Monitoring individual exposure. Measurements of volatile organic compounds in breathing-zone air, drinking water, and exhaled breath

Methods for determining individual exposure to volatile organic compounds (VOC) during normal daily activities were field tested on university student volunteers in Texas and North Carolina. The equipment tested included a personal monitor employing Tenax GC® to collect organic vapors for later analysis by GC-MS, and a specially designed spirometer for collecting samples of expired human breath on duplicate Tenax cartridges. The personal monitor and spirometer proved feasible for collecting abundant quantitative data on most of the 15 target organics. Air exposures to many VOC varied widely, sometimes over three orders of magnitude, among students on the same campus who had been monitored over the same time period and day. A log-linear relationship between breathing-zone air exposures and concentrations in exhaled breath was suggested for three chemicals: tetrachloroethylene, 1,1,1-trichloroethane, and vinylidene chloride. Air was the main route of exposure for all target compounds except the two trihalomethanes (chloroform and bromodichloromethane), which were transmitted mainly through water. Estimated total daily intake through air and water of the target organics ranged from 0.3 to 12.6 mg, with 1,1,1-trichloroethane at the highest concentrations in both geographic areas.     

Comparison of three sampling and analytical methods for the determination of airborne hexavalent chromium

A field study was conducted with the goal of comparing the performance of three recently developed or modified sampling and analytical methods for the determination of airborne hexavalent chromium (Cr(VI)). The study was carried out in a hard chrome electroplating facility and in a jet engine manufacturing facility where airborne Cr(VI) was expected to be present. The analytical methods evaluated included two laboratory-based procedures (OSHA Method ID-215 and NIOSH Method 7605) and a field-portable method (NIOSH Method 7703). These three methods employ an identical sampling methodology: collection of Cr(VI)-containing aerosol on a polyvinyl chloride (PVC) filter housed in a sampling cassette, which is connected to a personal sampling pump calibrated at an appropriate flow rate. The basis of the analytical methods for all three methods involves extraction of the PVC filter in alkaline buffer solution, chemical isolation of the Cr(VI) ion, complexation of the Cr(VI) ion with 1,5-diphenylcarbazide, and spectrometric measurement of the violet chromium diphenylcarbazone complex at 540 nm. However, there are notable specific differences within the sample preparation procedures used in three methods. To assess the comparability of the three measurement protocols, a total of 20 side-by-side air samples were collected, equally divided between a chromic acid electroplating operation and a spray paint operation where water soluble forms of Cr(VI) were used. A range of Cr(VI) concentrations from 0.6 to 960 microg m(-3), with Cr(VI) mass loadings ranging from 0.4 to 32 microg, was measured at the two operations. The equivalence of the means of the log-transformed Cr(VI) concentrations obtained from the different analytical methods was compared. Based on analysis of variance (ANOVA) results, no statistically significant differences were observed between mean values measured using each of the three methods. Small but statistically significant differences were observed between results obtained from performance evaluation samples for the NIOSH field method and the OSHA laboratory method.     

Toward a Practical Method for Setting Screening-Level, Ecological Risk-Based Water Temperature Criteria and Monitoring Compliance

We integrated basic concepts from fisheries science and toxicological risk assessment to form a potential method for setting screening-level, risk-based, site-specific water quality objectives for temperature. In summary, the proposed approach: (a) uses temperature impacts upon specific growth as a measure of chronic (cumulative) temperature effects; (b) explicitly incorporates the consequences of both magnitude and cumulative duration of exposures; (c) adjusts the result for local watershed conditions, reducing the likelihood that naturally warm systems are identified as thermally polluted while helping to ensure that naturally cool systems are closely monitored for ecologically harmful changes in thermal regime; and (d) expresses the net result both graphically and as a risk quotient, RQ, closely analogous to that used in toxicological risk assessments. The latter yields a site-specific, risk-based water quality objective and may serve as a straightforward decision rule for environmental managers. The method was applied to historical data from a small British Columbia stream subject to increasing urban development pressures. We also illustrate how the technique might be used to explore potential climatic change impacts, using coupled general circulation model predictions in conjunction with empirical downscaling. Overall, the method and results are presented as an introduction and illustration of concept, intended as a step toward the development of a logistically feasible risk-based approach to establishing screening-level, site-specific water temperature objectives, and monitoring compliance, in the context of large-scale, many-site, environmental monitoring networks. With further work, the technique offers potential to fill the gap between the temperature threshold-based targets typically specified in regulatory guidelines, which may be hydroecologically unrealistic, and detailed biophysical modelling, which typically is logistically infeasible in a day-to-day environmental monitoring and management context.     

Modelling temporal and spatial changes of PCBs in fish tissue from Lake Huron

A model has been developed to assess temporal and spatial changes in the concentration of polychlorinated biphenyl (PCB) contaminant in whole fish from Lake Huron during the years 1980 to 2004. The model uses log PCB concentration as the response variable and includes time trend, within-lake variability and dependence on age, weight and length as explanatory variables. A preliminary examination of the data revealed that some values are recorded as below detection limits (thus leading to the left censoring), and the PCB concentration appears to show declines in latter years. To this end, parametric log-location-scale regression models used in survival analysis were employed. It has been found that the Weibull model yields a better fit than the log-logistic or the log-normal models. The analysis provides strong evidence that, starting in 1996, the level of PCB concentration showed steady decline, which is most contributed by the Canadian and US governments?? actions carried out earlier to reduce the load of toxic contaminants to the Great Lakes. Spatially, fish from the north of the lake is less contaminated than fish from the south. The pattern and magnitude of the estimated spatial and temporal trends can provide useful information regarding the safety of fish consumption, the setting of regularity limits, the identifiability of PCB sources and the effects of remedial actions in the future. In addition, the developed model is not restricted to the current application but could be used for the analysis of other contaminants.     

Evaluation of wireless sensor networks (WSNs) for remote wetland monitoring: design and initial results

Here, we describe and evaluate two low-power wireless sensor networks (WSNs) designed to remotely monitor wetland hydrochemical dynamics over time scales ranging from minutes to decades. Each WSN (one student-built and one commercial) has multiple nodes to monitor water level, precipitation, evapotranspiration, temperature, and major solutes at user-defined time intervals. Both WSNs can be configured to report data in near real time via the internet. Based on deployments in two isolated wetlands, we report highly resolved water budgets, transient reversals of flow path, rates of transpiration from peatlands and the dynamics of chromophoric-dissolved organic matter and bulk ionic solutes (specific conductivity)—all on daily or subdaily time scales. Initial results indicate that direct precipitation and evapotranspiration dominate the hydrologic budget of both study wetlands, despite their relatively flat geomorphology and proximity to elevated uplands. Rates of transpiration from peatland sites were typically greater than evaporation from open waters but were more challenging to integrate spatially. Due to the high specific yield of peat, the hydrologic gradient between peatland and open water varied with precipitation events and intervening periods of dry out. The resultant flow path reversals implied that the flux of solutes across the riparian boundary varied over daily time scales. We conclude that WSNs can be deployed in remote wetland-dominated ecosystems at relatively low cost to assess the hydrochemical impacts of weather, climate, and other perturbations.     

Effective monitoring of agriculture: a response

The development of effective agricultural monitoring networks is essential to track, anticipate and manage changes in the social, economic and environmental aspects of agriculture. We welcome the perspective of Lindenmayer and Likens (J. Environ. Monit., 2011, 13, 1559) as published in the Journal of Environmental Monitoring on our earlier paper, "Monitoring the World's Agriculture" (Sachs et al., Nature, 2010, 466, 558-560). In this response, we address their three main critiques labeled as 'the passive approach', 'the problem with uniform metrics' and 'the problem with composite metrics'. We expand on specific research questions at the core of the network design, on the distinction between key universal and site-specific metrics to detect change over time and across scales, and on the need for composite metrics in decision-making. We believe that simultaneously measuring indicators of the three pillars of sustainability (environmentally sound, social responsible and economically viable) in an effectively integrated monitoring system will ultimately allow scientists and land managers alike to find solutions to the most pressing problems facing global food security.     

Hexavalent chromium reduction kinetics in rodent stomach contents

Reduction of hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)) in the stomach prior to absorption is a well-recognized detoxification process thought to limit the toxicity of ingested Cr(VI). However, administration of high concentrations of Cr(VI) in drinking water cause mouse small intestinal tumors, and quantitative measures of Cr(VI) reduction rate and capacity for rodent stomach contents are needed for interspecies extrapolation using physiologically-based toxicokinetic (PBTK) models. Ex vivo studies using stomach contents of rats and mice were conducted to quantify Cr(VI) reduction rate and capacity for loading rates (1-400 mg Cr(VI) L⁻¹ stomach contents) in the range of recent bioassays. Cr(VI) reduction was measured with speciated isotope dilution mass spectrometry to quantify dynamic Cr(VI) and Cr(III) concentrations in stomach contents at select time points over 1 h. Cr(VI) reduction followed mixed second-order kinetics, dependent upon concentrations of both Cr(VI) and the native reducing agents. Approximately 16 mg Cr(VI)-equivalents of reducing capacity per L of fed stomach contents (containing gastric secretions, saliva, water and food) was found for both species. The second-order rate constants were 0.2 and 0.3 L mg⁻¹ h⁻¹ for mice and rats, respectively. These findings support that, at the doses that caused cancer in the mouse small intestine (?20 mg Cr(VI) L⁻¹ in drinking water), the reducing capacity of stomach contents was likely exceeded. Thus, for extrapolation of target tissue dose in risk assessment, PBTK models are necessary to account for competing kinetic rates including second order capacity-limited reduction of Cr(VI) to Cr(III).     

Evaluation of Methods for Controlling Vehicular Exhaust

In late 1965 the Pennsylvania Air Pollution Commission appointed a Council of Technical Advisors to develop air quality criteria. Recently, this Council set forth its recommendations for ten pollutants. The philosophy of the Council is expressed. The major difficulties and rational are mentioned. The recommendations are given and the potential use of the criterion is also explained.     

Gamma aminobutyric acid radioreceptor‐assay a possible biomarker for human exposure to certain agrochemicals

Abstract

Cyclodiene insecticides, hexachlorocyclohexanes, pyrethroids, bicyclophosphates, the bicycloorthocarboxylate insecticides and some of their metabolites and environmental degradation products are central nervous system toxicants with high specific binding affinity to the chloride channel of the γ‐ aminobutyric acid (GABA)_A receptor‐ionophore sites. [³⁵S] tertiary‐butylbicyclophosphorothionate (TBPS) with specific activity higher than 60 Ci/mmole has a high binding affinity to the same sites and is now commercially available and can be used to label the GABA_A receptor for the development of a radioreceptor assay technique. The GABA receptor was prepared by ultra centnfugation and dialysis of brain homogenates of either cow, goat, rat or catfish. The receptor was then labeled with [³⁵S] TBPS and the assay was conducted by measuring the displacement of radioactivity following incubation with samples containing the analytes. A radioreceptor assay protocol was developed to measure the amount of the α‐endosulfan in blood samples. The assay was extremely sensitive, and can detect 0.2 nM of endosulfan at a level equivalent to 0.08 ppb or 8x10^‐11 gm of endosulfan in each ml of the blood samples.     

A microcomputer-based emergency response system*

A microcomputer-based system was developed to provide local officials responsible for disaster management with assistance during the crucial period immediately following a disaster, a period when incorrect decisions could have an adverse impact on the surrounding community.
While the paper focuses on a potential disaster resulting from an accident at a commercial nuclear power generating facility, the system can be applied to other disastrous situations. Decisions involving evacuation, shelter and the deployment of resources must be made in response to floods, earthquakes, accidents in the transportation of hazardous materials, and hurricanes to name a few examples.
As a decision aid, the system was designed to enhance data display by presenting the data in the form of representations (i.e. road maps, evacuation routes, etc.) as well as in list or tabular form. The potential impact of the event (i.e. the release of radioactive material) was displayed in the form of a cloud, representing the dispersion of the radioactive material. In addition, an algorithm was developed to assist the manager in assigning response resources to demands.
The capability for modelling the impact of a disaster is discussed briefly, with reference to a system installed in the communities surrounding the Indian Point nuclear power plant in New York State.
Results demonstrate both the technical feasibility of incorporating microcomputers indecision support systems for radiological emergency response, and the acceptance of such systems by those public officials responsible for implementing the response plans.