Evaluation of geochemical associations as a screening tool for identifying anthropogenic trace metal contamination

Geochemical association plots are used as a screening tool for environmental site assessments and use empirical log–log relationships between total trace metal concentrations and concentrations of a major (i.e., reference) soil metal constituent, such as iron (Fe), to discern sites with naturally elevated trace metal levels from sites with anthropogenic contamination. Log–log relationships have been consistently observed between trace metal and reference metal concentrations and are often considered constant. Consequently, we used a regional geochemistry data set to evaluate background trace metal/Fe log–log associations across soils with highly diverse composition. Our results indicate that, although geochemical associations may be proportional, they significantly differ across predominant United States Department of Agriculture (USDA) soil orders. This suggests that highly complex interactions between soil-forming factors and variable secondary clay mineral composition affect the ratio of trace metals to Fe concentrations in soils. Also, intra-order variability in trace metal/Fe ratios generally ranged multiple orders of magnitude which suggest that the order level of the USDA soil taxonomic system is insufficient to reasonably classify background trace metal concentrations. Consequently, geochemical association plots are a useful screening tool for environmental site assessments, but ubiquitous application of generic background metal data sets could result in erroneous conclusions. Because significantly different ratios were observed across predominant USDA soil orders, an agglomerative clustering technique was used to elucidate hierarchical patterns of association. We present these results as a mechanism to aid environmental assessors in screening candidate background metal data sets for their applicability to site-specific soil composition; although site-specific background metal data should be utilized if ample pristine reference sites with similar (i.e., sub-order) soil composition can be identified and sampled.     

Relating Background NO2 Concentrations in Air to Air Mass History Using Non-Parametric Regression Methods: Application at Two Background Sites in Ireland

The concentration of nitrogen dioxide (NO₂) in background air varies temporally and spatially and is influenced by meteorological and anthropogenic factors. Background concentrations used in local air quality modelling studies have a significant effect on the accuracy of the overall result and when based on short-term monitoring data, variation in concentrations with air mass history is often unaccounted for. The current paper presents a powerful tool for the quantification and separation of local and regional air mass effects on background air quality. The origin of and the regions traversed by an air mass prior to reaching a receptor has been modelled using HYsplit-4. Trajectories (between 12 and 96?h duration) were defined based on the frequency with which they passed into 16 predefined compass quadrants and each represented as a vector. Using this vector as the predictor variable and the background concentration as the response variable, non-parametric regression using a Gaussian kernel function was carried out. A graphical output indicated the trajectory direction of maximum NO₂ concentration, while allowing distinction to be made between spurious and true peaks. In all cases, air mass history was found to have a statistically significant effect on NO₂ concentrations. Incorporating emissions data into the analysis local and regional effects were separated and quantified. It was found that emissions in the UK and Europe have a significant effect on background NO₂ concentrations in Ireland and in some instances supersede domestic emissions. The methods can be used to identify source regions, separate local and regional effects and improve predictions of background concentrations based on limited monitoring data. In particular, the results highlight the importance of considering air mass history when assessing background concentration levels for use in local air quality modelling studies.     

Effect of dibenzopyrene measurement on assessing air quality in Beijing air and possible implications for human health

Size fractionated particulate matter (PM) was collected in summer and winter from Beijing, China for the characterization of an expanded list of PAHs and evaluation of air pollution metrics. Summertime ΣPAHs on PM was 14.6 ± 29(PM 1.5), 0.88 ± 0.49(PM 1.5-7.2) and 0.29 ± 0.076(PM 7.2) ng m(-3) air while wintertime concentrations were 493 ± 206(PM 1.5), 26.7 ± 14(PM 1.5-7.2) and 5.3 ± 2.5(PM 7.2) ng m(-3) air. Greater than 90% of the carcinogenic PAHs were concentrated on PM(1.5). Dibenzopyrene isomers made up a significant portion (～30%) of the total carcinogenic PAH load during the winter. To our knowledge, this is the first report of dibenzopyrenes in the Beijing atmosphere and among the few studies that report these highly potent PAHs in ambient particulate matter. Lifetime risk calculations indicated that 1 out of 10,000 to over 6 out of 100 Beijing residents may have an increased risk of lung cancer due to PAH concentration. Over half of the lifetime risk was attributed to Σdibenzopyrenes. The World Health Organization and Chinese daily PM(10) standard was exceeded on each day of the study, however, PAH limits were only exceeded during the winter. The outcomes of the air pollution metrics were highly dependent on the individual PAHs measured and seasonal variation.     

Impacts of groundwater metal loads from bedrock fractures on water quality of a mountain stream

Acid mine drainage and metal loads from hardrock mines to surface waters is a significant problem in the western USA and many parts of the world. Mines often occur in mountain environments with fractured bedrock aquifers that serve as pathways for metals transport to streams. This study evaluates impacts from current and potential future groundwater metal (Cd, Cu, and Zn) loads from fractures underlying the Gilt Edge Mine, South Dakota, on concentrations in Strawberry Creek using existing flow and water quality data and simple mixing/dilution mass balance models. Results showed that metal loads from bedrock fractures to the creek currently contribute <1% of total loads. Even if background water quality is achieved upstream in Strawberry Creek, fracture metal loads would be <5%. Fracture loads could increase substantially and cause stream water quality standards exceedances once groundwater with elevated metals concentrations in the aquifer matrix migrates to the fractures and discharges to the stream. Potential future metal loads from an upstream fracture would contribute a small proportion of the total load relative to current loads in the stream. Cd has the highest stream concentrations relative to standards. Even if all stream water was treated to remove 90% of the Cd, the standard would still not be achieved. At a fracture farther downstream, the Cd standard can only be met if the upstream water is treated achieving a 90% reduction in Cd concentrations and the median stream flow is maintained.     

Risk assessment of trihalomethanes from tap water in Fortaleza, Brazil

The cancer risks (CR) by oral ingestion, dermal absorption, and inhalation exposure of trihalomethanes (THM) from tap water of ten districts in Fortaleza, Brazil were estimated. The mean levels of THM compounds were obtained in Fortaleza tap water as follow: 63.9 microg L(-1) for chloroform (CHCl(3)), 40.0 microg L(-1) for bromodichloromethane (CHBrCl(2)), and 15.6 microg L(-1) for dibromochloromethane (CHBr(2)Cl). Bromoform (CHBr(3)) was not detected. The mean CR for THMs in tap water is 3.96 x 10(-4). The results indicate that Fortaleza residents have a higher CR by inhalation than dermal absorption and oral ingestion. The CR for CHCl(3) contributes with 68% as compared with the total CR, followed by CHBrCl(2) (21%), and CHBr(2)Cl (11%). The hazard index (HI) is about ten times lower than unity, not indicating non-cancer effects.