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Interaction mechanism of dissolved Cr(VI) and manganite in the presence of goethite coating
2020
Luo, Yao | Ding, Jiayu | Hai, Ju | Tan, Wenfeng | Hao, Rong | Qiu, Guohong
Hexavalent chromium has aroused a series of environmental concerns due to its high mobility and toxicity. Iron and manganese oxides usually coexist in the environments and influence the speciation and geochemical cycling of chromium. However, the interaction mechanism of iron-manganese oxides with dissolved Cr(VI) remains largely unknown. In this work, the interaction processes of dissolved Cr(VI) and manganite in the presence of goethite coating were investigated, and the effects of pH (2.0–9.0) and iron oxide content were also studied. Manganite-goethite composites were formed with uniform micromorphologies in the system of manganite and Fe(II). In the reaction system of single manganite and Cr(VI), manganite could only adsorb but not reduce Cr(VI), with the adsorption amount decreasing at higher pHs. In the reaction system of manganite-goethite composites and Cr(VI), adsorbed Cr(VI) was reduced to Cr(III) by Fe(II) on composites surface. The generated Cr(III) was then retained as Cr(OH)₃ on the mineral surface. Goethite coating suppressed the re-oxidation of newly formed Cr(III) by manganite. The amounts of adsorbed Cr(VI) and generated Cr(III) increased with increasing iron oxide content, and increased first and then decreased with increasing pH. The Cr(III) formation and Cr(VI) adsorption amount reached the maximum at pH 5.0–6.0. The present work highlights the transformation and retention of Cr(VI) by iron-manganese oxides and provides potential implications for the use of such oxides in the remediation of Cr(VI) polluted waters and soils.
Show more [+] Less [-]Hexavalent chromium leads to differential hormetic or damaging effects in alfalfa (Medicago sativa L.) plants in a concentration-dependent manner by regulating nitro-oxidative and proline metabolism
2020
Christou, Anastasis | Georgiadou, Egli C. | Zissimos, Andreas M. | Christoforou, Irene C. | Christofi, Christos | Neocleous, Damianos | Dalias, Panagiotis | Torrado, Sofia O.C.A. | Argyraki, Ariadne | Fotopoulos, Vasileios
Chromium has been proven to be extremely phytotoxic. This study explored the impacts of increasing Cr(VI) exposure (up to 10 mg L⁻¹ K₂Cr₂O₇) on the growth and development of alfalfa plants and adaptation responses employed, in an environmentally relevant context. The threshold concentration of K₂Cr₂O₇ in irrigation water beyond which stress responses are initiated is 1 mg L⁻¹. Lower Cr(VI) exposure (0.5 mg L⁻¹ K₂Cr₂O₇) induced hormesis, evident through increased biomass and larger leaves, likely mediated by increased NO content (supported by elevated NR enzymatic activity and overexpression of NR and ndh genes). Elevated Cr(VI) exposure (5 and 10 mg L⁻¹ K₂Cr₂O₇) resulted in reduced biomass and smaller leaves, and lower levels of photosynthetic pigment (10 mg L⁻¹ K₂Cr₂O₇). Higher levels of lipid peroxidation, H₂O₂ and NO contents in these plants suggested nitro-oxidative stress. Stress responses included increased SOD and CAT enzymatic activities, further supported to some extent by MnSOD, FeSOD, Cu/ZnSOD and CAT transcripts levels. GST7 and GST17 gene expression patterns, as well as proline content, P5CS enzymatic activity and corresponding P5CS and P5CR gene expression levels emphasized the role of proline and GSTs in the adaptation responses. Results highlight the importance of managing Cr(VI) levels in irrigation water.
Show more [+] Less [-]Preparation of 2D nitrogen-doped magnetic Fe3C/C by in-situ self-assembled double-template method for enhanced removal of Cr(VI)
2020
Su, Qiaohong | Su, Zhi | Xie, Wenyu | Tian, Chen | Su, Xintai | Lin, Zhang
Porous carbon, which can be functionalized, is considered as a potential carbon material. Herein, two-dimensional (2D) nitrogen-doped magnetic Fe₃C/C (NMC) was prepared by a simple carbonization method using potassium humate (HA-K) as raw material. Remarkably, two templates, g-C₃N₄ and KCl, were formed in situ during the carbonization process, which provide the necessary conditions for the formation of 2D NMC. The NMC was comprehensively studied by different characterization methods. The results show that NMC has a large surface area and mesoporous structure. The prepared NMC-0.50 was used to test the removal performance of Cr(VI). The effects of pH value, coexisting ions and time on Cr(VI) removal performance were investigated, and the adsorption kinetics, isotherm and thermodynamics were studied. The results showed that the adsorption isotherm model of NMC-50 accorded with the Langmuir model, and the maximum adsorption capacity was 423.73 mg g⁻¹. The reaction mechanism of Cr(VI) is adsorption and redox reaction. In addition, NMC-0.50 exhibit high selectivity, separability and regeneration performance. A convenient means for the synthesis of NMC was designed in this work, and demonstrate that NMC has practical value as an adsorbent.
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 [-]A comprehensive comparison and analysis of soil screening values derived and used in China and the UK
2020
Sun, Yiming | Wang, Jicai | Guo, Guanlin | Li, Hong | Jones, Kevin
China and the UK use different risk-based approaches to derive soil screening or guideline values (SSVs; SGVs) for contaminants. Here we compare the approaches and the derived values for 6 illustrative contaminants. China’s SSVs are derived using an approach developed in the US as follows: for carcinogens, acceptable level of risk (ACR) is set at 10−6 and the SSVs calculated as 10−6 divided by the soil exposure and toxicity data; for non-carcinogens, the hazard quotient is 1 and the SSV is calculated as 1 divided by the soil exposure and toxicity data. The UK’s SGVs are calculated by the CLEA model, for which the Average Daily Exposure (ADE) from soil sources by a specific exposure route equals the health criteria values (HCVs) for that route, whether for carcinogens or a non-carcinogens. The UK’s CLEA model is also used here to derive SSVs with Chinese input parameters. China’s SSVs, the UK’s SGVs and values for Chinese conditions derived using the UK approach were as follows (mg/kg): As, <1, 35, 20; Cd, 20, 18, 11; Cr (VI), <1, 14, 29; benzene, 1, 1, 2; toluene, 1200, 3005, 3800; ethyl-benzene, 7, 930, 1200. By comparing the differences in toxicity assessment and risk characterization, exposure assessment and parameter types in the methodologies to obtain SSVs in China and the UK, and by combining the CLEA model with Chinese parameterisation, these comparisons highlight that the difference in toxicity assessment and risk characterization methods of carcinogens results in the biggest difference in SSVs between the 2 countries. However, for non-carcinogenic substances, the difference of SSVs calculation method and SSVs is small. The difference in SSVs for carcinogenic substances is also related to the route of exposure. For volatile organic compounds, the presence of indoor respiratory exposure pathways greatly reduces the differences caused by toxicity assessment and risk characterization methods. For non-volatile substances such as heavy metals, the effects of toxicity assessment and risk characterization methods are significant. The SSV of As obtained by the CLEA model with Chinese parameters is closer to the background value of soil in China. In the management of non-volatile contaminated sites such as heavy metals in China, the CLEA model can be used for risk assessment and calculation of site specific SSVs. In the future, China can use the UK method to strengthen its toxicity assessment and risk characterization methods for carcinogenic substances, to reduce the uncertainty in the risk assessment of contaminated sites and improve the scientific management of contaminated sites.
Show more [+] Less [-]Seasonal variability of extremely metal rich acid mine drainages from the Tharsis mines (SW Spain)
2020
Moreno González, Raúl | Cánovas, Carlos Ruiz | Olías, Manuel | Macías, Francisco
The Tharsis mine is presently abandoned, but the past intense exploitation has left large dumps and other sulphide-rich mining wastes in the area generating acid mine drainages (AMD). The main goal of this work is to study the effect of hydrogeochemical processes, hydrological regime and the waste typology on the physicochemical parameters and dissolved concentrations of pollutants in a deeply AMD-affected zone. Extreme leachates are produced in the area, reaching even negative pH and concentrations of up to 2.2 g/L of As and 194 g/L of Fe. The results of the comparison of ore grades of sulphide deposits with dissolved concentrations in waters shows that Pb is the least mobile element in dissolution probably due to the precipitation of Pb secondary minerals and/or its coprecipitation on Fe oxyhydroxysulphates. Arsenic, Cr, and V are also coprecipitated with Fe minerals. Seasonal patterns in metal contents were identified: elements coming from the host rocks, such as Al, Mn and Ni, show their maximum values in the dry period, when dilution with freshwater is lower and the interaction of water-rock processes and evaporation is higher. On the other hand, As, Cr, Fe, Pb and V show minimum concentrations in the dry period due to intense Fe oxyhydroxysulphate precipitation. In this sense, large sulphide rich waste heaps would be a temporal sink of these elements (i.e. Pb, As, Cr and V) in the dry period, and a significant source upon intense rainfalls.
Show more [+] Less [-]Trace elements in shellfish from Shenzhen, China: Implication of coastal water pollution and human exposure
2020
Liu, Shan | Liu, Yanling | Yang, Dongfeng | Li, Chun | Zhao, Yang | Ma, Huimin | Luo, Xianru | Lu, Shaoyou
Shellfish constitute an important component of human diet, especially for those living in coastal regions. Shellfish have attracted extensive attention due to high enrichment of heavy metals. The aims of this study were to investigate the levels of trace elements in shellfish from coastal waters of Shenzhen, China and to assess human intake risks. Nine elements, including chromium (Cr), copper (Cu), iron (Fe), zinc (Zn), manganese (Mn), selenium (Se), cadmium (Cd), arsenic (As) and lead (Pb) were measured in 216 shellfish samples from eight species. Their concentrations (based on wet weight) were: Cr (0.28–21.4 mg kg⁻¹), Cu (1.40–158 mg kg⁻¹), Fe (16.5–5387 mg kg⁻¹), Zn (11.1–847 mg kg⁻¹), Mn (1.33–422 mg kg⁻¹), Se (0.15–11.8 mg kg⁻¹), Cd (0.02–18.4 mg kg⁻¹), Pb (<LOQ-10.9 mg kg⁻¹) and As (2.24–95.5 mg kg⁻¹), relatively greater than those reported in shellfish from other locations of China. Crassostrea ariakensis and Babylonia areolata were found to enrich As and Cd, respectively. The target hazard quotient (THQ) values of Cd and As were more than 1, suggesting considerable health risks from the consumption of shellfish of this zone. To our knowledge, this is the first study to assess the human risk exposure to trace elements via shellfish consumption in South China.
Show more [+] Less [-]Bioreduction of hexavalent chromium on goethite in the presence of Pseudomonas aeruginosa
2020
Li, Yihao | Wang, Huimin | Wu, Pingxiao | Yu, Langfeng | Rehman, Saeed | Wang, Junfeng | Yang, Shanshan | Zhu, Nengwu
The effective mineral absorption and bioreduction were considered as two preferred processes to alleviate the bioavailability and toxicity of toxic trace metals. In this study, the bioreduction of hexavalent chromium (Cr(VI)) on goethite (FeOOH) in the presence of Pseudomonas aeruginosa (P. aeruginosa) was investigated with different environmental factors, including carbon source concentrations, pH, temperature and initial Cr(VI) concentrations. The characterization of FeOOH–P. aeruginosa indicated that P. aeruginosa was surrounded by FeOOH, which could provide the essential iron for bacterial growth and reduce Cr(VI) to Cr(III). The optimal experimental conditions for Cr(VI) (initial concentration: 35 mg L⁻¹) absorption (∼46%) and bioreduction (∼54%) involved a temperature of 45 °C and pH of 5.5. Meanwhile, extracellular polymeric substances (EPS) secreted by P. aeruginosa and its functional groups played important roles in the reduction of Cr(VI). They could reduce Cr(VI) to Cr(III) and transform to Cr(OH)₃ or Feₓ-Cr₍₁₋ₓ₎(OH)₃ precipitation. These results of this study are of significant importance to better understand the environmental geochemical behavior of Cr(VI) with the interactions between soil minerals and microorganisms.
Show more [+] Less [-]Synthesis of nano-magnetic MnFe2O4 to remove Cr(III) and Cr(VI) from aqueous solution: A comprehensive study
2020
Eyvazi, Behzad | Jamshidi-Zanjani, Ahmad | Darban, Ahmad Khodadadi
The co-precipitation method was used to synthesize nano-magnetic adsorbent MnFe₂O₄ (nMFO), characterized through XRD, SEM, EDS, and BET techniques. The synthesized nMFO was used for hexavalent and trivalent chromium ions elimination from the aqueous phase. The optimum pH for the adsorption of Cr (VI) and Cr (III) was determined as 2 and 5, respectively. The chromium ions adsorption behavior was well interpreted through the pseudo-second order kinetics model. Furthermore, isotherm studies were conducted, and the obtained results indicated that Langmuir isotherm model could well justify the chromium ions adsorption process. Quick removal (less than 10 min) of both chromium ions and high removal efficiency were occurred using nMFO. The utmost adsorption capacity of trivalent and hexavalent chromium ions were determined as 39.6 and 34.84 mg g⁻¹, respectively. Thermodynamic studies on chromium adsorption revealed positive value for ΔH and negative value for ΔG, representing that chromium ions adsorption was an endothermic and spontaneous process. The multilinearity in the graphs of chromium ions adsorption was observed using intra-particle diffusion model. In this regard, the external mass transfer of chromium ions on synthesized nanoparticles was the important and controlling step in the adsorption process.
Show more [+] Less [-]Long-term exposure of high concentration heavy metals induced toxicity, fatality, and gut microbial dysbiosis in common carp, Cyprinus carpio
2020
Heavy metals (HMs) in an aquatic environment mainly affects fish, and thus, fish are convenient pollution bio-indicators. In this study, the toxic effects of HM mixture (chromium (Cr), cadmium (Cd), copper (Cu)) in 0 mg/L to 3.2 mg/L concentration range was investigated in Cyprinus carpio (28 days). HM accumulation, histopathology, oxidative stress, and gut microbial changes were evaluated. HMs accumulated in the order of Cr > Cu > Cd, primarily in the kidneys and finally scales. Reactive oxygen species generation increased in all exposure groups up to day 14, with maximum generation at 3.2 mg/L mixture, which later decreased on day 28 in all. Malondialdehydeand and superoxide dismutase levels increased from day 7 to 28 with increased HM concentrations, while total protein showed an inverse trend. Gill histopathology showed major changes such as uplifted and disintegrated primary lamella, and secondary lamella shortening. The kidneys were characterized by glomerular necrosis, Bowman’s capsule expansion, and tubular space dilatation. Proteobacteria and Firmicutes abundance increased up to 59.4% and 99.16% in 0.8 mg/L and 3.2 mg/L treatment groups, respectively. This study provided a better understanding on the physiology and gut microbiota alteration in C. carpio under multiple HM stress.
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