This research evaluates the analytical capabilities of a field portable X-ray fluorescence spectrometer (pXRF) for the measurement of contaminated soil samples using a matrix-matched calibration. The calibrated pXRF generated exceptional data quality from the measurement of ten soil reference materials. Elemental recoveries improved for all 11 elements post-calibration with reduced measurement variation and detection limits in most cases. Measurement repeatability of reference values ranged between 0.2 and 10% relative standard deviation, while the majority (82%) of reference recoveries were between 90 and 110%. Definitive data quality, the highest of the US EPA's three level quality ranking, was achieved for 15 of 19 elemental datasets. Measurement comparability against inductively coupled plasma atomic emission spectrometry (ICP-AES) values was excellent for most elements (e.g, r2 0.999 for Mn and Pb, r2 > 0.995 for Cu, Zn and Cd). Parallel measurement of reference materials revealed ICP-AES and ICP-MS measured Ti and Cr poorly when compared to pXRF. Individual recoveries of soil reference materials by both ICP-AES and pXRF showed that pXRF was equivalent to or better than ICP-AES values for all but two elements (Ni, As). This study demonstrates pXRF as a suitable alternative to ICP-AES analysis in the measurement of Ti, Cr, Mn, Fe, Cu, Zn, Sr, Cd, and Pb in metal-contaminated soils. Where funds are limited, pXRF provides a low-cost, high quality solution to increasing sample density for a more complete geochemical investigation.

Biodegradation of organic chemicals in the vapor phase of soils and vertical flow filters has gained attention as promising approach to clean up volatile organic compounds (VOC). The drivers of VOC biodegradation in unsaturated systems however still remain poorly understood. Here, we analyzed the processes controlling aerobic VOC biodegradation in a laboratory setup mimicking the unsaturated zone above a shallow aquifer. The setup allowed for diffusive vapor-phase transport and biodegradation of three VOC: non-deuterated and deuterated toluene as two compounds of highly differing biodegradability but (nearly) identical physical and chemical properties, and MTBE as (at the applied experimental conditions) non-biodegradable tracer and internal control. Our results showed for toluene an effective microbial degradation within centimeter VOC transport distances despite high gas-phase diffusivity. Degradation rates were controlled by the reactivity of the compounds while oxic conditions were found everywhere in the system. This confirms hypotheses that vadose zone biodegradation rates can be extremely high and are able to prevent the outgassing of VOC to the atmosphere within a centimeter range if compound properties and site conditions allow for sufficiently high degradation rates.

Although physiological traits and phenology are thought to be evolved traits, they often show marked variation within populations, which may be related to extrinsic factors. For example, trace elements such as mercury (Hg) and lead (Pb) alter biochemical processes within wildlife that may affect migration and breeding. While there is a growing understanding of how contaminants may influence wildlife physiology, studies addressing these interactions in free-living species are still limited. We examined how four non-essential trace elements (cadmium, Hg, Pb and selenium) interacted with physiological and breeding measures known to influence breeding in a free-living population of common eider ducks (Somateria mollissima). We collected blood from female eiders as they arrived at a breeding colony in northern Canada. Blood was subsequently assessed for baseline corticosterone (CORT), immunoglobulin Y (IgY), and the four trace elements. We used model selection to identify which elements varied most with CORT, IgY, arrival condition, and arrival timing. We then used path analysis to assess how the top two elements from the model selection process (Hg and Pb) varied with metrics known to influence reproduction. We found that arrival date, blood Hg, CORT, and IgY showed significant inter-annual variation. While blood Pb concentrations were low, blood Pb levels significantly increased with later arrival date of the birds, and varied negatively with eider body condition, suggesting that even at low blood concentrations, Pb may be related to lower investment in reproduction in eiders. In contrast, blood Hg concentrations were positively correlated with eider body condition, indicating that fatter birds also had higher Hg burdens. Overall, our results suggest that although blood Hg and Pb concentrations were below no-effect levels, these low level concentrations of known toxic metals show significant relationships with breeding onset and condition in female eider ducks, factors that could influence reproductive success in this species.

Diethylhexyl phthalate (DEHP) is considered to be an endocrine disruptor, which unlike other chemicals that have either non-specific (e.g., narcotics) or more generalized reactive modes of action, affect the Hypothalamic-pituitary-gonadal (HPG) axis and tend to have specific interactions with particular molecular targets within biochemical pathways. Responding to this challenge, a novel method for deriving predicted no-effect concentration (PNEC) and probabilistic ecological risk assessment (PERAs) for DEHP based on long-term exposure to potentially sensitive species with appropriate apical endpoints was development for protection of Chinese surface waters. PNECs based on potencies to cause lesions in reproductive tissues of fishes, which ranged from 0.04 to 0.20 μg DEHP L−1, were significantly less than those derived based on other endpoints or other taxa, such as invertebrates. An assessment of risks posed by DEHP to aquatic organisms in surface waters of China showed that 88.17% and 78.85% of surface waters in China were predicted to pose risks to reproductive fitness of fishes with thresholds of protection for aquatic organisms based on 5% (HC5) and 10% (HC10), respectively. Assessment of risks of effects based on effects mediated by the HPG-axis should consider effects on chronic, non-lethal endpoints for specific taxa, especially for reproductive fitness of fishes.

Air pollution by particulate matter is a serious problem in Beijing. Strict pollution control measures have been carried out in Beijing prior to and during the 2015 China Victory Day Parade in order to improve air quality. This distinct event provides an excellent opportunity for investigating the impact of such measures on the chemical properties of particulate matter with an aerodynamic diameter ≤2.5 μm (PM2.5). The water-soluble ions as well as sulfur and oxygen isotopes of sulfate in PM2.5 collected between August 19 and September 18, 2015 (n = 31) were analyzed in order to trace the sources and formation processes of PM2.5 in Beijing. The results exhibit a decrease in concentration of water-soluble ions in PM2.5 including aerosol sulfate. In contrast, the mean values of δ34Ssulfate (4.7 ± 0.8‰ vs. 5.0 ± 2.0‰) and δ18Osulfate (18.3 ± 2.3‰ vs. 17.2 ± 6.0) in PM2.5 during the air pollution control period and the non-source control period exhibit no significant differences, which suggests that despite a reduction in concentration, the sulfate source remains identical for the two periods. It is inferred that the decrease in concentration of sulfate in PM2.5 mainly results from variations in air mass transport. Notably, the air mass during the pollution control period originated mainly from north and northeast and changed to southerly directions thereafter. The sulfur and oxygen isotopes of the sulfate point to coal combustion as the major source of sulfate in PM2.5 from the Beijing area.

Biosolids are extensively used in agriculture as fertilizers while offering a practical solution for waste disposal. Many pharmaceutical and personal care products (PPCPs), such as triclosan and triclocarban, are enriched in biosolids. Biosolid amendment changes soil physicochemical properties, which may in turn alter the persistence of PPCPs and hence the risk for secondary contamination such as plant uptake. To delineate the effect of biosolids on PPCPs persistence, triclosan and triclocarban were used as model compounds in this study and their sorption (Kd) and persistence (t1/2) were determined in different soils before and after biosolid amendment. Biosolids consistently increased sorption of triclosan and triclocarban in soil. The Kd of triclosan increased by 3.9–21 times following amendment of a sandy loam soil with biosolids at 2–10%. The persistence of both compounds was prolonged, with t1/2 of triclosan increasing from 10 d in the unamended soil to 63 d after biosolid amendment at 10%. The relationship between t1/2 and Kd was further examined through a meta-analysis using data from this study and all relevant published studies. A significant linear relationship between t1/2 and Kd was observed for triclosan (r2 = 0.69, p < 0.01) and triclocarban (r2 = 0.38, p < 0.05) in biosolid-amended soils. On the average, when biosolid amendment increased by 1%, t1/2 of triclosan was prolonged by 7.5 d, while t1/2 of triclocarban was extended by 4.7 d. Therefore, biosolid amendment greatly enhances persistence of triclosan and triclocarban, likely due to enhanced sorption or decreased chemical bioavailability. This finding highlights the importance to consider the effect of biosolids when evaluating the environmental risks of these and other biosolid-borne PPCPs.

The Cleveland airshed comprises a complex mixture of industrial source emissions that contribute to periods of non-attainment for fine particulate matter (PM2.5) and are associated with increased adverse health outcomes in the exposed population. Specific PM sources responsible for health effects however are not fully understood. Size-fractionated PM (coarse, fine, and ultrafine) samples were collected using a ChemVol sampler at an urban site (G.T. Craig (GTC)) and rural site (Chippewa Lake (CLM)) from July 2009 to June 2010, and then chemically analyzed. The resulting speciated PM data were apportioned by EPA positive matrix factorization to identify emission sources for each size fraction and location. For comparisons with the ChemVol results, PM samples were also collected with sequential dichotomous and passive samplers, and evaluated for source contributions to each sampling site. The ChemVol results showed that annual average concentrations of PM, elemental carbon, and inorganic elements in the coarse fraction at GTC were ∼2, ∼7, and ∼3 times higher than those at CLM, respectively, while the smaller size fractions at both sites showed similar annual average concentrations. Seasonal variations of secondary aerosols (e.g., high NO3− level in winter and high SO42− level in summer) were observed at both sites. Source apportionment results demonstrated that the PM samples at GTC and CLM were enriched with local industrial sources (e.g., steel plant and coal-fired power plant) but their contributions were influenced by meteorological conditions and the emission source's operation conditions. Taken together the year-long PM collection and data analysis provides valuable insights into the characteristics and sources of PM impacting the Cleveland airshed in both the urban center and the rural upwind background locations. These data will be used to classify the PM samples for toxicology studies to determine which PM sources, species, and size fractions are of greatest health concern.

PCBs (polychlorinated biphenyls) were determined in sediment/soil profiles to a depth of 30 cm from three different wetlands (i.e., ditch wetlands, riparian wetlands and reclaimed wetlands) of the Pearl River Estuary to elucidate their levels, distribution and toxic risks along a 100-year chronosequence of reclamation. All detected PCB congeners and the total 15 PCBs (∑15 PCBs) decreased with depth along sediment/soil profiles in these three wetlands. The ∑15 PCBs concentrations ranged from 17.68 to 169.26 ng/g in surface sediments/soils. Generally, old wetlands tended to have higher PCB concentrations than younger ones. The dominant PCB congeners at all sampling sites were light PCB homologues (i.e., tetra-CBs and tri-CBs). According to the sediment quality guideline, the average PCB concentrations exceeded the threshold effects level (TEL, 21.6 ng/g) at most of the sampling sites, exhibiting possible adverse biological effects, which were dominantly caused by light PCB congeners. The total toxic equivalent (TEQ) concentrations of 10 dioxin-like PCBs (DL-PCBs) detected at all sampling sites ranged from 0.04 to 852.7 (10−3 ng/g), mainly affected by PCB126. Only DL-PCB concentrations in ditch and riparian wetland sediments with 40-year reclamation histories (i.e., D40 and Ri40) exhibited moderate adverse biological effects according to SQGQ values. Principal component analysis indicated that PCBs in three wetland sediments/soils mainly originated from Aroclor 1016, 1242, and 1248. Correlation analysis showed that sediment/soil organic carbon content had a significant correlation with the concentrations of several PCB congeners (P < 0.05), whereas no significant correlations were observed between any PCBs congeners and grain size or aggregate content (P > 0.05).