The transport and retention behavior of polymer- (PVP-AgNP) and surfactant-stabilized (AgPURE) silver nanoparticles in carbonate-dominated saturated and unconsolidated porous media was studied at the laboratory scale. Initial column experiments were conducted to investigate the influence of chemical heterogeneity (CH) and nano-scale surface roughness (NR) arising from mixtures of clean, positively charged calcium carbonate sand (CCS), and negatively charged quartz sands. Additional column experiments were performed to elucidate the impact of CH and NR arising from the presence and absence of soil organic matter (SOM) on a natural carbonate-dominated aquifer material. The role of the nanoparticle capping agent was examined under all conditions tested in the column experiments. Nanoparticle transport was well described using a numerical model that facilitated blocking on one or two retention sites. Results demonstrate that an increase in CCS content in the artificially mixed porous medium leads to delayed breakthrough of the AgNPs, although AgPURE was much less affected by the CCS content than PVP-AgNPs. Interestingly, only a small portion of the solid surface area contributed to AgNP retention, even on positively charged CCS, due to the presence of NR which weakened the adhesive interaction. The presence of SOM enhanced the retention of AgPURE on the natural carbonate-dominated aquifer material, which can be a result of hydrophobic or hydrophilic interactions or due to cation bridging. Surprisingly, SOM had no significant impact on PVP-AgNP retention, which suggests that a reduction in electrostatic repulsion due to the presence of SOM outweighs the relative importance of other binding mechanisms. Our findings are important for future studies related to AgNP transport in shallow unconsolidated calcareous and siliceous carbonate sands.

Fly ash generated from coal-fired power plants is a source of potential pollutants, but can be used as a soil ameliorant to increase plant biomass and yield in agriculture. However, the effects of fly ash soil application on plant biomass and the accumulation of both nutrient and toxic elements in plants remain unclear. Based on 85 articles, we conducted a comprehensive meta-analysis to evaluate changes in plant biomass and concentrations of 21 elements in plants in response to fly ash application. These elements included macro-nutrients (N, P, K, Ca, and S), micro-nutrients (B, Co, Cu, Fe, Mn, Mo, Ni, and Zn), and metal(loid)s (Al, As, Cd, Cr, Pb, and Se). Overall, fly ash application decreased plant biomass by 15.2%. However, plant biomass was enhanced by fly ash application by 11.6–29.2% at lower application rates (i.e. <25% of soil mass), and decreased by 45.8% at higher application rates (i.e. 50–100%). Belowground biomass was significantly reduced while yield was enhanced by fly ash application. Most of the element concentrations in plants were enhanced by fly ash application, and followed a descending order with metal(loid)s > micro-nutrients > macro-nutrients. Concentrations of elements tended to increase with an increase in fly ash application rate. Our syntheses indicated that fly ash should be applied at less than 25% in order to enhance plant biomass and yield but avoid high accumulations of metal(loid)s.

High-density polyethylene (HDPE) is a known sorbent for non-ionic organic compounds in technical applications. Nevertheless, there is little information available describing sorption to industrial HDPE for a broad range of compounds. With a better understanding of the sorption properties of synthetic polymers, environmental risk assessment would achieve a higher degree of accuracy, especially for microplastic interactions with organic substances. Therefore, a robust methodology for the determination of sorbent properties for non-ionic organic compounds by HDPE is relevant for the understanding of molecular interactions for both technical use and environmental risk assessment.In this work, sorption properties of HDPE material used for water pipes were characterized using a poly-parameter linear free-energy relationship (ppLFER) approach. Sorption batch experiments with selected probe sorbates were carried out in a three-phase system (air/HDPE/water) covering an aqueous concentration range of at least three orders of magnitude. Sorption in the concentration range below 10⁻² of the aqueous solubility was found to be non-linear and the Freundlich model was used to account for this non-linearity. Multiple regression analysis (MRA) using the determined distribution coefficients and literature-tabulated sorbate descriptors was performed to obtain the ppLFER phase descriptors for HDPE. Sorption properties of HDPE were then derived from the ppLFER model and statistical analysis of its robustness was conducted. The derived ppLFER model described sorption more accurately than commonly used single-parameter predictions, based i.e., on log Kₒ/w. The ppLFER predicted distribution data with an error 0.5 log units smaller than the spLFERs. The ppLFER was used for a priori prediction of sorption by the characterized sorbent material. The prediction was then compared to experimental data from literature and this work and demonstrated the strength of the ppLFER, based on the training set over several orders of magnitude.

Endocrine-disrupting chemicals (EDCs) are widely used in various consumer goods. Consequently, humans are constantly exposed to EDCs, which is associated with a variety of endocrine-related diseases. In this study, we demonstrated the effects of bisphenol A (BPA), benzyl butyl phthalate (BBP), and di(2-ethylhexyl) phthalate (DEHP) on estrogen receptor alpha (ERα) expression under normoxia and hypoxia. First, we confirmed the effects of EDCs on ER activity using OECD Test Guideline 455. Compared to the 100% activity induced by 1 nM 17-β-estradiol (positive control), BPA and BBP exhibited 50% ERα activation at concentrations of 1.31 μM and 4.8 μM, respectively. In contrast, and consistent with previous reports, DEHP did not activate ERα. ERα is activated and degraded by hypoxia in breast cancer cells. BPA, BBP, and DEHP enhanced ERα-mediated transcriptional activity under hypoxia. All three EDCs decreased ERα protein levels under hypoxia in MCF-7 cells. The transcriptional activity of hypoxia-inducible factor-1 was decreased and secretion of vascular endothelial growth factor (VEGF) was increased by BPA and BBP under hypoxia in MCF-7 cells, but not by DEHP. All three EDCs decreased the ERα protein expression level in Ishikawa human endometrial adenocarcinoma cells, and DEHP caused a weak decrease in VEGF secretion under hypoxia. These results demonstrate down-regulation of ERα by EDCs may influence the pathological state associated with hypoxia.

Estuaries are dynamic ecosystems which vary widely in loading of the contaminant methylmercury (MeHg), and in environmental factors which control MeHg exposure to the estuarine foodweb. Inputs of organic carbon and rates of primary production are important influences on MeHg loading and bioaccumulation, and are predicted to increase with changes in climate and land use pressures. To further understand these influences on MeHg levels in estuarine biota, we used a field study approach in sites across different temperature regions, and with varying organic carbon levels. In paired comparisons of sites with high vs. low organic carbon, fish had lower MeHg bioaccumulation factors (normalized to water concentrations) in high carbon sites, particularly subsites with large coastal wetlands and large variability in dissolved organic carbon levels in the water column. Across sites, MeHg level in the water column was strongly tied to dissolved organic carbon, and was the major driver of MeHg concentrations in fish and invertebrates. Higher primary productivity (chlorophyll-a) was associated with increased MeHg partitioning to suspended particulates, but not to the biota. These findings suggest that increased inputs of MeHg and loss of wetlands associated with climate change and anthropogenic land use pressure will increase MeHg concentrations in estuarine food webs.

Urban stormwater reuse is becoming increasingly prevalent to overcome the serious urban water scarcity being experienced around the world. Therefore, the adoption of reliable approaches to minimise the human health risk posed by pollutants commonly present in urban stormwater such as heavy metals and polycyclic aromatic hydrocarbons (PAHs) is critical for safe stormwater reuse. This study collected a total of 40 pollutant build-up samples and analysed the concentrations of nine heavy metals and 15 PAH species. Based on pollutant build-up data, pollutant concentrations in stormwater were estimated through modelling. Risk assessment was conducted using an existing model developed by previous studies. The study outcomes confirmed that simply evaluating the individual pollutant concentrations based on guideline threshold values cannot comprehensively estimate the overall human health risk posed by these pollutants. Accordingly, it is recommended that the assessment of the overall human health risk should be based on the pollutant mix present as provided by the models discussed in this paper. The study has also demonstrated the practical application of a robust risk assessment model to derive the hierarchy of hazard control to provide a reliable underpinning to urban stormwater risk management. The outcomes suggest that decentralised hazard control methods such as the provision of custom designed Water Sensitive Urban Design (WSUD) measures can be implemented in priority areas with high risk from stormwater pollution based on the risk assessment undertaken. Distributed hazard control methods can be applied to reduce the generation of primary toxic pollutants, especially chromium (Cr) and heavy PAHs, through elimination and substitution measures. The percentage reduction in traffic volume required to mitigate the human health risk can be quantified through the risk models presented. The study outcomes will contribute to the development of efficient, targeted and reliable stormwater management strategies and to identify viable opportunities for stormwater reuse.

To better understand the toxicological activities of perfluorooctanoic acid (PFOA), we examined the effects of PFOA on apoptosis and its molecular mechanism in SMMC-7721 hepatoma cells. Cell viability was evaluated by MTT assay and apoptosis was determined by flow cytometry. Western blot and quantitative real-time PCR were used to examine the protein and gene expressions of Bax and Bcl-2. Our results showed that PFOA inhibited SMMC-7721 cell growth and induced apoptosis. PFOA treatment increased Bax expression and increased Bcl-2 expression at both gene and protein levels. Our study demonstrated that PFOA had toxic effects on SMMC-7721 cells, such as inhibiting cell proliferation and inducing apoptosis. Furthermore, we showed that PFOA-mediated induction of apoptosis involved inducing Bax and decreasing Bcl-2 expression as a molecular mechanism of its toxicological effects.

Endocrine disrupting chemicals (EDCs) include a wide array of pollutants, such as some metals and other toxic elements, which may cause changes in hormonal homeostasis. In addition to affecting physiology of individuals directly, EDCs may alter the transfer of maternal hormones to offspring, i.e. causing transgenerational endocrine disruption. However, such effects have been rarely studied, especially in wild populations. We studied the associations between environmental elemental pollution (As, Cd, Cu, Ni, Pb) and maternally-derived egg thyroid hormones (THs) as well as nestling THs in great tits (Parus major) using extensive sampling of four pairs of polluted and reference populations across Europe (Finland, Belgium, Hungary, Portugal). Previous studies in these populations showed that breeding success, nestling growth and adult and nestling physiology were altered in polluted zones compared to reference zones. We sampled non-incubated eggs to measure maternally-derived egg THs, measured nestling plasma THs and used nestling faeces for assessing local elemental exposure. We also studied whether the effect of elemental pollution on endocrine traits is dependent on calcium (Ca) availability (faecal Ca as a proxy) as low Ca increases toxicity of some elements. Birds in the polluted zones were exposed to markedly higher levels of toxic elements than in reference zones at the populations in Finland, Belgium and Hungary. In contrast to our predictions, we did not find any associations between overall elemental pollution, or individual element concentrations and egg TH and nestling plasma TH levels. However, we found some indication that the effect of metals (Cd and Cu) on egg THs is dependent on Ca availability. In summary, our results suggest that elemental pollution at the studied populations is unlikely to cause overall TH disruption and affect breeding via altered egg or nestling TH levels with the current elemental pollution loads. Associations with Ca availability should be further studied.

Harmful algal blooms have emerged as a worldwide issue. After concentrations of herbicides entering water, herbicides in water may pose ecological effects on them. The present study investigates the toxicity and environmental behavior of the herbicides, napropamide and acetochlor as enantiomers and as racemates on Microcystis aeruginosa which is the main specie known to produce hepatotoxins. S-napropamide/acetochlor are degraded faster than their corresponding isomer R-napropamide/acetochlor, with the latter more prone to accumulate in algal cells. Moreover, all the enantiomers did not undergo measurable racemization in the medium and algal cells. S-napropamide/acetochlor exhibited much higher toxicity than R-napropamide/acetochlor, with the S-enantiomer inducing a much greater production of antioxidant defense enzymes (superoxide dismutase (SOD) and malondialdehyde (MDA)) and microcystins (MC). SOD and MC increased after treatment with the herbicides and these increases were dependent on the exposure time, whereas MDA showed no apparent change. The information provided in this work will be useful for understanding the toxicity mechanism and environmental behaviors of different amide herbicides (napropamide and acetochlor) in aquatic environments at the enantiomeric level. Additionally, analysis of chiral herbicides in aquatic system needs more attention to aide in the environmental assessment of chiral herbicides.

Urban population exposure to tropospheric ozone is a serious health concern in Europe countries. Although there are insufficient evidence to derive a level below which ozone has no effect on mortality WHO (World Health Organization) uses SOMO35 (sum of means over 35 ppb) in their health impact assessments. Is this paper, the artificial neural network (ANN) approach was used to forecast SOMO35 at the national level for a set of 24 European countries, mostly EU members. Available ozone precursors’ emissions, population and climate data for the period 2003–2013 were used as inputs. Trend analysis had been performed using the linear regression of SOMO35 over time, and it has demonstrated that majority of the studied countries have a decreasing trend of SOMO35 values.The created models have made majority of predictions (≈60%) with satisfactory accuracy (relative error <20%) on testing, while the best performing model had R² = 0.87 and overall relative error of 33.6%. The domain of applicability of the created models was analyzed using slope/mean ratio derivate from the trend analysis, which was successful in distinguishing countries with high from countries with low prediction errors. The overall relative error was reduced to <14%, after the pool of countries was reduced based on the abovementioned criterion.