Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils requires a higher microbial viability and an increased PAH bioavailability. The clay/modified clay-modulated bacterial degradation could deliver a more efficient removal of PAHs in soils depending on the bioavailability of the compounds. In this study, we modified clay minerals (smectite and palygorskite) with mild acid (HCl) and alkali (NaOH) treatments (0.5–3 M), which increased the surface area and pore volume of the products, and removed the impurities without collapsing the crystalline structure of clay minerals. In soil incubation studies, supplements with the clay products increased bacterial growth in the order: 0.5 M HCl ≥ unmodified ≥0.5 M NaOH ≥3 M NaOH ≥3 M HCl for smectite, and 0.5 M HCl ≥3 M NaOH ≥0.5 M NaOH ≥3 M HCl ≥ unmodified for palygorskite. A14C-tracing study showed that the mild acid/alkali-treated clay products increased the PAH biodegradation (5–8%) in the order of 0.5 M HCl ≥ unmodified > 3 M NaOH ≥ 0.5 M NaOH for smectite, and 0.5 M HCl > 0.5 M NaOH ≥ unmodified ≥ 3 M NaOH for palygorskite. The biodegradation was correlated (r = 0.81) with the bioavailable fraction of PAHs and microbial growth as affected particularly by the 0.5 M HCl and 0.5 M NaOH-treated clay minerals. These results could be pivotal in developing a clay-modulated bioremediation technology for cleaning up PAH-contaminated soils and sediments in the field.

Clay minerals are the most popular adsorbents/amendments for immobilizing heavy metals in contaminated soils, but the dissolved organic matter (DOM) in soil environment would potentially affect the adsorption/immobilization capacity of clay minerals for heavy metals. In this study, the effects of DOM derived from chicken manure (CM) on the adsorption of cadmium (Cd2+) on two clay minerals, bentonite and zeolite, were investigated. The equilibrium data for Cd2+ sorption in the absence or presence of CM-DOM could be well-fitted to the Langmuir equation (R2 > 0.97). The presence of CM-DOM in the aqueous solution was found to greatly reduce the adsorption capacity of both minerals for Cd2+, in particular zeolite, and the percentage decreases for Cd2+ sorption increased with increasing concentrations of Cd2+ as well as CM-DOM in aqueous solutions. The adsorption of CM-DOM on zeolite was greater than that on bentonite in the absence of Cd2+, however, a sharp increase was observed for CM-DOM sorption on bentonite with increasing Cd2+ concentrations but little change for that on zeolite, which can be attributed to the different ternary structures on mineral surface. The CM-DOM modified clay minerals were utilized to investigate the effect of mineral-adsorbed CM-DOM on Cd2+ sorption. The adsorbed form was found to inhibit Cd2+ sorption, and further calculation suggested it primarily responsible for the overall decrease in Cd2+ sorption on clay minerals in the presence of CM-DOM in aqueous solutions. An investigation for the mineral surface morphology suggested that the mineral-adsorbed CM-DOM decreased Cd2+ sorption on bentonite mainly through barrier effect, while in the case of zeolite, it was the combination of active sites occupation and barrier effect. These results can serve as a guide for evaluating the performance of clay minerals in immobilizing heavy metals when animal manure is present in contaminated soils.

The usage of inadequately processed industrial waste water (WW) can lead to strong soil alkalinity and soil salinization of agricultural fields with negative consequences on soil properties and biota. Gypsum as a soil amendment to saline-sodic soils is widely used in agricultural fields to improve their soil physical, chemical and hence biological properties. This study aimed at analysing the effects of intensive WW irrigation on the structure and composition of soil-dwelling arthropods on spinach fields (Spinacia oleracea L.) in a West African urban vegetable production system. We used gypsum as a soil amendment with the potential to alleviate soil chemical stress resulting in a potentially positive impact on soil arthropods. A total of 32 plots were established that showed a gradient in soil pH ranging from slight to strong soil alkalinity and that were irrigated with WW (n = 12) or clean water (CW; n = 20), including eight plots into which gypsum was incorporated. Our study revealed a high tolerance of soil-dwelling arthropods for alkaline soils, but spinach fields with increased soil electrical conductivity (EC) showed a reduced abundance of Hymenoptera, Diptera and Auchenorrhyncha. Arthropod abundance was positively related to a dense spinach cover that in turn was not affected by WW irrigation or soil properties. Gypsum application reduced soil pH but increased soil EC. WW irrigation and related soil pH affected arthropod composition in the investigated spinach fields which may lead to negative effects on agronomical important arthropod groups such as pollinators and predators.

4-nitrophenol (PNP), isolated from diesel exhaust particles, has estrogenic and anti-androgenic activities, and affects the hypothalamus-pituitary-gonad axis in male rats. However, the effect of PNP on the reproduction of the female rats is still unknown. The aim of the study was to investigate the effect of neonatal PNP exposure on the ovarian function of female rats. The neonatal female rats were exposed to PNP (10 mg/kg, subcutaneously injection), the ovary and serum samples were collected at postnatal day (PND) 7, 14 and 21. The results showed that the ratio of primordial and primary follicles increased whereas the ratio of antral follicles decreased in the PNP treated ovaries at PND21. Even though no abnormality was observed in cyclicity, there was a significantly delayed timing of vaginal opening in PNP treated rats. The ovarian expressions of steroidogenic enzymes including StAR, P450scc, P450c17 and P450arom increased at PND14 in the PNP treated rats compared with the control rats. In consistent with the gene expressions, the concentration of estradiol-17β showed the similar pattern. However, PNP exposure failed to cause any significant change in the expressions of steroidogenic enzymes in cultured neonatal ovaries. Furthermore, PNP suppressed the expression of estrogen receptor β (ERβ), but not estrogen receptor α (ERα), in cultured ovaries or developmental ovaries. These results suggested that PNP might directly affect the expression of ERβ in the rat ovaries, resulting in the disrupted steroidogenesis during ovarian development and the delayed puberty.

Polybrominated diphenyl ethers (PBDEs) have been used in a broad array of polymeric materials such as plastics, foams, resins and adhesives to inhibit the spread of fires since the 1970s. The widespread environmental contamination and well documented toxic effects of PBDEs have led to bans and voluntary withdrawals in many jurisdictions. Replacement novel brominated flame retardants (NBFRs) have, however, exhibited many of the same toxic characteristics as PBDEs and appear to share similar environmental fate. This paper presents a critical review of the scientific literature regarding PBDE and NBFR contamination of surface soils internationally, with the secondary objective of identifying probable pollution sources. An evaluation of NBFR distribution in soil was also conducted to assess the suitability of the newer compounds as replacements for PBDEs, with respect to their land contamination potential. Principle production of PBDEs and NBFRs and their consequent use in secondary polymer manufacture appear to be processes with strong potential to contaminate surrounding soils. Evidence suggests that PBDEs and NBFRs are also released from flame retarded products during disposal via landfill, dumping, incineration and recycling. While the land application of sewage sludge represents another major pathway of soil contamination it is not considered in this review as it is extensively covered elsewhere. Both PBDEs and NBFRs were commonly detected at background locations including Antarctica and northern polar regions. PBDE congener profiles in soil were broadly representative of the major constituents in Penta-, Octa- and Deca-BDE commercial mixtures and related to predicted market place demand. BDE-209 dominated soil profiles, followed by BDE-99 and BDE-47. Although further research is required to gain baseline data on NBFRs in soil, the current state of scientific literature suggests that NBFRs pose a similar risk to land contamination as PBDEs.

Recent studies demonstrated that the common pyrethroid insecticides are present in aquatic biota tissues. In this study, 123 samples of unhatched eggs of 16 wild bird species collected from 2010 to 2012 in Doñana National and Natural Park were analysed to determine 13 pyrethroids. This study represents the first time that pyrethroids are detected in tissues of terrestrial biota, 93% of these samples being positive to those pollutants. Levels of total pyrethroids ranged from not detected to 324 ng g−1 lw. The samples were characterized by stable isotope analysis. Species with diets based on anthropogenic food showed higher levels of pyrethroids and lower values of δ15N. Finally, we characterized the isomers of pyrethroids and discerned some isomeric- and enantiomeric-specific accumulations. In particular, tetramethrin and cyhalothrin showed an enantiomeric-selective accumulation of one enantiomer, highlighting the need to assess toxicological effects of each enantiomer separately to be able to make a correct risk assessment of pyrethroids in birds.

Many studies have been conducted focusing on the contribution of land emission sources to PM2.5 in China; however, little attention had been paid to other contributions, especially the secondary contributions from shipping emissions to atmospheric PM2.5. In this study, a combined source apportionment approach, including principle component analysis (PCA) and WRF-CMAQ simulation, was applied to identify both primary and secondary contributions from ships to atmospheric PM2.5. An intensive PM2.5 observation was conducted from April 2014 to January 2015 in Qinhuangdao, which was close to the largest energy output port of China. The chemical components analysis results showed that the primary component was the major contributor to PM2.5, with proportions of 48.3%, 48.9%, 55.1% and 55.4% in spring, summer, autumn and winter, respectively. The secondary component contributed higher fractions in summer (48.2%) and winter (36.8%), but had lower percentages in spring (30.1%) and autumn (32.7%). The hybrid source apportionment results indicated that the secondary contribution (SC) of shipping emissions to PM2.5 could not be ignored. The annual average SC was 2.7%, which was comparable to the primary contribution (2.9%). The SC was higher in summer (5.3%), but lower in winter (1.1%). The primary contributions to atmospheric PM2.5 were 3.0%, 2.5%, 3.4% and 2.7% in spring, summer, autumn and winter, respectively. As for the detailed chemical components, the contributions of shipping emissions were 2.3%, 0.5%, 0.1%, 1.0%, 1.7% and 0.1% to elements & sea salt, primary organic aerosol (POA), element carbon (EC), nitrate, sulfate and secondary organic carbon (SOA), respectively. The results of this study will further the understanding of the implications of shipping emissions in PM2.5 pollution.

Various toxic chemicals used in hydraulic fracturing fluids may influence the inherent health risks associated with these operations. This study investigated the possible occupational inhalation exposures and potential risks related to the volatile organic compounds (VOCs) from chemical storage tanks and flowback pits used in hydraulic fracturing. Potential risks were evaluated based on radial distances between 5 m and 180 m from the wells for 23 contaminants with known inhalation reference concentration (RfC) or inhalation unit risks (IUR). Results show that chemicals used in 12.4% of the wells posed a potential acute non-cancer risks for exposure and 0.11% of the wells with may provide chronic non-cancer risks for exposure. Chemicals used in 7.5% of the wells were associated with potential acute cancer risks for exposure. Those chemicals used in 5.8% of the wells may be linked to chronic cancer risks for exposure. While eight organic compounds were associated with acute non-cancer risks for exposure (>1), methanol the major compound in the chemical storage tanks (1.00–45.49) in 7,282 hydraulic fracturing wells. Wells with chemicals additives containing formaldehyde exhibited both acute and chronic cancer risks for exposure with IUR greater than 10⁻⁶, suggesting formaldehyde was the dominant contributor to both types of risks for exposure in hydraulic fracturing. This study also found that due to other existing on-site emission sources of VOCs and the geographically compounded air concentrations from other surrounding wells, chemical emissions data from storage tanks and flowback pits used in this study were lower than reported concentrations from field measurements where higher occupational inhalation risks for exposure may be expected.

Hypoxia is a global problem in aquatic systems and often co-occurs with pollutants. Despite this, little is known about the combined effects of these stressors on aquatic organisms. The objective of this study was to investigate the combined effects of hypoxia and copper, a toxic metal widespread in the aquatic environment. We used the three-spined stickleback (Gasterosteus aculeatus) as a model because of its environmental relevance and amenability for environmental toxicology studies. We focused on embryonic development as this is considered to be a sensitive life stage to environmental pollution. We first investigated the effects of hypoxia alone on stickleback development to generate the information required to design subsequent studies. Our data showed that exposure to low oxygen concentrations (24.7 ± 0.9% air saturation; AS) resulted in strong developmental delays and increased mortalities, whereas a small decrease in oxygen (75.0 ± 0.5%AS) resulted in premature hatching. Stickleback embryos were then exposed to a range of copper concentrations under hypoxia (56.1 ± 0.2%AS) or normoxia (97.6 ± 0.1%AS), continuously, from fertilisation to free swimming larvae. Hypoxia caused significant changes in copper toxicity throughout embryonic development. Prior to hatching, hypoxia suppressed the occurrence of mortalities, but after hatching hypoxia significantly increased copper toxicity. Interestingly, when exposures were conducted only after hatching, the onset of copper-induced mortalities was delayed under hypoxia compared to normoxia, but after 48 h, copper was more toxic to hatched embryos under hypoxia. This is the second species for which the protective effect of hypoxia on copper toxicity prior to hatching, followed by its exacerbating effect after hatching is demonstrated, suggesting the hypothesis that this pattern may be common for teleost species. Our research highlights the importance of considering the interactions between multiple stressors, as understanding these interactions is essential to facilitate the accurate prediction of the consequences of exposure to complex stressors in a rapidly changing environment.