Tungstate enrichment in aquatic systems may cause negative environmental and health effects. This study addresses tungstate removal from aqueous solution by nanocrystalline iowaite, an iron-bearing layered double hydroxide, which has not been used for treatment of tungstate-rich waters so far. Tungstate sorption experiments were conducted with various contact times, temperatures, initial tungstate concentrations (0.001–2 mM), and solution pH values (2–13), the results indicating that iowaite sorbed aqueous tungstate effectively and quickly, and the sorption maximum can be up to 71.9 mg/g. Moreover, the tungsten sorption capacity keeps nearly constant at a wide pH range from 3 to 11. Duo to its pH buffering effect, the alkaline conditions were generated by the addition of iowaite, which are favorable for the removal of aqueous tungstate because the polymerization of tungstate can be prohibited at alkaline pH values. Zeta potential, XRD and XPS analyses were employed to clarify the sorption mechanisms, and it was concluded that tungstate was sorbed via its exchange with the chloride originally intercalated into iowaite interlayers as well as its stronger inner-sphere complexation with the Fe atoms located in iowaite layers. Nanocrystalline iowaite is suitable for treating both tungstate-bearing natural waters with moderately high tungstate concentrations and industrial wastewaters extremely rich in tungstate.

Tetracycline (TC) can enter the human body via the soil-vegetable-human food chain; therefore, it is necessary to understand the toxicity of TC to humans through vegetables grown on contaminated soils. The present study combined an enzyme-linked immunosorbent assay method and an HL-7702 cell model and assessed the bioavailability and toxicity of TC from pak choi (Brassica campestris L. ssp. chinensis) grown on TC-contaminated soils. The results showed that the degradation rate of TC in black soil was significantly higher than that in purplish clay, while the results for TC uptake in pak choi were opposite. The bioaccessibility of TC was found to be higher in pak choi grown on purplish clay (5.67–7.59%) than in that grown on black soil (5.22–6.77%). It is suggested that soil properties contribute to the uptake of TC by pak choi. More fertile soil contained lower TC concentrations and thus mediated lower TC toxicity to humans. It may seem comforting that TC concentrations in the edible parts of pak choi are often found to be below safe limits. However, the TC diagnosis method showed that even moderate increases in TC concentrations in pak choi may induce oxidative stress, liver injury, mitochondrial cristae and rough endoplasmic reticulum swelling, and early apoptosis in liver cells HL-7702. The pak choi grown in purplish clay showed higher TC cytotoxicity than that grown in black soil. The TC cytotoxicity of raw pak choi was found to be higher than that of cooked pak choi. These results provide direct evidence of effective ways to prevent TC toxicity in humans.

We studied the size distribution of ions (Cl⁻, NO₃⁻, SO₄⁼, Na⁺, NH₄⁺, K⁺, Mg⁺⁺, Ca⁺⁺) and elements (As, Ba, Cd, Co, Cs, Cu, Fe, Li, Mn, Ni, Pb, Rb, Sb, Se, Sn, Sr, Ti, Tl, V, Zn) during the winter and summer seasons of seven consecutive years (2008–2014) in an area of the Po Valley (Northern Italy) characterised by industrial, agricultural and urban settings. The study included the collection and analysis of 41 series of size-segregated samples (MOUDI sampler, 10 stages, cut sizes from 0.18 to 18 μm). Ions were analysed by ion chromatography; elemental analysis was carried out by ICP-MS, by applying a chemical fractionation method able to increase the selectivity of PM source tracers.Our results indicate that important winter/summer variations occurred in both the concentration and size distribution of most PM components. These variations were explained in terms of variations in the strength of the prevailing sources of each component.The contribution of biomass burning for domestic heating was highlighted by the well-known tracer K⁺ but also by the soluble fraction of Rb, Cs and Li. Biomass burning contribution to atmospheric PM was mostly contained in the fine fraction, with a broad size-distribution from 0.18 to 1.8 μm. This source also appreciably increased the concentration of other elements in fine PM (As, Cd, Co, Mn, Pb, Sb, Sn).A few PM components (tracers of sea-spray, brake lining and some industries) did not show marked seasonal variations in concentration and size distribution. However, during winter, for brake lining and industry tracers we observed an upward shift in the dimension of fine particles and a downward shift in the dimension of coarse particles, due to the ageing of the air masses.

Disinfection byproducts (DBPs) generated by ballast water treatment have become a concern worldwide because of their potential threat to the marine environment. Predicting the relative DBP concentrations after disinfection could enable better control of DBP formation. However, there is no appropriate method of evaluating DBP formation in a full-scale ballast water treatment system (BWTS). In this study, multiple regression models were developed for predicting the dibromochloromethane (DBCM) and bromoform (TBM) concentrations produced by an emergency BWTS using field experimental data from ballast water treatments conducted at Dalian Port, China. Six combinations of independent variables [including several water parameters and/or the total residual oxidant (TRO) concentration] were evaluated to construct mathematical prediction formulas based on a polynomial linear model and logarithmic regression model. Further, statistical analyses were performed to verify and determine the appropriate mathematical models for DBCM and TBM formation, which were ultimately validated using additional field experimental data. The polynomial linear model with four variables (temperature, salinity, chlorophyll, and TRO) and the logarithmic regression model with seven variables (temperature, salinity, dissolved oxygen, pH, turbidity, chlorophyll, and TRO) exhibited good reproducibility and could be used to predict the DBCM and TBM concentrations, respectively. The validation results indicated that the developed models could accurately predict DBP concentrations, with no significant statistical difference from the measured values. The results of this work could provide a theoretical basis and data reference for ballast water treatment control in engineering applications of emergency BWTSs.

Compound-specific isotope analysis (CSIA) was firstly applied to explore the biodegradation of hexachlorcyclohexane (HCH) isomers in contaminated soil. Concentrations and compound-specific carbon isotope ratio profiles of HCH in different specific ex-situ pilot-scale contaminated soil mesocosms were determined. The addition of nutrients and Sphingobium spp. significantly enhanced the degradation of HCH in contaminated soils within 90 days. Isomer specific biodegradation of HCHs was observed with α- and γ-HCH being more degradable than β and δ-HCH. Stable carbon isotope fractionation of HCH was observed and the δ¹³C values shifted from −28.8 ± 0.3‰ to −24.8 ± 0.7‰ upon 87.3% removal, −27.9 ± 0.2‰ to −25.9 ± 0.5‰ upon 72.8% removal, −29.4 ± 0.3‰ to −19.9 ± 0.6‰ upon 95.8% removal, and −27.8 ± 0.5‰ to −23.6 ± 0.7‰ after 96.9% removal for α, β, γ, and δ-HCH, respectively. Furthermore, the enrichment factor ε for α, β, γ, and δ-HCH biodegradation in soil was obtained for the first time as −2.0‰, −1.5‰, −3.2‰, and −1.4‰, which could play a critical role in assessing in situ biodegradation of HCH isomers in field site soil. Results from ex-situ pilot-scale experiments clearly demonstrated that CSIA could be a promising tool to qualitatively and quantitatively evaluate in situ biodegradation of HCH in contaminated field site.

Exploring traditional neonicotinoid pesticides substitutes has become one of the global scientific attentions because of their hazardous environmental impacts. Cycloxaprid (CYC) is considered to be a promising candidate alternative. But the environmental behaviors and fate of CYC in different planting system remain poorly understood. The accumulation of 14C-labeled CYC stereoisomers within different parts of Chinese cabbage (Brassica chinensis L.) was investigated, with a particular focus on the foliar absorption, translocation and stereoselectivity of CYC, during a laboratory trial. In general, the stereoisomers 14C-5R,8S-CYC and 14C-5S,8R-CYC, their metabolites, as well as the breakdown and reaction products can be transferred in both acropetal and basipetal directions. Most of the two stereoisomers absorbed by plants remained in the treated leaves, whereas a small amount was distributed to the roots. The amount of 14C in the stalks varied among the experimental time points. At 192 h after treatment (HAT), the detected radioactivity of both 14C-5R,8S-CYC and 14C-5S,8R-CYC in the leaves above the treated leaf (LATL) was higher than that in the leaves below the treated leaf (LBTL). However, the stereoisomers of CYC underwent nonstereoselective absorption and translocation in this trial. This information implies that racemic CYC and its metabolites should be a main research focus. Thus, the obtained results provide implications for a more accurate prediction about the risk assessment of CYC, which will be helpful for guiding its rational use as well as securing the ecological environment safety and human health.

Solubilization of arsenate in guts of deposit-feeders is a key process for their dietary uptake of arsenate from contaminated sediments. The present study explored this digestive solubilization with in vitro extraction experiments that quantified arsenic (As) release from substrates (natural sediment and As-enriched iron oxides) in the presence of various digestive agents (proteins, amino acids and surfactants collected from gut fluid of a sipunculan worm). To investigate potential mechanisms for the influence of digestive agents, analyses determined correlations between As and Fe concentrations, the size distribution of the As bound to the digestive agents, and the adsorption of the digestive agents on the substrates. Both the digestive surfactants and proteinaceous materials increased arsenate mobilization, with the surfactants enhancing the effects of the proteinaceous materials. Arsenate reduction and reductive dissolution of iron oxides were not observed and correlations between the concentrations of released As and Fe were weak. These findings indicate that dissolution release of Fe did not appear to be the main route by which the digestive agents mobilized particle-associated As. Most of the released As (>70%) was distributed in the <10 kDa fraction of the digestive agents, showing that the As mobilization was also not caused by complexation with proteins in the digestive agents. In contrast, adsorption of the digestive agents occurred along with the release of arsenate from the arsenate-rich substrates, suggesting that competitive adsorption was the mechanism by which the digestive agents mobilized sedimentary arsenate. Our work demonstrated that the presence of digestive surfactants significantly enhances arsenate availability during deposit feeding.

The Fort McMurray region in northeastern Alberta (Canada) is rich in natural sources of polycyclic aromatic compounds (PACs) from exposed bitumen beds; anthropogenic sources are being released with increased oil sands industry expansion. Here we report on investigations of PACs (47 compounds) in three species of forage fish collected during the 2012–2013 Joint Oil Sands Monitoring Program (JOSMP) fish health investigations and compare results with PAC data for sediment and water collected under JOSMP and earlier programs. PAC concentrations in sediments varied three orders in magnitude and were highest at downstream tributary mouths, which flowed through the exposed McMurray Formation, and along reaches of the Athabasca River where the formation was exposed. PAC concentrations in water were less variable but with higher concentrations near exposed bitumen beds. Forage fish exhibited the weakest spatial gradients in ΣPACs concentration, which averaged 102 ± 32 ng/g in trout-perch from the Athabasca River, 125 ± 22 ng/g in lake chub from the Ells River, and 278 ± 267 ng/g in slimy sculpin from the Steepbank, Firebag, and Dunkirk Rivers. Low-molecular weight compounds, particularly naphthalenes and fluorenes, dominated fish PACs. Phenanthrenes occurred in greater percent composition in fish caught in areas where PAC concentrations in sediments were higher due to the proximity of bitumen sources than in other areas. Dibenzothiophene, a major component of bitumen PAC, was a minor component of fish ΣPACs. Forage fish PAC concentrations were below fish consumption guidelines established by the European Commission (2011) and for the reopening of the commercial fisheries closed by the Deepwater Horizon oil spill. PAC concentrations in forage fish were similar to concentrations observed in many other studies (fish market surveys, estuaries, and marine waters) and lower than in fish sampled from highly impacted areas (near refineries, harbors, and other industrialized areas).

Frequently detected residuals of antibiotics in crops has drawn increasing attention from research community and the general public. This study was conducted under the controlled environmental conditions to investigate the uptake, translocation and distribution of three different veterinary antibiotics (VAs) in plants of Zea mays L. (maize, the third largest crop in the world, especially in China) and the associated mechanisms. The distribution color-maps of mixed-VAs showed that the highest RCF (root concentration factors) values of chlortetracycline (CTC) and sulfamethoxazole (SMZ) were found in the 0.5–2.0 mm zone (cell division zone), while the highest RCF value of sulfathiazole (ST) was in the 6.0–8.0 mm zone (elongation zone) of root tips (0.5–10.0 mm) after 120 h of exposure to VAs. The translocation factor (TF) of CTC was greater than 1.0, but the TFs of SMZ and ST were less than 1.0 under addition of single antibiotic. However, the TFs of three VAs were all greater than 1.0 at the end of exposure under addition of mixed-VAs. The dissipation of antibiotics by maize was also demonstrated by harvesting all plant parts in an enclosed system. The possible mechanisms for uptake and translocation of VAs in maize were investigated by adding multiple respiration inhibitors into the culture solution. The RCFs of VAs were suppressed heavily by salicylhydroxamic acid (SHAM) and sodium azide (NaN3), which indicates that the uptake of VAs was an active process. The results of TFs and stem concentration factors (SCFs) of CTC and SMZ in HgCl2 treatments revealed that the translocation of VAs was associated with the aquaporin activity in maize. The findings from this study will have significant implications for the management of crop food contamination by VAs and for the development of phytoremediation technology for antibiotics in the environment.

The increasing release of engineered nanoparticles (NPs) from consumer products has raised great concerns about their impacts on biological wastewater treatment. In this study, the widely-used ZnO NP was selected as a model NP to investigate its impact on high-rate denitrifying granular sludge in terms of sludge properties and community structure. A hormesis effect was observed during short-term exposure, in which the specific denitrification activity (SDA) was stimulated by 10% at 1 mg L⁻¹ ZnO NPs, but inhibited by 23% at 5.0 mg L⁻¹ ZnO NPs. When continuously exposed to 2.5 mg L⁻¹ ZnO NPs, the nitrogen removal capacity of the denitrification reactor was nearly deprived within 15 days, and the relative abundance of the dominant denitrifying bacterium (Castellaniella) was decreased from 51.0 to 8.0%. Meanwhile, the dehydrogenase activity (DHA) and the content of extracellular polymeric substance (EPS) significantly decreased to 22.3 and 61.1%, respectively. Nevertheless, the presence of phosphate substantially weakened the adverse effects of ZnO NPs on the SDA, EPS, DHA and the relative abundance of functional genes even exposed to 6.25 mg L⁻¹ ZnO NPs, which was associated with the fact that the level of Zn(II) released from ZnO NPs was significantly reduced in the presence of phosphate. Therefore, the toxicity of ZnO NPs may be mainly attributed to the release of toxic Zn(II) and could be attenuated in the presence of phosphate. Overall, this study provided further reference and meaningful insights into the impact of engineered NPs on biological wastewater treatment.