Presence and distribution of wastewater-derived pharmaceuticals in soil irrigated with reclaimed water.

Three sites in the Front Range of Colorado, USA, were monitored from May through September 2003 to assess the presence and distribution of pharmaceuticals in soil irrigated with reclaimed water derived from urban wastewater. Soil cores were collected monthly, and 19 pharmaceuticals, all of which were detected during the present study, were measured in 5-cm increments of the 30-cm cores. Samples of reclaimed water were analyzed three times during the study to assess the input of pharmaceuticals. Samples collected before the onset of irrigation in 2003 contained numerous pharmaceuticals, likely resulting from the previous year's irrigation. Several of the selected pharmaceuticals increased in total soil concentration at one or more of the sites. The four most commonly detected pharmaceuticals were erythromycin, carbamazepine, fluoxetine, and diphenhydramine. Typical concentrations of the individual pharmaceuticals observed were low (0.02-15 microg/kg dry soil). The existence of subsurface maximum concentrations and detectable concentrations at the lowest sampled soil depth might indicate interactions of soil components with pharmaceuticals during leaching through the vadose zone. Nevertheless, the present study demonstrates that reclaimed-water irrigation results in soil pharmaceutical concentrations that vary through the irrigation season and that some compounds persist for months after irrigation.

Earthworm bioassays and seedling emergence for monitoring toxicity, aging and bioaccumulation of anthropogenic waste indicator compounds in biosolids-amended soil.

Land application of biosolids (treated sewage sludge) can be an important route for introducing xenobiotic compounds into terrestrial environments. There is a paucity of available information on the effects of biosolids amendment on terrestrial organisms. In this study, the influence of biosolids and biosolids aging on earthworm (Eisenia fetida) reproduction and survival and lettuce (Lactuca sativa) seedling emergence was investigated. Earthworms were exposed to soils amended with varying quantities of biosolids (0, 1, 2, 3, or 4% dry mass). To investigate the influence of biosolids aging, the biosolids used in the study were aged for differing lengths of time (2 or 8 weeks) prior to exposure. All of the adult earthworms survived in the biosolids-amended soils at all concentrations that were aged for 2 weeks; however, only 20% of the adults survived in the soil amended with the highest concentration of biosolids and aged for 8 weeks. Reproduction as measured by mean number of juveniles and unhatched cocoons produced per treatment correlated inversely with biosolids concentration, although the effects were generally more pronounced in the 8-week aged biosolids-soil samples. Latent seedling emergence and reduced seedling fitness correlated inversely with biosolids concentration, but these effects were tempered in the 8-week aged versus the 2-week aged soil-biosolids mixtures. Anthropogenic waste indicator compounds (AWIs) were measured in the biosolids, biosolids-soil mixtures, and earthworm samples. Where possible, bioaccumulation factors (BAFs) were calculated or estimated. A wide variety of AWIs were detected in the biosolids (51 AWIs) and earthworm samples (≤19 AWI). The earthworms exposed to the 8-week aged biosolids-soil mixtures tended to accumulate greater quantities of AWIs compared to the 2-week aged mixture, suggesting that the bioavailability of some AWIs was enhanced with aging. The BAFs for a given AWI varied with treatment. Notably large BAFs were determined for some AWIs. For example, the maximum BAF determined for para-cresol, methyl salicylate, bisphenol-A, and cholesterol was greater than 100 in some treatments.

Selective uptake and biological consequences of environmentally relevant antidepressant pharmaceutical exposures on male fathead minnows.

Antidepressant pharmaceuticals have been reported in wastewater effluent at the nanogram to low microgram-per-liter range, and include bupropion (BUP), fluoxetine (FLX), sertraline (SER), and venlafaxine (VEN). To assess the effects of antidepressants on reproductive anatomy, physiology, and behavior, adult male fathead minnows (Pimephales promelas) were exposed for 21 days either to a single concentration of the antidepressants FLX, SER, VEN, or BUP, or to an antidepressant mixture. The data demonstrated that exposure to VEN (305 ng/L and 1104 ng/L) and SER (5.2 ng/L) resulted in mortality. Anatomical alterations were noted within the testes of fish exposed to SER and FLX, both modulators of the neurotransmitter serotonin. Additionally, FLX at 28 ng/L induced vitellogenin in male fish--a common endpoint for estrogenic endocrine disruption. Significant alterations in male secondary sex characteristics were noted with single exposures. Effects of single compound exposures neither carried over, nor became additive in the antidepressant mixtures, and reproductive behavior was not affected. Analysis of brain tissues from the exposed fish suggested increased uptake of FLX, SER and BUP and minimal uptake of VEN when compared to exposure water concentrations. Furthermore, the only metabolite detected consistently in the brain tissues was norfluoxetine. Similar trends of uptake by brain tissue were observed when fish were exposed to antidepressant mixtures. The present study demonstrates that anatomy and physiology, but not reproductive behavior, can be disrupted by exposure to environmental concentrations of some antidepressants. The observation that antidepressant uptake into fish tissues is selective may have consequences on assessing the mode-of-action and effects of these compounds in future studies.

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.

Bioaccumulation of pharmaceuticals and other anthropogenic waste indicators in earthworms from agricultural soil amended with biosolid or swine manure.

Analysis of earthworms offers potential for assessing the transfer of organic anthropogenic waste indicators (AWIs) derived from land-applied biosolid or manure to biota. Earthworms and soil samples were collected from three Midwest agricultural fields to measure the presence and potential for transfer of 77 AWIs from land-applied biosolids and livestock manure to earthworms. The sites consisted of a soybean field with no amendments of human or livestock waste (Site 1), a soybean field amended with biosolids from a municipal wastewater treatment plant (Site 2), and a cornfield amended with swine manure (Site 3). The biosolid applied to Site 2 contained a diverse composition of 28 AWls, reflecting the presence of human-use compounds. The swine manure contained 12 AWls, and was dominated by biogenic sterols. Soil and earthworm samples were collected in the spring (about30 days after soil amendment) and fall (140-155 days after soil amendment) at all field sites. Soils from Site 1 contained 21 AWIs and soil from Sites 2 and 3 contained 19 AWls. The AWI profiles at Sites 2 and 3 generally reflected the relative composition of AWls present in waste material applied. There were 20 AWls detected in earthworms from Site 1 (three compounds exceeding concentrations of 1000 microg/kg), 25 AWls in earthworms from Site 2 (seven compounds exceeding concentrations of 1000 microg/ kg), and 21 AWls in earthworms from Site 3 (five compounds exceeding concentrations of 1000 microg/kg). A number of compounds thatwere present in the earthworm tissue were at concentrations less than reporting levels in the corresponding soil samples. The AWIs detected in earthworm tissue from the three field sites included pharmaceuticals, synthetic fragrances, detergent metabolites, polycyclic aromatic hydrocarbons (PAHs), biogenic sterols, disinfectants, and pesticides, reflecting a wide range of physicochemical properties. For those contaminants detected in earthworm tissue and soil, bioaccumulation factors (BAF) ranged from 0.05 (galaxolide) to 27 (triclosan). This study documents that when AWls are present in source materials that are land applied, such as biosolids and swine manure, AWls can be transferred to earthworms.

Survey of organic wastewater contaminants in biosolids destined for land application.

In this study, the presence, composition, and concentrations of organic wastewater contaminants (OWCs) were determined in solid materials produced during wastewater treatment. This study was undertaken to evaluate the potential of these solids, collectively referred to as biosolids, as a source of OWCs to soil and water in contact with soil. Nine different biosolid products, produced by municipal wastewater treatment plants in seven different states, were analyzed for 87 different OWCs. Fifty-five of the OWCs were detected in at least one biosolid product. The 87 different OWCs represent a diverse cross section of emerging organic contaminants that enter wastewater treatment plants and may be discharged without being completely metabolized or degraded. A minimum of 30 and a maximum of 45 OWCs were detected in any one biosolid. The biosolids used in this study are produced by several production methods, and the plants they originate from have differing population demographics, yet the percent composition of total OWC content, and of the most common OWCs, typically did not vary greatly between the biosolids tested. The summed OWC content ranged from 64 to 1811 mg/kg dry weight. Six biosolids were collected twice, 3-18 months apart, and the total OWC content of each biosolid varied by less than a factor of 2. These results indicate that the biosolids investigated in this study have OWC compositions and concentrations that are more similar than different and that biosolids are highly enriched in OWCs (as mass-normalized concentrations) when compared to effluents or effluent-impacted water. These results demonstrate the need to better describe the composition and fate of OWCs in biosolids since about 50% of biosolids are land applied and thus become a potentially ubiquitous nonpoint source of OWCs into the environment.

Transport of chemical and microbial compounds from known wastewater discharges: potential for use as indicators of human fecal contamination.

The quality of drinking and recreational water is currently (2005) determined using indicator bacteria. However, the culture tests used to analyze forthese bacteria require a long time to complete and do not discriminate between human and animal fecal material sources. One complementary approach is to use chemicals found in human wastewater, which would have the advantages of (1) potentially shorter analysis times than the bacterial culture tests and (2) being selected for human-source specificity. At 10 locations, water samples were collected upstream and at two successive points downstream from a wastewaster treatment plant (WWTP); a treated effluent sample was also collected at each WWTP. This sampling plan was used to determine the persistence of a chemically diverse suite of emerging contaminants in streams. Samples were also collected at two reference locations assumed to have minimal human impacts. Of the 110 chemical analytes investigated in this project, 78 were detected at least once. The number of compounds in a given sample ranged from 3 at a reference location to 50 in a WWTP effluent sample. The total analyte load at each location varied from 0.018 microg/L at the reference location to 97.7 microg/L in a separate WWTP effluent sample. Although most of the compound concentrations were in the range of 0.01-1.0 microg/L, in some samples, individual concentrations were in the range of 5-38 microg/L. The concentrations of the majority of the chemicals present in the samples generally followed the expected trend: they were either nonexistent or at trace levels in the upstream samples, had their maximum concentrations in the WWTP effluent samples, and then declined in the two downstream samples. This research suggests that selected chemicals are useful as tracers of human wastewater discharge.