# Presentation: 186321

## Regional Case Study of Alkylphenol Ethoxylates1

- Region 5 US EPA
- Al Alwan, George Azevedo, John Dorkin, Dan Hopkins, Peter Howe, Bryan Nielsen, Mari Nord, Rob Pepin, Robert L. Thompson, Marc Tuchman, Dennis Wesolowski, Larry Zintek

- 1Contents of this presentation do not reflect official U.S. EPA policy

## Alkylphenol CompoundsHow Are They Used ?

-  Industrial, Institutional and Domestic Surfactants
-  Antioxidant in Plastics
-  PVC Stabilizer
-  Oil Additives
-  Oil Field Recovery
-  Metal Extractants

- Alkylphenol CompoundsHow Are They Used ?

## Alkylphenolpolyethoxylates(APEs)

- Degradation products
- Extremely toxic to aquatic organisms
- Will probably be the regulatory end point
- Endocrine disruption to aquatic organisms
- To date water quality standards have not addressed this

## Common Environmental Metabolites of  Nonylphenol Ethoxylates (Adapted from Ahel et al., 1994; Naylor, 1992)

- NP ethoxylate

- NP1EC

- NP2EO

- NP1EO

- NP

- NP2EC

- n = 1 to 100; avg. = 9-17

## DAILY ENVIRONMENT

- Friday, March 28, 2003
-                                                                    Page A-8
- ISSN 1521-9402
-                                                                    News
- Toxic Substances
- European Parliament On Show of Hands Acts to Limit Damage, Ban Sale to General Public and Restrict Industrial Use to Specific Authorized Purposes of Nonylphenol, Nonylphenol Ethoxylate
- BRUSSELS--Legislation approved by the European Parliament March 27 seeks to limit environmental damage caused by nonylphenol (NP) and nonylphenol ethoxylate (NPE), which are classified as "very toxic."

**DAILY ENVIRONMENT**

## Canadian Environmental Protection Act (CEPA)Priority Substance List Assessment ReportNonylphenol and Its EthoxylatesEnvironment CanadaHealth CanadaMarch 2000

- It is proposed that NP and its ethoxylates be considered “toxic” as defined in Section 64 of the CEPA.

## Brief APE Literature Review(“Slightly” Biased)

## NP Bioconcentration Factors

- Bluegill 				220
- Fathead Minnow		271
- Fathead Minnow		293

- Reported by Keith et al. (2001)

## Depuration Half-Life (Hours)

- Gammerus pulex	38
- Killifish	  9
- Mussels	  7
- Salmon	96

- Summarized in Gross-Sorokin et al. (2003)

## NP Aquatic Criteria Document (draft March 2003)

- Freshwater
- Chronic criterion :			  5.9 ppb
- Acute criterion : 			27.9 ppb
- Saltwater
- Chronic criterion :			  1.4 ppb
- Acute criterion :		 	  6.7 ppb

- * Does not include toxicity of ethoxylates
- * Does not address endocrine disruption

## Canadian Risk Assessment

- Based on cumulative toxicity of all APEs
- Estimated toxicity of NP1EO and NP2EO at half that for NP
- Recognized endocrine disruption but was not the major regulatory end point
- “Apparently” APEs will be controlled through mandatory pollution prevention

## Japanese killifish chart

## Additional ORD / Region 5 Activities

- ORD provided funds for Region 5 Central Regional Laboratory to conduct acute toxicity testing on NP1EO and NP2EO to develop TEQ for aquatic toxicity
- QAPP under development

## British Streams Summary(Johnson and Sumpter 2001)

- Hypothesized Endocrine Disruption Effects in Fish Outside Immediate Discharge Due Primarily to:
- 17 α-ethinylestradiol (EE2)
- Major Issue is How Far Downstream EE2 Persists
- Alkylphenols

## Biomarkers for Endocrine Disruption (ED) in Fish

- Decrease or cessation of egg production
- Imposex
- Oocytes in testes
- Vitellogenin (VTG) - Egg yolk protein formed primarily in female fish
- Produced by liver in response to estrogen
- Males can produce if exposed to estrogen or estrogen mimics
- NP exposure known to cause all of these effects
- Relevance to population effects needs to be addressed

## NP Endocrine Disruption in Fathead Minnows

- Miles-Richardson et al. (1999)
- NOAEL estimated from effects on endocrine disruption six fold less than standard chronic toxicity for early life stage of fathead minnow
- Question biological relevance of endocrine disruption to fish populations
- Acknowledged that risk assessment does not include APEs other than NP

## Other Considerations Related to Endocrine Disruption in Effluent Dominated Streams

- Hormones are another major factor

## Effects of Exposure to 17 β-estradiol

- Effects of Exposure to 17 β-estradiol (E2) to Male Fathead Minnows1
- Threshold for histologic changes in testes = ~ 0.04 ppt
- Threshold for vitellogenin induction = ~ 0.04 ppt 1(Miles-Richardson et al., 1999)
- Effluent Concentrations2
- 17 β-estradiol effluent concentrations at four Michigan STPs
- Average = 1.5 ppt ( range = nd – 3.7 ppt )    2(Snyder et al., 1999)

## Relative Potencies of Steroidal Estrogens in Fish (Thorpe et al., 2003) 

- VTG induction in 14 day exposure to juvenile female rainbow trout
- EE2       >         E2          >         E1 (Estrone)

- (11 – 22 X)            (2.3 – 3.2 X)

## Minneapolis Metro Plant Inconsistencies

- Male fish collected in effluent
- Carp VTG increase and testosterone decrease (Folmar et al., 1996)
- Walleye VTG increase and testosterone decrease (Folmar et al., 2000)
- Laboratory Study
- Goldfish, exposed to effluent samples for 10 weeks exhibited no change in testosterone. (Schoenfuss et al., 2002)

## Metro Minneapolis Walleye APE Fish Tissue Concentrationsppm (μg/g wet weight) 

**NP      ****	****=****	****0.2**
**NP1EO  ****	****=****	****2.0**
**NP2EO ****	****=****	****3.1**
**NP3EO ****	****=****	****0.8**
**NP4EO ****	****=****	****0.1**
**NP5EO ****	****=****	****0.0**
**Total     ****	****=****	****6.2**

- Rice et al. (2003)
- N=6, fish collected in effluent by MDNR

## Fox River (Wisconsin) 1995 APEConcentrations (μg/L)15 paper mill effluents ranked

**Fox River (Wisconsin) 1995 APE****Concentrations (μg/L)****15 paper mill effluents ranked**

- Naylor et al. (1996)

## Fox River (Wisconsin) 1995 APEConcentrations (μg/L)6 POTW’s ranked

**Fox River (Wisconsin) 1995 APE****Concentrations (μg/L)****6 POTW’s ranked**

## Fox River APE Concentrations (μg/L)(Upstream Green Bay WWTP)

**Alkylphenol****	****Concentration**
**NP****	****0.58**
**NPE****	****2.78**
**NPIEC****	****1.70**
**NP2EC****	****11.80**
**Total****	****16.86**

- Naylor et al. (1996) and Fields et al. (1996) Data Combined

**Fox River APE Concentrations (μg/L)****(Upstream Green Bay WWTP)**

## Alkylphenol Effluent Concentrations (μg/L) at 8 Large Region 5 POTW'sFebruary and March 1998 (Barber et al., 2000)

- Stickney (IL)	1.7	4.1	5.5	nd	nd	16	92	9.5	6.1
- North Side (IL)	1.6	13.0	7.0	nd	nd	26	64	4.1	1.3
- Calumet (IL)	1.4	5.8	3.7	nd	nd	29	44	4.3	1.7
- Seneca (MN)	1.5	6.0	2.9	nd	nd	60	80	7.8	2.3
- Metro St. Paul (MN)	2.1	12.0	19	2.0	1.2	25	56	13	6.5
- Blue Lake (MN)	0.9	1.5	0.78	nd	nd	21	100	11	5.4
- Jones Island (WI)	2.5	9.0	29	3.0	nd	48	120	16	3.6
**Detroit (MI)****	****19****	****55****	****110****	****17****	****5.0****	****34****	****70****	****4.6****	****1.8**

- Alkylphenol Effluent Concentrations (μg/L) at 8 Large Region 5 POTW'sFebruary and March 1998 (Barber et al., 2000)

## Environment Canada graph

- Bennie et al. (2000)

## Chicago Waterways

## Major Chicago WTPs Flow

| WTP | Design Average Flow(cfs) | Location | % of low flow |
| --- | --- | --- | --- |
| Northside | 515 | NBCR | ~ 100% |
| Stickney | 1857 | CS&SC | ~ 100% |
| Calumet | 545 | Cal Sag Ch | ~ 100% |
| Total Flow | 2917 |  |  |

| Lockport
Lock and Dam | 3200 (cfs)
average annual flow |
| --- | --- |

## Estimated Percent of Daily Flow at Lockport Due to Combined Effluent Flow From MWRGDC WRP’s in 2002

- Does not consider lag time of WRP Flow to Lockport

## Chicago Waterway 7 Day average Flows and Total Precipitation

## Region 5 CRL APEs Method Initiative

- CRL Director (Dennis Wesolowski) Developed Methods Initiative Proposal in Cooperation with ORD
- Methods developed for water and sediments
- SOP available if desired

## Chicago Waterways

- ng/l

- Locations

##  Chicago Waterways

- ng/l

- Locations

## North Branch Chicago River Alkylphenol Sediment Concentrations (PPM)

|  | NP | NP1EO | NP2EO |
| --- | --- | --- | --- |
| Mean | 24.0 | 14.1 | 1.8 |
| Range | 2.5 – 49.0 | ND  – 49.0 | ND  – 16.0 |

- Samples Collected by John Dorkin, May 24 – 28, 1999.  N=39
- Samples Analyzed By Region 5 Central Regional Lab. (Report Date: 4/19/2000)

## Average Concentration of NP and NPEs in Carp from North Branch Chicago River1

- Average Concentration of NP and NPEs in Carp from North Branch Chicago River1

- 1Rice et al. (2003)

## National Pollution Discharge Elimination System (NPDES) Permits

- Water Quality Based Effluent Limits (WQBEL)
- Controls traditional toxics
- Question whether WQBEL’s facilitate full recovery of large effluent dominated streams

## MWRDGC and Region 5 Central Regional Laboratory Toxicity Testing

- Cooperative Whole Effluent Toxicity (WET) testing at 3 major WRP’s
- To date no chronic toxicity
- Region 5 Chicago Waterways toxicity testing at Lockport
- To date no chronic toxicity

## MWRDGC Stream Quality graph

- Stream quality as determined by the Index of Biotic Integrity downstream from the North Side, Stickney and Calumet WRP effluent outfalls (from Report # 98-10, June 1998)

## Other Contributing Factors

- Combined Sewer Overflows
- Contaminated sediments
- Barge traffic
- Habitat limitations

## Conclusions

- Widespread APE occurrence in Region 5 water, sediment and fish tissue
- Appears that some effluents may exceed proposed water quality criteria for NP
- Region 5 Central Regional Laboratory has SOP for NP, NP1EO and NP2EO
- Region 5 developing TEQ for NP, NP1EO and NP2EO to account for the toxicity of ethoxylates
- Consideration should be given to phasing out APEs in US due to increased cost associated with removing from POTW effluents