[Reactivation of Passivated Biochar/Nanoscale Zero-Valent Iron by an Electroactive Microorganism for Cooperative Hexavalent Chromium Removal and Mechanisms].

Nanoscale zero-valent iron (nZVI) shows excellent reduction of Cr(Ⅵ), but the passivation on its outer surface can restrict its longevity and performance. To tackle this problem, this work introduced Shewanella oneidensis MR-1, a dissimilatory iron-reducing bacterium, into the chemical reduction system of aged nZVI/biochar (B) and Cr(Ⅵ). The potential synergistic effect of Cr(Ⅵ) reduction of aged nZVI/B and MR-1 was systematically investigated under varying conditions. The results indicated that aged nZVI/B and MR-1 exhibited a synergistic effect at a pH of 7, and the removal rate of Cr(Ⅵ) increased by 51.3%. Further research showed that the synergistic effect could be attenuated with the increase in the initial Cr(Ⅵ) concentration and enhanced with the increase in the MR-1 concentration. The XPS spectra confirmed that Cr(Ⅵ) was mainly removed through reduction. The dissimilatory iron-reducing ability of MR-1 played a key role in enhancing the Cr(Ⅵ) reduction. The reductive dissolution of the oxidation layers not only released reactive sites inside the nZVI, but also reduced Cr(Ⅵ) by producing ferrous ions. Moreover, B promoted the reduction by dispersing the nZVI and mediating the extracellular electron transfer. This study provides a new insight into solving the passivation problem of the long-term application of nZVI for Cr(Ⅵ) removal, which is considered a promising solution for synergistically improving the performance of nZVI in environmental remediation.

[Distribution and Bioaccumulation Characteristics of Cadmium in Fish Species from the Longjiang River in the Guangxi Autonomous Region].

Emergent cadmium pollution can cause water quality deterioration in rivers, which destroys the aquatic eco-environment and poses threats to human health. Fish species in these aquatic systems are prone to such pollution incidents and act as important indicators of the pollution level. Because cadmium enters the systematic circulation of fish and is non-biodegradable, the investigation of cadmium accumulation in fish bodies provides insights into the detrimental effects of cadmium pollution on the aquatic biological system. This research aims to validate the eco-environmental risks associated with emergent cadmium pollution incidents based on the investigation of the different tissues and organs of diverse fish species. The investigation was conducted six times along the Longjiang River using sampling methods during which all fish species were also classified and analyzed based on the water layer they reside in and their feeding habits. The results show that the cadmium concentration in the fish tissues is significantly higher in the former three investigations compared with that of the latter three analyses. For herbivorous, carnivorous, and omnivorous fish species, the cadmium concentration of their different tissues and organs follows the order:kidney > liver > gut > gill > egg > scale ≈ muscle. The cadmium concentration in the kidney is significantly higher (P<0.05) than that in any other organs of the fish species. This agrees with the fact that the kidney intensively metabolizes and accumulates heavy metals. The cadmium concentration in the same tissues or organs of the fish species living in different water layers follows the trend:demersal fish species > middle lower-layer species > middle upper-layer species. The sequence of the cadmium bioaccumulation factors in the muscles of different fish species is omnivore > carnivorous > herbivorous, that is, 8.32, 6.33, and 5.15, respectively, while the bioaccumulation factors in the muscles of the fish species in different water layers decrease in the following sequence:demersal fish species (8.18) > middle bottom-layer fish species (7.70) > middle upper-layer fish species (4.99). These experimental results indicate the biomagnification effects in heavy metal-polluted aquatic environments, where the bioaccumulation of heavy metals by fish is related to both the overall pollution level and local residential environment.

[Effect of Iron on the Release of Arsenic in Flooded Paddy Soils].

Amorphous iron oxides in paddy soil are critical adsorbents of arsenic. The flooding period during rice cultivation contributes to the reductive dissolution of these amorphous iron oxides, which releases sorbed arsenic into the paddy soil solution. However, more detailed work should be conducted to evaluate quantitatively arsenic immobilization, release, and transformation regulated by metastable amorphous iron oxides. In previous studies, arsenic in the soil solution phase and solid phase were classified into F1 (exchangeable arsenic), F2 (specifically sorbed arsenic), F3 (amorphous iron oxide bound arsenic), and F4 (crystalline iron oxide bound arsenic), according to a sequential extraction procedure using reagents of increasing dissolution strength. In this study, soil samples were collected from the vicinity of a silver smelting plant in Chenzhou, Hunan Province, and the contribution of different arsenic speciation (F1, F2, F3, and F4) to arsenic release during anaerobic enrichment incubation of paddy soil was investigated. Sample analysis was conducted at the end of the first phase (day 15) and the second phase (day 30). The effects of amorphous iron oxides in paddy soil on migration and transformation of arsenic were discussed. Results showed significant elevation of dissolved Fe(Ⅱ) and arsenic concentration (P<0.05) in enrichment solutions in the second phase compared with that in the first phase. Arsenic released in the soil solution in both phases originated from exchangeable arsenic and specifically sorbed arsenic, as indicated by its significantly positive correlation with F1 and F2 (r=0.73, P<0.05; r=0.657, P<0.05). However, an insignificant positive correlation was found between the arsenic released and F3. Moreover, HCl-extractable Fe(Ⅱ) was significantly and positively correlated with arsenic (r=0.577, P<0.05; r=0.613, P<0.05), while amorphous iron oxides were significantly and negatively correlated with arsenic (r=-0.428, P=0.126; r=-0.564, P<0.05). In conclusion, arsenic in the F1 and F2 fractions acted as the major source of released arsenic. Despite elevated levels of HCl-extractable Fe(Ⅱ) that might result from the slight reductive dissolution of amorphous iron oxide, the significant negative correlation between dissolved arsenic and amorphous iron oxides indicated that metastable amorphous iron oxides in anaerobic paddy soil can generally sorb dissolved arsenic effectively, resulting in lower mobility of arsenic. Increasing the level of amorphous iron oxides in paddy soil is conducive to inactivation of arsenic.

[Effect of Calcium Silicate-biological Humus Fertilizer Composite on Uptake of Cd by Shallots from Contaminated Agricultural Soil].

The safety of vegetable production is a key link in reducing cadmium consumption through the food chains. Field experiments were conducted to investigate the effects of composite materials (calcium silicate-biological humus fertilizer) on the growth of shallots and the uptake of Cd by shallots from contaminated agricultural soil. Four treatments (T1: 0.5% calcium silicate+0.5% biological humus fertilizer; T2: 0.5% calcium silicate+1.0% biological humus fertilizer; T3: 1.0% calcium silicate+0.5% biological humus fertilizer; and T4: 1.0% calcium silicate+1.0% biological humus fertilizer) and a control group (CK) were adopted. The changes in soil pH, DTPA-extractable Cd, biomass of shallots, and cadmium concentrations in shallots over time under different treatments were analyzed. The results show that the application of composite amendments decreased the concentrations of DTPA-extractable Cd in the soil. In particular, after T3 treatment, the concentrations of soil DTPA-extractable Cd decreased by 60.71%, 49.54%, 44.63%, and 58.94% after 14, 28, 42, and 56 d, respectively. The biomass of the shallots aboveground increased significantly by 107.99% and 107.19% after T3 and T4 treatment, respectively. The composite amendments exhibited different effects on the uptake of Cd by the shallots from the soil, and the T4 treatment was the most effective in immobilizing Cd and inhibiting translocation of Cd into the shallots. The cadmium concentration in the shallots decreased by 43.80% after 56 d with the T4 treatment. In conclusion, T4 is the optimum treatment for soil cadmium immobilization.

[Characteristics and Evaluation of Heavy Metal Pollution in Vegetables in Guangzhou].

Vegetable is an indispensible component of human daily diet,and contamination of vegetables by heavy metals directly threatens human health.In this study,116 vegetable samples were collected from 12 administrative districts of Guangzhou City for analysis of six heavy metals,Cu,Zn,Pb,Cd,Ni,Cr.A combination of single factor evaluation and Nemero Index analysis was employed to determine specific heavy metals exceeding allowable standards and analyze the characteristics of pollution.Risk of exposure was utilized to assess human health risks originating from eating locally planted vegetables contaminated by heavy metals.The results showed that contents of Cu,Zn in the 8 sorts of vegetables were below the standards of maximum allowable content and the contents of heavy mental Cr of up to 91.67% vegetable samples were higher than their standard.Lettuce sativa var.angustana Irish,Luffa acutangula L.,Lycopersicon esculentum Mill.and Daucus carota L.were the 4 species of Pb exceeding vegetables,with the exceed ratio reaching up to 35.71% and Daucus carota L.exceeded the target value most seriously.Only the content of Cd in Lycopersicon esculentum Mill.was over-standard,with the rate of 31.25%.And the highest rate of over-standard of the content of Ni in 3 species of vegetables,which included Lactuca sativa L.,Ipomoea aquatica Forsk and Brassica parachinensis,reached 8.33%.For the contamination level of the eight kinds of vegetable,Lactuca sativa L.,Ipomoea aquatica Forsk,Brassica parachinensis,Raphanus sativus L.and Daucus carota L.were put into the class of alarming,while Lettuce sativa var.angustana Irish,Luffa acutangula L.and Lycopersicon esculentum Mill.were classified as secure.Heavy metals' comprehensive pollution degree of 4 species of vegetables presented a trend of leafy vegetables >rootstalk vegetables >stem vegetables >solanaceous fruits.Health risk assessment showed that Guangzhou citizens eat more frequently Ipomoea aquatica Forsk and Lactuca sativa L.and Brassica parachinensis were prone to higher accumulation of heavy metals,and the dietary intake of heavy metal Cr might cause harm to human health and intake of Cd would bring potential health risk to the human body.Risk of exposure to heavy metal through oral ingestion of vegetables was proved to be higher for children than adults.

[Influencing Mechanism of Eh, pH and Iron on the Release of Arsenic in Paddy Soil].

The massive release of soil arsenic and its enrichment in rice are significantly associated with the flooded and anaerobic management in paddy soil. Soil redox potential (Eh), pH and iron oxides exert remarkable impacts on arsenic release, which remain to be explored. In this study, long-term aerobic and anaerobic as well as intermittent aerobic incubation treatments were applied to investigate the influences of Eh, pH and iron content on arsenic release. It was found that anaerobic and flooded treatment contributed to the highest arsenic release. With decreasing Eh, significant enhancement in As(Ⅲ) and As(Ⅴ) contents in soil solution was observed. Particularly, As(Ⅲ) and As(Ⅴ) contents during the second phase increased by 1.37 and 0.99 µg·L-1compared with those in the first phase. Conversely, significant reduction in soil arsenic release (P<0.05) occurred when intermittent aerobic treatment was adopted, and the lowest level of arsenic release was observed along with the longest treatment time (6 d). The exponent relationships between arsenic and soil Eh, pH and Fe2+ content were also established, which indicated that arsenic release could be accelerated by lower pH and elevated Eh. In addition, a significant positive correlation was also found between iron(Ⅱ) content and arsenic content in soil solution. Since low Eh and elevated pH served as critical factors driving arsenic release, intermittent and aerobic water management was proved to be an effective method for the inhibition of arsenic release and uptake and accumulation of arsenic by rice.

[Effect of Different Iron Minerals on Bioaccessibility of Soil Arsenic Using in vitro Methods].

To explore the effects of different iron minerals on soil arsenic bioaccessibility, ferrihydrite, goethite and hematite were used in PBET, SBRC and IVG in-vitro experiments in this study. The relationship between arsenic bioavailability in gastric, small intestinal phases and arsenic speciation was also studied. The results showed that when 1% ferrihydrite was added, arsenic bioavailability in gastric phase was 2.22%, 5.11% and 7.43% by PBET, SBRC and IVG methods, respectively, while in the small intestinal phase it was 3.39%, 2.33% and 6.18%. At an elevated ferrihydrite dosage of 2%, significant difference in arsenic bioavailability was observed in both phases (P<0.05). According to in vitro experiments, the addition of the same amount of different iron minerals had contributed to the decrease in arsenic bioavailability to varying extents in contrast with the blank group, in the descending order of ferrihydrite(F1) > goethite(G1) > hematite(H1) (F2 > G2 > H2). Total arsenic in exchangeable (F1) and specifically sorbed (F2) state was found positively correlated with arsenic bioavailability in gastric phase by PBET, SBRC and IVG methods, the correlation coefficient of which being r=0.93, P=0.002, r=0.90, P=0.004 and r=0.89,P=0.006, respectively. It was also found that arsenic bioavailability in gastric phase was positively correlated with total arsenic in F1 and F2 states by PBET(r=0.94,P=0.001) and IVG (r=0.87,P=0.009) methods, but no significant correlation was observed by SBRC method. Additionally, three in vitro experiments showed that amorphous iron bound arsenic had significant negative correlation with arsenic bioavailability in gastric phase and small intestinal phase, except that no correlation was found in small intestinal phase by SBRC method.

[Effect of Stabilizer Addition on Soil Arsenic Speciation and Investigation of Its Mechanism].

Arsenic toxicity, mobility and bioaccessibility are influenced by its different speciation in soil, which exerts different impacts on the environment. In this study, coal fly ash, dried sludge, ferrous sulfate and broken peanut shell were used as stabilizers to investigate their stabilizing effects on As in soil as well as relationships between pH, soil organic matter content, cation exchange capacity and speciation of soil As. The results showed rise in soil pH, soil organic matter content and residual arsenic content after the addition of stabilizers. Addition of 10% coal fly ash and 10% dried sludge led to the decrease in the content of exchangeable As, carbonate bound As, Fe-Mn oxide bound As, organic bound As by 34.2%, 17.5%, 19.9%, 53.7%, respectively. Addition of ferrous sulfate could preferably stabilize As in soil. When 10% coal fly ash, 10% dried sludge and 1% ferrous sulfate were added concurrently, the decrease in the content of exchangeable As, carbonate bound As, Fe-Mn oxide bound As, organic bound As was 62.3%, 55.2%, 29.6%, 58.2%, respectively, with an increase in residual arsenic content by 8.1%. After the addition of 10% coal fly ash, 10% dried sludge, 1% ferrous sulfate and 1% broken peanut shell, a most conspicuous decrease in the content of exchangeable As by 73.3% was observed. Appropriate application of coal fly ash, dry sludge and ferrous sulfate converted a proportion of exchangeable, carbonate bounded, Fe-Mn bounded, organic bounded As into residual As, which reduced As's toxicity. The rise in pH led to increasing residual As content and decreasing exchangeable As, carbonate bounded As, Fe-Mn bounded As and organic bounded As content, and As was most stable at the approach of neutral condition. The rise in organic matter content led to increasing carbonate bounded As and residual As content and decreasing exchangeable As, Fe-Mn bounded As, organic bounded As content. The rise in cation exchange capacity led to increasing residual As content and decreasing exchangeable As, carbonate bounded As, Fe-Mn bounded As and organic bounded As content.