Contaminant exposure in terrestrial vertebrates

Here we review mechanisms and factors influencing contaminant exposure among terrestrial vertebrate wildlife. There exists a complex mixture of biotic and abiotic factors that dictate potential for contaminant exposure among terrestrial and semi-terrestrial vertebrates. Chemical fate and transport in the environment determine contaminant bioaccessibility. Species-specific natural history characteristics and behavioral traits then play significant roles in the likelihood that exposure pathways, from source to receptor, are complete. Detailed knowledge of natural history traits of receptors considered in conjunction with the knowledge of contaminant behavior and distribution on a site are critical when assessing and quantifying exposure. We review limitations in our understanding of elements of exposure and the unique aspects of exposure associated with terrestrial and semi-terrestrial taxa. We provide insight on taxa-specific traits that contribute, or limit exposure to, transport phenomenon that influence exposure throughout terrestrial systems, novel contaminants, bioavailability, exposure data analysis, and uncertainty associated with exposure in wildlife risk assessments. Lastly, we identify areas related to exposure among terrestrial and semi-terrestrial organisms that warrant additional research.     

Effect of chelating agents and solubility of cadmium complexes on uptake from soil by Brassica juncea

Brassica juncea, or Indian mustard, was grown in soil artificially contaminated with either a soluble salt, CdCl(2), at 186mg Cdkg(-1), or alternately an insoluble, basic salt, CdCO(3), at 90mg Cdkg(-1). These experiments study the range of Cd uptake by Indian mustard from conditions of very high Cd concentration in a soluble form to the other extreme with an insoluble Cd salt. After plants were established, four different chelating agents were applied. Chelating agents increased plant uptake of Cd from the CdCl(2) soil but did not significantly increase plant uptake of Cd from the CdCO(3) contaminated soil. Addition of ethylenediaminetetraacetic acid (EDTA) increased the plant concentration of Cd by almost 10-fold in soils contaminated with CdCl(2), with a concentration of 1283mg Cdkg(-1) in the dried EDTA-treated plants over a concentration of 131mg Cdkg(-1) in plants without added chelate. However, EDTA increased the aqueous solubility of Cd by 36 times over the soil matrix without added chelator, and thereby, increased the possibility of leaching. Other chelators used in both experiments were ethylenebis(oxyethylenenitrilo)tetraacetic acid, trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, and diethylenetriaminepentaacetic acid (DTPA) increasing Cd in plants to 1240, 962, and 437mg Cdkg(-1), respectively. The other chelating agents increased the solubility of Cd in the leachate but not to the extent of EDTA. Comparing all chelating agents studied, DTPA increased plant uptake in terms of Cd in dried plant concentration most relative to the solubility of complexed Cd in runoff water.     

Using environmental analytical data to estimate levels of community consumption of illicit drugs and abused pharmaceuticals

A solid phase extraction (SPE) method has been developed and applied in conjunction with a previously reported liquid chromatography tandem mass spectrometry (LC-MS-MS) procedure for the determination of illicit drugs and abused pharmaceuticals in treated wastewater and surface water samples at the ng L(-1) level. A full method validation was also performed and determined levels of analytical sensitivity were found to lie in the 1-10 ng L(-1) range using river water as a test sample matrix and a sample size of 500 mL. The developed procedure was successfully applied for the determination of the chosen analytes in wastewater treatment plants in Dublin, Ireland and rapidly expanding commuter towns in the surrounding counties. Cocaine was detected in 70% of the collected samples in the range of 25-489 ng L(-1), its primary metabolite, benzoylecognine (BZE) was also detected in the range of 22-290 ng L(-1). Other substances detected included morphine, Tempazepam and the primary metabolite of methadone.     

Source to sink tracking of selected human pharmaceuticals from two Oslo city hospitals and a wastewater treatment works

The occurrence of twenty pharmaceutical compounds was quantitatively determined in effluents from two major Oslo city hospitals, Rikshospitalet and Ullev?l, along with influent, sludge and final effluent from the city's VEAS wastewater treatment works (WTW). Composite hospital effluents were collected over a twelve week period and were showed to contain paracetamol, metoprolol, diclofenac, ibuprofen, 17beta-Estradiol, estriol, estrone, oxytetracycline, tetracycline, doxycycline, chlorotetracycline, demeclocycline, trimethoprim, ciprofloxacin, sulfamethoxazole, cyclophosphamide and ifosfamide. Three pharmaceuticals were not detected above the limit of detection; cefuroxime, 17alpha-ethinylestradiol and meclocycline. Composite influent, sludge and effluent samples were collected from VEAS WTW over a seven week period. The influent into VEAS WTW contained all of the same selected substances detected in the hospital effluents, except for oxytetracycline, chlorotetracycline, demeclocycline, cyclophosphamide and ifosfamide. The percentage of pharmaceuticals entering the works from the hospitals was <10% for all of the selected compounds. VEAS sludge samples contained a different profile of substances reflecting their physico-chemical properties. Hydrophobic antibiotics, such as oxytetracycline, tetracycline and ciprofloxacin, were detected in all of the collected sludge samples. Their absence in the collected influent samples suggests that they enter the works bound to effluent particles, with the dissolved fraction observed in the hospital effluents partitioning onto particulate matter within the sewerage network. The final effluent from VEAS WTW contained reduced concentrations of many pharmaceuticals, including paracetamol, ibuprofen and sulfamethoxazole. For other compounds, such as metoprolol, diclofenac and trimethoprim, there were often higher concentrations in the effluent than the influent. These effluent concentrations represent median inputs varying from low g day(-1) (e.g. paracetamol and ibuprofen) to nearly 200 g day(-1) (e.g. metoprolol and trimethoprim) into Oslofjord. A simple risk assessment showed that the antibiotic ciprofloxacin may at times pose an acute risk to the Oslofjord aquatic environment.     

Coupling GIS and mulitvariate approaches to reference site selection for wadeable stream monitoring

Geographic Information System (GIS) was used to identify potential reference sites for wadeable stream monitoring, and multivariate analyses were applied to test whether invertebrate communities reflected a priori spatial and stream type classifications. We identified potential reference sites in segments with unmodified vegetation cover adjacent to the stream and in >85% of the upstream catchment. We then used various landcover, amenity and environmental impact databases to eliminate sites that had potential anthropogenic influences upstream and that fell into a range of access classes. Each site identified by this process was coded by four dominant stream classes and seven zones, and 119 candidate sites were randomly selected for follow-up assessment. This process yielded 16 sites conforming to reference site criteria using a conditional-probabilistic design, and these were augmented by an additional 14 existing or special interest reference sites. Non-metric multidimensional scaling (NMS) analysis of percent abundance invertebrate data indicated significant differences in community composition among some of the zones and stream classes identified a priori providing qualified support for this framework in reference site selection. NMS analysis of a range standardised condition and diversity metrics derived from the invertebrate data indicated a core set of 26 closely related sites, and four outliers that were considered atypical of reference site conditions and subsequently dropped from the network. Use of GIS linked to stream typology, available spatial databases and aerial photography greatly enhanced the objectivity and efficiency of reference site selection. The multi-metric ordination approach reduced variability among stream types and bias associated with non-random site selection, and provided an effective way to identify representative reference sites.     

Dehalogenation of polychlorinated biphenyls and polybrominated diphenyl ethers using a hybrid bioinorganic catalyst

The environmentally prevalent polybrominated diphenyl ether (PBDE) #47 and polychlorinated biphenyls (PCBs) #28 and #118 were challenged for 24 hours with a novel biomass-supported Pd catalyst (Bio-Pd(0)). Analysis of the products via GC-MS revealed the Bio-Pd(0) to cause the challenged compounds to undergo stepwise dehalogenation with preferential loss of the least sterically hindered halogen atom. A mass balance for PCB #28 showed that it is degraded to three dichlorobiphenyls (33.9%), two monochlorobiphenyls (12%), and biphenyl (30.7%). The remaining mass was starting material. In contrast, while PCB #118 underwent degradation to yield five tetra- and five trichlorinated biphenyls, no less chlorinated products or biphenyl were detected, and the total mass of degraded products was 0.3%. Although the Bio-Pd(0) material was developed for treatment of PCBs, a mass balance for PBDE #47 showed that the biocatalyst could prove a potentially useful method for treatment of PBDEs. Specifically, 10% of PBDE #47 was converted to identifiable lower brominated congeners, predominantly the tribrominated PBDE #17 and the dibrominated PBDE #4, 75% remained intact, while 15% of the starting mass was unaccounted for.     

Trends analysis of ambient 8 hour ozone and precursor monitoring data in the south central U.S

For the south central U.S., lower tropospheric ozone pollution has been a persistent and challenging problem. This paper provides long-term trends analyses of the ozone and precursor monitoring data collected over the past 20 years in four south central U.S. cities. The results of these analyses should be useful to air quality scientists, managers, planners, and modelers in assessing the effectiveness of ozone pollution control strategies being implemented or being planned for the future. Results of the data analyses show that all areas have monitored significant decreases in ozone and precursor concentrations over the past 20 years, especially in El Paso, Texas. Continuing challenges include the reduction of the percentage of time that monitors record 8 hour ozone concentrations over the U.S. 8 hour ozone standard, and the future control of highly reactive volatile organic compounds.     

Drinking water risk assessment in practice: the case of Swedish drinking water producers at risk from floods

To achieve a safe and reliable drinking water supply, water producers need to manage a large range of risks regarding both water quality and quantity. A risk management approach where risks are systematically identified and handled in a preventive manner is promoted by the World Health Organization and supported by researchers and drinking water experts worldwide. Risk assessment is an important part of such a management approach, and a variety of tools for risk assessment are described in the literature. There is, however, little knowledge of how drinking water risk assessment is performed in practice, including which tools that are actually used. This study investigates the use of risk assessment tools, and the approach to risk management, on a local level in the Swedish water sector. It is based on interviews with key persons from a targeted selection of water producers. We find that the application of tools as well as the approach to risk assessment and management differs considerably between the water producers. The tools most frequently used are mainly the ones promoted or required by Swedish national organizations. Although many of the water producers have done some kind of risk assessment, most have not implemented a risk management approach. Furthermore, their knowledge of the concepts of risk and risk management is often limited. The largest challenge identified is to prioritize risk assessment, so that it is actually performed and then used as a basis for managing risk in a systematic way.     

Fatty acids composition of Caenorhabditis elegans using accurate mass GCMS-QTOF

The free living nematode Caenorhabditis elegans is a proven model organism for lipid metabolism research. Total lipids of C. elegans were extracted using chloroform and methanol in 2:1 ratio (v/v). Fatty acids composition of the extracted total lipids was converted to their corresponding fatty acids methyl esters (FAMEs) and analyzed by gas chromatography/accurate mass quadrupole time of flight mass spectrometry using both electron ionization and chemical ionization techniques. Twenty-eight fatty acids consisting of 12 to 22 carbon atoms were identified, 65% of them were unsaturated. Fatty acids containing 12 to17 carbons were mostly saturated with stearic acid (18:0) as the major constituent. Several branched-chain fatty acids were identified. Methyl-14-methylhexadecanoate (iso- 17:0) was the major identified branched fatty acid. This is the first report to detect the intact molecular parent ions of the identified fatty acids in C. elegans using chemical ionization compared to electron ionization which produced fragmentations of the FAMEs.     

Factors affecting TCLP lead leachability from computer CPUs

The factors impacting lead leachability from computer central processing units (CPUs) during the toxicity characteristic leaching procedure (TCLP) were investigated. Several CPUs were disassembled and their component materials were decreased in size to meet the requirements of the TCLP. The impact of CPU composition was examined by leaching different combinations of the CPU components. The ferrous metal content of the mixture greatly impacted lead leaching. TCLP lead concentrations of CPUs predicted by leaching the lead-bearing printed wire boards alone were much greater than those measured when the ferrous metal of the CPU was included in the mixture. The leaching of iron and zinc from the galvanized steel components of the CPU created electrochemical conditions where lead was less soluble. Additional size reduction beyond that required by the TCLP did not result in additional lead leaching. As the volume of head space above the leaching solution increased, the concentration of lead measured increased as well.