Apportionment of Ambient Primary and Secondary Pollutants during a 2001 Summer Study in Pittsburgh Using U.S. Environmental Protection Agency UNMIX

Abstract

Apportionment of primary and secondary pollutants during the summer 2001 Pittsburgh Air Quality Study (PAQS) is reported. Several sites were included in PAQS, with the main site (the supersite) adjacent to the Carnegie Mellon University campus in Schenley Park. One of the additional sampling sites was located at the National Energy Technology Laboratory, located ～18 km southeast of downtown Pittsburgh. Fine particulate matter (PM_2.5) mass, gas-phase volatile organic material (VOM), particulate semivolatile and nonvolatile organic material (NVOM), and ammonium sulfate were apportioned at the two sites into their primary and secondary contributions using the U.S. Environmental Protection Agency UNMIX 2.3 multivariate receptor modeling and analysis software. A portion of each of these species was identified as originating from gasoline and diesel primary mobile sources. Some of the organic material was formed from local secondary transformation processes, whereas the great majority of the secondary sulfate was associated with regional transformation contributions. The results indicated that the diurnal patterns of secondary gas-phase VOM and particulate semivolatile and NVOM were not correlated with secondary ammonium sulfate contributions but were associated with separate formation pathways. These findings are consistent with the bulk of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport and, thus, decoupled from local activity involving organic pollutants in the metropolitan area.     

Reconstructions of Soil Moisture for the Upper Colorado River Basin Using Tree‐Ring Chronologies1

Anderson, SallyRose, Glenn Tootle, and Henri Grissino‐Mayer, 2012. Reconstructions of Soil Moisture for the Upper Colorado River Basin Using Tree‐Ring Chronologies. Journal of the American Water Resources Association (JAWRA) 48(4): 849‐858. DOI: 10.1111/j.1752‐1688.2012.00651.x Abstract: Soil moisture is an important factor in the global hydrologic cycle, but existing reconstructions of historic soil moisture are limited. We used tree‐ring chronologies to reconstruct annual soil moisture in the Upper Colorado River Basin (UCRB). Gridded soil moisture data were spatially regionalized using principal components analysis and k‐nearest neighbor techniques. We correlated moisture sensitive tree‐ring chronologies in and adjacent to the UCRB with regional soil moisture and tested the relationships for temporal stability. Chronologies that were positively correlated and stable for the calibration period were retained. We used stepwise linear regression to identify the best predictor combinations for each soil moisture region. The regressions explained 42‐78% of the variability in soil moisture data. We performed reconstructions for individual soil moisture grid cells to enhance understanding of the disparity in reconstructive skill across the regions. Reconstructions that used chronologies based on ponderosa pines (Pinus ponderosa) and pinyon pines (Pinus edulis) explained more variance in the datasets. Reconstructed soil moisture data was standardized and compared with standardized reconstructed streamflow and snow water equivalent data from the same region. Soil moisture and other hydrologic variables were highly correlated, indicating reconstructions of soil moisture in the UCRB using tree‐ring chronologies successfully represent hydrologic trends.     

Polychlorinated biphenyls in vacuum dust and blood of residents in 20 Wisconsin households

Human exposure to PCBs is nearly universal in North America. While most exposure can be linked to consumption of contaminated fish, detection of PCBs in non-fish eating populations suggests that other routes of exposure including inhalation of PCB-laden particles or volatile congeners, ingestion of contaminated soil or dust, or dermal absorption following direct contact are also important. In an effort to assess the role of the residential environment as a source of exposure, vacuum dust was collected from the homes of 26 Wisconsin residents whose serum PCB levels had been measured approximately 2 years earlier. More than 60 congeners were detected in dust with all of the samples containing congeners 101, 110, 138 and 153. Total PCB levels ranged from 8.8 to 1186 ng g⁻¹ with levels being highest in vacuum dust from homes built between 1959 and 1970. Total PCB levels ranged from 0.05 to 8.34 μg L⁻¹ in serum collected from the adults living in these households, with congeners 138, 153 and 180 predominating. Hexa- and hepta-chlorinated biphenyls comprised 73% of the total residues detected in serum. However, most of the residues found in dust were lower chlorinated congeners with tetra- and penta-chlorinated biphenyls being dominant. Following log transformation, a positive association was found between serum and house dust PCB levels. This association was stronger among infrequent consumers of Great Lake fish, but of borderline statistical significance. This exploratory study suggests that house dust may be a significant source of exposure to PCBs and supports the need for further investigations.     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in breast milk of first-time Irish mothers: impact of the 2008 dioxin incident in Ireland

The 2008 dioxin incident in Ireland resulted in elevated concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in Irish pork and pork products, due to the consumption of contaminated animal feed by pigs. In order to investigate any resulting impact on the Irish population, these contaminants were measured in pooled breast milk samples from 109 first-time mothers, collected in 2010. A comparison of the results with similar data from 2002 revealed generally lower concentrations of PCDD/Fs and dioxin-like PCBs in the 2010 samples, confirming the declining trend reported by many authors. Contaminant concentration levels for both 2002 and 2010 were generally slightly lower than those reported internationally, with a mean combined PCDD/F and PCB WHO-TEQ of 9.66 pg g⁻¹ fat, for an overall pooled sample of milk from 2010. An apparent slight increase in PCDFs was observed between 2002 and 2010 (from 2.73 pg WHO-TEQ g⁻¹ fat to 3.21 pg WHO-TEQ g⁻¹ fat), with the main contributory congener being 2,3,4,7,8-PentaCDF. While it cannot be totally discounted that the slight increase in 2,3,4,7,8-PentaCDF and in the overall PCDF WHO-TEQ in breast milk could be attributable to consumption of Irish pork during the 2008 incident, we consider that it is more likely that this was due to other factors, including the predominantly urban/industrial sampling locations for the 2010 samples, compared to 2002.     

Environmental Condition Assessment of US Military Installations Using GIS Based Spatial Multi-Criteria Decision Analysis

Environment functions in various aspects including soil and water conservation, biodiversity and habitats, and landscape aesthetics. Comprehensive assessment of environmental condition is thus a great challenge. The issues include how to assess individual environmental components such as landscape aesthetics and integrate them into an indicator that can comprehensively quantify environmental condition. In this study, a geographic information systems based spatial multi-criteria decision analysis was used to integrate environmental variables and create the indicator. This approach was applied to Fort Riley Military installation in which land condition and its dynamics due to military training activities were assessed. The indicator was derived by integrating soil erosion, water quality, landscape fragmentation, landscape aesthetics, and noise based on the weights from the experts by assessing and ranking the environmental variables in terms of their importance. The results showed that landscape level indicator well quantified the overall environmental condition and its dynamics, while the indicator at level of patch that is defined as a homogeneous area that is different from its surroundings detailed the spatiotemporal variability of environmental condition. The environmental condition was mostly determined by soil erosion, then landscape fragmentation, water quality, landscape aesthetics, and noise. Overall, environmental condition at both landscape and patch levels greatly varied depending on the degree of ground and canopy disturbance and their spatial patterns due to military training activities and being related to slope. It was also determined the environment itself could be recovered quickly once military training was halt or reduced. Thus, this study provided an effective tool for the army land managers to monitor environmental dynamics and plan military training activities. Its limitation lies at that the obtained values of the indicator vary and are subjective to the experts' knowledge and experience. Thus, further advancing this approach is needed by developing a scientific method to derive the weights of environmental variables.     

Atrazine and alachlor transport in claypan soils as influenced by differential antecedent soil water content

Increased attention to ground water contamination has encouraged an interest in mechanisms of solute transport through soils. Few studies have investigated the effect of the initial soil water content on the transport and degradation of herbicides for claypan soils. We investigated the effect of claypan soils at initial field capacity vs. permanent wilting level on atrazine and alachlor transport. The soil studied was Mexico silt loam (fine, smectitic, mesic Aeric Vertic Epiaqualf) with a subsoil clay content, primarily montmorillonite, of >40%. Strontium bromide, atrazine, and alachlor were applied to plots; half were at field capacity (Wet treatment), and half were near the permanent wilting point (Dry treatment). Soil cores were removed at selected depths and times, and cores were analyzed for bromide and herbicide concentrations. Bromide, atrazine, and alachlor were detected at the 0.90-m depth in dry plots within 15 d after experiment initiation. Bromide was detected 0.15 m deeper (P < 0.05) in the Dry compared with the Wet treatment at 1, 7, and 60 d after application and >0.30 m deeper (P < 0.01) in the Dry treatment at 15 and 30 d after application; similar treatment results were found for atrazine and alachlor, although on fewer dates with significant differences. The mobility order of the applied chemicals was bromide > atrazine > alachlor. The atrazine apparent half-life was significantly longer in the Dry plots compared with the Wet plots. The retardation factor determined from the relative velocity of each herbicide to that of bromide was higher for alachlor than for atrazine. This study identifies the impact that shrinkage cracks have for different moisture conditions on preferential transport of herbicides in claypan soils.     

Influence of prairie restoration on CT-measured soil pore characteristics

Restored prairies are expected to improve soil physical properties, yet little is known about the extent of change to soil properties and how rapidly these changes take place. The objective of this study was to compare effects of prairie restoration on computed tomography (CT)-measured pore parameters. Undisturbed soil cores (76 mm diam. by 76 mm long) from native prairie (NP), restored prairie (RP), conservation reserve program (CRP), and no-till corn (Zea mays L.)-soybean (Glycine max (L.) Merr.; CS) sites were collected with six replicates from the 0- to 40-cm depth in 10-cm increments. Five CT images were acquired from each soil core using a medical CT scanner with 0.2 by 0.2 mm pixel resolution with 0.5 mm slice thickness, and then images were analyzed. Soil bulk density and hydraulic conductivity (K(sat)) were also measured. Soils under NP, RP, CRP, and CS areas had 83, 43, 48, and 26 pores on a 2500 mm(2) area, respectively, for the 0- to 40-cm depth. The number of pores, number of macropores (>1000 microm diam.), macroporosity, mesoporosity (200-1000 microm diam.), and fractal dimension were significantly higher and pore circularity was lower for NP, RP, and CRP than the CS treatment. The CT-measured mesoporosity and macroporosity of the CS treatment were 20 and 18% of the values for the NP site. CT-measured number of pores and macropores explained 43 and 40% of the variation for K(sat). The study showed that prairie restoration improves CT-measured soil pore parameters and decreases bulk density which are related to soil water infiltration.     

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.     

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.