AWWARF Project # 2758

Investigators: Shane Snyder, Paul Westerhoff, Rengo Song, Bruno Levine, Bruce Long

AWWARF Project Officer: Kim Linton: klinton@awwarf.com

Project Abstract

Compounds that can alter the endocrine systems of animals have been detected in water supplies around the world as the result of human activities. These substances are known as endocrine-disrupting compounds (EDCs) and have been linked to a variety of adverse effects in both humans and wildlife, including hormone-dependent cancers, reproductive tract disorders, and reduction in reproductive fitness. Pharmaceutical compounds and their metabolites have been collectively termed pharmaceutically active compounds (PhACs). Many PhACs have now been detected in surface waters, a few of which have been detected in finished drinking water. Personal care products (PCPs) create another class of emerging contaminants that have been detected in surface and ground waters. Some PhACs and PCPs (PPCPs) are highly persistent and can function as EDCs. The majority of EDCs and PPCPs are more polar than traditional contaminants, such as polychlorinated biphenyls, and several have acidic or basic moieties. These properties, coupled with trace quantities, create unique challenges for both removal processes and analytical detection. Reports of EDCs and PPCPs in water have raised substantial concern among the public and regulatory agencies; however, very little is known as to the fate of these compounds during drinking water treatment. Preliminary experiments by our research team suggest that activated carbon and ozone are much more effective at removing EDCs and PPCPs than conventional treatment processes. We propose to gather imperative data by evaluating the efficiencies of various conventional and advanced water treatment processes to remove EDCs and PPCPs. Our approach will involve bench-, pilot-, and full-scale testing. The first phase will include development of surrogate and characteristic compounds for specific classes of EDCs and PPCPs based on our past experiences and a thorough literature review including published manuscripts, government documents, and conference abstracts and proceedings. The second phase of the project will involve testing of various treatment processes to determine removal efficiencies at environmentally relevant concentrations at bench-, pilot- and full-scale. In the bench-scale experiments, waters of various qualities will be fortified with a surrogate matrix comprised of various EDCs and PPCPs and tested in batches. Likewise, pilot studies will use metering pumps to maintain constant influx of the surrogates to the raw waters in a dynamic system. Full-scale plants of various treatment trains will also be investigated by testing for various EDCs and PPCPs in not only the raw and finished waters, but also between each unit process. Concentrations of selected EDCs and PPCPs in both natural and fortified waters will be determined using state of the art analytical instrumentation such as liquid chromatography coupled with high-resolution mass spectrometry, gas chromatography with tandem triple-quadrupole mass spectrometry, and gas chromatography with atomic emission detection. These instruments were equipped and purchased specifically for EDC and PPCP analyses and provide great sensitivity and selectivity. Quantitative structure activity relationship (QSAR) models will be generated from these data to predict the fate of compounds not yet investigated. The data generated from the proposed research will provide much needed information to the drinking water industry on conventional and advanced treatment processes for the removal of these emerging contaminants.

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Research Approach

The objective of this project will be to determine removal efficiencies of conventional and advanced treatment processes for compounds classified as Endocrine Disrupting Chemicals (EDCs), plus Pharmaceutically Active Compounds (PhACs) and Personal Care Products (PPCPs). This research proposal includes Personal Care Products, although not stated in the RFP, due to there detection in water supplies, widespread use, unknown health effects, and chemical structure which varies from EDCs or PhACs. The ultimate goal will be to predict contaminant removal a priori by a given treatment process or set of treatment processes for general classes EDCs of PPCPs that are identified in the future as a health or regulatory concern.

The project will consist of two phases. The first phase will include development of surrogate or characteristic compounds for specific classes of EDC and PPCP categories, in conjunction with the development of a framework where contaminants could be evaluated. The second phase of the project will involve testing of various treatment processes to determine removal efficiencies at environmentally relevant concentrations.  The activities in each of the two phases are summarized below:

Phase I – Identification Criteria and Selection of EDC and PPCP Classes and Compounds

  • Task 1 – Literature Review of EDC and PPCP Occurrence and Compound Classification
  • Task 2 – Literature Review of EDC and PPCP Treatment
  • Task 3 – Selection of Target EDC and PPCP Compounds and Surrogates
  • Task 4 – Bench-scale Evaluation of Conventional and Advanced Treatment Processes
  • Task 5 – QSAR Evaluation of EDC and PPCP Removal

Phase II – Field Scale Evaluation

  • Task 6 – Pilot-scale Evaluation of Conventional and Advanced Treatment Processes
  • Task 7 – Full-scale Evaluation of Conventional and Advanced Treatment Processes

Recommendations (Task 8)

Project Management and Reporting (Task 9)

Ongoing Activities
The project is scheduled to start January 1, 2002. Information on this website will be updated approximately every 3 months.

The Project Advisory Committee Kick-off meeting was held in Las Vegas, NV on February 1, 2002.

  • ES&T Technology News – September 4, 2002

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Keeping drugs out of drinking water

The first systematic investigation of how effectively drinking water treatment technologies remove pharmaceutical products has found that the technologies being used in Germany appear to do a good job, according to new ES&T research (Environ. Sci. Technol. 2002, 36, 3855-3863). However, the paper’s lead author, Thomas Ternes of Germany’s Institute for Water Research and Water Technology (ESWE), says that some of the technologies used elsewhere in the world—particularly in the United States—may be letting pharmaceuticals through.

Although research shows that pharmaceutically active products are found in surface waters throughout the United States (Environ. Sci. Technol. 2002, 36, 1202-1211) and Europe, there is as yet very little information on how effectively different drinking water treatment technologies remove these pharmaceutical residues. Ternes’s work, which represents the most comprehensive assessment published to date, was funded in part by the European Union’s (EU’s) ongoing Poseidon program for assessing technologies for removing pharmaceuticals and personal care products in sewage and drinking water treatment facilities. The program is also aimed at evaluating the ability of advanced wastewater treatment technologies like membranes and source separation to reduce the volume of pharmaceuticals being discharged into EU waters.

Ternes and his fellow researchers at ESWE and two other institutions associated with the German Technical and Scientific Association on Gas and Water (DVGW), the Technologiezentrum Wasser (TZW) and the Institute for Water Research (IfW), investigated how effectively treatment technologies were able to eliminate five pharmaceutical products often found in German waters: two epilepsy medications: carbamazepine and primidone; one lipid regulator, bezafibrate, and a metabolite of the lipid regulator clofibrate, clofibric acid; and diclofenac, an arthritis drug. The paper is notable for evaluating the removal efficiency of a number of popular technologies—flocculation, ozonation, granular activated carbon (GAC), bank filtration, and slow sand filtration—both in the laboratory and in waterworks treatment facilities.

Only GAC and ozonation were very effective at removing carbamazepine and diclofenac at both laboratory and waterworks scales, Ternes found. Laboratory-scale ozonation treatments showed that 0.5 milligrams/liter (mg/L) of ozone reduced the two pharmaceuticals by more than 90%.

Although GAC was very successful in removing bezafibrate during waterworks testing, laboratory-scale ozonation treatments with much higher concentrations of ozone (3.0 mg/L) were required to reduce it by 90%. The laboratory scale also showed that 3.0 mg/L of ozone cut primidone levels by nearly 90%. Although neither GAC nor ozonation at any concentration was fully successful with clofibric acid separately, the two in combination cut levels of the drug to below the limits of detection during waterworks testing.

GAC is effective because carbon can bind a broad category of compounds, and many pharmaceuticals have components like benzene rings or amine groups that enhance their ability to be taken up by the activated carbon, Ternes explains. The powdered form of activated carbon can be even more effective, removing virtually every possible pharmaceutical and personal care product, adds Shane Snyder, the project manager for research and development at the Southern Nevada Water Authority. But he stresses that GAC—like all technologies—is only effective if used properly.

Ozone’s effectiveness is tied to its ability to chemically attack the pharmaceutical molecules, Snyder says. For example, it can oxidize different kinds of functional aromatic bonds in pharmaceuticals, he says. Ternes adds that his research has shown ozone capable of easily oxidizing 90% of 51 different pharmaceuticals. It is particularly effective with compounds with amine groups and phenolic hydroxyl groups, he says.

On the basis of testing he has conducted thus far, Ternes concludes that contamination of German drinking water by the chemicals he investigated is “rather unlikely”, given that the country’s waterworks use either ozonation or activated carbon—or perhaps both—to treat the surface water most likely to contain pharmaceutical residues. He believes that other advanced techniques such as membrane filtration and advanced oxidative processes using a combination of ozone and UV or ozone and hydrogen peroxide should also remove pharmaceuticals. Most pharmaceutical products are not removed by conventional flocculation technology because their polarity makes them unlikely to adsorb to organic matter, he explains.

The paper does not address the multitude of degradation products that can be produced by oxidative treatments such as ozone, points out Christian Daughton, chief of the environmental chemistry branch of the U.S. EPA’s National Exposure Research Laboratory’s Environmental Sciences division. Recent research conducted by Roberto Andreozzi of the University of Naples in Italy (Water Res. 2002, 36, 2869-2877) shows that numerous metabolites can persist after carbamazepine has been treated with ozonation, he says.

Ternes says that he is already investigating such oxidation products—as well as other drinking water treatment technologies, including membrane filtration—through the Poseidon program. Between the Poseidon program and a project begun this year by the American Water Works Association’s Research Foundation (AWWARF), virtually all treatment technologies in current use are being tested, says Snyder, who is the AWWARF project’s principal investigator.

The AWWARF program’s goal is to evaluate how well different drinking water treatments remove 42 compounds representative of the pharmaceutical products found in U.S. waters. It is notable for its goal of developing quantitative structure-activity relationship (QSAR) computer models that predict how pharmaceuticals will respond to different treatments based on their chemical structure. The study therefore includes a wide array of different types of compounds—such as acidic, basic, large, and small molecules—chosen to represent the pharmaceuticals and personal care products that can be found in the environment.

The AWWARF project will have succeeded in its goal if “when we read a paper in ES&T with the newest endocrine disrupter of the month, we can go back to our data set, put it in, and see how these treatment processes will remove them,” says Snyder, who is the project’s principal investigator. However, Snyder and his colleagues have not yet published any results.

Although more study is clearly needed, Ternes’s findings hint that conventional water treatment plants such as those that use coagulation and flocculation followed by filtration and disinfection with a chlorine product cannot efficiently remove trace organic pollutants such as low levels of pharmaceuticals and personal care products, says Jörg Drewes, an assistant professor in the Colorado School of Mines’ Environmental Science and Engineering division. In such systems, “it may be possible that these compounds add up to the contamination of drinking water,” Ternes adds.

Most countries outside central Europe—including the United States—use either chlorine, chloramines, or ozone to disinfect drinking water, Drewes continues. To date, the AWWARF studies have shown that chlorination can add another barrier to pharmaceutically active compounds, but it is not nearly as effective as ozone, Snyder says, stressing that the results are as yet unpublished. He and his fellow researchers haven’t yet tackled chloramines, but he doesn’t expect it to be as effective as chorine.

The popularity of both ozonation and GAC are increasing in the United States, but they are still only used by a relatively small number of larger drinking water treatment facilities, says Steve Via, a regulation engineer at AWWA. According to a survey of how U.S. facilities treat surface water by the U.S. EPA in 1997, the latest year for which figures are available, 5.4% of U.S. facilities serving 50,000-100,000 people used ozone and 7.7% used GAC. Of drinking water providers for over 100,000 people, 5.8% used ozone and 6.4% used GAC.

Although the pharmaceutical compounds that Ternes studied have been reported in wastewater and surface water outside of Germany, Drewes says that clofibrate is no longer commonly used as a lipid regulator in the United States, and studies by his lab and others have found it only in some U.S. wastewater effluents. Drewes says he believes that Ternes’s carbamazepine results are most relevant in the United States; he notes that his studies of recharging groundwater have shown that the compound can survive intact after traveling 8-10 years through the subsurface.

Because of the increasing popularity of groundwater recharging in places like the United States, all of the scientists interviewed for this article concurred that this groundwater may be contaminated with pharmaceuticals. Ternes adds that the risk that pharmaceutical compounds will be found in groundwater is “relatively high” for locations where surface water intrudes into the groundwater.

Although the risk associated with consuming the low levels of pharmaceuticals found in U.S. and European waters is as yet unknown (Environ. Sci. Technol. 2002, 36, 140A-145A), Ternes notes that any antibiotics that find their way into surface waters and other natural water bodies could promote antibiotic resistance.

“The major concern associated with the presence of [pharmaceutically active compounds] in drinking water is not acute effects on human health (since environmental concentrations are orders of magnitude below the therapeutic dosages), but rather the manifestation of imperceptible effects that can accumulate over time to yield truly profound changes,” Drewes says. “And the latter is extremely difficult to determine.”

On the positive side, the new technologies that are likely to be put in place to reduce the probability of pharmaceuticals making their way into drinking water, such as activated carbon, could have the additional benefit of removing “all sorts of other chemicals we don’t even know about at the present,” Daughton says. “The analytical chemists have gotten way ahead of us,” in terms of their ability to devise new ways to detect chemicals that may be found in the environment, he explains. Because environmental chemists regularly discover new and unexpected compounds in the nation’s waters, he predicts that greater use of advanced drinking water treatment technologies could represent a “much, much higher reduction of overall risk” from such compounds. —KELLYN S. BETTS

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Links
The Top 200 Prescriptions for 2000 by Number of US Prescriptions Dispensed
Generic name link leads to Drug Monograph information where available: http://www.rxlist.com/top200.htm

EU-Project Poseidon Assessment of Technologies for the Removal of Pharmaceuticals and Personal Care Products in Sewage and Drinking Water Facilities to Improve the Indirect Potable Water Reuse : http://www.eu-poseidon.com

USGS STUDY OF PHARMACEUTICALS & OTHER ORGANIC SUBSTANCES IN US SURFACE WATERS PUBLISHED http://www.epa.gov/esd/chemistry/pharma/index.htm

As part of its ongoing reconnaissance program of US waters, USGS sampled 139 streams in 30 states during 1999-2000 for what it calls OWCs (organic wastewater constituents) using new analytical methods for 95 compounds. The OWCs, which include many pharmaceuticals and hormones commonly used in agriculture, industry and households, were found in 80% of the streams sampled. Generally low levels were detected that did not exceed any health advisories but such guidelines are not available for many compounds. The complete USGS report (http://toxics.usgs.gov/pubs/OFR-02-94/index.html) is available and the March 13th issue of Environmental Science and Technology (http://pubs.acs.org/journals/esthag/index.html) (see “Hot Article” box at top of page) features a paper which emphasizes the analytical methodology used in the study. The study received wide attention in the print media with headlines such as Beauty Aids Contaminating Waterways (LA Times, March 13) and Drug Wastes Pollute Waterways (Washington Post, March 13).

This study will add fuel to the ongoing activity of USEPA to develop an overall program to address these chemicals and other endocrine disruptors. The USEPA effort was mandated by the 1996 Food Quality Protection Act and was reinforced by a provision in the 1996 SDWA Amendments which gave EPA authority to provide for the testing, under the FFDCA Screening Program, “of any other substance that may be found in sources of drinking water if the Administrator determines that a substantial population may be exposed to such substance.” (42 U.S.C. 300j-17)

In 2001, USGS conducted a second phase of the reconnaissance study (http://toxics.usgs.gov/regional/emc_sourcewater.html) with a total of 76 drinking water source waters sampled including 51 surface waters and 25 groundwater sources. A report on that second phase has not yet been published.

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Personnel
Principal Investigator:
Name: Dr. Shane Snyder
Organization: Southern Nevada Water Authority
Address: 243 Lakeshore Road; Boulder City, NV 89005
Phone/Fax/e-mail: (702) 567-2317 / (702) 564-7222 / shane.snyder@lvvwd.com

Co-Principal Investigator:
Name: Dr. Paul Westerhoff
Organization: Arizona State University
Address: Department of Civil and Environmental Engineering Box 5306 Tempe, AZ 85287-5306
Phone/Fax/e-mail: (480) 965-2885 / (480) 965-0557 / p.westerhoff@asu.edu

Co-Principal Investigator:
Name: Dr. Rengao Song
Organization: Louisville Water Company
Address: 3018 Frankfort Avenue, Louisville, KY 40201
Phone/Fax/e-mail: (502) 569-3600#2449 / (502) 569-0813 / rsong@lwcky.com

Co-Principal Investigator:
Name: Mr. Bruce Long
Organization: Black & Veach
Address: 8400 Ward Parkway; Kansas City, MO 64114
Phone/Fax/e-mail: (913) 458-2000 / (913) 458-3730 / longbw@bv.com

Co-Principal Investigator:
Name: Dr. Bruno Levine
Organization: United Water
Address: 200 Old Hook Road; Harrington Park, NJ 07460
Phone/Fax/e-mail: (201) 986-4983 / (201) 634-4220 / bruno.levine@unitedwater.com

Participating Utilities and Other Organizations
Southern Nevada Water Authority
Louisville Water District
United Water
Metropolitan Water District of Southern California
City of Cincinnati
Kansas City

Technical Advisors:
David Sedlak
Vernon Snoeyink

AWWARF Project Officer:
Kim Linton  klinton@awwarf.com

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Evaluation of Conventional and Advanced Treatment Processes to Remove Endocrine Disruptors and Pharmaceutically Active Compounds

Investigators: Shane Snyder, Paul Westerhoff, Rengo Song, Bruno Levine, Bruce Long

AWWARF Project Officer: Kim Linton: klinton@awwarf.com

Project Abstract
Compounds that can alter the endocrine systems of animals have been detected in water supplies around the world as the result of human activities. These substances are known as endocrine-disrupting compounds (EDCs) and have been linked to a variety of adverse effects in both humans and wildlife, including hormone-dependent cancers, reproductive tract disorders, and reduction in reproductive fitness. Pharmaceutical compounds and their metabolites have been collectively termed pharmaceutically active compounds (PhACs). Many PhACs have now been detected in surface waters, a few of which have been detected in finished drinking water. Personal care products (PCPs) create another class of emerging contaminants that have been detected in surface and ground waters. Some PhACs and PCPs (PPCPs) are highly persistent and can function as EDCs. The majority of EDCs and PPCPs are more polar than traditional contaminants, such as polychlorinated biphenyls, and several have acidic or basic moieties. These properties, coupled with trace quantities, create unique challenges for both removal processes and analytical detection. Reports of EDCs and PPCPs in water have raised substantial concern among the public and regulatory agencies; however, very little is known as to the fate of these compounds during drinking water treatment. Preliminary experiments by our research team suggest that activated carbon and ozone are much more effective at removing EDCs and PPCPs than conventional treatment processes. We propose to gather imperative data by evaluating the efficiencies of various conventional and advanced water treatment processes to remove EDCs and PPCPs. Our approach will involve bench-, pilot-, and full-scale testing. The first phase will include development of surrogate and characteristic compounds for specific classes of EDCs and PPCPs based on our past experiences and a thorough literature review including published manuscripts, government documents, and conference abstracts and proceedings. The second phase of the project will involve testing of various treatment processes to determine removal efficiencies at environmentally relevant concentrations at bench-, pilot- and full-scale. In the bench-scale experiments, waters of various qualities will be fortified with a surrogate matrix comprised of various EDCs and PPCPs and tested in batches. Likewise, pilot studies will use metering pumps to maintain constant influx of the surrogates to the raw waters in a dynamic system. Full-scale plants of various treatment trains will also be investigated by testing for various EDCs and PPCPs in not only the raw and finished waters, but also between each unit process. Concentrations of selected EDCs and PPCPs in both natural and fortified waters will be determined using state of the art analytical instrumentation such as liquid chromatography coupled with high-resolution mass spectrometry, gas chromatography with tandem triple-quadrupole mass spectrometry, and gas chromatography with atomic emission detection. These instruments were equipped and purchased specifically for EDC and PPCP analyses and provide great sensitivity and selectivity. Quantitative structure activity relationship (QSAR) models will be generated from these data to predict the fate of compounds not yet investigated. The data generated from the proposed research will provide much needed information to the drinking water industry on conventional and advanced treatment processes for the removal of these emerging contaminants.

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Research Approach
The objective of this project will be to determine removal efficiencies of conventional and advanced treatment processes for compounds classified as Endocrine Disrupting Chemicals (EDCs), plus Pharmaceutically Active Compounds (PhACs) and Personal Care Products (PPCPs). This research proposal includes Personal Care Products, although not stated in the RFP, due to there detection in water supplies, widespread use, unknown health effects, and chemical structure which varies from EDCs or PhACs. The ultimate goal will be to predict contaminant removal a priori by a given treatment process or set of treatment processes for general classes EDCs of PPCPs that are identified in the future as a health or regulatory concern.

The project will consist of two phases. The first phase will include development of surrogate or characteristic compounds for specific classes of EDC and PPCP categories, in conjunction with the development of a framework where contaminants could be evaluated. The second phase of the project will involve testing of various treatment processes to determine removal efficiencies at environmentally relevant concentrations.  The activities in each of the two phases are summarized below:

Phase I – Identification Criteria and Selection of EDC and PPCP Classes and Compounds

  • Task 1 – Literature Review of EDC and PPCP Occurrence and Compound Classification
  • Task 2 – Literature Review of EDC and PPCP Treatment
  • Task 3 – Selection of Target EDC and PPCP Compounds and Surrogates
  • Task 4 – Bench-scale Evaluation of Conventional and Advanced Treatment Processes
  • Task 5 – QSAR Evaluation of EDC and PPCP Removal

Phase II – Field Scale Evaluation

  • Task 6 – Pilot-scale Evaluation of Conventional and Advanced Treatment Processes
  • Task 7 – Full-scale Evaluation of Conventional and Advanced Treatment Processes

Recommendations (Task 8)

Project Management and Reporting (Task 9)

Ongoing Activities
The project is scheduled to start January 1, 2002. Information on this website will be updated approximately every 3 months.

The Project Advisory Committee Kick-off meeting was held in Las Vegas, NV on February 1, 2002.

  • ES&T Technology News – September 4, 2002

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Keeping drugs out of drinking water
The first systematic investigation of how effectively drinking water treatment technologies remove pharmaceutical products has found that the technologies being used in Germany appear to do a good job, according to new ES&T research (Environ. Sci. Technol. 2002, 36, 3855-3863). However, the paper’s lead author, Thomas Ternes of Germany’s Institute for Water Research and Water Technology (ESWE), says that some of the technologies used elsewhere in the world—particularly in the United States—may be letting pharmaceuticals through.

Although research shows that pharmaceutically active products are found in surface waters throughout the United States (Environ. Sci. Technol. 2002, 36, 1202-1211) and Europe, there is as yet very little information on how effectively different drinking water treatment technologies remove these pharmaceutical residues. Ternes’s work, which represents the most comprehensive assessment published to date, was funded in part by the European Union’s (EU’s) ongoing Poseidon program for assessing technologies for removing pharmaceuticals and personal care products in sewage and drinking water treatment facilities. The program is also aimed at evaluating the ability of advanced wastewater treatment technologies like membranes and source separation to reduce the volume of pharmaceuticals being discharged into EU waters.

Ternes and his fellow researchers at ESWE and two other institutions associated with the German Technical and Scientific Association on Gas and Water (DVGW), the Technologiezentrum Wasser (TZW) and the Institute for Water Research (IfW), investigated how effectively treatment technologies were able to eliminate five pharmaceutical products often found in German waters: two epilepsy medications: carbamazepine and primidone; one lipid regulator, bezafibrate, and a metabolite of the lipid regulator clofibrate, clofibric acid; and diclofenac, an arthritis drug. The paper is notable for evaluating the removal efficiency of a number of popular technologies—flocculation, ozonation, granular activated carbon (GAC), bank filtration, and slow sand filtration—both in the laboratory and in waterworks treatment facilities.

Only GAC and ozonation were very effective at removing carbamazepine and diclofenac at both laboratory and waterworks scales, Ternes found. Laboratory-scale ozonation treatments showed that 0.5 milligrams/liter (mg/L) of ozone reduced the two pharmaceuticals by more than 90%.

Although GAC was very successful in removing bezafibrate during waterworks testing, laboratory-scale ozonation treatments with much higher concentrations of ozone (3.0 mg/L) were required to reduce it by 90%. The laboratory scale also showed that 3.0 mg/L of ozone cut primidone levels by nearly 90%. Although neither GAC nor ozonation at any concentration was fully successful with clofibric acid separately, the two in combination cut levels of the drug to below the limits of detection during waterworks testing.

GAC is effective because carbon can bind a broad category of compounds, and many pharmaceuticals have components like benzene rings or amine groups that enhance their ability to be taken up by the activated carbon, Ternes explains. The powdered form of activated carbon can be even more effective, removing virtually every possible pharmaceutical and personal care product, adds Shane Snyder, the project manager for research and development at the Southern Nevada Water Authority. But he stresses that GAC—like all technologies—is only effective if used properly.

Ozone’s effectiveness is tied to its ability to chemically attack the pharmaceutical molecules, Snyder says. For example, it can oxidize different kinds of functional aromatic bonds in pharmaceuticals, he says. Ternes adds that his research has shown ozone capable of easily oxidizing 90% of 51 different pharmaceuticals. It is particularly effective with compounds with amine groups and phenolic hydroxyl groups, he says.

On the basis of testing he has conducted thus far, Ternes concludes that contamination of German drinking water by the chemicals he investigated is “rather unlikely”, given that the country’s waterworks use either ozonation or activated carbon—or perhaps both—to treat the surface water most likely to contain pharmaceutical residues. He believes that other advanced techniques such as membrane filtration and advanced oxidative processes using a combination of ozone and UV or ozone and hydrogen peroxide should also remove pharmaceuticals. Most pharmaceutical products are not removed by conventional flocculation technology because their polarity makes them unlikely to adsorb to organic matter, he explains.

The paper does not address the multitude of degradation products that can be produced by oxidative treatments such as ozone, points out Christian Daughton, chief of the environmental chemistry branch of the U.S. EPA’s National Exposure Research Laboratory’s Environmental Sciences division. Recent research conducted by Roberto Andreozzi of the University of Naples in Italy (Water Res. 2002, 36, 2869-2877) shows that numerous metabolites can persist after carbamazepine has been treated with ozonation, he says.

Ternes says that he is already investigating such oxidation products—as well as other drinking water treatment technologies, including membrane filtration—through the Poseidon program. Between the Poseidon program and a project begun this year by the American Water Works Association’s Research Foundation (AWWARF), virtually all treatment technologies in current use are being tested, says Snyder, who is the AWWARF project’s principal investigator.

The AWWARF program’s goal is to evaluate how well different drinking water treatments remove 42 compounds representative of the pharmaceutical products found in U.S. waters. It is notable for its goal of developing quantitative structure-activity relationship (QSAR) computer models that predict how pharmaceuticals will respond to different treatments based on their chemical structure. The study therefore includes a wide array of different types of compounds—such as acidic, basic, large, and small molecules—chosen to represent the pharmaceuticals and personal care products that can be found in the environment.

The AWWARF project will have succeeded in its goal if “when we read a paper in ES&T with the newest endocrine disrupter of the month, we can go back to our data set, put it in, and see how these treatment processes will remove them,” says Snyder, who is the project’s principal investigator. However, Snyder and his colleagues have not yet published any results.

Although more study is clearly needed, Ternes’s findings hint that conventional water treatment plants such as those that use coagulation and flocculation followed by filtration and disinfection with a chlorine product cannot efficiently remove trace organic pollutants such as low levels of pharmaceuticals and personal care products, says Jörg Drewes, an assistant professor in the Colorado School of Mines’ Environmental Science and Engineering division. In such systems, “it may be possible that these compounds add up to the contamination of drinking water,” Ternes adds.

Most countries outside central Europe—including the United States—use either chlorine, chloramines, or ozone to disinfect drinking water, Drewes continues. To date, the AWWARF studies have shown that chlorination can add another barrier to pharmaceutically active compounds, but it is not nearly as effective as ozone, Snyder says, stressing that the results are as yet unpublished. He and his fellow researchers haven’t yet tackled chloramines, but he doesn’t expect it to be as effective as chorine.

The popularity of both ozonation and GAC are increasing in the United States, but they are still only used by a relatively small number of larger drinking water treatment facilities, says Steve Via, a regulation engineer at AWWA. According to a survey of how U.S. facilities treat surface water by the U.S. EPA in 1997, the latest year for which figures are available, 5.4% of U.S. facilities serving 50,000-100,000 people used ozone and 7.7% used GAC. Of drinking water providers for over 100,000 people, 5.8% used ozone and 6.4% used GAC.

Although the pharmaceutical compounds that Ternes studied have been reported in wastewater and surface water outside of Germany, Drewes says that clofibrate is no longer commonly used as a lipid regulator in the United States, and studies by his lab and others have found it only in some U.S. wastewater effluents. Drewes says he believes that Ternes’s carbamazepine results are most relevant in the United States; he notes that his studies of recharging groundwater have shown that the compound can survive intact after traveling 8-10 years through the subsurface.

Because of the increasing popularity of groundwater recharging in places like the United States, all of the scientists interviewed for this article concurred that this groundwater may be contaminated with pharmaceuticals. Ternes adds that the risk that pharmaceutical compounds will be found in groundwater is “relatively high” for locations where surface water intrudes into the groundwater.

Although the risk associated with consuming the low levels of pharmaceuticals found in U.S. and European waters is as yet unknown (Environ. Sci. Technol. 2002, 36, 140A-145A), Ternes notes that any antibiotics that find their way into surface waters and other natural water bodies could promote antibiotic resistance.

“The major concern associated with the presence of [pharmaceutically active compounds] in drinking water is not acute effects on human health (since environmental concentrations are orders of magnitude below the therapeutic dosages), but rather the manifestation of imperceptible effects that can accumulate over time to yield truly profound changes,” Drewes says. “And the latter is extremely difficult to determine.”

On the positive side, the new technologies that are likely to be put in place to reduce the probability of pharmaceuticals making their way into drinking water, such as activated carbon, could have the additional benefit of removing “all sorts of other chemicals we don’t even know about at the present,” Daughton says. “The analytical chemists have gotten way ahead of us,” in terms of their ability to devise new ways to detect chemicals that may be found in the environment, he explains. Because environmental chemists regularly discover new and unexpected compounds in the nation’s waters, he predicts that greater use of advanced drinking water treatment technologies could represent a “much, much higher reduction of overall risk” from such compounds. —KELLYN S. BETTS

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Links
The Top 200 Prescriptions for 2000 by Number of US Prescriptions Dispensed
Generic name link leads to Drug Monograph information where available: http://www.rxlist.com/top200.htm

EU-Project Poseidon Assessment of Technologies for the Removal of Pharmaceuticals and Personal Care Products in Sewage and Drinking Water Facilities to Improve the Indirect Potable Water Reuse : http://www.eu-poseidon.com

USGS STUDY OF PHARMACEUTICALS & OTHER ORGANIC SUBSTANCES IN US SURFACE WATERS PUBLISHED http://www.epa.gov/esd/chemistry/pharma/index.htm

As part of its ongoing reconnaissance program of US waters, USGS sampled 139 streams in 30 states during 1999-2000 for what it calls OWCs (organic wastewater constituents) using new analytical methods for 95 compounds. The OWCs, which include many pharmaceuticals and hormones commonly used in agriculture, industry and households, were found in 80% of the streams sampled. Generally low levels were detected that did not exceed any health advisories but such guidelines are not available for many compounds. The complete USGS report (http://toxics.usgs.gov/pubs/OFR-02-94/index.html) is available and the March 13th issue of Environmental Science and Technology (http://pubs.acs.org/journals/esthag/index.html) (see “Hot Article” box at top of page) features a paper which emphasizes the analytical methodology used in the study. The study received wide attention in the print media with headlines such as Beauty Aids Contaminating Waterways (LA Times, March 13) and Drug Wastes Pollute Waterways (Washington Post, March 13).

This study will add fuel to the ongoing activity of USEPA to develop an overall program to address these chemicals and other endocrine disruptors. The USEPA effort was mandated by the 1996 Food Quality Protection Act and was reinforced by a provision in the 1996 SDWA Amendments which gave EPA authority to provide for the testing, under the FFDCA Screening Program, “of any other substance that may be found in sources of drinking water if the Administrator determines that a substantial population may be exposed to such substance.” (42 U.S.C. 300j-17)

In 2001, USGS conducted a second phase of the reconnaissance study (http://toxics.usgs.gov/regional/emc_sourcewater.html) with a total of 76 drinking water source waters sampled including 51 surface waters and 25 groundwater sources. A report on that second phase has not yet been published.

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Personnel
Principal Investigator:
Name: Dr. Shane Snyder
Organization: Southern Nevada Water Authority
Address: 243 Lakeshore Road; Boulder City, NV 89005
Phone/Fax/e-mail: (702) 567-2317 / (702) 564-7222 / shane.snyder@lvvwd.com

Co-Principal Investigator:
Name: Dr. Paul Westerhoff
Organization: Arizona State University
Address: Department of Civil and Environmental Engineering Box 5306 Tempe, AZ 85287-5306
Phone/Fax/e-mail: (480) 965-2885 / (480) 965-0557 / p.westerhoff@asu.edu

Co-Principal Investigator:
Name: Dr. Rengao Song
Organization: Louisville Water Company
Address: 3018 Frankfort Avenue, Louisville, KY 40201
Phone/Fax/e-mail: (502) 569-3600#2449 / (502) 569-0813 / rsong@lwcky.com

Co-Principal Investigator:
Name: Mr. Bruce Long
Organization: Black & Veach
Address: 8400 Ward Parkway; Kansas City, MO 64114
Phone/Fax/e-mail: (913) 458-2000 / (913) 458-3730 / longbw@bv.com

Co-Principal Investigator:
Name: Dr. Bruno Levine
Organization: United Water
Address: 200 Old Hook Road; Harrington Park, NJ 07460
Phone/Fax/e-mail: (201) 986-4983 / (201) 634-4220 / bruno.levine@unitedwater.com

Participating Utilities and Other Organizations
Southern Nevada Water Authority
Louisville Water District
United Water
Metropolitan Water District of Southern California
City of Cincinnati
Kansas City

Technical Advisors:
David Sedlak
Vernon Snoeyink

AWWARF Project Officer:
Kim Linton  klinton@awwarf.com

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