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Remediation of artificially contaminated soil and groundwater with copper using hydroxyapatite/calcium silicate hydrate recovered from phosphorus-rich wastewater
2021
Liu, Yiyang | Zhang, Rongbin | Sun, Zhenjie | Shen, Qin | Li, Yuan | Wang, Yuan | Xia, Siqing | Zhao, Jianfu | Wang, Xuejiang
Excessive copper (Cu) in contaminated soil and groundwater has attracted continuous attentions due to the bioaccumulation and durability. In this study, the feasibility of remediation of heavy metal pollution in soil and groundwater was investigated using hydroxyapatite/calcium silicate hydrate (HAP/C–S–H) recovered from phosphorus-rich wastewater in farmland. The results show that the pH has a strong effect on copper removal from Cu-contaminated groundwater but the impact of ion strength on the removal is weak. In general, high pH and low ion strength give better results in copper removal. Kinetic and isotherm data from the study fit well with Pseudo-second-order kinetic model and Langmuir isotherm model, respectively. The maximum adsorption capacity of HAP/C–S–H (138 mg/g) was higher than that of C–S–H (90.3 mg/g) when pH value, temperature, and ionic strength were 5, 308 K, and 0.01 M, respectively. Thermodynamics results indicate that Cu removal is a spontaneous and endothermic process. X-ray diffraction (XRD) results show that the mechanism of copper removal involves physical adsorption, chemical precipitation and ion exchange. For the remediation of Cu-contaminated soil, 76.3% of leachable copper was immobilized by HAP/C–S–H after 28 d. Acid soluble Cu, the main contributor to biotoxicity, decreased significantly while reducible and residual Cu increased. After immobilization, the acid neutralization capacity of the soil increased and the dissolution of copper was substantially reduced in near-neutral pH. It can be concluded that HAP/C–S–H is an effective, low-cost and eco-friendly reagent for in-situ remediation of heavy metal polluted soil and groundwater.
Show more [+] Less [-]In vitro renal toxicity evaluation of copper-based metal–organic framework HKUST-1 on human embryonic kidney cells
2021
Chen, Yi-Chun | Andrew Lin, Kun-Yi | Chen, Ku-Fan | Jiang, Xin-Yu | Lin, Chia-Hua
HKUST-1 is currently studied for a very diverse range of applications. Despite its exciting potential, significant concerns remain regarding the safety of HKUST-1. Therefore, human embryonic kidney 293 (HEK293) cells were used to verify the renal toxicity of HKUST-1. In this study, HKUST-1 induced concentration-dependent cytotoxic effects in HEK293 cells. The depolarization of mitochondrial membrane potential and formation of apoptotic bodies and autophagic vesicles were observed in HKUST-1–treated HEK293 cells. Oxidative (oxidative stress and haem oxygenase-1 activation) and inflammatory responses (NF-κB and NLRP3 activation) in HEK293 cells were induced by HKUST-1 exposure. In addition, the observed reduction in NAD(P)H levels in HKUST-1–treated HEK293 cells may be attributable to PARP-1 activation following DNA single- and double-strand breaks. The HKUST-1–induced depletion of zonula occludens proteins in HEK293 cells might lead to altered renal barrier integrity. The variations of α1-antitrypsin, oxidised α1-antitrypsin and NLRP3 protein expression in HEK293 cells suggested that HKUST-1 increases the risk of chronic kidney diseases. However, most of these adverse effects were significantly induced only by high HKUST-1 concentration (100 μg/mL), which do not reflect the actual exposure. Thus, the toxic risk of HKUST-1 appears to be negligible.
Show more [+] Less [-]Influence of sulfur fertilization on CuO nanoparticles migration and transformation in soil pore water from the rice (Oryza sativa L.) rhizosphere
2020
Sun, Lijuan | Xue, Yong | Peng, Cheng | Xu, Chen | Shi, Jiyan
The biogeochemical cycling of sulfur in soil is closely associated with the mobility and bioavailability of heavy metals; however the influence of sulfur on the behavior of metal-based nanoparticles has not yet been studied. The influence of S fertilizer (S⁰ and Na₂SO₄) applied in paddy soils on CuO NPs behavior in soil pore water was explored in the present study. Synchrotron-based techniques were applied to investigate the migration and speciation transformation of CuO NPs in soil pore water colloids. The application of sulfur fertilizer increased the zeta potential of soil colloids from the rice rhizosphere region and reduced the size of the colloids. Sulfur fertilization decreased the concentration of Cu in soil pore water in the rice rhizosphere region. S⁰ fertilizer reduced the Cu concentration in soil colloids (by 55.8%–73.5%), while Na₂SO₄ increased the Cu concentration in soil colloids (by 173.8%–265.1%). Sulfur fertilization changed the spatial distribution of Fe³⁺ and Cu²⁺ in colloids, making these ions more likely to be aggregated on the edges of soil colloids. Speciation transformation of CuO NPs happened during the process of migration. The main Cu speciation in the soil colloids were CuO NPs, Cu-Cysteine, Cu₂S and Cu-Citrate. Sulfur fertilization increased the proportion of Cu₂S (by 40.5%) in soil pore water colloids from the rice rhizosphere region, while the proportion of CuO NPs was reduced (by 18.4%). Sulfur fertilization changed the morphology and elementary composition of colloids in soil pore water, thus influencing the migration of CuO NPs in the soil column through soil colloids.
Show more [+] Less [-]Benthic trace metal fluxes in a heavily contaminated bay in China: Does the sediment become a source of metals to the water column?
2020
Li, Li | Zhen, Xiaotong | Wang, Xiaojing | Ren, Yijun | Hu, Limin | Bai, Yazhi | Liu, Jihua | Shi, Xuefa
Over three different seasons, seawater, porewater and sediment samples were collected from Jinzhou Bay, a previously heavily contaminated bay, to quantitatively assess the benthic flux of trace metals after a reduction in fluvial/sewage discharge for almost three decades. The spatial distribution patterns of trace metals in seawater, surface sediment, as well as the vertical distribution patterns of metals in porewater and solid phases in short sediment cores were reported. Metal concentrations in seawater and sediment all showed much higher Cd and Zn concentrations inside the Jinzhou Bay compared to the rest of Bohai Sea area. Zn, Ni, Pb and Co all had average benthic fluxes coming out of the sediments to the water column, contributing about 0.5%, 0.3%, 1.4% and 14% to their current standing stock in Jinzhou Bay. Seasonal difference was also identified in seawater and porewater, as well as in the benthic fluxes. In general, benthic fluxes and porewater concentrations all tended to be higher in summer, implying a close relationship between benthic flux and the temperature-dependent organic matter degradation process at the sediment-water interface.Currently, there are clearly still other sources, possibly fluvial/sewage discharge, as the main source of trace metals in Jinzhou Bay waters. For Cd and Cu, concentrations in the water column remain high on an annual basis indicating that sediment still acts as a sink. Conversely, for Pb, Zn, Co, and Ni, the sediment is beginning to act as a source to the water column. Although this may not yet be significant, it will become more and more important with time, and can last for hundreds to thousands of years.
Show more [+] Less [-]Strong temporal and spatial variation of dissolved Cu isotope composition in acid mine drainage under contrasted hydrological conditions
2020
Masbou, J. | Viers, J. | Grande, J.-A. | Freydier, R. | Zouiten, C. | Seyler, P. | Pokrovsky, O.S. | Behra, P. | Dubreuil, B. | de la Torre, M.-L.
Copper export and mobility in acid mine drainage are difficult to understand with conventional approaches. Within this context, Cu isotopes could be a powerful tool and here we have examined the relative abundance of dissolved (<0.22 μm) Cu isotopes (δ⁶⁵Cu) in the Meca River which is an outlet of the Tharsis mine, one of the largest abandoned mines of the Iberian Pyrite Belt, Spain. We followed the chemical and isotopic composition of the upstream and downstream points of the catchment during a 24-h diel cycle. Additional δ⁶⁵Cu values were obtained from the tributary stream, suspended matter (>0.22 μm) and bed sediments samples. Our goals were to 1) assess Cu sources variability at the upstream point under contrasted hydrological conditions and 2) investigate the conservative vs. non conservative Cu behavior along a stream. Average δ⁶⁵Cu values varied from −0.47 to −0.08‰ (n = 9) upstream and from −0.63 to −0.31‰ downstream (n = 7) demonstrating that Cu isotopes are heterogeneous over the diel cycle and along the Meca River. During dry conditions, at the upstream point of the Meca River the Cu isotopic composition was heavier which is in agreement with the preferential release of heavy isotopes during the oxidative dissolution of primary sulfides. The more negative values obtained during high water flow are explained by the contribution of soil and waste deposit weathering. Finally, a comparison of upstream vs. downstream Cu isotope composition is consistent with a conservative behavior of Cu, and isotope mass balance calculations estimate that 87% of dissolved Cu detected downstream originate from the Tharsis mine outlet. These interpretations were supported by thermodynamic modelling and sediment characterization data (X-ray diffraction, Raman Spectroscopy). Overall, based on contrasted hydrological conditions (dry vs flooded), and taking the advantage of isotope insensitivity to dilution, the present work demonstrates the efficiency of using the Cu isotopes approach for tracing sources and processes in the AMD regions.
Show more [+] Less [-]Occurrence, sources and health risks of toxic metal(loid)s in road dust from a mega city (Nanjing) in China
2020
Wang, Xiaoyu | Liu, Enfeng | Lin, Qi | Liu, Lin | Yuan, Hezhong | Li, Zijun
Potential toxic metal(loid)s (PTMs) in road dust are a major concern in relation to urban environmental quality. Identifying pollution hotspots and sources of PTMs is an essential prerequisite for pollution control and management. Herein, the concentrations, pollution and potential health risks of 8 PTMs (As, Cd, Co, Cu, Hg, Mo, Pb and Zn) in road dust from the highly urbanized areas of Nanjing were studied. Spatial occurrences and sources of PTMs were explored using geostatistics, principal component analysis (PCA) and local Moran’s index. The contamination factor (CF) results showed that Co was mainly natural in origin, while the other PTMs were polluted, with average CFs ranging from 1.4 to 11.0 as follows: Hg > Mo > Cd > Cu > Pb > Zn > As, indicating moderate to very high contamination. Except for Co and Hg, the other PTMs were heavily loaded on PC1, which explained 44.72% of the total variance. Combining the statistical results and distributions of potential sources, we deduced that industrial emissions dominated the spatial patterns of all polluted PTMs in road dust, which showed high levels in the northern parts of the study region and generally decreasing levels southwards. Moreover, Pb and Zn in the south-central area and Cd in the north-central area displayed hotspots, with maximum CFs of 5.5 (Pb), 4.2 (Zn) and 16.2 (Cd), which were related to additional automotive and railway braking emissions, respectively. The resuspension of legacy pesticides in soil is likely responsible for the As pollution hotspot in the southwestern part. Despite the high anthropogenic contributions (27% for As and 68–88% for the other metals) to the PTMs in road dust, their noncarcinogenic and carcinogenic health risks were rarely found for children and adults based on the values of the hazard index and carcinogenic risk index. However, attention still should be paid to the pollution hotspots in the northern region.
Show more [+] Less [-]Maize roots and shoots show distinct profiles of oxidative stress and antioxidant defense under heavy metal toxicity
2020
AbdElgawad, Hamada | Zinta, Gaurav | Hamed, Badreldin A. | Selim, Samy | Beemster, Gerrit | Hozzein, Wael N. | Wadaan, Mohammed A.M. | Asard, Han | Abuelsoud, Walid
Heavy metal accumulation in agricultural land causes crop production losses worldwide. Metal homeostasis within cells is tightly regulated. However, homeostasis breakdown leads to accumulation of reactive oxygen species (ROS). Overall plant fitness under stressful environment is determined by coordination between roots and shoots. But little is known about organ specific responses to heavy metals, whether it depends on the metal category (redox or non-redox reactive) and if these responses are associated with heavy metal accumulation in each organ or there are driven by other signals. Maize seedlings were subjected to sub-lethal concentrations of four metals (Zn, Ni, Cd and Cu) individually, and were quantified for growth, ABA level, and redox alterations in roots, mature leaves (L1,2) and young leaves (L3,4) at 14 and 21 days after sowing (DAS). The treatments caused significant increase in endogenous metal levels in all organs but to different degrees, where roots showed the highest levels. Biomass was significantly reduced under heavy metal stress. Although old leaves accumulated less heavy metal content than root, the reduction in their biomass (FW) was more pronounced. Metal exposure triggered ABA accumulation and stomatal closure mainly in older leaves, which consequently reduced photosynthesis. Heavy metals induced oxidative stress in the maize organs, but to different degrees. Tocopherols, polyphenols and flavonoids increased specifically in the shoot under Zn, Ni and Cu, while under Cd treatment they played a minor role. Under Cu and Cd stress, superoxide dismutase (SOD) and dehydroascorbate reductase (DHAR) activities were induced in the roots, however ascorbate peroxidase (APX) activity was only increased in the older leaves. Overall, it can be concluded that root and shoot organs specific responses to heavy metal toxicity are not only associated with heavy metal accumulation and they are specialized at the level of antioxidants to cope with.
Show more [+] Less [-]Arsenic enrichment in groundwater and associated health risk in Bari doab region of Indus basin, Punjab, India
2020
Kumar, Anand | Singh, Chander Kumar
Contaminated groundwater is considered as one of the most important pathways of human exposure to the geogenic contaminants. Present study has been conducted in a part of Indus basin to investigate the presence and spatial distribution of arsenic (As) and other trace metals in groundwater. The As concentration varies from bdl-255.6 μg/L and 24.6% of the 73 collected groundwater samples have As above world health organization (WHO) guideline of 10 μg/L. High concentration of As is found along the newer alluvium of Ravi River. As is found with high bicarbonate (HCO3−) and Iron (Fe) and low nitrate (NO3−) indicating reductive dissolution of Fe bearing minerals. However, silicate weathering along with high sulphate (SO42) and positive oxidation-reduction potential (ORP) indicates mixed redox conditions. Weathering of minerals along with other major hydrogeochemical process are responsible for composition of groundwater. With 31.5% of the samples, sodium bicarbonate (Na–HCO3) is the major water facies followed by magnesium bicarbonate (Mg–HCO3) in 30% of samples. As, Fe and other trace metals including copper (Cu), cadmium (Cd), chromium (Cr), zinc (Zn) were used to calculate the health risk for children and adults in the region. Out of 73 samples, 58% has high Fe, 32.8% has high Zn, and 4.1% has high Cd which are above the prescribed limits of WHO guidelines. Health risk of the population has been assessed using chronic dose index (CDI), hazardous quotients (HQ) and hazardous index (HI) for children and adults. The mean CDI values follows the order as Fe > Zn > Cu > As > Cr > Cd, while the HQ values indicates high As hazards for both children and adults. 43.8% of the groundwater samples have high HI for adults, however, 49.3% has high HI for children indicating higher risk for children compared to adults. A large-scale testing should be prioritized to test the wells for As and other trace metals in the study region to reduce health risks.
Show more [+] Less [-]Thermal discharge influences the bioaccumulation and bioavailability of metals in oysters: Implications of ocean warming
2020
Lan, Wang-Rong | Huang, Xu-Guang | Lin, Lu-xiu | Li, Shun-Xing | Liu, Feng-Jiao
Human-induced temperature changes influence coastal regions, both via thermal pollution and ocean warming, which exerts profound effects on the chemistry of metals and the physiology of organisms. However, it remains unknown whether the increased temperature of discharged water or ocean warming, as a result of climate change, lead to an increase of human health risks associated with the consumption of sea foods. In this study, the influence of temperature on metal accumulation by oysters was studied in individuals collected from a coastal area affected by the thermal water discharge of the Houshi Power Plant, China. The bioaccumulation factor (BAF) and oral bioavailability (OBA) of metals in oysters was determined. Elevated temperatures led to an increase in BAF for Cu, Zn, Hg, and Cd (p < 0.05), but no change was observed for As and Pb (p > 0.05). The OBA for Cd, As, and Pb correlated positively to elevated temperatures (p < 0.05). However, for Cu and Zn, OBA was negatively correlated with increasing temperature (p < 0.05). As, Pb, and Cd in the trophically available metal (defined as a sum of heat-stable proteins, heat-denaturable proteins, and organelles) was significantly elevated at the highest temperature seawater site (site A) compared to the lowest seawater site (site B). Thus, the irregular variation of OBA for each metal may be the result of variations in the subcellular distribution of metals and the protein quality influenced by the increased temperature. Moreover, the increased temperature and increased the hazard quotient values of As and Cd (p < 0.05 for As, n = 6, p < 0.05 for Cd, n = 6), which provided an indication of the potential risks of the consumption of oysters or other seafood to future warming under climate change scenarios.
Show more [+] Less [-]A global metabolomic insight into the oxidative stress and membrane damage of copper oxide nanoparticles and microparticles on microalga Chlorella vulgaris
2020
Wang, Lei | Huang, Xulei | Sun, Weiling | Too, Hui Zhen | Laserna, Anna Karen Carrasco | Li, Sam Fong Yau
To compare aquatic organisms’ responses to the toxicity of copper oxide (CuO) nanoparticles (NPs) with those of CuO microparticles (MPs) and copper (Cu) ions, a global metabolomics approach was employed to investigate the changes of both polar and nonpolar metabolites in microalga Chlorella vulgaris after 5-day exposure to CuO NPs and MPs (1 and 10 mg/L), as well as the corresponding dissolved Cu ions (0.08 and 0.8 mg/L). Unchanged growth, slight reactive oxygen species production, and significant membrane damage (at 10 mg/L CuO particles) in C. vulgaris were demonstrated. A total of 75 differentiated metabolites were identified. Most metabolic pathways perturbed after CuO NPs exposure were shared by those after CuO MPs and Cu ions exposure, including accumulation of chlorophyll intermediates (max. 2.4–5.2 fold), membrane lipids remodeling for membrane protection (decrease of phosphatidylethanolamines (min. 0.6 fold) and phosphatidylcholines (min. 0.2–0.7 fold), as well as increase of phosphatidic acids (max. 1.5–2.9 fold), phosphatidylglycerols (max. 2.2–2.3 fold), monogalactosyldiacylglycerols (max. 1.2–1.4 fold), digalactosylmonoacylglycerols (max. 1.9–3.8 fold), diacylglycerols (max. 1.4 fold), lysophospholipids (max. 1.8–3.0 fold), and fatty acids (max. 3.0–6.2 fold)), perturbation of glutathione metabolism induced by oxidative stress, and accumulation of osmoregulants (max. 1.3–2.6 fold) to counteract osmotic stress. The only difference between metabolic responses to particles and those to ions was the accumulation of fatty acids oxidation products: particles caused higher fold changes (particles/ions ratio 1.9–3.0) at 1 mg/L and lower fold changes (particles/ions ratio 0.4–0.7) at 10 mg/L compared with ions. Compared with microparticles, there was no nanoparticle-specific pathway perturbed. These results confirm the predominant role of dissolved Cu ions on the toxicity of CuO NPs and MPs, and also reveal particle-specific toxicity from a metabolomics perspective.
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