Application of the U.S. EPA Mode of Action Framework for Purposes of Guiding Future Research: A Case Study Involving the Oral Carcinogenicity of Hexavalent Chromium

Mode of action (MOA) analysis provides a systematic description of key events leading to adverse health effects in animal bioassays for the purpose of informing human health risk assessment. Uncertainties and data gaps identified in the MOA analysis may also be used to guide future research to improve understanding of the MOAs underlying a specific toxic response and foster development of toxicokinetic and toxicodynamic models. An MOA analysis, consistent with approaches outlined in the MOA Framework as described in the Guidelines for Carcinogen Risk Assessment, was conducted to evaluate small intestinal tumors observed in mice chronically exposed to relatively high concentrations of hexavalent chromium (Cr(VI)) in drinking water. Based on review of the literature, key events in the MOA are hypothesized to include saturation of the reductive capacity of the upper gastrointestinal tract, absorption of Cr(VI) into the intestinal epithelium, oxidative stress and inflammation, cell proliferation, direct and/or indirect DNA modification, and mutagenesis. Although available data generally support the plausibility of these key events, several unresolved questions and data gaps were identified, highlighting the need for obtaining critical toxicokinetic and toxicodynamic data in the target tissue and in the low-dose range. Experimental assays that can address these data gaps are discussed along with strategies for comparisons between responsive and nonresponsive tissues and species. This analysis provides a practical application of MOA Framework guidance and is instructive for the design of studies to improve upon the information available for quantitative risk assessment

Using Wind To Power a Groundwater Circulation Well—Preliminary Results

In areas of the country where the U.S. Department of Energy has classified the available wind resources as Class 3 or greater, the use of wind turbines to provide power to relatively small remediation systems such as groundwater circulation wells may be technically and economically feasible. Groundwater circulation wells are a good candidate technology to couple with renewable energy, because the remediation system removes contamination from the subject aquifer with no net loss of the groundwater resource, while the wind turbine does not create potentially harmful air emissions. Wind data collected in the vicinity of the former Nebraska Ordnance Plant Superfund site were used to select a wind turbine system to provide a portion of the energy necessary to power a groundwater circulation well located in an area of high trichloroethylene groundwater contamination. Because utility power was already installed at the remediation system, a 10 kW grid inter-tie wind turbine system supplements the utility system without requiring batteries for energy storage. The historical data from the site indicate that the quantity of energy purchased correlates poorly with the quantity of groundwater treated. Preliminary data from the wind turbine system indicate that the wind turbine provides more energy than the remediation system treatment components and the well submersible pump require on a monthly average. The preliminary results indicate that the coupling of wind turbines and groundwater circulation wells may be an attractive alternative in terms of the system operation time, cost savings, and contaminant mass removal

Haloalkane hydrolysis by Rhodococcus erythropolis cells: Comparison of conventional aqueous phase dehalogenation and nonconventional gas phase dehalogenation

Biofiltration of air polluted by volatile organic compounds is now recognized by the industrial and research communities as an effective and viable alternative to standard environmental technologies. Whereas many studies have focused on solid/liquid/gas biofilters, there have been fewer reports on waste air treatment using other biological processes, especially in a solid/gas biofilter. In this study, a comparison was made of the hydrolysis of halogenated compounds (such as 1-chlorobutane) by lyophilized Rhodococcus erythropolis cells in a novel solid/ gas biofilter and in the aqueous phase. We first determined the culture conditions for the production of R. erythropolis cells with a strong dehalogenase activity. Four different media were studied and the amount of 1-chlorobutane was optimized. Next, we report the possibility to use R. erythropolis cells in a solid/gas biofilter in order to transform halogenated compounds in corresponding alcohols. The effect of experimental parameters (total flow into the biofilter, thermodynamic activity of the substrates, temperature, carbon chain length of halogenated substrates) on the activity and stability of lyophilized cells in the gas phase was determined. A critical water thermodynamic activity (aw) of 0.4 is necessary for the enzyme to become active and optimal dehalogenase activity for the lyophilized cells is obtained for an aw of 0.9. A temperature of reaction of 40jC represents the best compromise between stability and activity. Activation energy of the reaction was determined and found equal to 59.5 KJ/mol. The pH effect on the dehalogenase activity of R. erythropolis cells was also studied in the gas phase and in the aqueous phase. It was observed that pH 9.0 provided the best activity in both systems. We observed that in the aqueous phase R. erythropolis cells were less sensitive to the variation in pH than R. erythropolis cells in the gas phase. Finally, the addition of volatile Lewis base (triethylamine) in the gaseous phase and the action of the lysozyme in order to permeabilize the cells was found to be highly beneficial to the effectiveness of the biofilter

Refinement of arsenic attributable health risks in rural Pakistan using population specific dietary intake values

Background: Previous risk assessment studies have often utilised generic consumption or intake values when evaluating ingestion exposure pathways. If these values do not accurately reflect the country or scenario in question, the resulting risk assessment will not provide a meaningful representation of cancer risks in that particular country/scenario. Objectives: This study sought to determine water and food intake parameters for one region in South Asia, rural Pakistan, and assess the role population specific intake parameters play in cancer risk assessment. Methods: A questionnaire was developed to collect data on sociodemographic features and 24-hour water and food consumption patterns from a rural community. The impact of dietary differences on cancer susceptibility linked to arsenic exposure was evaluated by calculating cancer risks using the data collected in the current study against standard water and food intake levels for the USA, Europe and Asia. A probabilistic cancer risk was performed for each set of intake values of this study. Results: Average daily total water intake based on drinking direct plain water and indirect water from food and beverages was found to be 3.5 L day-1 (95% CI: 3.38, 3.57) exceeding the US Environmental Protection Agency’s default (2.5 L day-1) and World Health Organization’s recommended intake value (2 L day-1). Average daily rice intake (469 g day-1) was found to be lower than in India and Bangladesh whereas wheat intake (402 g day−1) was higher than intake reported for USA, Europe and Asian sub-regions. Consequently, arsenic-associated cumulative cancer risks determined for daily water intake was found to be 17 in children of 3-6 years (95% CI: 0.0014, 0.0017), 14 in children of age 6-16 years (95% CI: 0.001, 0.0011) and 6 in adults of 16-67 years (95% CI: 0.0006, 0.0006) in a population size of 10000. This is higher than the risks estimated using the US Environmental Protection Agency and World Health Organization’s default recommended water intake levels. Rice intake data showed early life cumulative cancer risks of 15 in 10000 for children of 3-6 years (95% CI: 0.0012, 0.0015), 14 in children of 6-16 years (95% CI: 0.0011, 0.0014) and later life risk of 8 in adults (95% CI: 0.0008, 0.0008) in a population of 10000. This is lower than cancer risks in countries with higher rice intake and elevated arsenic levels (Bangladesh and India). Cumulative cancer risk from arsenic exposure showed the relative risk contribution from total water to be51%, from rice to be44% and wheat intake 5%. Conclusions: The study demonstrates the need to use population specific dietary information for risk assessment and risk management studies. Probabilistic risk assessment concluded the importance of dietary intake in estimating cancer risk, along with arsenic concentrations in water or food and age of exposed rural population

Urbanisation Alters Fatty Acids in Stream Food Webs

Fatty acids are essential to macroinvertebrate growth and reproduction and can indicate food web structure and nutritional quality of basal resources. However, broad‐scale examinations of how catchment land cover and associated stressors affect the proportions of fatty acids (FAs) in stream food webs are few. Here, we: (1) examine relationships among proportions of FAs among benthic periphyton and macroinvertebrate collector/gatherers, shredders, and predators; and (2) test if relationships between periphytic and macroinvertebrate FAs were altered due to the intensity of urban development in catchments. Proportions of the ≥20‐C eicosapentaenoic acid (EPA 20:5ω3), arachidonic acid (ARA 20:4ω6), and docosahexaenoic acid (22:6ω3) indicated collector/gatherers had a diet richer in periphyton than in shredders, which had significantly lower proportions of these FAs. Collector/gatherers were in turn likely to be high‐quality sources of ω3 and ≥ 20‐C FAs for predators, which also had significantly greater EPA and ARA proportions than those in shredders. Linoleic (18:2ω6) and α‐linolenic acid (18:3ω3) comprised the greatest proportions of FAs in shredders, which suggested a diet dominated by leaf litter and associated hyphomycetes. As catchment urbanisation increased, proportions of total ω3 FAs and EPA in periphyton were significantly greater. This pattern also was seen through macroinvertebrate consumers and predators, given that proportions of these FAs in macroinvertebrates also were significantly correlated with factors associated with catchment urbanisation. The significant increase in total ω3 FAs and EPA proportions within shredders indicated that periphyton growth, and their FAs, increased on leaf litter, probably due to greater nutrient concentrations associated with catchment urbanisation. Proportions of total ω6 FAs in biota were not significantly correlated with factors associated with urban development, which could indicate that they were of sufficient abundance for consumers regardless of urban intensity or possible changes in their sources. Our study provides an informative first step that identified notable differences in proportions of FAs among macroinvertebrates in urban streams and an increase in proportions of total ω3 FAs and EPA in periphyton, consumers, and predators as catchment urbanisation increases. Identifying how FA relationships within food webs change in response to catchment alterations and stressors could inform land use and management decisions by linking environmental changes to measures important to ecosystem outcomes

Vacuum-assisted sorbent extraction: An analytical methodology for the determination of ultraviolet filters in environmental samples

Vacuum-assisted sorbent extraction (VASE) has been applied for the first time in the determination of UV filters in water samples in combination with gas chromatography-mass spectrometry. VASE is a variant of headspace extraction which was developed in conjunction with the sorbent pen (SP) technology. This technique combines the advantages of both stir-bar assisted extraction and headspace solid-phase microextraction. The SP traps allowed both reduced pressure in-vial extraction and direct thermal desorption via a unique gas chromatographic injection port. The main parameters that affect the performance of VASE, including both extraction and desorption conditions, were extensively optimized. Under optimum conditions, extraction required 10 mL of sample within 40 mL vials, pH 3.5, ∼30 s of air-evacuation, 14 h incubation at 70 °C, stirring at 200 rpm, and a final water management step conducted at ∼ −17 °C for 15 min. Optimal thermal desorption required preheating at 260 °C for 2 min followed by desorption at 300 °C for 2 min. The beneficial effect of reduced-pressure extraction was demonstrated by comparing the UV filter extraction time profiles collected using VASE to an analogous atmospheric pressure procedure, resulting in up to a 3-fold improvement under optimized conditions. The VASE methodology enabled simultaneous extractions using different SPs without compromising the method reproducibility, which increases the overall sample throughput. The method was characterized by low limits of detection, from 0.5 to 80 ng L−1, and adequate reproducibility, with inter-SP and inter-day relative standard deviation lower than 14%. Tap and lake water was successfully analyzed with the proposed methodology, resulting in relative recoveries of spiked samples ranging between 70.0 and 120%