Chad A. Kinney

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 years 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.

Uptake of human pharmaceuticals by plants grown under hydroponic conditions.

Cabbage (Brassica rapa var. pekinensis) and Wisconsin Fast Plants (Brassica rapa) were chosen for a proof of concept study to determine the potential uptake and accumulation of human pharmaceuticals by plants. These plants were grown hydroponically under high-pressure sodium lamps in one of two groups including a control and test group exposed to pharmaceuticals. The control plants were irrigated with a recirculating Hoaglands nutrient solution while the test plants were irrigated with a Hoaglands nutrient solution fortified with the pharmaceuticals carbamazepine, salbutamol, sulfamethoxazole, and trimethoprim at 232.5 microg L(-1). When plants reached maturity, nine entire plants of each species were separated into components such as roots, leaves, stems, and seedpods where applicable. An analytical method for quantifying pharmaceuticals and personal care products was developed using pressurized liquid extraction and liquid chromatography electrospray ionization mass spectrometry (LC/ESI/MS) in positive and negative ion modes using single ion monitoring. The method detection limits ranged from 3.13 ng g(-1) to 29.78 ng g(-1) with recoveries ranging from 66.83% to 113.62% from plant matrices. All four of the pharmaceuticals were detected in the roots and leaves of the cabbage. The maximum wet weight concentrations of the pharmaceuticals were detected in the root structure of the cabbage plants at 98.87 ng g(-1) carbamazepine, 114.72 ng g(-1) salbutamol, 138.26 ng g(-1) sulfamethoxazole, and 91.33 ng g(-1) trimethoprim. Carbamazepine and salbutamol were detected in the seedpods of the Wisconsin Fast Plants while all four of the pharmaceuticals were detected in the leaf/stem/root of the Wisconsin Fast Plants. Phloroglucinol staining of root cross-sections was used to verify the existence of an intact endodermis, suggesting that pharmaceuticals found in the leaf and seedpods of the plants were transported symplastically.

The biogeochemical controls of the δ15N and δ18O of N2O produced in landfill cover soils

We document an enrichment of both the δ18OAtm.O2 and δ15NAtm.N2 values of soil-derived N2O collected from landfill cover soils relative to tropospheric N2O. The isotopic values of N2O vary from −5.1‰ to +l9.4‰ and from +19.0‰ to +33.5‰ for δ 15NAtm.N2 and δ18OAtm.O2,, respectively. A tight linear correlation for δ18OAtm.O2 versus δ15NAtm.N2 is apparent, reflecting coupled microbial processes that produce N2O that may be isotopically enriched or depleted in relation to tropospheric N2O. Several explanations are provided to explain this correlation, including evidence for NH3 limitation during nitrification, which would be expected to diminish isotopic fractionation and consequently result in more enriched isotopic values of N2O. Desiccation effects on nitrification were also observed, which contribute to NH3 limitation and thus could influence the isotopic signature of N2O. Our results indicate that the N2O isotopic composition from soils may vary greatly depending on the season and soil moisture conditions and may at times be enriched in 15N and 18O relative to tropospheric N2O.

Presence and transport of the antimicrobials triclocarban and triclosan in a wastewater-dominated stream and freshwater environment.

The presence of the antimicrobials triclocarban (TCC) and triclosan (TCS)in Fountain Creek, a wastewater-dominated stream, and the Arkansas River, Colorado, USA was measured in the surface water, suspended sediments, and bed sediments during spring runoff (high flow) and summer base flow (low flow) conditions. Fountain Creak is a tributary of the Arkansas River. Passive polar organic chemical integrative samplers (POCIS) were used along with active sampling (water grab samples) to measure and TCS concentrations in these surface waters. The concentration of TCC and TCS, based on POCIS measurements, ranged from 4.5 to 47.3 ng/L and 3.9 to 28.3 ng/L, respectively, at the five sample sites monitored in this study under both flow conditions. The range of concentrations of TCC and TCS in suspended sediments was 0.7-57.3 ng/g and 0.7-13.3 ng/g, respectively, and was closely tied to the quantity of organic carbon in the suspended sediment, which ranged from 1.6 to 14.5%. The quantity of organic carbon in suspended sediment during the summer base flow was influenced by runoff from the burn area of a large forest fire that occurred between the two sampling periods. The primary transport mechanism of TCC and TCS in these surface waters was in the dissolved phase, with 64-99% of TCC and 68-99% of TCS transported in the dissolved phase. The total amount of TCS and TCC in bed-sediments was relatively low, with the maximum amount at any one site being 0.38 ± 0.15 ng/g TCS and 4.09 ± 5.26 ng/g TCC. Fountain Creek contributed up to 76% and 69% of the TCC and TCS, respectively, that is transported directly below its confluence with Arkansas River. Fountain Creek drained approximately 3.0 g/day TCS (in spring), 2.9 g/day TCS (in summer) and 1.9 g/day TCC (in spring), 2.0 g/day TCC (in-summer) into the Arkansas River, which suggests consistent input of TCC and TCS into Fountain Creek, such as in discharge of treated wastewater that is independent of changing creek flow conditions.

Transformation Products and Human Metabolites of Triclocarban and Triclosan in Sewage Sludge Across the United States

Removal of triclocarban (TCC) and triclosan (TCS) from wastewater is a function of adsorption, abiotic degradation, and microbial mineralization or transformation, reactions that are not currently controlled or optimized in the pollution control infrastructure of standard wastewater treatment. Here, we report on the levels of eight transformation products, human metabolites, and manufacturing byproducts of TCC and TCS in raw and treated sewage sludge. Two sample sets were studied: samples collected once from 14 wastewater treatment plants (WWTPs) representing nine states, and multiple samples collected from one WWTP monitored for 12 months. Time-course analysis of significant mass fluxes (α = 0.01) indicate that transformation of TCC (dechlorination) and TCS (methylation) occurred during sewage conveyance and treatment. Strong linear correlations were found between TCC and the human metabolite 2′-hydroxy-TCC (r = 0.84), and between the TCC-dechlorination products dichlorocarbanilide (DCC) and monochlorocarbanilide (r = 0.99). Mass ratios of DCC-to-TCC and of methyl-triclosan (MeTCS)-to-TCS, serving as indicators of transformation activity, revealed that transformation was widespread under different treatment regimes across the WWTPs sampled, though the degree of transformation varied significantly among study sites (α = 0.01). The analysis of sludge sampled before and after different unit operation steps (i.e., anaerobic digestion, sludge heat treatment, and sludge drying) yielded insights into the extent and location of TCC and TCS transformation. Results showed anaerobic digestion to be important for MeTCS transformation (37–74%), whereas its contribution to partial TCC dechlorination was limited (0.4–2.1%). This longitudinal and nationwide survey is the first to report the occurrence of transformation products, human metabolites, and manufacturing byproducts of TCC and TCS in sewage sludge.

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.

Comprehensive Investigations of Kinetics of Alkaline Hydrolysis of TNT (2,4,6-Trinitrotoluene), DNT (2,4-Dinitrotoluene), and DNAN (2,4-Dinitroanisole)

Combined experimental and computational techniques were used to analyze multistep chemical reactions in the alkaline hydrolysis of three nitroaromatic compounds: 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), and 2,4-dinitroanisole (DNAN). The study reveals common features and differences in the kinetic behavior of these compounds. The analysis of the predicted pathways includes modeling of the reactions, along with simulation of UV-vis spectra, experimental monitoring of reactions using LC/MS techniques, development of the kinetic model by designing and solving the system of differential equations, and obtaining computationally predicted kinetics for decay and accumulation of reactants and products. Obtained results suggest that DNT and DNAN are more resistant to alkaline hydrolysis than TNT. The direct substitution of a nitro group by a hydroxide represents the most favorable pathway for all considered compounds. The formation of Meisenheimer complexes leads to the kinetic first-step intermediates in the hydrolysis of TNT. Janovsky complexes can also be formed during hydrolysis of TNT and DNT but in small quantities. Methyl group abstraction is one of the suggested pathways of DNAN transformation during alkaline hydrolysis.

Effects of the fungicides mancozeb and chlorothalonil on fluxes of CO2, N2O, and CH4 in a fertilized Colorado grassland soil

[1] Management of agricultural soil plays an important role in present and future atmospheric concentrations of the greenhouse gases carbon dioxide (CO 2 ), nitrous oxide (N 2 O), and methane (CH 4 ). Pesticides are used as management tools in crop production, but little is known about their effects on soil-atmosphere exchange of CO 2 , N 2 O, and CH 4 . Field studies described in this paper determined the effect of two commonly used fungicides, mancozeb and chlorothalonil, on trace gas exchange. Separate experimental plots, 1 m 2 , were established in nitrogen fertilized no-tilled native grassland and tilled soils with and without fungicide application. Two studies were conducted. The first study was initiated in June 1999 and lasted for 1 year with monthly flux measurements from tilled and no-till soils. The second study commenced in August 2001 with twelve weekly measurements from tilled soils only. From both studies mancozeb suppressed emissions of CO 2 and N 2 O in the tilled soil by an average of 28% and 47%, respectively. This suppression corresponded with efficacy periods of 14-29 and 56-77 days, respectively. From the no-till soils mancozeb decreased CO 2 and N 2 O emissions by 33% and 80% for periods of 29 and 94 days, respectively. Mancozeb inhibited CH 4 consumption in the first study by 46% and 71% in the tilled and no-till soil for periods of 8 and 29 days, respectively, but had no effect in the second study. From both studies chlorothalonil initially suppressed CO 2 and N 2 O emissions and enhanced CH 4 uptake in the tilled soil by an average of 37%, 40%, and 115%, respectively. These effects corresponded with efficacy periods of 14-29, 21-56, and 1-14 days, respectively. In the no-till soil chlorothalonil inhibited CO 2 and N 2 O emissions and enhanced CH 4 uptake by 29%, 48%, and 86% for periods of 29, 56, and 56 days, respectively. Following the initial period of suppression, chlorothalonil subsequently enhanced N 2 O emissions in the tilled soil by an average of 51% and in the no-till soil by 81% before returning to near background levels. The beginning of increased N 2 O emissions from the chlorothalonil-amended plots corresponded with a maximum soil concentration of the chlorothalonil degradate, 4-hydroxy-2, 5, 6-trichloroisophthalonitrile. The site specific global warming potential (GWP) resulting from the fluxes of CO 2 , N 2 O, and CH 4 from all soils was determined to decrease by an average 26% and 21% as a result of a single application of mancozeb or chlorothalonil, respectively. The decrease in CO 2 emissions in the fungicide-amended plots potentially could result in the conservation of as much as 1200 and 2400 kg C ha -1 yr -1 organic carbon in the tilled and no-till plots, respectively. Therefore it is feasible that application of certain fungicides to agricultural soil might lead to enhanced soil carbon sequestration and thus have additional positive effects on atmospheric CO 2 concentrations.

Occurrence, temporal variation, and estrogenic burden of five parabens in sewage sludge collected across the United States

Five parabens used as preservatives in pharmaceuticals and personal care products (PPCPs) were measured in sewage sludges collected at 14 U.S. wastewater treatment plants (WWTPs) located in nine states. Detected concentration ranges (ng/g, dry weight) and frequencies were as follows: methyl paraben (15.9 to 203.0; 100%), propyl paraben (0.5 to 7.7; 100%), ethyl paraben (<0.6 to 2.6; 63%), butyl paraben (<0.4 to 4.3; 42%) and benzyl paraben (<0.4 to 3.3; 26%). The estrogenicity inherent to the sum of parabens detected in sewage sludge (ranging from 10.1 to 500.1pg/kg 17β-estradiol equivalents) was insignificant when compared to the 106-times higher value calculated for natural estrogens reported in the literature to occur in sewage sludge. Temporal monitoring at one WWTP provided insights into temporal and seasonal variations in paraben concentrations. This is the first report on the occurrence of five parabens in sewage sludges from across the U.S., and internationally, the first on temporal variations of paraben levels in sewage sludge. Study results will help to inform the risk assessment of sewage sludge destined for land application (biosolids).

Impacts of Pharmaceuticals on Terrestrial Wildlife

Essentially ubiquitous in our environment, residues of human and veterinary pharmaceuticals somewhat paradoxically represent an emerging and increasing risk to wild biota. Whilst in recent years a great deal of analytical effort has been expended to quantify the presence of many pharmaceutical contaminants, especially in freshwater systems, our real understanding of the risks posed to most clades of wildlife, aquatic and terrestrial alike, still lags behind. In particular, relevant field-based studies regarding possible chronic impacts in higher terrestrial wildlife (birds, mammals, reptiles, etc.) remain all too scarce. Yet, for example, over the past two decades Old World Gyps vultures on the Indian subcontinent have been virtually extirpated due to non-target exposure to a single synthetic pharmaceutical compound, diclofenac (a non-steroidal anti-inflammatory drug). Here, we highlight and discuss the myriad possible exposure routes to terrestrial wildlife, consider the analytical and monitoring approaches that are already in use or that could be used in future research, and reflect upon a selection of legislative approaches currently being applied to identified terrestrial impacts. Finally, with the ultimate aim of encouraging further applied ecotoxicology-based research in this emerging field, we highlight several priorities for future inquiry, with special emphasis on non-target effects in previously overlooked but potentially vulnerable or highly representative clades of wildlife exposed within environmentally relevant, real-world scenarios.