 2009. Biological Effects and Environmental Fate; Biotechnology. Volume 11.06. ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA, 1942 8-2959 USA. 1538 p.

American Society for Testing and Materials (ASTM). 200 4. ASTM E1439. Standard Guide for Conducting the Frog Embryo Teratogenesis Assay-Xenopus (FETAX ). Volume 11.06. ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA, 19428-2959 USA.

Bistodeau, T. J., L. B. Barber, S. E. Bartell, R. A. Cediel, K. J. Grove, J. Klaus termeier, J. C. Woodar d, K. E. Lee & H. L. Schoenfuss (2006) Larval exposure to environmen tally relevant mixtures of alkylphenolethoxylates reduces reproductive competen ce in male fathead minnows. Aquatic Toxicology, 79, 268.

Brausch, J. M., Philip N. Smith (2007) Toxicity of Thr ee Polyethoxylated Tallowamine Surfactant Formulations to Laboratory and Field Collected Fair y Shrimp, Thamnocephalus platyurus. Arch. Environ. Contam. Toxicol, 52

, 217.

Bridges, C. M., F. J. Dwyer, D. K. Hardesty & D. W. Whites (2002) Comparativ e contaminant toxicity: are amphibian larvae more sensitive than fish? Bulletin of environmental contamination and toxicology, 69

, 562.

Brooke, L. T. (1993) Acute and Chronic toxicity of nonylphenol to ten species of aquatic organisms. Report to the U.S. EPA for Work Assignment No . 02 of Contract No. 68-C1-0034. , Lake Superior Research Institute, University of Wisconsi n-Superior, Superior, WI, 34 p.

Comber, M. H. I., Williams, T. D., Stewart, K. M. (1993) The effects of nony lphenol on Daphnia magna. Water Research, 27

, 273.

Dwyer, F. J., D.K. Hardesty, C. G. Ingersoll, J.L. Kunz and D.W. Whites (2000) Assessing Contaminant Sensitivity of American Shad, Atlantic Sturgeon and Shortnose Sturgeon. U.S. Geological Survey, Columbia
Environmental Research Center

.

Dwyer, F. J., D.K. Hardesty, C.E. He nke, C.G. Ingersoll, D.W. Whites, D. R. Mount and C.M. Bridges (1999) Assessing contaminant sensitivity of endangered and threatened species: Toxicant classes. EPA/600/R99/098. National Technical Informatio n Service, Springfield, VA. 15 pp.

Dwyer, F. J., Sappington, L.C., Buckle r, D.R., Jones, S.B. (1995) Use of surrogate species in assessing contaminant risk to endangered and threatened fishes: final report - September. U.S. Environmental Protection Agency. (EPA/600/R-96/029). 78 p.

England, D. E. and J. B. Bussard. (1993) Toxicity of nonylphenol to the midge Chironomus tentans. Report No. 40597, ABC Laboratories, Inc., Columbia, MO

.

19England, D. E. and J. B. Bussard . (1995.) Toxicity of nonylphenol to the amphipod Hyalella azteca. Report No., 41569. ABC Laboratories, Inc., Columbia, MO

. Federal Register. June 17, 2009. Testing of Certain Nonylphenol and Nonylphenol Ethoxylate Substances. Vol. 74, No. 115. pp. 28654-28662.

Hirano, M., H. Ishibashi, N. Matsumura, Y. Nagao, N. Wa tanabe, A. Watanabe, N. Onikura, K. Kishi & K. Arizono (2004) Acute Toxicity Responses of Two Crustacean s, Americamysis bahia and Daphnia magna, to Endocrine Disrupters. Journal of Health Science, 50

, 97.

Holcombe, G. W., G. L. Phi pps, M. L. Knuth & T. Felhaber (1984) The acute toxicity of selected substituted phenols, benzenes and benzoic acid es ters to fathead minnows Pimephales. Environmental Pollution. Series A, Ecological and Biological, 35

, 367.

Isidori, M., M. Lavorgna, A. Narde lli, A. Parrella (2006) Toxicity on cr ustaceans and endocrine disrupting activity on Saccharomyces cere visiae of eight alkylphenols. Chemosphere, 64

, 135.

Kashiwada, S., H. Ishikawa, N. Miyamoto, Y. Ohnishi & Y. Magara (2002) Fish test for endocrine-disruption and estimation of water quality of Japanese rivers. Water Research, 36

, 2161.

Kwak, H. I., M. O. Bae, M. H. L ee, Y. S. Lee, B. J. Lee, K. S. Kang, C. H. Chae, H. J. Sung , J. S. Shin, J. H. Kim, W. C. Mar, Y. Y. Sheen & M. H. Cho (2001) Effects of nonylphenol, bisphenol A, and their mixture on the viviparous swordtail fish (Xiphophorus helleri). Environmental toxicology and chemistry, 20

, 787.

Lee, K. E., Larry B. Barber, Edward T. Furlong, Jeffery D. Cahill, Dana W. Kolpin, Michael T. Meyer, and Steven D. Zaugg (2004) Presence and Distribution of Orga nic Wastewater Compounds in Wastewater, Surface, Ground, and Drinking Waters, Minnesota, 2000–02. U.S. Geological Survey Scientific Investigation Report 2004-5138, 47 p.

Mann, R. M. & J. R. Bidwell (2000) Application of the FETAX protocol to assess the developmental toxicity of nonylphenol ethoxylate to Xenopus laevis and two Australian frogs. Aquatic toxicology, 51

, 19.

Minnesota Department of Health (MDH) (2009) He alth based guidance request form: nonylphenol, nonylphenol ethoxylates, and nonylphenol carbox ylates. Requested from MPCA April 28, 2009; returned from MDH on June 10, 2009.

Milam, C. D., J. L. Farris, F. J. Dwyer, D. K. Hardesty (2005) Acute Toxic ity of Six Freshwater Mussel Species (Glochidia) to Six Chemicals: Implications for Dap hnids and Utterbackia imbecillis as Surrogates for Protection of Freshwater Mussels (Unionidae). Arch. Environ. Contam. Toxicol, 48

, 166.

Sappington, L. C., F. L. Mayer, F. J. Dwyer, D. R. Buckler, J. R. Jones & M. R. Ellersieck (2001) Contaminant Sensitivity of Threatened and Endangered Fishes Compared to Standard Surrogate Species. Environmental Toxicology & Chemistry, 20

, 2869.

2021 Schoenfuss, H. L., J. T. Levitt, G. Van der Kraak & P. W. Sorensen (2002) Ten-week exposure to treated sewage discharge has relatively minor, va riable effects on reproductive be havior and sperm production in goldfish. Environmental toxicology and chemistry, 21, 2185.

Servos, M. R. (1999) Review of the aquatic toxicity, es trogenic responses and bioacc umulation of alkylphenols and alkylphenol polyethoxylates Water quality research journal of Canada 34, 123.

Soares, A., B. Guieysse, B. Jefferson, E. Cartmell, J. N. Lester, (2008) Nonyl phenol in the environment: A critical review on occurrence, fate, toxicity and treatment in wastewaters. Environment International, 34,

1033.

USEPA (1985) Guidelines for deriving numerical national water quality crit eria for the protection of aquatic organisms and their uses. PB85- 227049. National Technical Information Service, Springfield, VA. (ed C. E. Stephan, D.I. Mount, D.J. Hansen, J. H. Gentile, G.A. Chapman, W.A. Brungs).

Teneyck, M. C. & T. P. Markee ( 2007) Toxicity of nonylphenol, nonylphe nol monoethoxylate, and nonylphenol diethoxylate and mixtures of these compounds to Pimephales promelas (fathead minnow) and Ceriodaphnia dubia. Archives of environmenta l contamination and toxicology, 53, 599.

Vazquez-Duhalt, R., F. Marques-Rocha, E. Ponce, A. F. Licea, M.T. Vi ana (2005) Nonylphenol, an integrated vision of a pollutant. Scientific review Applie d Ecology and Environmen tal Research, 4(1), 1.

US EPA, (2005) Ambient Aquatic Life Water Quality Crit eria: Nonylphenol. Office of Water, Washington, DC, EPA-822-R-05-005, 88.

US EPA (2000) Stressor Identification Guidance Document. U.S. Environmental Protection Agency Office of Water, Washington, DC 20460. EPA- 822-B-00-025. cfpub.epa.gov/caddis.

Zaugg, S.D., Smith, S.G., and Schroe der, M.P., 2006, Determination of wa stewater compounds in whole water by continuous liquid–liquid extraction and capilla ry-column gas chromatography/mass spectrometry: U.S. Geological Survey Techniques and Methods, book 5, chap. B4, 30 p.