There are limited ambient air measurements of extended (beyond EPA Priority 16) lists of polycyclic aromatic hydrocarbons (PAHs). We measured air concentrations of 45 PAHs using passive and active air sampling at 15 sites in a central urban community and one rural site for two years. Passive sampling was conducted with cylindrical XAD-based samplers deployed to capture spatial variability. High volume active samplers with quartz fiber filters for particles and XAD-4 absorbent for gases were deployed at two urban sites and the rural site to calibrate the passive measurements directly. Estimated passive sampling rates (PSRs) were evaluated as functions of meteorological data, seasons, locations, study year, and compared with other studies. Possible particle collection by the passive samplers was evaluated using a variety of particle measurements (TSP, PM10, PM2.5 and ultrafines <100 nm). Total PAHs were statistically associated with ultrafine particle concentrations and to a lesser extent PM2.5 and PM10, but not TSP. PSRs were more variable when PAH mass loadings were lower and near method detection limits; this occurred more often at the rural site. The PSRs were not statistically associated with meteorological conditions in this study, but wind speed had the highest potential to impact PSR results. The resulting passive PAH measurements are reported with respect to proximity to major roadways and other known air emissions types. PSRs were quantifiable for some PAHs that were found predominantly in the particulate phase in active sampling. This information, together with particle fraction calculations from active sampling, were used to estimate the particulate PAH capture of the passive sampler. Summed PAH (∑PAH) passive concentrations were measured within the range of 10–265 ng/m3, with the highest concentrations from naphthalene and the lowest detected concentrations from anthracene. These results indicated a stronger seasonal signal within 200 m of a major roadway.

Metal detoxification in plants is a complex process that involves different mechanisms, such as the retention of metals to the cell wall and their chelation and subsequent compartmentalization in plant vacuoles. In order to identify the mechanisms involved in metal accumulation and tolerance in Betula pubescens, as well as the role of mycorrhization in these processes, mycorrhizal and non-mycorrhizal plants were grown in two industrial soils with contrasting concentrations of heavy metals.Mycorrhization increased metal uptake at low metal concentrations in the soil and reduced it at high metal concentrations, which led to an enhanced growth and biomass production of the host when growing in the most polluted soil. Our results suggest that the sequestration on the cell wall is the main detoxification mechanism in white birch exposed to acute chronic metal-stress, while phytochelatins play a role mitigating metal toxicity inside the cells. Given its high Mn and Zn root-to-shoot translocation rate, Betula pubescens is a very promising species for the phytoremediation of soils polluted with these metals.

Natural attenuation of organic contaminants in groundwater can give rise to a series of complex biogeochemical reactions that release secondary contaminants to groundwater. In a crude oil contaminated aquifer, biodegradation of petroleum hydrocarbons is coupled with the reduction of ferric iron (Fe(III)) hydroxides in aquifer sediments. As a result, naturally occurring arsenic (As) adsorbed to Fe(III) hydroxides in the aquifer sediment is mobilized from sediment into groundwater. However, Fe(III) in sediment of other zones of the aquifer has the capacity to attenuate dissolved As via resorption. In order to better evaluate how long-term biodegradation coupled with Fe-reduction and As mobilization can redistribute As mass in contaminated aquifer, we quantified mass partitioning of Fe and As in the aquifer based on field observation data. Results show that Fe and As are spatially correlated in both groundwater and aquifer sediments. Mass partitioning calculations demonstrate that 99.9% of Fe and 99.5% of As are associated with aquifer sediment. The sediments act as both sources and sinks for As, depending on the redox conditions in the aquifer. Calculations reveal that at least 78% of the original As in sediment near the oil has been mobilized into groundwater over the 35-year lifespan of the plume. However, the calculations also show that only a small percentage of As (∼0.5%) remains in groundwater, due to resorption onto sediment. At the leading edge of the plume, where groundwater is suboxic, sediments sequester Fe and As, causing As to accumulate to concentrations 5.6 times greater than background concentrations. Current As sinks can serve as future sources of As as the plume evolves over time. The mass balance approach used in this study can be applied to As cycling in other aquifers where groundwater As results from biodegradation of an organic carbon point source coupled with Fe reduction.

Over 700 million people in Sub-Saharan Africa depend on solid biomass fuel and use simple cookstoves in poorly ventilated kitchens, which results in high indoor concentrations of household air pollutants. Switching from biomass to biogas as a cooking fuel can reduce airborne emissions of fine particulate matter (PM2.5) and carbon monoxide (CO), but households often only partially convert to biogas, continuing to use solid biomass fuels for part of their daily cooking needs. There is little evidence of the benefits of partial switching to biogas. This study monitored real-time PM2.5 and CO concentrations in 35 households in Cameroon and Uganda where biogas and firewood (or charcoal) were used. The 24 h mean PM2.5 concentrations in households that used: (1) firewood and charcoal; (2) both firewood (mean 54% cooking time) and biogas (mean 46% cooking time); and (3) only biogas, were 449 μg m⁻³, 173 μg m⁻³ and 18 μg m⁻³ respectively. The corresponding 24 h mean CO concentrations were 14.2 ppm, 2.7 ppm and 0.5 ppm. Concentrations of both PM2.5 and CO were high and exceeded the World Health Organisation guidelines when firewood and charcoal were used. Partially switching to biogas reduced CO exposure to below the World Health Organisation guidelines, but PM2.5 concentrations were only below the 24 h recommended limits when households fully converted to biogas fuel. These results indicate that partial switching from solid fuels to biogas is not sufficient and continues to produce concentrations of household air pollution that are likely to harm the health of those exposed. Programmes introducing biogas should aim to ensure that household energy needs can be fully achieved using biogas with no requirement to continue using solid fuels.

Pharmaceutical and personal care products (PPCPs) are continuously introduced into the soil-plant system, through practices such as agronomic use of reclaimed water and biosolids containing these trace contaminants. Plants may accumulate PPCPs from soil, serving as a conduit for human exposure. Metabolism likely controls the final accumulation of PPCPs in plants, but is in general poorly understood for emerging contaminants. In this study, we used diclofenac as a model compound, and employed 14C tracing, and time-of-flight (TOF) and triple quadruple (QqQ) mass spectrometers to unravel its metabolism pathways in Arabidopsis thaliana cells. We further validated the primary metabolites in Arabidopsis seedlings. Diclofenac was quickly taken up into A. thaliana cells. Phase I metabolism involved hydroxylation and successive oxidation and cyclization reactions. However, Phase I metabolites did not accumulate appreciably; they were instead rapidly conjugated with sulfate, glucose, and glutamic acid through Phase II metabolism. In particular, diclofenac parent was directly conjugated with glutamic acid, with acyl-glutamatyl-diclofenac accounting for >70% of the extractable metabolites after 120-h incubation. In addition, at the end of incubation, >40% of the spiked diclofenac was in the non-extractable form, suggesting extensive sequestration into cell matter. The rapid formation of non-extractable residue and dominance of diclofenac-glutamate conjugate uncover previously unknown metabolism pathways for diclofenac. In particular, the rapid conjugation of parent highlights the need to consider conjugates of emerging contaminants in higher plants, and their biological activity and human health implications.

The impact of chronic exposure to air pollution and outcomes in the acute respiratory distress syndrome (ARDS) is unknown. The Nationwide Inpatient Sample (NIS) from 2011 was utilized for this analysis. The NIS is a national database that captures 20% of all US in-patient hospitalizations from 47 states. Patients with ARDS who underwent mechanical ventilation from the highest 15 ozone pollution cities were compared with the rest of the country. Secondary analyses assessed outcomes of ARDS patients for ozone pollution and particulate matter pollution on a continuous scale by county of residence. A total of 8,023,590 hospital admissions from the 2011 NIS sample were analyzed. There were 93,950 patients who underwent mechanical ventilation for ARDS included in the study. Patients treated in high ozone regions had significantly higher unadjusted hospital mortality (34.9% versus 30.8%, p < 0.01) than patients in cities with control levels of ozone. After controlling for all variables in the model, treatment in a hospital located in a high ozone pollution area was associated with an increased odds of in-hospital mortality (OR 1.11, 95% CI 1.08–1.15, p < 0.01). After adjustment for all variables in the model, for each increase in ozone exposure by 0.01 ppm the OR for death was 1.07 (95% CI 1.06–1.08, p < 0.01). Similarly, for each increase in particulate matter exposure by 10 μg/m³, the OR for death was 1.08 (95% CI 1.02–1.16, p < 0.01).Chronic exposure to both ozone and particulate matter pollution is associated with higher rates of mortality in ARDS. These preliminary findings need to be confirmed by further detailed studies.

Antimony (Sb) is a contaminant of increased prevalence in the environment, but there is little knowledge about the mechanisms of its uptake and translocation within plants. Here, we applied for the synchrotron based X-ray absorption near-edge structure (XANES) spectroscopy to analyze the speciation of Sb in roots and shoots of rye grass (Lolium perenne L. Calibra). Seedlings were grown in nutrient solutions to which either antimonite (Sb(III)), antimonate (Sb(V)) or trimethyl-Sb(V) (TMSb) were added. While exposure to Sb(III) led to around 100 times higher Sb accumulation in the roots than the other two treatments, there was no difference in total Sb in the shoots. Antimony taken up in the Sb(III) treatment was mainly found as Sb-thiol complexes (roots: >76% and shoots: 60%), suggesting detoxification reactions with compounds such as glutathione and phytochelatins. No reduction of accumulated Sb(V) was found in the roots, but half of the translocated Sb was reduced to Sb(III) in the Sb(V) treatment. Antimony accumulated in the TMSb treatment remained in the methylated form in the roots. By synchrotron based XANES spectroscopy, we were able to distinguish the major Sb compounds in plant tissue under different Sb treatments. The results help to understand the translocation and transformation of different Sb species in plants after uptake and provide information for risk assessment of plant growth in Sb contaminated soils.

We developed a novel indicator, daily excessive concentration hours (DECH), to explore the acute mortality impacts of ambient fine particulate matter pollution (PM2.5) in Hong Kong. The DECH of PM2.5 was calculated as daily concentration-hours >25 μg/m3. We applied a generalized additive models to quantify the association between DECH and mortality with adjustment for potential confounders. The results showed that the DECH was significantly associated with mortality. The excess mortality risk for an interquartile range (565 μg/m3*hours) increase in DECH of PM2.5 was 1.65% (95% CI: 1.05%, 2.26%) for all natural mortality at lag 02 day, 2.01% (95% CI: 0.82%, 3.21%) for cardiovascular mortality at lag 03 days, and 1.41% (95% CI: 0.34%, 2.49%) for respiratory mortality at lag 2 day. The associations remained consistent after adjustment for gaseous air pollutants (daily mean concentration of SO2, NO2 and O3) and in alternative model specifications. When compared to the mortality burden of daily mean PM2.5, DECH was found to be a relatively conservative indicator. This study adds to the evidence by showing that daily excessive concentration hours of PM2.5 might be a new predictor of mortality in Hong Kong.

The aim of the present study was to link Pb toxicokinetics to toxicodynamics in Enchytraeus crypticus. The enchytraeids were exposed for 14 d to different Pb concentrations (uptake phase) in natural Lufa 2.2 soil, followed by a 14-d elimination phase in clean soil. Pb accumulation and enchytraeid mortality were determined at different time intervals. At each exposure concentration, internal Pb concentration increased with exposure time and achieved equilibrium in approximately 7 d. Median lethal concentration (LC50) based on total Pb concentration in soil decreased with exposure time, but did not reach a steady-state level. Pb toxicity, therefore, showed a delay compared to accumulation in E. crypticus. LC50s based on internal Pb concentrations in the surviving animals did reach steady state in approx.14 d, suggesting that linking toxicokinetics to toxicodynamics may reduce the effects of time. This study highlighted that exposure time, as an important factor in metal uptake and toxicity, should be taken into account in ecotoxicological tests for risk assessment.

Perfluorooctanoic acid (PFOA) has received an increasing attention in the agricultural and food industries due to its risk to human health. To facilitate the development of novel biomarkers of Escherichia coli against PFOA through multi-omics technologies, and to reveal the resistance mechanism of E. coli against PFOA at protein levels, the interactions among pollutant stress, protein expression and cell metabolism was investigated by using iTRAQ-based quantitative proteomic analysis. The results revealed that the 63 up-regulated proteins mainly involved in tricarboxylic acid cycle, glyoxylate and dicarboxylate metabolism and fatty acid biosynthesis, whereas, the 69 down-regulated proteins related to oxidative phosphorylation, pyruvate metabolism and the cell cycle-caulobacter pathway, were also associated with the increase of membrane permeability, excessive expenditure of ATP, disruption of fatty acid biosynthesis under PFOA stress. The results provide novel insights into the influence mechanisms of PFOA on fatty acid and protein networks.