Larry B. Barber

A national reconnaissance for pharmaceuticals and other organic wastewater contaminants in the United States - II) Untreated drinking water sources

Numerous studies have shown that a variety of manufactured and natural organic compounds such as pharmaceuticals, steroids, surfactants, flame retardants, fragrances, plasticizers and other chemicals often associated with wastewaters have been detected in the vicinity of municipal wastewater discharges and livestock agricultural facilities. To provide new data and insights about the environmental presence of some of these chemicals in untreated sources of drinking water in the United States targeted sites were sampled and analyzed for 100 analytes with sub-parts per billion detection capabilities. The sites included 25 ground- and 49 surface-water sources of drinking water serving populations ranging from one family to over 8 million people. Sixty-three of the 100 targeted chemicals were detected in at least one water sample. Interestingly, in spite of the low detection levels 60% of the 36 pharmaceuticals (including prescription drugs and antibiotics) analyzed were not detected in any water sample. The five most frequently detected chemicals targeted in surface water were: cholesterol (59%, natural sterol), metolachlor (53%, herbicide), cotinine (51%, nicotine metabolite), beta-sitosterol (37%, natural plant sterol), and 1,7-dimethylxanthine (27%, caffeine metabolite); and in ground water: tetrachloroethylene (24%, solvent), carbamazepine (20%, pharmaceutical), bisphenol-A (20%, plasticizer), 1,7-dimethylxanthine (16%, caffeine metabolite), and tri (2-chloroethyl) phosphate (12%, fire retardant). A median of 4 compounds were detected per site indicating that the targeted chemicals generally occur in mixtures (commonly near detection levels) in the environment and likely originate from a variety of animal and human uses and waste sources. These data will help prioritize and determine the need, if any, for future occurrence, fate and transport, and health-effects research for subsets of these chemicals and their degradates most likely to be found in water resources used for drinking water in the United States.

A national reconnaissance of pharmaceuticals and other organic wastewater contaminants in the United States — I) Groundwater

As part of the continuing effort to collect baseline information on the environmental occurrence of pharmaceuticals, and other organic wastewater contaminants (OWCs) in the Nations water resources, water samples were collected from a network of 47 groundwater sites across 18 states in 2000. All samples collected were analyzed for 65 OWCs representing a wide variety of uses and origins. Site selection focused on areas suspected to be susceptible to contamination from either animal or human wastewaters (i.e. down gradient of a landfill, unsewered residential development, or animal feedlot). Thus, sites sampled were not necessarily used as a source of drinking water but provide a variety of geohydrologic environments with potential sources of OWCs. OWCs were detected in 81% of the sites sampled, with 35 of the 65 OWCs being found at least once. The most frequently detected compounds include N,N-diethyltoluamide (35%, insect repellant), bisphenol A (30%, plasticizer), tri(2-chloroethyl) phosphate (30%, fire retardant), sulfamethoxazole (23%, veterinary and human antibiotic), and 4-octylphenol monoethoxylate (19%, detergent metabolite). Although sampling procedures were intended to ensure that all groundwater samples analyzed were indicative of aquifer conditions it is possible that detections of some OWCs could have resulted from leaching of well-construction materials and/or other site-specific conditions related to well construction and materials. Future research will be needed to identify those factors that are most important in determining the occurrence and concentrations of OWCs in groundwater.

Antidepressant Pharmaceuticals in Two U.S. Effluent-Impacted Streams: Occurrence and Fate in Water and Sediment, and Selective Uptake in Fish Neural Tissue

Antidepressant pharmaceuticals are widely prescribed in the United States; release of municipal wastewater effluent is a primary route introducing them to aquatic environments, where little is known about their distribution and fate. Water, bed sediment, and brain tissue from native white suckers (Catostomus commersoni) were collected upstream and at points progressively downstream from outfalls discharging to two effluent-impacted streams, Boulder Creek (Colorado) and Fourmile Creek (Iowa). A liquid chromatography/tandem mass spectrometry method was used to quantify antidepressants, including fluoxetine, norfluoxetine (degradate), sertraline, norsertraline (degradate), paroxetine, citalopram, fluvoxamine, duloxetine, venlafaxine, and bupropion in all three sample matrices. Antidepressants were not present above the limit of quantitation in water samples upstream from the effluent outfalls but were present at points downstream at ng/L concentrations, even at the farthest downstream sampling site 8.4 km downstream from the outfall. The antidepressants with the highest measured concentrations in both streams were venlafaxine, bupropion, and citalopram and typically were observed at concentrations of at least an order of magnitude greater than the more commonly investigated antidepressants fluoxetine and sertraline. Concentrations of antidepressants in bed sediment were measured at ng/g levels; venlafaxine and fluoxetine were the predominant chemicals observed. Fluoxetine, sertraline, and their degradates were the principal antidepressants observed in fish brain tissue, typically at low ng/g concentrations. A qualitatively different antidepressant profile was observed in brain tissue compared to streamwater samples. This study documents that wastewater effluent can be a point source of antidepressants to stream ecosystems and that the qualitative composition of antidepressants in brain tissue from exposed fish differs substantially from the compositions observed in streamwater and sediment, suggesting selective uptake.

Antidepressants at environmentally relevant concentrations affect predator avoidance behavior of larval fathead minnows (Pimephales promelas).

The effects of embryonic and larval exposure to environmentally relevant (ng/L) concentrations of common antidepressants, fluoxetine, sertraline, venlafaxine, and bupropion (singularly and in mixture) on C-start escape behavior were evaluated in fathead minnows (Pimephales promelas). Embryos (postfertilization until hatching) were exposed for 5 d and, after hatching, were allowed to grow in control well water until 12 d old. Similarly, posthatch fathead minnows were exposed for 12 d to these compounds. High-speed (1,000 frames/s) video recordings of escape behavior were collected and transferred to National Institutes of Health Image for frame-by-frame analysis of latency periods, escape velocities, and total escape response (combination of latency period and escape velocity). When tested 12 d posthatch, fluoxetine and venlafaxine adversely affected C-start performance of larvae exposed as embryos. Conversely, larvae exposed for 12 d posthatch did not exhibit altered escape responses when exposed to fluoxetine but were affected by venlafaxine and bupropion exposure. Mixtures of these four antidepressant pharmaceuticals slowed predator avoidance behaviors in larval fathead minnows regardless of the exposure window. The direct impact of reduced C-start performance on survival and, ultimately, reproductive fitness provides an avenue to assess the ecological relevance of exposure in an assay of relatively short duration.

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5–25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

Demasculinization of male fish by wastewater treatment plant effluent

Adult male fathead minnows (Pimephales promelas) were exposed to effluent from the City of Boulder, Colorado wastewater treatment plant (WWTP) under controlled conditions in the field to determine if the effluent induced reproductive disruption in fish. Gonadal intersex and other evidence of reproductive disruption were previously identified in white suckers (Catostomus commersoni) in Boulder Creek downstream from this WWTP effluent outfall. Fish were exposed within a mobile flow-through exposure laboratory in July 2005 and August 2006 to WWTP effluent (EFF), Boulder Creek water (REF), or mixtures of EFF and REF for up to 28 days. Primary (sperm abundance) and secondary (nuptial tubercles and dorsal fat pads) sex characteristics were demasculinized within 14 days of exposure to 50% and 100% EFF. Vitellogenin was maximally elevated in both 50% and 100% EFF treatments within 7 days and significantly elevated by 25% EFF within 14 days. The steroidal estrogens 17β-estradiol, estrone, estriol, and 17α-ethynylestradiol, as well as estrogenic alkylphenols and bisphenol A were identified within the EFF treatments and not in the REF treatment. These results support the hypothesis that the reproductive disruption observed in this watershed is due to endocrine-active chemicals in the WWTP effluent.

Long-term fate of organic micropollutants in sewage-contaminated groundwater

Disposal of secondary sewage effluent by rapid infiltration has produced a plume of contaminated groundwater over 3500 m long near Falmouth, MA. Approximately 50 volatile organic compounds were detected and identified in the plume, at concentrations ranging from 10 ng/L to 500 {mu}g/L, by closed-loop stripping and purge-and-trap in conjunction with gas chromatography-mass spectrometry. The dominant contaminants were di-, tri- and tetrachloroethene, o- and p-dichlorobenzene, C{sub 1} to C{sub 6} alkylbenzenes, 2,6-di-tert-butylbenzoquinone, and several isomers of p-nonylphenol. The chloroethenes and chlorobenzenes had the same general distribution as chloride and boron and appear to be transported with little retardation. Less soluble compounds, such as nonylphenol and di-tert-butylbenzoquinone, appear to be retarded during subsurface transport by sorption processes. Although biodegradation of labile organic compounds occurs near the infiltration beds, many trace compounds, including chlorinated benzenes, alkylbenzenes, and aliphatic hydrocarbons, have persisted for more than 30 years in the aquifer.

Contamination of estuarine water, biota, and sediment by halogenated organic compounds: A field study

Studies conducted in the vicinity of an industrial outfall in the Calcasieu River estuary, Louisiana, have shown that water, bottom and suspended sediment, and four different species of biota are contaminated with halogenated organic compounds (HOC) including haloarenes. A salting-out effect in the estuary moderately enhanced the partitioning tendency of the contaminants into biota and sediments. Contaminant concentrations in water, suspended sediments, and biota were found to be far below the values predicted on the basis of the assumption of phase equilibria with respect to concentrations in bottom sediment. Relative concentration factors of HOC between biota and bottom sediment increased with increasing octanol/estuarine water partition coefficients (K/sub ow*/), maximizing at log K/sub ow*/ of about 5, although these ratios were considerably less than equilibrium values. In contrast, contaminant concentrations in water, biota, and suspended sediments were much closer to equilibrium values. Bioconcentration factors of HOC determined on the basis of lipid content for four different biotic species correlated reasonably well with equilibrium triolein/water partition coefficients (K/sub tw/).

Sewage contamination in the upper Mississippi River as measured by the fecal sterol, coprostanol

Abstract The molecular sewage indicator, coprostanol, was measured in bed sediments of the Mississippi River for the purpose of determining sewage contamination. Coprostanol is a non-ionic, non-polar, organic molecule that associates with sediments in surface waters, and concentrations of corpostanol in bed sediments provide an indication of long-term sewage loads. Because coprostanol concentrations are dependent on particle size and percent organic carbon, a ratio between coprostanol (sewage sources) and cholestanol + cholesterol (sewage and non-sewage sources) was used to remove the biases related to particle size and percent organic carbon. The dynamics of contaminant transport in the Upper Mississippi River are influenced by both hydrologic and geochemical parameters. A mass balance model incorporating environmental parameters such as river and tributary discharge, suspended sediment concentration, fraction of organic carbon, sedimentation rates, municipal discharges and coprostanol decay rates was developed that describes coprostanol concentrations and therefore, expected patterns of municipal sewage effects on the Upper Mississippi River. Comparison of the computed and the measured coprostanol concentrations provides insight into the complex hydrologic and geochemical processes of contaminant transport and the ability to link measured chemical concentrations with hydrologic characteristics of the Mississippi River.

Conservative and reactive solute transport in constructed wetlands

[1] The transport of bromide, a conservative tracer, and rhodamine WT (RWT), a photodegrading tracer, was evaluated in three wastewater-dependent wetlands near Phoenix, Arizona, using a solute transport model with transient storage. Coupled sodium bromide and RWT tracer tests were performed to establish conservative transport and reactive parameters in constructed wetlands with water losses ranging from (1) relatively impermeable (15%), (2) moderately leaky (45%), and (3) significantly leaky (76%). RWT first-order photolysis rates and sorption coefficients were determined from independent field and laboratory experiments. Individual wetland hydraulic profiles influenced the extent of transient storage interaction in stagnant water areas and consequently RWT removal. Solute mixing and transient storage interaction occurred in the impermeable wetland, resulting in 21% RWT mass loss from main channel and storage zone photolysis (10%) and sorption (11%) reactions. Advection and dispersion governed solute transport in the leaky wetland, limiting RWT photolysis removal (1.2%) and favoring main channel sorption (3.6%). The moderately leaky wetland contained islands parallel to flow, producing channel flow and minimizing RWT losses (1.6%). INDEX TERMS: 1890 Hydrology: Wetlands; 1871 Hydrology: Surface water quality; 3230 Mathematical Geophysics: Numerical solutions; KEYWORDS: constructed wetlands, OTIS, transient storage