Phytochelatins (PCs) play a vital role in the tolerance and enrichment of cadmium (Cd) in higher plants by chelating with Cd2+. The aim of this study was to perform a full-scale metabolomics analysis of metabolic responses highly correlated with PCs generation. These metabolites and metabolic pathways were expected to promote PCs generation and further optimize Cd absorption in plants. In the current study, Amaranthus hypochondriacus, a potential species for phytoremediation, was first adopted to investigate physiological responses to Cd stress via LCMS/MS-based metabolomics and the HPLC based determination of thiol compounds. The results showed that the leaves of A. hypochondriacus under high Cd stress accumulated 40 times the amount of Cd compared to the leaves of the plants not under Cd stress and had an increased content of three types of PCs. Metabolomics qualitatively identified 12084 substances in total, among which 41 were significantly different metabolites (SDMs) between the two groups and involved in 7 metabolic pathways. Among the SDMs, 12 metabolites were highly linearly correlated with PCs involved in three pathways (Val, Leu and Ile biosynthesis; Ala, Asp and Glu metabolism; and Arg and Pro metabolism). These results provide an innovative method to promote PCs synthesis for the restoration of Cd-contaminated-soil.

Batch experiments, in conjunction with chromatographic and spectroscopic measurements, were performed to comparatively investigate the degradation of various chlorophenolic (CP) compounds (e.g., 2-CP, 4-CP, 2,3-DCP, 2,4-DCP, 2,4,6-TCP, 2,3,4,6-TeCP) by a modified Fenton process using pyrite as the catalyst. The batch results show that the CP removal by pyrite-Fenton process was highly dependent on chemical conditions (e.g., pH, CP and pyrite concentration), CP type, number and location of chlorine atoms on the aromatic ring. With the exception of 2,3,4,6-TeCP and 2,3-DCP, the CP removal decreased with increasing the number of chlorine constituents. While the main mechanism responsible for monochlorophenol removal (e.g., 2-CP and 4-CP) was the hydroxyl radical attack on aromatic rings, the CP removal for multichlorophenolic compounds (e.g., 2,3,4,6-TeCP) was driven by both: (1) hydroxyl radical attack on aromatic rings by both solution and surface-bound hydroxyl radicals and (2) adsorption onto pyrite surface sites. The adsorption affinity increased with increasing the number of Cl atoms on the aromatic ring due to enhanced hydrophobic effect. The TOC removal was not 100% complete for all CPs investigated due to formation of chemically less degradable chlorinated intermediate organic compounds as well as low molecular weight organic acids such as formic and acetic acid. Spectroscopic measurements with SEM-EDS, zeta potential and XPS provided evidence for the partial oxidation of pyrite surface Fe(II) and disulfide groups under acidic conditions.

A soil column migration trough was used to study the leaching behavior and geochemical partitioning of fifteen elements Al, As, Cr, Cu, Fe, Mg, Sn, Sb, Zn, V, Co, Mn, Pb, Ni and Cd in simulated ash reclaimed soil. According to the results of cluster analysis for the sampling stations, there were three clusters: Cluster 1 of 7 wells with relative good groundwater quality originated from the background control area, Cluster 2 of 9 wells with worst groundwater quality in the downstream parts of the simulated ash reclaimed soil, and Cluster 3 of 2 wells with representative of samples influenced by the combined effect of injection of leaching solution and the main current. Statistical analysis identified five factor types that accounted for 83.055% of the total variance, which declined in the order: ash-soil rate > leaching intensity > water depths > flow velocity > leaching time. As, Sb, Cd, Pb and Ni were the dominant contaminants. The water around ash reclaimed soil was unsuitable for drinking. As, Mn, Cd, Sb, Co and V were the largest contributors to health risks. Soils reclaimed with fly ash can consequently be a long-time source for the transfer of toxic elements into groundwater.

The conversion of natural saltmarshes to shrimp aquaculture ponds can potentially influence the biogeochemical cycling of nutrients in coastal wetlands, but its impact on the dynamics of sediment dissimilatory nitrate (NO3−) reduction remains poorly understood. In this study, three sediment NO3− reduction processes including denitrification (DNF), anaerobic ammonium oxidation (ANAMMOX), and dissimilatory NO3− reduction to ammonium (DNRA) were examined simultaneously in a natural saltmarsh and two shrimp culture ponds (5- and 18-year-old) in July and November, using nitrogen (N) isotope-tracing experiments. Our results showed that sediment potential DNF, ANAMMOX and DNRA rates were generally higher in the shrimp culture ponds than the natural saltmarsh in the two seasons. The rates of all three processes generally increased with the age of shrimp ponds, with the magnitude of increase being less pronounced for DNF and ANAMMOX than DNRA. The contribution of DNRA to total NO3− reduction increased significantly following saltmarsh conversion to shrimp ponds, suggesting that DNRA became an increasingly important biogeochemical process under shrimp culture. DNRA competed with DNF and limited reactive N loss to some extent after natural saltmarshes converted to shrimp culture ponds. The results of redundancy analysis revealed that the availability of substrates and sulfides in sediments, rather than the bacteria gene abundance, were the most important factor influencing the NO3− reduction processes. Overall, our findings highlighted that shrimp-aquaculture reclamation may aggravate nitrogen loading in coastal wetlands by promoting the production of bioavailable ammonium.

Modeling for the toxicity of ionic liquids (ILs) is necessary to fill data gaps for untested chemicals and to understand the relevant mechanisms at the molecular level. In order for many researchers to easily predict toxicity and/or develop some prediction model, simple method(s) based on a single parameter should be proposed. Therefore, previously our group developed a comprehensive toxicity prediction model with unified linear free-energy relationship descriptors to address the single parameter for predicting the toxicities, as follows (Cho et al., 2016b).Log 1/toxicity in the unit of mM= (2.254 Ec – 2.545 Sc + 0.646 Ac – 1.471 Bc + 1.650 Vc + 2.917 J+ – 0.201 Ea + 0.418 Va + 0.131 J−) – 0.709.It is considered that the model can calculate the general toxicological effect of ILs in parenthesis, as it was developed on the basis of numerous toxic effects i.e., 58 toxicity testing methods and about 1600 data points. In order to check the hypothesis, the values calculated by the model were correlated with four different datasets from insect cell line (Spodoptera frugiperda 9), earthworm (Eisenia fetida), nematode (Caenorhabditis elegans), and fish (Danio rerio). The results clearly showed that the calculated values are in good agreement with each dataset. In the case of S. frugiperda 9 cells, the calculated parameters were correlated with log1/LC50 values, measured after 24 h and 48 h incubation, in R2 of 0.67 and 0.88, respectively. The R2 values for the earthworm, nematode, and fish were 0.88, 0.96, and 0.94–0.95, respectively. This study confirmed that the comprehensive model can be simply and accurately used to predict toxicity of ILs.

The current study investigates the concentration of eleven trace elements in biomaterials including hair (85) and nails (85) along with seventy five (75) road dust samples collected from a healthy population of habitable urban-industrial areas of Hefei, China. The samples were acid digested and analyzed using ICP-MS for trace elements content. The mean concentration of Elements followed descending order of Zn > Mg > Fe > Cr > Al > Sn > Sr > Ti > Cu > As > Cd and Mg > Zn > Fe > Cr > Al > Sn > Ti > Cu > Sr > As > Cd in hair and nails, respectively. Overall, the concentration of elements was found to be high in female subject as compared to male. The concentration of trace elements in hair and nail exceeded the maximum permissible limits in most cases. The corresponding mean values from dust samples were fairly high as compared to background values of trace elements. Middle age groups (21–30 years and 31–40 years) were observed to be the most vulnerable there-by posing a high health risk, as the concentration of trace elements was significantly high in these groups except for Al, which was detected high in age < 20 in case of both male and female. A significantly high correlation was found between trace elements in biomaterials and those detected in dust samples. In hair samples, a significantly positive correlation was noticed for As with Mg, Zn, Sn and Fe, Sn/Mg and Mg/Ti. In the case of nails, a significant correlation was observed for elements like Al, Mg, Zn, Cr, and Cu. The Cluster and principal component analysis revealed industrial and vehicular emissions as main sources for trace elements exposure in humans.

Microplastics are emerging contaminants in the marine environment. They enter the ocean in a variety of sizes and shapes, with plastic microfiber being the prevalent form in seawater and in the guts of biota. Most of the laboratory experiments on microplastics has been performed with spheres, so knowledge on the interactions of microfibers and marine organisms is limited. In this study we examined the ingestion of microfibers by the sea anemone Aiptasia pallida using three different types of polymers: nylon, polyester and polypropylene. The polymers were offered to both symbiotic (with algal symbionts) and bleached (without algal symbionts) anemones. The polymers were introduced either alone or mixed with brine shrimp homogenate. We observed a higher percentage of nylon ingestion compared to the other polymers when plastic was offered in the absence of shrimp. In contrast, we observed over 80% of the anemones taking up all types of polymers when the plastics were offered in the presence of shrimp. Retention time differed significantly between symbiotic and bleached anemones with faster egestion in symbiotic anemones. Our results suggest that ingestion of microfibers by sea anemones is dependent both on the type of polymers and on the presence of chemical cues of prey in seawater. The decreased ability of bleached anemones to reject plastic microfiber indicates that the susceptibility of anthozoans to plastic pollution is exacerbated by previous exposure to other stressors. This is particularly concerning given that coral reef ecosystems are facing increases in the frequency and intensity of bleaching events due to ocean warming.

Polychlorinated biphenyls (PCBs) in dated sediment cores from the East China Marginal Seas (ECMSs) and the chronology of the net fluxes to sediments were analyzed. The accumulation of 27 PCBs (ΣPCBs) in the ECMS sediments is about 5–26 ng cm⁻², with the net depositional fluxes of ΣPCBs 10 times lower than those observed in the Great Lakes during the 1960s–1970s. Exponential increases in PCB deposition to the ECMS sediments since the 1990s were observed, which closely follows the fast growth of PCB emissions from industrial thermal processes and e-waste related sources in China. Recent PCB fluxes to the study sites in the ECMSs and the Great Lakes are comparable; the former surged forward with a rising tendency, while the latter showed continued decline after the late 1970s. Due to the different PCB application histories and sources between the two regions, the ECMS sediments may remain as a net sink for land-derived PCBs, while sediments in the Great Lake may have been acting as a secondary source releasing PCBs to water. A higher proportion of trichlorobiphenyls in the ECMS sediments than the Great Lakes was indicated, which may imply the net transport of atmospheric PCBs from China.

The occurrence and spatial distribution of selected pesticides were investigated along a 200-km reach of the St. Lawrence River (SLR) and tributaries in Quebec, Canada. Surface water samples (n = 68) were collected in the summer 2017 and analyzed for glyphosate, atrazine (ATZ), 8 systemic insecticides (acetamiprid, clothianidin, dinotefuran, fipronil, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam) and some metabolites. Overall, 99% of the surface water samples were positive to at least one of the targeted pesticides. The most recurrent compounds were glyphosate (detection frequency: 84%), ATZ (82%), thiamethoxam (59%), desethylatrazine (DEA: 47%), and clothianidin (46%). Glyphosate displayed variable levels (4–3,000 ng L−1), with higher concentrations in south tributaries (e.g., Nicolet and Yamaska). In positive samples, the sum of ATZ and DEA varied between 5 and 860 ng L−1, and the sum of 6 priority neonicotinoids between 1.5 and 115 ng L−1. From Repentigny to the Sorel Islands, the spatial distribution of pesticides within the St. Lawrence River was governed by the different upstream sources (i.e., Great Lakes vs. Ottawa River) due to the limited mixing of the different water masses. Cross-sectional patterns revealed higher concentrations of glyphosate and neonicotinoids in the north portions of transects, while the middle and south portions showed higher levels of atrazine. In Lake St. Pierre and further downstream, cross-sections revealed higher levels of the targeted pesticides near the southern portions of the SLR. This may be due to the higher contributions from south shore tributaries impacted by major agricultural areas, compared to north shore tributaries with forest land and less cropland use. Surface water samples were compliant with guidelines for the protection of aquatic life (chronic effects) for glyphosate and atrazine. However, 31% of the samples were found to surpass the guideline value of 8.3 ng L−1 for the sum of six priority neonicotinoids.