The causation between bioavailability of heavy metals and environmental factors are generally obtained from field experiments at local scales at present, and lack sufficient evidence from large scales. However, inferring causation between bioavailability of heavy metals and environmental factors across large-scale regions is challenging. Because the conventional correlation-based approaches used for causation assessments across large-scale regions, at the expense of actual causation, can result in spurious insights. In this study, a general approach framework, Intervention calculus when the directed acyclic graph (DAG) is absent (IDA) combined with the backdoor criterion (BC), was introduced to identify causation between the bioavailability of heavy metals and the potential environmental factors across large-scale regions. We take the Pearl River Delta (PRD) in China as a case study. The causal structures and effects were identified based on the concentrations of heavy metals (Zn, As, Cu, Hg, Pb, Cr, Ni and Cd) in soil (0–20 cm depth) and vegetable (lettuce) and 40 environmental factors (soil properties, extractable heavy metals and weathering indices) in 94 samples across the PRD. Results show that the bioavailability of heavy metals (Cd, Zn, Cr, Ni and As) was causally influenced by soil properties and soil weathering factors, whereas no causal factor impacted the bioavailability of Cu, Hg and Pb. No latent factor was found between the bioavailability of heavy metals and environmental factors. The causation between the bioavailability of heavy metals and environmental factors at field experiments is consistent with that on a large scale. The IDA combined with the BC provides a powerful tool to identify causation between the bioavailability of heavy metals and environmental factors across large-scale regions. Causal inference in a large system with the dynamic changes has great implications for system-based risk management.

Silvopastoral systems aim to enhance economic, cultural and social principles by sustainably combining forest management with agriculture. In these typically high-nitrogen (N) environments, plant species selection can profoundly influence N fluxes. For grazed pastures, plants may be exposed to urine patches that have received the equivalent of up to 1000 kg N ha−1. We aimed to determine the growth and N fluxes in three potential trees that may be used in silvopastoral systems: L. scoparium, K. robusta and P. radiata. Plants were grown in a greenhouse lysimeter experiment, with controlled irrigation and temperature and exposed to N at rates of 200 kg ha−1 equiv. for 15 weeks, followed by the addition of 800 kg ha−1 N equiv, to simulate a urine patch. Urea produced a positive growth response of all plant species. Treatments containing L. scoparium and K. robusta leached lower amounts of nitrate (NO3−) (2 kg ha−1 NO3−) compared to P. radiata (53 kg ha−1). Measurements of N2O over 20 days after the application of 800 kg N ha−1 indicated an inhibitory effect of L. scoparium and K. robusta on denitrification, hence loss of N via N2O. Both L. scoparium and K. robusta demonstrated that they have potential to reduce N-losses in silvopastural systems, while producing valuable biomass.

The present study was performed to determine the effect of Zn exposure influencing endoplasmic reticulum (ER) stress, explore the underlying molecular mechanism of Zn-induced hepatic lipolysis in a fish species of significance for aquaculture, yellow catfish Pelteobagrus fulvidraco. We found that waterborne Zn exposure evoked ER stress and unfolded protein response (UPR), and activated cAMP/PKA pathway, and up-regulated hepatic lipolysis. The increase in ER stress and lipolysis were associated with activation of cAMP/PKA signaling pathway. Zn also induced an increase in intracellular Ca2+ level, which could be partially prevented by dantrolene (RyR receptor inhibitor) and 2-APB (IP3 receptor inhibitor), demonstrating that the disturbed Ca2+ homeostasis in ER contributed to ER stress and dysregulation of lipolysis. Inhibition of ER stress by PBA attenuated UPR, inhibited the activation of cAMP/PKA pathway and resulted in down-regulation of lipolysis. Inhibition of protein kinase RNA-activated-like ER kinase (PERK) by GSK2656157 and inositol-requiring enzyme (IRE) by STF-083010 differentially influenced Zn-induced changes of lipolytic metabolism, indicating that PERK and IRE pathways played different regulatory roles in Zn-induced lipolysis. Inhibition of PKA by H89 blocked the Zn-induced activation of cAMP/PKA pathway with a concomitant inhibition of ER stress-mediated lipolysis. Taken together, our findings highlight the importance of the ER stress–cAMP/PKA axis in Zn-induced lipolysis, which provides new insights into Zn toxicology in fish and probably in other vertebrates.

Selenium (Se) speciation in soil is critically important for understanding the solubility, mobility, bioavailability, and toxicity of Se in the environment. In this study, Se fractionation and chemical speciation in agricultural soils from seleniferous areas were investigated using the elaborate sequential extraction and X-ray absorption near-edge structure (XANES) spectroscopy. The speciation results quantified by XANES technique generally agreed with those obtained by sequential extraction, and the combination of both approaches can reliably characterize Se speciation in soils. Results showed that dominant organic Se (56–81%) and lesser Se(IV) (19–44%) were observed in seleniferous agricultural soils. A significant decrease in the proportion of organic Se to the total Se was found in different types of soil, i.e., paddy soil (81%) > uncultivated soil (69–73%) > upland soil (56–63%), while that of Se(IV) presented an inverse tendency. This suggests that Se speciation in agricultural soils can be significantly influenced by different cropping systems. Organic Se in seleniferous agricultural soils was probably derived from plant litter, which provides a significant insight for phytoremediation in Se-laden ecosystems and biofortification in Se-deficient areas. Furthermore, elevated organic Se in soils could result in higher Se accumulation in crops and further potential chronic Se toxicity to local residents in seleniferous areas.

Nine N-nitrosamines (i.e., N-nitrosomethylamine, N-nitrosodiethylamine (NDEA), N-nitrosodimethylamine (NDMA), N-nitrosodi-n-propylamine (NDPA), N-nitrosomorpholine (NMor), N-nitrosopyrrolidine (NPyr), N-nitrosopiperidine (NPip), N-nitorosodi-n-butylamine (NDBA), and N-nitrosodiphenylamine (NDPhA) in atmospheric PM2.5 collected in the fall season from an roadside site and a residential in Seoul, Korea have been analyzed using a newly developed method consisting of simple direct liquid extraction assisted by ultrasonication and subsequent quantification using a gas chromatography-triple quadrupole mass spectrometry (GC-TQMS). Excellent recovery values (92–100%) and method detection limits for the target compounds atmospheric PM samples could be achieved even without an evaporation step for sample concentration. The concentration of total N-nitrosamines in PM2.5 was ranged from 0.3 to 9.4 ng m−3 in this study; NDMA, NDEA, NDBA, NPyr, and NMor in PM2.5 were found to be the most frequently encountered compounds at the sampling sites. Since no industrial plant is located in Seoul, vehicle exhausts were considered major cause of the formation of nitrosamines in this study. The mechanisms how these compounds are formed and detected in the atmosphere are explained from the viewpoint of secondary organic aerosol. Considering the concentrations of N-nitrosamines and their associated potential health risks, a systematic monitoring of nitrosamines present in both ambient air and PM2.5 including seasonal and diurnal variations of selected sites (including potential precursor sources) should be carried out in the future. The proposed sample pretreatment method along with the analytical method will definitely help us perform the monitoring study.

Metal exposure can produce oxidative stress by disrupting the prooxidant/antioxidant balance. It has been suggested that calcium (Ca) may provide protection against metal toxicity in the organism. The objective of this study is to explore the effects of Ca availability and metal pollution on oxidative stress biomarkers in pied flycatcher (Ficedula hypoleuca) nestlings. For this purpose, we performed a Ca-supplementation experiment with birds inhabiting a Ca-poor and metal-polluted area in SW Finland. An array of oxidative stress biomarkers (GSH, GSH:GSSG ratio, GPx, GST, CAT, SOD, lipid peroxidation and protein carbonylation) was measured in red blood cells. The effects of antioxidant molecules and oxidative damage on nestling size, growth, fledging success and fledgling number were evaluated. We observed an up-regulation of GST activity and increased protein carbonyl content in the polluted zone, probably related to a combination of higher metal exposure and reduced food quantity and quality in this area. As expected, birds from the unpolluted zone showed higher GSH:GSSG ratio but, unexpectedly, also showed signs of higher lipid peroxidation (not statistically significant, p = 0.056), both responses likely being related with the lower Ca availability. Our study suggests that different measures of oxidative damage are affected by different factors: while damage to proteins was the target of metal exposure/food limitation, poor Ca availability may enhance damage to lipids in growing birds. The intercorrelations found between Ca in plasma, metal exposure and the different oxidative stress biomarkers show that the antioxidant defense is finely regulated to cope with increased oxidative challenges. Finally, our results suggest that the antioxidant status during early development, conditioned by environmental pollution and Ca availability, is one factor affecting nestling survival and fledgling number.

On-road emissions vary widely on time scales as short as minutes and length scales as short as tens of meters. Detailed data on emissions at these scales are a prerequisite to accurately quantifying ambient pollution concentrations and identifying hotspots of human exposure within urban areas. We construct a highly resolved inventory of hourly fluxes of CO, NO2, NOx, PM2.5 and CO2 from road vehicles on 280,000 road segments in eastern Massachusetts for the year 2012. Our inventory integrates a large database of hourly vehicle speeds derived from mobile phone and vehicle GPS data with multiple regional datasets of vehicle flows, fleet characteristics, and local meteorology. We quantify the ‘excess’ emissions from traffic congestion, finding modest congestion enhancement (3–6%) at regional scales, but hundreds of local hotspots with highly elevated annual emissions (up to 75% for individual roadways in key corridors). Congestion-driven reductions in vehicle fuel economy necessitated ‘excess’ consumption of 113 million gallons of motor fuel, worth ∼ $415M, but this accounted for only 3.5% of the total fuel consumed in Massachusetts, as over 80% of vehicle travel occurs in uncongested conditions. Across our study domain, emissions are highly spatially concentrated, with 70% of pollution originating from only 10% of the roads. The 2011 EPA National Emissions Inventory (NEI) understates our aggregate emissions of NOx, PM2.5, and CO2 by 46%, 38%, and 18%, respectively. However, CO emissions agree within 5% for the two inventories, suggesting that the large biases in NOx and PM2.5 emissions arise from differences in estimates of diesel vehicle activity. By providing fine-scale information on local emission hotspots and regional emissions patterns, our inventory framework supports targeted traffic interventions, transparent benchmarking, and improvements in overall urban air quality.

Sediment cores were collected in urban (0–50 cm), rural (0–40 cm) and reclamation-affected river (0–40 cm) environments in the Pearl River Delta. Concentrations of 16 organochlorine pesticides (OCPs) were determined in all collected samples to identify the depth-distribution, possible sources and ecotoxicological risks of OCPs in river sediments affected by urbanization and reclamation in a Chinese delta. The results showed that the top 10 cm of rural river sediments had slightly lower concentrations of the 16 OCPs compared to urban and reclamation-affected rivers, whereas the 30–40 cm sediment layers in the rural river showed higher levels of the 16 OCPs. However, higher OCPs levels were observed in the 20–30 cm sediment layers in the urban river than in the rural and reclamation-affected rivers. The principal OCPs in most deeper sediment layers were hexachlorobezene (HCB), the combination of aldrin, endrin and dieldrin (ΣDRINs) and the combination of α-HCH, β-HCH and γ-HCH (ΣHCHs). The predominant OCPs in surface sediments were HCB, ΣDRINs and the combination of p,p’-DDD, o,p’-DDT, p,p’-DDT and p,p’-DDE (ΣDDTs). Generally, OCP concentrations decreased with depth along sediment profiles at most sampling sites in the three types of rivers. The source analyses indicated that some sampling sites were still suffering from the recent use of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and aldrin. According to the soil quality thresholds of China, the levels of HCHs and DDTs at most sampling sites were below class Ⅰ criteria. Based on the sediment quality guideline quotient (SQGQ), the combined ecotoxicological risk of OCPs (γ-HCH, dieldrin, p,p'-DDD, p,p'-DDE and p,p'-DDT) in surface sediments (0–10 cm) was higher than deeper sediments, and the rural river sediments exhibited a higher combined ecotoxicological risk than the sediments in urban and reclamation-affected rivers.

Oil sands process-affected water (OSPW) — a byproduct of the oil sands industry in Northern Alberta, Canada – is currently stored in on-site tailings ponds. The goal of the present study was to investigate the interaction of OSPW with the olfactory system and olfactory-mediated behaviours of fish upon the first encounter with OSPW. The response of rainbow trout (Oncorhynchus mykiss) to different concentrations (0.1, 1, and 10%) of OSPW was studied using a choice maze and electro-olfactography (EOG), respectively. The results of the present study showed that rainbow trout are capable of detecting and avoiding OSPW at a concentration as low as 0.1%. Exposure to 1% OSPW impaired (i.e. reduced sensitivity) the olfactory response of rainbow trout to alarm and food cues within 5 min or less. The results of the present study demonstrated that fish could detect and avoid minute concentrations of OSPW. However, if fish were exposed to OSPW-contaminated water and unable to escape, their olfaction would be impaired.