Use of SOFEA to predict 1,3-D concentrations in air in high-use regions of California

Methyl bromide, a commonly used soil fumigant, is being phased out per the Montreal Protocol and multiple fumigants are being positioned as replacements. Most effective soil fumigants, including methyl bromide, have the potential for inhalation exposure if the material volatilizes from soil. Chronic exposures for the fumigant 1,3-dichloropropene (1,3-D) are managed in part by the California Department of Pesticide Regulation by limiting the annual amount that can be used within a given township. A stochastic/deterministic numerical system (SOil Fumigant Exposure Assessment system [SOFEA]) was developed using the USEPA air dispersion model ISCST3, field study observations for flux loss, and links to Geographic Information Systems (GIS). SOFEA was used retrospectively to simulate concentrations of 1,3-D in air for direct comparison with monitoring program observations conducted by California Air Resources Board in Fresno County. These results indicated slight overprediction but correct magnitudes for regional air concentrations, especially at the higher percentiles, and provide a performance test. SOFEA was also used, prospectively, to predict air concentrations in potential future-use scenarios. These simulations of chronic air concentrations in two high-use 1,3-D counties of California (Ventura, Merced) consisted of 25 contiguous townships treated either at 1.5 times the current township allocation (40,937 kg) or at the maximum levels of 1,3-D used between 1999 and 2006. Exposure predictions for large regions are necessary to evaluate chronic population-based lifetime exposure and risk to 1,3-D should use patterns change. SOFEA provides a tool to estimate regional air concentrations within high-use areas required for such risk assessments.     

Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

High resolution direct-push profiling over short vertical distances was used to investigate CH(4) attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH(4) and CO(2), and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in δ(13)C(CH4) from an average of -57.6‰ (±1.7‰) in the methanogenic zone to -39.6‰ (±8.7‰) at 105m downgradient, strongly suggest CH(4) attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5m below the water table suggesting that transport of O(2) across the water table is leading to aerobic degradation of CH(4) at this interface. Dissolved N(2) concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O(2) through aerobic degradation of CH(4) or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O(2) rich recharge water were important O(2) transport mechanisms.     

Chemical contamination of the Rybinsk Reservoir, northwest Russia: relationship between liver polychlorinated biphenyls (PCB) content and health indicators in bream (Abramis brama)

The Rybinsk Reservoir (Russia) is the largest artificial waterbody in Europe (4550 km2) and provides drinking water for population of the cities located along the coast line. Industrialization in Cherepovets at the northeastern portion of the reservoir, including one of the largest metallurgical facilities in Europe, has resulted in chemical contamination of the reservoir. The extent of polychlorinated biphenyls (PCB) contamination in bream liver, a common fish species, taken from six locations in the Rybinsk Reservoir and Volga River, and biochemical and morphometric biomarkers of fish health were investigated. Liver PCB concentrations ranged from non-detected to 3.4 microg/g wet wt of liver, with the greatest concentrations found in fish taken near the industrialized area in Sheksna Reach of Rybinsk Reservoir. The source of the bream contamination is the PCB pollution of bottom organisms and sediments conditioned with industrialization facilities of Cherepovets. The patterns of the PCB congeners in the livers of bream taken near Cherepovets were similar at all of the stations that were sampled around the reservoir and Volga River. Among the common fish health biomarkers used only liver total ChE activity and liver-somatic index in bream near Cherepovets can reflect environmental pollution. Other morphometric (FCF, Clark's condition factors, and spleen-somatic index) and biochemical (protein content and acetylcholinesterase activity in the brain) biomarkers related with fish health varied among locations, but were not correlated to the concentrations of PCBs in the bream livers.     

Inverse modeling of BTEX dissolution and biodegradation at the Bemidji, MN crude-oil spill site

The U.S. Geological Survey (USGS) solute transport and biodegradation code BIOMOC was used in conjunction with the USGS universal inverse modeling code UCODE to quantify field-scale hydrocarbon dissolution and biodegradation at the USGS Toxic Substances Hydrology Program crude-oil spill research site located near Bemidji, MN. This inverse modeling effort used the extensive historical data compiled at the Bemidji site from 1986 to 1997 and incorporated a multicomponent transport and biodegradation model. Inverse modeling was successful when coupled transport and degradation processes were incorporated into the model and a single dissolution rate coefficient was used for all BTEX components. Assuming a stationary oil body, we simulated benzene, toluene, ethylbenzene, m,p-xylene, and o-xylene (BTEX) concentrations in the oil and ground water, respectively, as well as dissolved oxygen. Dissolution from the oil phase and aerobic and anaerobic degradation processes were represented. The parameters estimated were the recharge rate, hydraulic conductivity, dissolution rate coefficient, individual first-order BTEX anaerobic degradation rates, and transverse dispersivity. Results were similar for simulations obtained using several alternative conceptual models of the hydrologic system and biodegradation processes. The dissolved BTEX concentration data were not sufficient to discriminate between these conceptual models. The calibrated simulations reproduced the general large-scale evolution of the plume, but did not reproduce the observed small-scale spatial and temporal variability in concentrations. The estimated anaerobic biodegradation rates for toluene and o-xylene were greater than the dissolution rate coefficient. However, the estimated anaerobic biodegradation rates for benzene, ethylbenzene, and m,p-xylene were less than the dissolution rate coefficient. The calibrated model was used to determine the BTEX mass balance in the oil body and groundwater plume. Dissolution from the oil body was greatest for compounds with large effective solubilities (benzene) and with large degradation rates (toluene and o-xylene). Anaerobic degradation removed 77% of the BTEX that dissolved into the water phase and aerobic degradation removed 17%. Although goodness-of-fit measures for the alternative conceptual models were not significantly different, predictions made with the models were quite variable.     

The effects of organotin on female gastropods

Female masculinisation (FM) in gastropods (imposex, intersex and ovo-testis) has been documented in > 260 species globally. Biomonitoring studies use FM to indirectly assess the presence of tributyltin (TBT), a once popular biocide in antifouling paint, which has since been regulated. Laboratory studies confirm that FM in gastropods can be induced not only by TBT, but other tin (Sn) compounds, Sn "cocktails", steroids, and other contaminants such as Aroclor 1260. Even though FM in gastropods in the field has been attributed to TBT from boating activity, there is evidence that imposex occurred prior to the advent use of TBT in the 1960s, and for some species imposex occurs naturally. There are roughly 42 species that do not elicit a FM response even if they are exposed to TBT under laboratory conditions, collected sympatrically with other species displaying FM, and/or have TBT in their tissues. A geographic analysis of field studies in four regions indicates that the bulk of studies were conducted in Europe > Asia and Oceania > North America > Latin America. More data are needed regarding FM in Africa, the Middle East, and Latin America since data regarding the masculinisation of female gastropods in these areas are lacking. The most studied gastropod species used in TBT biomonitoring studies is the dogwhelk, Nucella lapillus. This review summarizes the progression of the literature from 1962 to 2009 outlining how the terminology, science, and theories have evolved over time.     

Ambient site, home outdoor and home indoor particulate concentrations as proxies of personal exposures

Despite strong longitudinal associations between particle personal exposures and ambient concentrations, previous studies have found considerable inter-personal variability in these associations. Factors contributing to this inter-personal variability are important to identify in order to improve our ability to assess particulate exposures for individuals. This paper examines whether ambient, home outdoor and home indoor particle concentrations can be used as proxies of corresponding personal exposures. We explore the strength of the associations between personal, home indoor, home outdoor and central outdoor monitoring site ("ambient site") concentrations of sulfate, fine particle mass (PM(2.5)) and elemental carbon (EC) by season and subject for 25 individuals living in the Boston, MA, USA area. Ambient sulfate concentrations accounted for approximately 70 to 80% of the variability in personal and indoor sulfate levels. Correlations between ambient and personal sulfate, however, varied by subject (0.1-1.0), with associations between personal and outdoor sulfate concentrations generally mirroring personal-ambient associations (median subject-specific correlations of 0.8 to 0.9). Ambient sulfate concentrations are good indicators of personal exposures for individuals living in the Boston area, even though their levels may differ from actual personal exposures. The strong associations for sulfate indicate that ambient concentrations and housing characteristics are the driving factors determining personal sulfate exposures. Ambient PM(2.5) and EC concentrations were more weakly associated with corresponding personal and indoor levels, as compared to sulfate. For EC and PM(2.5), local traffic, indoor sources and/or personal activities can significantly weaken associations with ambient concentrations. Infiltration was shown to impact the ability of ambient concentrations to reflect exposures with higher exposures to particles from ambient sources during summer. In contrast in the winter, lower infiltration can result in a greater contribution of indoor sources to PM(2.5) and EC exposures. Placing EC monitors closer to participants' homes may reduce exposure error in epidemiological studies of traffic-related particles, but this reduction in exposure error may be greater in winter than summer. It should be noted that approximately 20% of the EC data were below the field limit of detection, making it difficult to determine if the weaker associations with the central site for EC were merely a result of methodological limitations.     

Effects of pre-exposure to ultraviolet-B radiation on responses of tomato (Lycopersicon esculentum cv. New Yorker) to ozone in ambient and elevated carbon dioxide

Patterns of environmental change in the biosphere include concurrent and sequential combinations of increasing ultraviolet (UV-B) and ozone (O(3)) at increasing carbon dioxide (CO(2)) levels; long-term changes are resulting mainly from stratospheric O(3) depletion, greater tropospheric O(3) photochemical synthesis, and increasing CO(2) emissions. Effects of selected combinations were evaluated in tomato (Lycopersicon esculentum cv. New Yorker) seedlings using sequential exposures to enhanced UV-B radiation and O(3) in differential CO(2) concentrations. Ambient (7.2 kJ m(-2 )day(-1)) or enhanced (13.1 kJ m(-2) day(-1)) UV-B fluences and ambient (380 microl l(-1)) or elevated (600 microl l(-1)) CO(2) were imposed for 19 days before exposure to 3-day simulated O(3) episodes with peak concentrations of 0.00, 0.08, 0.16 or 0.24 microl l(-1) O(3) in ambient or elevated CO(2). CO(2) enrichment increased dry mass, leaf area, specific leaf weight, chlorophyll concentration and UV-absorbing compounds per unit leaf area. Exposure to enhanced UV-B increased leaf chlorophyll and UV-absorbing compounds but decreased leaf area and root/shoot ratio. O(3) exposure generally inhibited growth and leaf photosynthesis and did not affect UV-absorbing compounds. The highest dose of O(3) eliminated the stimulating effect of CO(2) enrichment after ambient UV-B pre-exposure on leaf photosynthesis. Pre-exposure to enhanced UV-B mitigated O(3) damage to leaf photosynthesis at elevated CO(2).     

The effects of pruning and nodal adventitious roots on polychlorinated biphenyl uptake by Cucurbita pepo grown in field conditions

Two cultivation techniques (i-pruning and ii-nodal adventitious root encouragement) were investigated for their ability to increase PCB phytoextraction by Cucurbita pepo ssp pepo cv. Howden (pumpkin) plants in situ at a contaminated industrial site in Ontario (Aroclor 1248, mean soil [PCB] = 5.6 μg g⁻¹). Pruning was implemented to increase plant biomass close to the root where PCB concentration is known to be highest. This treatment was found to have no effect on final shoot biomass or PCB concentration. However, material pruned from the plant is not included in the final shoot biomass. The encouragement of nodal adventitious roots at stem nodes did significantly increase the PCB concentration in the primary stem, while not affecting shoot biomass. Both techniques are easily applied cultivation practices that may be implemented to decrease phytoextraction treatment time.     

Biomagnetic monitoring of industry-derived particulate pollution

Clear association exists between ambient PM₁₀ concentrations and adverse health outcomes. However, determination of the strength of associations between exposure and illness is limited by low spatial-resolution of particulate concentration measurements. Conventional fixed monitoring stations provide high temporal-resolution data, but cannot capture fine-scale spatial variations. Here we examine the utility of biomagnetic monitoring for spatial mapping of PM₁₀ concentrations around a major industrial site. We combine leaf magnetic measurements with co-located PM₁₀ measurements to achieve inter-calibration. Comparison of the leaf-calculated and measured PM₁₀ concentrations with PM₁₀ predictions from a widely-used atmospheric dispersion model indicates that modelling of stack emissions alone substantially under-predicts ambient PM₁₀ concentrations in parts of the study area. Some of this discrepancy might be attributable to fugitive emissions from the industrial site. The composition of the magnetic particulates from vehicle and industry-derived sources differ, indicating the potential of magnetic techniques for source attribution.     

Calibration of sharp cut impactors for indoor and outdoor particle sampling

A low-flow rate, sharp cut point inertial impaction sampler was developed in 1986 that has been widely used in PM exposure studies in the United States and several other countries. Although sold commercially as the MS&T Area Sampler, this sampler is widely referred to as the Harvard Impactor, since the initial use was at the Harvard School of Public Health. Impactor nozzles for this sampler have been designed and characterized for flows of 4, 10, 20, and 23 L/min and cut points of 1, 2, 5, and 10 microns. An improved method for determining the actual collecting efficiency curve was developed and used for the recent impactor calibrations reported here. It consists of placing a multiplet reduction impactor inline just downstream of the vibrating orifice aerosol generator to remove the multiplets, thus allowing only the singlet particle s to penetrate through to the impactor being calibrated This paper documents the techniques and results of recent nozzle calibrations for this sampler and compares it with other size-selective inertial impactors. In general, the impactors were found to have sharp cutoff characteristics. Particle interstage losses for all of the impactors were very low, with the exception of the 10-micron cut size 20 L/min impactor, which had greater losses due to the higher flow rate. All of the 2.5-micron cut nozzle laboratory calibrations compare favorably to the U.S. Environmental Protection Agency (EPA) WINS-96 fine particle mass (PM2.5) impactor calibration data.