Concentrations of Hydrophobic Organic Pollutants in U.S. Wastewater

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Chapter 21

Concentrations of Hydrophobic Organic Pollutants in U.S. Wastewater Treatment Plants and in Receiving Surface Waters Modeled from EPA Biosolids Monitoring Data Alex Weir,1 William E. Moiles,1 Brian Brockman,1 Carolyn S. Mattick,1 Kristin McClellan,1,2 Lisa Gerwe,1 Randhir P. Deo,2 and Rolf U. Halden*,1,2 1School

of Sustainable Engineering and the Built Environment, Arizona State University, Tempe, AZ 85287 2Center for Environmental Biotechnology, The Biodesign Institute at Arizona State University, Tempe, AZ 85287 *Corresponding author: The Biodesign Institute at Arizona State University, 1001 South McAllister Avenue, P.O. Box 875701, Tempe, AZ 85287-5701. E-mail: [email protected].

Organic microcontaminants such as pharmaceuticals and personal care products (PPCPs) are currently not regulated with regards to wastewater treatment removal. To provide a basis for risk assessment, the U.S. Environmental Protection Agency (EPA) conducted a nationwide sampling campaign at seventy-four publicly owned treatment works, to assess contamination of biosolids with 145 different pollutants. However, a similar nationwide study of PPCPs contained in treated effluent of such a large number of wastewater treatment plants has never been conducted. In this study, a published empirical model was modified, and applied, to estimate from the biosolids concentrations reported by the EPA, the concentrations in raw and treated wastewater of pharmaceuticals and other organic contaminants. Target chemicals included eight organic compounds: (benzo(a)pyrene, beta-estradiol-3-benzoate, fluoranthene, miconazole, norgestimate, pyrene, triclocarban and triclosan. © 2010 American Chemical Society In Contaminants of Emerging Concern in the Environment: Ecological and Human Health Considerations; Halden, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.


These compounds were selected based on the hydrophobicity range for which the model previously had been validated. The results of the mass loading estimations are compared to measured concentrations in treatment plant influent and effluent and also are put in relation to contaminant concentrations found in effluent receiving U.S. surface waters. Potential impacts on sensitive environmental receptors as well as potentially effective treatment methods for wastewater are identified and discussed. The removal efficiencies predicted by the model ranged from ≥13% for triclosan to ≥82% for benzo(a)pyrene. Modeled contaminant concentrations in treatment plant influent ranged from 0.025 to 12 µg/L whereas modeled contaminant concentrations in effluent ranged from 0.0062 to 10 µg/L. A comparison of predicted and observed removal efficiencies for triclosan and triclocarban indicated that the model predictions are conservative in nature and comparable to actual measurements made at sewage treatment plants. This study produced the first concentration estimates for beta-estradiol-3-benzoate, miconazole, and norgestimate in surface waters and identified important information gaps concerning ambient concentrations of microcontaminants and associated ecotoxicological effects.

Introduction Several studies have shown that secondary treatment of wastewater, with activated sludge processes, results in the incomplete removal of pharmaceuticals and personal care products (PPCPs), as well as other organic chemicals (1–6). Trace concentrations of biologically active contaminants are known to enter ground and surface water supplies mainly through effluent discharge from wastewater treatment plants (WWTPs) (7, 8). Partly because no regulation exists to control these contaminants, the spotlight has recently turned toward the issue of microcontaminants and potential associated risks posed to public health and the environment. Municipalities typically collect wastewater from residences and convey it in sewerage systems to WWTPs for treatment. Effluent water, having met regulatory standards, is then discharged to surface water. In the United States, secondary wastewater treatment, or better, is applied to over 92% of domestic sewage (9). Secondary treatment relying on activated sludge unit operations is the process of choice due to its greater efficiency as compared to other treatment methods. Activated sludge treatment produces excess biological mass referred to as (municipal) sludge. The amount of sludge produced depends on the composition of the influent as well as the design and operation of the treatment facility. The term ‘biosolids’ specifically refers to sewage sludge that has undergone treatment to meet federal and state standards for beneficial use, thereby allowing for its 422 In Contaminants of Emerging Concern in the Environment: Ecological and Human Health Considerations; Halden, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.


application on (agricultural) land as a soil amendment; alternatively, unwanted municipal sludge is incinerated or disposed of in landfills (10, 13). According to the Toxic Substances Control Act (TSCA), approximately 84,000 inventoried chemicals are manufactured, imported, or processed in the United States (http://epw.senate.gov/tsca.pdf). Numerous chemical pollutants can therefore potentially be present in biosolids and aqueous discharge from WWTPs with little to no monitoring or regulation. Since biosolids and reclaimed water are often put to beneficial use, there is a risk of contaminants reaching the general public and negatively impacting the environment. In January 2009, to provide a basis for risk assessment of this issue, the U.S. Environmental Protection Agency (EPA) published the Targeted National Sewage Sludge Survey (TNSSS) (11) that evaluated the level of 145 contaminants found in biosolids from WWTPs across the United States. The report presents statistical methodology and evaluations related to the data collected. It provides estimates of contaminant concentrations in biosolids that are representative of the nation’s largest 3,337 WWTPs, all of which use secondary activated sludge treatment or better and combined treat approximately 94% of the wastewater generated in the U.S. (11). While researchers have published many models predicting the fate of contaminants in WWTPs, none have used the tool to estimate influent and effluent concentrations of WWTPs on a national scale. The goal of this study was to estimate concentrations of select PPCPs and hydrophobic organics in treated wastewater based on the biosolids concentrations reported by the USEPA. In 2009, a simple, yet robust empirical model was introduced allowing for the estimation of levels of hydrophobic organics in biosolids based on influent and effluent concentrations using the pH dependent n-octanol-water partitioning coefficient (DOW) as the only input requirement (12). The model identified sorption as the main removal mechanism for hydrophobic organic compounds. Whether wastewater constituents persist in either biosolids or effluent discharge depends to a large degree on the chemicals’ hydrophobicity, a property represented by the DOW value (12). In addition, this simplistic model takes into account all removal mechanisms during wastewater treatment through a parameterized value, termed pfit. Of the 145 contaminants measured in the TNSSS, eight were evaluated in this study based on their applicability to the model. The results of the mass loading estimates were compared to measured contaminant concentrations in surface water reported in the peer-reviewed literature.

Method The prediction of aqueous concentrations of selected organic pollutants in treated wastewater effluent was made possible by a previously-published empirical model (12) in conjunction with biosolids concentration data by the U.S. Environmental Protection Agency (EPA) published in early 2009 (11). The model applied in this investigation was derived from empirical data published in the peer-reviewed literature (12). Its previous use was to estimate the fraction of hydrophobic organic compounds (HOCs) that will persist in digested 423 In Contaminants of Emerging Concern in the Environment: Ecological and Human Health Considerations; Halden, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.


sewage sludge produced during wastewater treatment (fi(biosolids)). This model (12) (see equation 1) uses tabulated pH-corrected values of the n-octanol-water partitioning coefficient (i.e., DOW values) to account for partitioning behavior of the HOCs. It approximates the combined effect of all loss mechanisms occurring during treatment, including biodegradation, chemical and physical degradation as well as volatilization, by using a dimensionless fitting parameter, pfit:

For the purposes of this study, DOW values corresponding to pH 7.5 were used, which is the average pH of effluent leaving conventional wastewater treatment plants (12). In addition, a pfit value of 1.76 x 10-6 was applied, based on literature information (12). In this investigation, because HOC concentrations in biosolids are known but influent concentrations are not, the empirical model is essentially used in reverse: to predict the HOC concentrations entering the WWTP based on the concentrations in the dry biosolids. Figure 1 depicts a simple diagram applicable to this study. The value of fi(biosolids) obtained from the empirical model expressed in equation 1 can also be expressed as a relationship between the concentration of a given HOC in the biosolids versus those found in influent:

where Ci(influent) is the concentration of analyte i arriving in influent in units of mass per liquid volume, Ci(biosolids) is the concentration of analyte i found in biosolids in units of mass per dry mass of biosolids produced, and Y is the yield of biosolids per volume of raw wastewater treated in units of dry mass of biosolids per liquid volume of wastewater treated. A representative value for Y was taken from the literature as 1.296 x 10-4 kg/L or 129.6 mg/L (12). This value is in good agreement with the generally accepted range of 100–300 mg/L also reported in the literature (14) and therefore was adopted for the purposes of this study. Through means of a mass balance, and assuming constant volume of influent and aqueous effluent stream as well as constant loss to biodegradation and other relevant loss processes, the concentration of HOCs in influent can be calculated. Accordingly, this relationship can be written as follows:

424 In Contaminants of Emerging Concern in the Environment: Ecological and Human Health Considerations; Halden, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.


Figure 1. Conceptual diagram showing relevant input, outputs and loss terms in a wastewater treatment plant. (see color insert) Note that the fi(biosolids) accounts through the pfit value (eq. 1), for losses of the target compound in the treatment plant. Rearrangement of equation 3 yields the final expression for HOC concentrations leaving the WWTP:

Results and Discussion The model is applicable for HOCs that have DOW values in the range from 4.9 to 6.4 (12). Eight analytes from the EPA study fall within this DOW range and thus were considered in this study. The selected compounds are listed in Table 1 along with their DOW values and information on sources, uses and potential human health and ecological impacts.


426


Table 1. Overview of organic compounds considered in this study

CAS Number

pH adjusted n-Octanol-water partitioning coefficient log (Dow) at pH 7.5

Organics (PAH)

50-32-8

6.4

Beta-estradiol3-benzoate

Steroids and Hormones

50-50-0

Fluoranthene

Organics (PAH)

Miconazole

Sources

Potential Impacts

No practical use

Incomplete combustion of organics

Probable human carcinogen; mutagenic

6.24

Contra-ception

Manufactured (derived from Cholesterol)

Endocrine disruptor

206-44-0

5.17

No practical use

Combustion of organic matter

Carcinogen (EPA priority PAH)

Pharmaceuticals

22916-47-8

5.84

Antifungal: Micatin, Monistat, etc

Manufactured

Antifungal Agent with some anti-bacterial properties

Norgestimate

Pharmaceuticals

35189-28-7

5

Treatment of menopause symptoms

Manufactured

Endocrine disruptor

Pyrene

Organics

129-00-0

5.17

Dye-making

Combustion

Toxic to kidneys & liver

Triclocarban

Pharmaceuticals

101-20-2

5.74

Disinfectants, soaps

Manufactured

Anti-fungal, anti-bacterial

Triclosan

Pharmaceuticals

3380-34-5

4.93

Personal Care Products

Manufactured

Anti-fungal, anti-bacterial

Analyte

Group

Benzo(a)pyrene

Uses

In Contaminants of Emerging Concern in the Environment: Ecological and Human Health Considerations; Halden, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.

Analyte

Concentration in Biosolids a [ g/kg]

a

log DOW (pH 7.5) b

Concentration in Influent [ g /L]

Concentration in Effluent [ g /L]

Calculated Removal Efficiency [%]

Literature Removal Efficiencies [%]

661

6.4

0.1

0.019

82

None Found

Beta-estradiol3-benzoate

146.9

6.24

0.025

0.006

75

None Found

Fluoranthene

1419

5.17

0.89

0.707

21

None Found

Miconazole

979.7

5.84

0.23

0.104

55

None Found

Norgestimate

27.5

5

0.024

0.02

15

None Found

Pyrene

1646

5.17

1

0.82

21

None Found

Triclocarban

38744

5.74

10

5.192

49

18-100 c

Triclosan

12112

4.93

12

10.479

13

50-96 c

Benzo(a) pyrene

427


Table 2. Summary of modeling results and literature information available for target analytes

Data taken from (11).

b

Data taken from SciFinder online database.

c

Data taken from (2, 15, 16, 28) and references cited therein.

In Contaminants of Emerging Concern in the Environment: Ecological and Human Health Considerations; Halden, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.


Microcontaminant concentrations measured empirically in biosolids were used to calculate the contaminant levels in wastewater influent and effluent. Results from the empirical model for the select wastewater contaminants are presented in Table 2. Analyte concentrations in raw sewage (WWTP influent) ranged from 0.024 and 0.025 µg/L for norgestimate and beta-estradiol-3-benzoate, respectively, to 10 and 12 µg/L for triclocarban and triclosan, respectively. This is in agreement with a prior study examining the fate of organic wastewater contaminants that found triclosan and triclocarban influent concentrations to be among the highest, whereas those of hormones such as beta-estradiol-3-benzoate were among the lowest influent concentrations (2). Calculated aqueous-phase removal efficiencies ranged from 13 to 82% and were dependent mostly on the hydrophobicity (log DOW) of the analytes. Triclosan with the lowest DOW value had the lowest calculated removal efficiency while benzo(a)pyrene with the highest DOW value had the highest removal efficiency. This was expected because for hydrophobic compounds, such as the ones included in this study, sorption to organic matter has been identified in previous studies as a master variable governing the removal of organic contaminants during wastewater treatment (2). The calculated aqueous removal efficiency for triclosan of 13% was in the same order of magnitude but lower than the removal efficiencies of 50 - 96% observed in prior studies (2, 16). The aqueous removal efficiency for triclocarban calculated at 49% was found to be similar to values of 18 - 100% reported in the literature (Table 2). Triclosan and triclocarban represent the only analytes from which to judge the accuracy of the model for calculating removal efficiencies. In summary, a comparison of calculated and empirically observed removal efficiencies indicates that the model’s estimates reflect either the mid range of actual WWTP performance (Table 2; triclocarban) or they tend to be conservative in nature, i.e., prone to underestimation of the actual removal (Table 2; triclosan). To evaluate the accuracy of concentrations calculated for influent and effluent, the model output shown in Table 2 was compared to empirical datasets from WWTPs. A study conducted between 2005 and 2008 by the EPA examined influent and effluent data from nine WWTPs featuring several variations of the activated sludge process (15). Samples were analyzed for contaminants of emerging concern, which included triclosan, triclocarban, norgestimate, miconazole, and beta-estradiol-3-benzoate among others. Samples collected for norgestimate, miconazole, and beta-estradiol-3-benzoate had influent or effluent concentrations below the laboratory reporting limit thus their removal efficiencies were not quantified (15). Furthermore, effluent concentrations calculated here for both triclosan and triclocarban were found to be in the same order of magnitude as empirically observed concentrations made at plants across the U.S. (Figure 2). For the remaining compounds data are lacking. Upon discharge to surface waters, residual levels of unwanted substances in treated wastewater are further diluted. In this study an average dilution factor of 10 was applied to effluent concentrations to estimate potential impacts on surface waters. Where available, empirical data from waterways were compared with estimated surface water concentrations calculated from the modeled WWTP effluent concentrations shown in Table 2. As can be seen in Figure 3, measured 428 In Contaminants of Emerging Concern in the Environment: Ecological and Human Health Considerations; Halden, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.


concentrations correlate well with the surface water concentrations obtained from the model. A nationwide study conducted by the U.S. Geological Survey (USGS) in 1999 and 2000, sampled surface water from 139 streams in the U.S. (7). All samples were analyzed for a range of pharmaceuticals and organic contaminants. Concentrations reported by the USGS are similar to those predicted here. While that study is the only one so far that sampled streams across the U.S., other studies have been conducted to analyze surface waters for concentrations of a smaller number of specific organic contaminants (16–18). One study (16) reports levels of triclosan in experimental wetlands in north Texas from 0.03 to 0.29 µg/L. In another study (17), median concentrations of triclocarban in 13 states, measured upstream and downstream of WWTPs, were on the order of 7 and 20 ng/L, respectively. However, maximum concentrations of up to 6,750 ng/L have been reported for urban streams impacted by sewerage leaks (29, 30). Empirical values were available for five of the eight analytes modeled. Calculated concentrations of the polycyclic aromatic hydrocarbons pyrene and fluoranthene as well as the disinfectants triclosan and triclocarban are within the range of data reported in the literature. The estimated concentration for benzo(a)pyrene is about one order of magnitude below the lowest reported concentration (Figure 3), a fact that may be explained simply by the various additional point and non-point sources of this compound, such as deposition of air pollution. Overall, the observed discrepancies are not unexpected given the average dilution factor of 10 that was applied when estimating treated effluent discharge to surface water. In practice dilution factors can be as small as unity or much greater than 100, depending on the size of the receiving water body. The error bars in Figure 3 show how contaminant concentrations in surface water can vary based on dilution factors ranging from 1 to 100. The occurrence of the contaminants in different parts of the country drives uncertainty as well. The standard deviations for the analyte concentration in the biosolids input data ranged from 1.19 to 2.36 times the mean concentration. The concentrations in the influent and effluent would mimic the variance observed in the biosolids concentration. In addition to uncertainties associated with the dilution and concentration variance, the amount of empirical data available for the contaminants is very limited compared to the large dataset from the sludge survey that was used to estimate this parameter. No empirical information was available from the literature on the concentrations in natural waterways of the remaining three compounds, beta-estradiol-3-benzoate, miconazole, and norgestimate. Thus, this study provides the first recorded concentration estimates for these substances in surface water.



Figure 2. Comparison of modeled effluent concentrations (shown as bars) with effluent concentrations reported for various U.S. wastewater treatment plants. Also shown are the highest reported effluent concentrations as well as the lowest reported effluent concentrations above the detection limit. (see color insert)

Figure 3. Comparison of surface water concentrations calculated assuming a dilution factor of 10 (data shown as bars) with measured concentrations reported for U.S. streams. Error bars indicate the range of surface water concentrations obtained when using dilution factors ranging from 1 to 100. (see color insert)



Table 3. Overview of toxicity threshold values reported in the literature for the compounds considered in the present study Chemical Name

Group

CAS Number

Species Affected

End point

Effect Concentration [µg/L)

Reference

Benzo(a) pyrene

PAH

50-32-8

Polychaete Worm

LC50

3.890

(19)

Fluoranthene

PAH

206-44-0

Winter Flounder

LC50

0.100

(20)

Pyrene

PAH

129-00-0

Clam

EC50

0.230

(21)

Triclocarban

PPCP

101-20-2

Opossum Shrimp

EC50

0.209

(22)

Triclosan

PPCP

3380-34-5

Blue Green Algae

EC50

0.700

(23)

Toxicology Analysis Toxicity data for all analytes were gathered from the EPA ECOTOX database and compared against the estimated surface water concentrations. The lowest reported effect concentration for each analyte is reported in Table 3. The ECOTOX database contained no entries for beta-estradiol-3-benzoate, minconazole, and norgestimate. LC50 values are the concentration lethal to 50% of the test organisms. EC50 values represent the concentrations affecting 50% of the test organisms or causing 50% inhibition of the measured effect. When compared to toxicity data from the EPA Ecotox database, modeled surface water concentrations of this study’s select organic compounds show the possibility of impact on aquatic life (Figure 4). Modeled surface water concentrations for three of the five compounds with documented toxicity data (fluoranthene, triclocarban, and triclosan) exceed the lower threshold effect concentration for aquatic organisms. Pyrene, while modeled lower than the effect concentration for clams, has already been measured in surface waters at levels exceeding this threshold. Note that the LC50 and EC50 concentrations are for acute toxicity of the contaminants, implying exposure of the organism to such doses for short periods of time. Chronic toxicity values representative of exposure to a lower dose for a longer period of time ideally should be considered but were unavailable. As mentioned previously, for the purposes of this study, a surface water to effluent dilution factor of 10 was used to predict the likelihood of toxicological effects in susceptible receptor organisms. It should be noted, that in some situations across the United States (e.g., the arid southwest) surface waters can be dominated by treated effluent, implying dilution factors of near one. Under these conditions, any potential effects on aquatic species would be exacerbated.



Figure 4. Comparison of modeled and measured surface water concentrations (shown as bars) with ecotoxicological effect concentrations (EC50 values) for aquatic organisms. (see color insert) Most intriguing is the lack of both surface water concentration data and toxicity data for the same three organic compounds within this study’s limited focus. Beta-estradiol-3-benzoate, miconazole, and norgestimate all have modeled surface water concentrations ranging from 0.6-10 ng/L when assuming a dilution factor of 10:1. Even though no toxicity studies have been conducted for beta-estradiol3-benzoate or norgestimate, endocrine disrupting effects have been found for hormones similar in structure and function. As an example, the Clark County Water Reclamation District, the Southern Nevada Water Authority and the USGS have all extensively researched possible effects of endocrine disrupters on aquatic life in the lower Colorado River basin. A 1996 USGS study (24) found endocrine disruption by hormones and other water contaminants, including organochlorines, in male and female feral carp in Lake Mead, Nevada. Another study (25) later confirmed some of these findings and correlated gonad underdevelopment to exposure to wastewater treatment plant effluent. This study’s model output shows that hormones are likely present in treated wastewater across the United States, including arid areas like the lower Colorado River basin which may be more susceptible to negative aquatic effects from hormones due to dilution factors of treated wastewater approaching unity. If existing levels are found to be problematic, opportunities exist for municipalities and water authorities to explore more extensive treatment of wastewater to prevent endocrine disruption of resident aquatic species.

Treatment Options A number of techniques exist to remove PPCPs and other problematic organic contaminants from water, including common methods currently employed by many drinking water authorities. Nanofiltration, reverse-osmosis, and activated 432 In Contaminants of Emerging Concern in the Environment: Ecological and Human Health Considerations; Halden, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.

carbon filtration methods have all been shown capable of removing over 90% of most PPCPs and related organic wastewater compounds (26). Alternatively, ozone treatment has been shown to be over 90% effective for PPCP compounds, including the majority of those typically present in wastewater effluent (27). While this method is cost intensive due to high energy consumption, the oxidation of chemicals alleviates some of the brine disposal concerns associated with filtration techniques and may serve as the best treatment method for wastewater effluent.


Conclusions The results show that modeled concentrations of microcontaminants were generally in good agreement with reported literature concentrations in the wastewater influent and effluent. However, for many of the contaminants analyzed, there was no reported empirical concentration data or toxicology data available. Further research needs to be conducted in both the area of surface water monitoring and toxicology of PPCPs. In the specific categories of hormones and antibiotics/antifungal agents, there appears to be a stark deficiency in empirical data for both ambient concentrations and toxicological threshold values. In addition, the effects of chronic exposure to these types of contaminants on aquatic life as well as on humans are largely unknown. High research costs may influence the lack of study concerning these types of products, but the growing evidence of endocrine disruption of exposed aquatic species may justify the costly examinations. These studies are needed for environmental and water agencies to evaluate risk and assess the need for the establishment of total maximum daily loads of PPCPs and other microcontaminants where applicable. For WWTP effluent dominated U.S. surface waters, the obtained data suggest that there may be a need for advanced treatment of effluent to achieve residual concentrations of organic wastewater compounds below the toxicity threshold values of susceptible aquatic species.

Acknowledgments The project described was supported in part by Award Number R01ES015445 from the National Institute of Environmental Health Sciences (NIEHS) and by the Johns Hopkins University Center for a Livable Future. The content is solely the responsibility of the author(s) and does not necessarily represent the official views of the NIEHS or the National Institutes of Health. The authors acknowledge the feedback and discussions provided by the graduate students enrolled during Fall 2009 in the course CEE563 Environmental Chemistry Laboratory at Arizona State University.


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