The desorption kinetics and mechanism were investigated using a Tenax extraction technique on different sediments spiked with radiocarbon-labeled benzo[a]pyrene (BaP). Five sedimentary fractions were sequentially fractionated, and the only nonhydrolyzable organic carbon fractions (NHC) were characterized using advanced solid-state 13C nuclear magnetic resonance spectroscopy (NMR), improved six end-member model, and a CO2 gas adsorption technique. The sediments contained high percentages of algaenan and/or sporopollenin but low percentages of black carbon and lignin. A first-order, two-compartment kinetics model described the desorption process very well (R2 > 0.990). Although some of the organic carbon fractions were significantly related to the desorption kinetics parameters, the NHC fractions showed the highly significant correlation. Moreover, the nanoporosity or specific surface area (SSA) of the NHC fractions was highly related to their OC contents and aliphatic C (R2 = 0.960, p < 0.01). The multiple regression equations among the desorption kinetics parameters, structural parameters, and nanoporosity were well established (R2=>0.999). Nanoporosity and aromatic C were the dominant contributors. Furthermore, the enhanced percentages of desorbed BaP at elevated temperatures significantly showed a linear regression with the structure and nanoporosity. To our knowledge, the above evidence demonstrates for the first time that the transfer (or diffusion) of BaP in the nanopores of condensed aromatic components is the dominant mechanism of the desorption kinetics of BaP at organic matter particle scale.

The effects of salinity on metal toxicity are complex: not only affecting metal bioaccumulation, but also altering the physiology and sensitivity of organisms. In this study, we used a toxicokinetic-toxicodynamic (TK-TD) model to separate and quantify the dual effects of salinity on copper (Cu) toxicity in a euryhaline clam Potamocorbula laevis. The toxicokinetics of Cu was determined using the stable isotope 65Cu as a tracer at concentrations (10–500 μg L−1) realistic to contaminated environments and at salinities ranging from 5 to 30. At low Cu concentrations (ca. 10 μg L−1), Cu bioaccumulation decreased monotonically with salinity, and the uptake rate constant (ku, 0.546 L g−1 h−1 to 0.213 L g−1 h−1) fitted well with an empirical equation, ku = 1/(1.35 + 0.116·Salinity), by treating salinity as a pseudo-competitor. The median lethal concentrations (LC50s) of Cu were 269, 224, and 192 μg L−1 at salinity 5, 15, and 30, respectively. At high Cu concentrations (ca. 500 μg L−1), elevating salinity were much less effective in decreasing Cu bioaccumulation; whereas Cu toxicity increased with salinity. The increased toxicity could be explained by the increases in Cu killing rates (kks), which were estimated to be 0.44–2.08 mg μg−1 h−1 and were presumably due to the osmotic stress caused by the deviation from the optimal salinity of the clams. The other toxicodynamic parameter, internal threshold concentration (CIT), ranged from 79 to 133 μg−1 g−1 and showed no clear trend with salinity.

Polycyclic aromatic hydrocarbons (PAHs) are a category of over 100 various chemicals released from numerous combustion sources. The ubiquity and toxicity of PAHs have posed high health risks on human populations. This study aims to examine the long-term trends of atmospheric PAHs at the national-level in the U.S., and evaluate their cancer risks. Daily concentrations of PAHs measured at 169 monitoring stations between 1990 and 2014 were obtained from the U.S. Environmental Protection Agency's Air Quality System. Temporal trends were examined using generalized linear model with generalized estimating equations. Random-effects analysis of variance was performed to explore variance between regions, sites, years, and months with a hierarchical structure. Source categories were identified using diagnostic ratios. National population level cancer risks were estimated using the relative potency factors and inhalation unit risk method. Ambient PAH concentrations displayed an overall downward trend (6–9% annual reduction) in urban areas, but not in rural areas. Seasonal and weekday/weekend effects were significant. Urban concentrations were twice of the rural level. The between-site variation outweighed the temporal variation, indicating large spatial heterogeneity. The predominant PAH sources were from traffic and non-traffic related fuel combustions with a dominant contribution from diesel emissions. The average excess lifetime cancer risk was estimated to be 9.3 ± 30.1 × 10−6 (GM: 4.2 × 10−6) from exposure to ten carcinogenic PAHs. This is the first comprehensive study of the spatiotemporal trends of ambient PAHs at the U.S. national level. The results indicate that future efforts aimed to reduce PAH exposures should focus on diesel emission controls and extending the geographic coverage of air monitoring.

Knowledge of the heterogeneous distribution of humic substances (HS) reactivities along a continuum of molecular weight (MW) is crucial for the systems where the HS MW is subject to change. In this study, two dimensional correlation spectroscopy combined with size exclusion chromatography (2D-CoSEC) was first utilized to obtain a continuous and heterogeneous presence of copper binding characteristics within bulk HS with respect to MW. HS solutions with varying copper concentrations were directly injected into a size exclusion chromatography (SEC) system with Tris-HCl buffer as a mobile phase. Several validation tests confirmed neither structural disruption of HS nor competition effect of the mobile phase used. Similar to batch systems, fluorescence quenching was observed in the chromatograms over a wide range of HS MW. 2D-CoSEC maps of a soil-derived HS (Elliot soil humic acid) showed the greater fluorescence quenching degrees with respect to the apparent MW on the order of 12500 Da > 10600 Da > 7000 Da > 15800 Da. The binding constants calculated based on modified Stern-Volmer equation were consistent with the 2D-CoSEC results. More heterogeneity of copper binding affinities within bulk HS was found for the soil-derived HS versus an aquatic HS. The traditional fluorescence quenching titration method using ultrafiltered HS size fractions failed to delineate detailed distribution of the copper binding characteristics, exhibiting a much shorter range of the binding constants than those obtained from the 2D-CoSEC. Our proposed technique demonstrated a great potential to describe metal binding characteristics of HS at high MW resolution, providing a clear picture of the size-dependent metal-HS interactions.

Laccase is a widely present extracellular phenoloxidase excreted by fungi, bacteria, and high plants. It is able to catalyze one-electron oxidation of phenolic compounds into radical intermediates that can subsequently couple to each other via covalent bonds. These reactions are believed to play an important role in humification process and the transformation of contaminants containing phenolic functionalities in the environment. In this study, we investigated the kinetics of triclosan transformation catalyzed by laccase. It was found that the rate of triclosan oxidation was first order to the concentrations of both substrate and enzyme. Humic acid (HA) could inhibit the reaction by quenching the radical intermediate of triclosan generated by laccase oxidation. Such inhibition was more significant in the presence of divalent metal cations. This is because that binding to metal ions neutralized the negative charge of HA molecules, thus making them more accessible to laccase molecule that is also negatively charged. Therefore, it has greater chance to quench the radical intermediate that is very unstable and can only diffuse a limited distance after being released from the enzyme catalytic center. Based on these understandings, a reaction model was developed by integration of metal-HA binding equilibriums and kinetic equations. This model precisely predicted the transformation rate of triclosan in the presence of HA and divalent metal ions including Ca2+, Mg2+, Cd2+, Co2+, Mn2+, Ba2+, and Zn2+. Overall, this work reveals important insights into laccase catalyzed oxidative coupling process.

Recently, portable monitors have been increasingly used to quantify air pollutant concentrations at high spatiotemporal resolution. A sampling campaign was conducted to measure the fine particulate matter (PM2.5) and carbon monoxide (CO) exposure concentrations in transport microenvironments (TMEs) in Hong Kong in January and June 2015 using TSI DustTrak and Q-Trak portable monitors. The objectives were to: (1) calibrate DustTrak and Q-Trak; (2) evaluate variability between seasons and microenvironments; (3) estimate indoor/outdoor relationships; and (4) determine minimum sample size. Calibration equations, obtained through side-by-side measurement against stationary reference methods in winter and summer, were applied to correct the measured PM2.5 data set. In general, PM2.5 concentrations in all TMEs were significantly higher in winter than in summer. The mean PM2.5 concentration in winter was lower for underground sections of the Mass Transit Railway (MTR) metro system (31 μg/m3) than for other TMEs, whereas in summer TMEs had mean PM2.5 concentrations in the range of 10–15 μg/m3, with above-ground MTR train as an exception, at 23 μg/m3. PM2.5 concentrations measured in TMEs were strongly correlated with nearby air quality monitoring stations (AQMSs) measurements in winter, but in summer there was little correlation. The minimum sample size estimates varied more among TMEs in summer versus winter because of the differences in PM2.5 concentration distributions related to changes in ambient PM2.5 concentrations and ventilation practices. This study provides a feasible protocol on the calibration and application of portable monitors in TME air quality measurement and develops a method for estimating minimum sample size.

Polycyclic aromatic hydrocarbons (PAHs) are important organic pollutants in the aquatic environment due to their persistence and bioaccumulation potential both in organisms and in sediments. Benzo(a)anthracene (BaA) and phenanthrene (PHE), which are in the priority pollutant list of the U.S. EPA (Environmental Protection Agency), are selected as model compounds of the present study. Bioaccumulation and depuration experiments with local Mediterranean mussel species, Mytilus galloprovincialis were used as the basis of the study. Mussels were selected as bioindicator organisms due to their broad geographic distribution, immobility and low enzyme activity. Bioaccumulation and depuration kinetics of selected PAHs in Mytilus galloprovincialis were described using first order kinetic equations in a three compartment model. The compartments were defined as: (1) biota (mussel), (2) surrounding environment (seawater), and (3) algae (Phaeodactylum tricornutum) as food source of the mussels. Experimental study had been performed for three different concentrations. Middle concentration of the experimental data was used as the model input in order to represent other high and low concentrations of selected PAHs. Correlations of the experiment and model data revealed that they are in good agreement. Accumulation and depuration trend of PAHs in mussels regarding also the durations can be estimated effectively with the present study. Thus, this study can be evaluated as a supportive tool for risk assessment in addition to monitoring studies.

Many regulatory screening level exposure assessments are based on simple large scale conceptual scenarios. However, exposure, and therefore risks associated with chemicals, are characterised by high spatial variability. The Scenario assembly tool (ScenAT) is a global screening level model to enable spatially resolved local predictions of environmental concentrations of home and personal care chemicals. It uses the European Union Technical Guidance Document (TGD) equation to predict local scale freshwater concentrations (predicted environmental concentrations - PECs) of chemicals discharged via wastewater. ScenAT uses Geographic Information System (GIS) layers for the underlying socio-economic (population) and environmental parameters (per capita water use, sewage treatment plant connectivity, dilution factor). Using a probabilistic approach, we incorporate sources of uncertainty in the input data (tonnage estimation, removal in sewage treatment plants and seasonal variability in dilution factors) for two case-study chemicals: the antimicrobial triclosan (TCS) and the anionic surfactant linear alkylbenzene sulphonate (LAS). We then compare model estimates of wastewater and freshwater concentrations of TCS and LAS to UK monitoring data. Comparison showed that modeled PECs were on average higher than mean measured data for TCS and LAS by a factor 1.8 and 1.4, respectively. Considering the uncertainty associated with both model and monitoring data, the use of a probabilistic approach using the ScenAT model for screening assessment is reasonable. The combination of modelled and monitoring data enables the contextualisation of monitoring data. Spatial PECs can be used to identify areas of elevated concentration for further refined assessment.A probabilistic approach for large scale screening assessments to contextualise monitoring data for risk assessment.

Metal-salt amended soils (MA, n = 23), and historically-contaminated urban soils from two English cities (Urban, n = 50), were investigated to assess the effects of soil properties and contaminant source on metal lability and solubility. A stable isotope dilution method, with and without a resin purification step, was used to measure the lability of Cd, Cu, Ni, Pb and Zn. For all five metals in MA soils, lability (%E-values) could be reasonably well predicted from soil pH value with a simple logistic equation. However, there was evidence of continuing time-dependent fixation of Cd and Zn in the MA soils, following more than a decade of storage under air-dried conditions, mainly in high pH soils. All five metals in MA soils remained much more labile than in Urban soils, strongly indicating an effect of contaminant source on metal lability in the latter. Metal solubility was predicted for both sets of soil by the geochemical speciation model WHAM-VII, using E-value as an input variable. For soils with low metal solution concentrations, over-estimation of Cd, Ni and Zn solubility was associated with binding to the Fe oxide fraction while accurate prediction of Cu solubility was dependent on humic acid content. Lead solubility was most poorly described, especially in the Urban soils. Generally, slightly poorer estimation of metal solubility was observed in Urban soils, possibly due to a greater incidence of high pH values. The use of isotopically exchangeable metal to predict solubility is appropriate both for historically contaminated soils and where amendment with soluble forms of metal is used, as in toxicological trials. However, the major limitation to predicting solubility may lie with the accuracy of model input variables such as humic acid and Fe oxide contents where there is often a reliance on relatively crude analytical estimations of these variables.Trace metal reactivity in urban soils depends on both soil properties and the original source material; the WHAM geochemical model predicts solubility using isotopically exchangeable metal as an input.

We evaluated the maternal transfer of mercury to eggs in songbirds, determined whether this relationship differed between songbird species, and developed equations for predicting mercury concentrations in eggs from maternal blood. We sampled blood and feathers from 44 house wren (Troglodytes aedon) and 34 tree swallow (Tachycineta bicolor) mothers and collected their full clutches (n = 476 eggs) within 3 days of clutch completion. Additionally, we sampled blood and feathers from 53 tree swallow mothers and randomly collected one egg from their clutches (n = 53 eggs) during mid to late incubation (6–10 days incubated) to evaluate whether the relationship varied with the timing of sampling the mother's blood. Mercury concentrations in eggs were positively correlated with mercury concentrations in maternal blood sampled at (1) the time of clutch completion for both house wrens (R2 = 0.97) and tree swallows (R2 = 0.97) and (2) during mid to late incubation for tree swallows (R2 = 0.71). The relationship between mercury concentrations in eggs and maternal blood did not differ with the stage of incubation when maternal blood was sampled. Importantly, the proportion of mercury transferred from mothers to their eggs decreased substantially with increasing blood mercury concentrations in tree swallows, but increased slightly with increasing blood mercury concentrations in house wrens. Additionally, the proportion of mercury transferred to eggs at the same maternal blood mercury concentration differed between species. Specifically, tree swallow mothers transferred 17%–107% more mercury to their eggs than house wren mothers over the observed mercury concentrations in maternal blood (0.15–1.92 μg/g ww). In contrast, mercury concentrations in eggs were not correlated with those in maternal feathers and, likewise, mercury concentrations in maternal blood were not correlated with those in feathers (all R2 < 0.01). We provide equations to translate mercury concentrations from maternal blood to eggs (and vice versa), which should facilitate comparisons among studies and help integrate toxicity benchmarks into a common tissue.