Clifford P. Rice

Effect of solids concentration on the sorptive partitioning of hydrophobic pollutants in aquatic systems

Etude menee sur des sediments du Lac Michigan avec 4 polluants prioritaires hydrophobes: chlorobenzene, naphtolene, trichlorobiphenyle et hexachlorobiphenyle

Evidence of currently-used pesticides in air, ice, fog, seawater and surface microlayer in the Bering and Chukchi Seas

Abstract Investigation of currently-used pesticides (triazines, acetanilides, organophosphates and organochlorines) was carried out in the Bering and Chukchi marine ecosystems in the summer of 1993. Chlorpyrifos and trace levels of endosulphan were the most frequently identified contaminants in seawater, chlorpyrifos and atrazine were found in marine ice, and chlorothalonil and trifluralin were found in surface microlayer samples. Concentrations of chlorpyrifos were highest (170 ng l−1) in marine ice and higher in seawater (19–67 ng l−1) at locations which were closest to the ice edge. Endosulphan was found as a widely distributed currently used pesticide in the polar atmosphere. The greatest concentration of any one single agrochemical was trifluralin (1.15 μg l−1) in a Bristol Bay surface microlayer sample. Arctic marine fog was sampled and for the first time, several currently-used pesticides (chlorpyrifos, trifluralin, metolachlor, chlorothalonil, terbufos and endosulphan) were detected at concentrations several times higher than in adjacent waters or ice.

Management of antibiotic residues from agricultural sources: use of composting to reduce chlortetracycline residues in beef manure from treated animals.

Chlortetracycline (CTC) is one of only ten antibiotics licensed in the U.S.A. for use as growth promoters for livestock. The widespread use and persistence of CTC may contribute in development of antibiotic-resistant bacteria. The objective of this study was to determine the effect of composting on the fate of CTC residues found in manure from medicated animals. The effect of CTC residues on composting was also investigated. Five beef calves were medicated for 5 days with 22 mg/kg/day of CTC. Manure samples collected from calves prior to and after medication were mixed with straw and woodchips, and aliquots of the subsequent mixtures were treated in laboratory composters for 30 days. In addition, aliquots of the CTC-containing mixture were incubated at 25 degrees C or sterilized followed by incubation at 25 degrees C and 55 degrees C (composting temperature). The presence of CTC did not appear to affect the composting process. Concentrations of CTC/ECTC (the summed concentrations of CTC and its epimer ECTC) in the composted mixture (CM) and sterilized mixture incubated at 55 degrees C (SM55) decreased 99% and 98% (from 113 microg/g dry weight (DW) to 0.7 microg/g DW and 2.0 microg/g DW), respectively, in 30 days. In contrast, levels of CTC/ECTC in room temperature incubated (RTIM) and sterilized mixture incubated at 25 degrees C (SM25) decreased 49% and 40% (to 58 microg/g DW and 68 microg/g DW), respectively, after 30 days. Concentrations of the CTC metabolite, iso-chlortetracycline (ICTC), in CM and SM55 decreased more than 99% (from 12 microg/g DW to below quantitation limit of 0.3 microg/g DW) in 30 days. ICTC levels in RTIM and SM25 decreased 80% (to 4 microg/g DW) in 30 days. These results confirm and extend those from previous studies that show the increased loss of extractable CTC residues with increased time and incubation temperature. In addition, our results using sterile and non-sterile samples suggest that the decrease in concentrations of extractable CTC/ECTC at 25 degrees C and 55 degrees C (composting temperature) is due to abiotic processes.

Fate of Triclocarban, Triclosan and Methyltriclosan during wastewater and biosolids treatment processes

Triclocarban (TCC) and Triclosan (TCS) are two antibacterial chemicals present in household and personal care products. Methyltriclosan is a biodegradation product of TCS formed under aerobic conditions. TCC and TCS are discharged to Waste Water Treatment Plants (WWTP) where they are removed from the liquid phase mainly by concentrating in the solids. This study presents a thorough investigation of TCC, TCS and MeTCS concentrations in the liquid phase (dissolved + particulate) as well as solid phases within a single, large WWTP in the U.S. Total TCC and TCS concentrations decreased by >97% with about 79% of TCC and 64% of TCS transferred to the solids. The highest TCC and TCS removal rates from the liquid phase were reached in the primary treatment mainly though sorption and settling of solids. The TCC mass balances showed that TCC levels remain unchanged through the secondary treatment (activated sludge process) and about an 18% decrease was observed through the nitrification-denitrification process. On the other hand, TCS levels decreased in both processes (secondary and nitrification-denitrification) by 10.4 and 22.6%, respectively. The decrease in TCS levels associated with observed increased levels of MeTCS in secondary and nitrification-denitrification processes providing evidence of TCS biotransformation. Dissolved-phase concentrations of TCC and TCS remained constant during filtration and disinfection. TCC and TCS highest sludge concentrations were analyzed in the primary sludge (13.1 ± 0.9 μg g(-1) dry wt. for TCC and 20.3 ± 0.9 μg g(-1) dry wt. for TCS) but for MeTCS the highest concentrations were analyzed in the secondary sludge (0.25 ± 0.04 μg g(-1) dry wt.). Respective TCC, TCS and MeTCS concentrations of 4.15 ± 0.77; 5.37 ± 0.97 and 0.058 ± 0.003 kg d(-1) are leaving the WWTP with the sludge and 0.13 ± 0.01; 0.24 ± 0.07 and 0.021 ± 0.002 kg d(-1) with the effluent that is discharged.

Fate of triclosan in agricultural soils after biosolid applications

Triclosan (5-chloro-2-[2,4-dichloro-phenoxy]-phenol (TCS) is an antimicrobial compound that is added to a wide variety of household and personal care products. The consumer use of these products releases TCS into urban wastewater and this compound ends up in the environment when agricultural land is fertilized with wastewater biosolids. This study examines the occurrence of TCS in biosolids and its fate in biosolid-treated soils. TCS levels in biosolids generated from one repeatedly-sampled wastewater treatment plant averaged 15.6 + or - 0.6 mg kg(-1) dry wt. (mean + or - standard error) with a slight increase from 2005 to 2007. Surface soil samples were collected from several farms in northern Virginia, US that had received no biosolids, one biosolid application or multiple biosolid applications since 1992. Farm soils that received one application presented TCS concentrations between 4.1 and 4.5 ng g(-1) dry wt. when time since application was over 16 months and between 23.6 and 66.6 ng g(-1) dry wt. for farms where sampling time after application was less than a year. Our results suggest that TCS content of biosolids are rapidly dissipated (estimated half-life of 107.4 d) when applied to agricultural fields. Statistical differences were found (p<0.05) for residual build-up of TCS between multiple-application farms (at least 480 d after application) and controls suggesting that there was a slight build-up of TCS, although the concentrations for these farms were low (<10 ng g(-1) dry wt.).

Determination of alkylphenol and alkylphenolethoxylates in biota by liquid chromatography with detection by tandem mass spectrometry and fluorescence spectroscopy.

A quantitative method for the simultaneous determination of octylphenol, nonylphenol and the corresponding ethoxylates (1 to 5) in biota is presented. Extraction methods were developed for egg and fish matrices based on accelerated solvent extraction followed by a solid-phase extraction cleanup, using octadecylsilica or aminopropyl cartridges. Identification and quantitation were accomplished by liquid chromatography-electrospray tandem mass spectrometry (LC-MS-MS) and compared to the traditional liquid chromatography with fluorescence spectroscopy detection. LC-MS-MS provides high sensitivity and specificity required for these complex matrices and an accurate quantitation with the use of 13C-labeled internal standards. Quantitation limits by LC-MS-MS ranged from 4 to 12 ng/g in eggs, and from 6 to 22 ng/g in fish samples. These methods were successfully applied to osprey eggs from the Chesapeake Bay and fish from the Great Lakes area. Total levels found in osprey egg samples were up to 18 ng/g wet mass and as high as 8.2 microg/g wet mass in the fish samples.

Hydroxamic acid content and toxicity of rye at selected growth stages

Rye (Secale cereale L.) is an important cover crop that provides many benefits to cropping systems including weed and pest suppression resulting from allelopathic substances. Hydroxamic acids have been identified as allelopathic compounds in rye. This research was conducted to improve the methodology for quantifying hydroxamic acids and to determine the relationship between hydroxamic acid content and phytotoxicity of extracts of rye root and shoot tissue harvested at selected growth stages. Detection limits for an LC/MS-MS method for analysis of hydroxamic acids from crude aqueous extracts were better than have been reported previously. (2R)-2-β-d-Glucopyranosyloxy-4-hydroxy-(2H)-1,4-benzoxazin-3(4H)-one (DIBOA-G), 2,4-dihydroxy-(2H)-1,4-benzoxazin-3(4H)-one (DIBOA), benzoxazolin-2(3H)-one (BOA), and the methoxy-substituted form of these compounds, (2R)-2-β-d-glucopyranosyloxy-4-hydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA glucose), 2,4-hydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA), and 6-methoxy-benzoxazolin-2(3H)-one (MBOA), were all detected in rye tissue. DIBOA and BOA were prevalent in shoot tissue, whereas the methoxy-substituted compounds, DIMBOA glucose and MBOA, were prevalent in root tissue. Total hydroxamic acid concentration in rye tissue generally declined with age. Aqueous crude extracts of rye shoot tissue were more toxic than extracts of root tissue to lettuce (Lactuca sativa L.) and tomato (Lycopersicon esculentum Mill.) root length. Extracts of rye seedlings (Feekes growth stage 2) were most phytotoxic, but there was no pattern to the phytotoxicity of extracts of rye sampled at growth stages 4 to 10.5.4, and no correlation of hydroxamic acid content and phytotoxicity (I50 values). Analysis of dose–response model slope coefficients indicated a lack of parallelism among models for rye extracts from different growth stages, suggesting that phytotoxicity may be attributed to compounds with different modes of action at different stages. Hydroxamic acids may account for the phytoxicity of extracts derived from rye at early growth stages, but other compounds are probably responsible in later growth stages.

Endocrine disrupting alkylphenolic chemicals and other contaminants in wastewater treatment plant effluents, urban streams, and fish in the Great Lakes and Upper Mississippi River Regions

Urban streams are an integral part of the municipal water cycle and provide a point of discharge for wastewater treatment plant (WWTP) effluents, allowing additional attenuation through dilution and transformation processes, as well as a conduit for transporting contaminants to downstream water supplies. Domestic and commercial activities dispose of wastes down-the-drain, resulting in wastewater containing complex chemical mixtures that are only partially removed during treatment. A key issue associated with WWTP effluent discharge into streams is the potential to cause endocrine disruption in fish. This study provides a long-term (1999-2009) evaluation of the occurrence of alkylphenolic endocrine disrupting chemicals (EDCs) and other contaminants discharged from WWTPs into streams in the Great Lakes and Upper Mississippi River Regions (Indiana, Illinois, Michigan, Minnesota, and Ohio). The Greater Metropolitan Chicago Area Waterways, Illinois, were evaluated to determine contaminant concentrations in the major WWTP effluents and receiving streams, and assess the behavior of EDCs from their sources within the sewer collection system, through the major treatment unit processes at a WWTP, to their persistence and transport in the receiving stream. Water samples were analyzed for alkylphenolic EDCs and other contaminants, including 4-nonylphenol (NP), 4-nonylphenolpolyethoxylates (NPEO), 4-nonylphenolethoxycarboxylic acids (NPEC), 4-tert-octylphenol (OP), 4-tert-octylphenolpolyethoxylates (OPEO), bisphenol A, triclosan, ethylenediaminetetraacetic acid (EDTA), and trace elements. All of the compounds were detected in all of the WWTP effluents, with EDTA and NPEC having the greatest concentrations. The compounds also were detected in the WWTP effluent dominated rivers. Multiple fish species were collected from river and lake sites and analyzed for NP, NPEO, NPEC, OP, and OPEO. Whole-body fish tissue analysis indicated widespread occurrence of alkylphenolic compounds, with the highest concentrations occurring in streams with the greatest WWTP effluent content. Biomarkers of endocrine disruption in the fish indicated long-term exposure to estrogenic chemicals in the wastewater impacted urban waterways.

Fate of Triclosan and Methyltriclosan in soil from biosolids application.

This study investigates the persistence of Triclosan (TCS), and its degradation product, Methyltriclosan (MeTCS), after land application of biosolids to an experimental agricultural plot under both till and no till. Surface soil samples (n = 40) were collected several times over a three years period and sieved to remove biosolids. Concentration of TCS in the soil gradually increased with maximum levels of 63.7 ± 14.1 ng g(-1) dry wt., far below the predicted maximum concentration of 307.5 ng g(-1) dry wt. TCS disappearance corresponded with MeTCS appearance, suggesting in situ formation. Our results suggest that soil incorporation and degradation processes are taking place simultaneously and that TCS background levels are achieved within two years. TCS half-life (t(0.5)) was determined as 104 d and MeTCS t(0.5), which was more persistent than TCS, was estimated at 443 d.

Time trends (1983-1999) for organochlorines and polybrominated diphenyl ethers in rainbow smelt (Osmerus mordax) from Lakes Michigan, Huron, and Superior, USA.

The U.S. Geological Service Great Lakes Science Center has archived rainbow smelt (Osmerus mordax) collected from the early 1980s to the present. These fish were collected to provide time- and site-dependent contaminant residue data needed by researchers and managers to fill critical data gaps regarding trends and behavior of persistent organic contaminants in the Great Lakes ecosystem. In the present study, data are presented for concentrations of several organochlorine (OC) contaminants in the archived smelt, including DDT, polychlorinated biphenyls (PCBs), toxaphene, and chlordanes in Lakes Michigan and Huron (MI, USA) and in Lake Superior (MN, USA). The trends for all the OCs were declining as a first-order decay over the sampled time series (1983/1985-1993/1999) with the exception of toxaphene in Lake Superior and PCBs at the Charlevoix/Little Traverse Bay site in Lake Michigan. Concentration of the emerging contaminant, polybrominated diphenyl ethers (PBDEs), also was traced from its apparent entry into this ecosystem in approximately 1980 until 1999. Time trends for the PBDEs were increasing exponentially at all sites, with concentration-doubling times varying from 1.58 to 2.94 years.