Multifunctional Roles of Zinc in Cadmium Transport in Soil-Rice Systems: Novel Insights from Stable Isotope Fractionation and Gene Expression.

The effect of Zn on Cd accumulation in rice varies under flooding and drainage conditions, and the underlying mechanism during uptake and transport from the soil to grains remains unclear. Isotope fractionation and gene expression were investigated using pot experiments under distinct water regimes and with Zn addition to gain a deeper understanding of the molecular effects of Zn on Cd uptake and transport in rice. The higher OsHMA2 expression but constitutively lower expression of zinc-regulated, iron-regulated transporter-like protein (ZIP) family genes in roots under the drainage regime than the flooding regime caused the enrichment of nonheavy Zn isotopes in the shoots relative to roots but minimally affected Cd isotopic fractionation. Drainage regime seem to exert a striking effect on the root-to-shoot translocation of Zn rather than Cd, and increased Zn transport via OsHMA2. The changes in expression patterns in response to Zn addition were similar to those observed upon switching from the flooding to drainage regime, except for OsNRAMP1 and OsNRAMP5. However, soil solution-to-rice plants and root-to-shoot fractionation toward light Zn isotopes with Zn addition (Δ66Znrice plant-soil solution = -0.49 to -0.40‰, Δ66Znshoot-root = -0.36 to -0.27‰) indicated that Zn transport occurred via nonspecific uptake pathways and OsHMA2, respectively. Accordingly, the less pronounced and minimally varied Cd isotope fractionation suggested that OsNRAMP5 and OsHMA2 are crucial for Cd uptake and root-to-shoot transport, respectively, facilitating Cd accumulation in grains. This study demonstrated that a high Zn supply promotes Cd uptake and root-to-shoot transport in rice by sharing distinct pathways, and by utilizing a non-Zn-sensitive pathway with a high affinity for Cd.

Integrated influence of sulfide modification on the reactivity of nanoscale zero-valent iron towards decabromodiphenyl ether under an electromagnetic field.

Individual application of sulfide modification and electromagnetic field (EMF) can enhance the reactivity of nanoscale zero-valent iron (nZVI), yet the potential of both in combination is not clear. This work found that the reactivity of nZVI towards decabromodiphenyl ether was significantly enhanced by the combined effect of sulfidation and EMF. The specific reaction rate constant of nZVI increased by 7 to 10 times. A series of characterization results revealed that the sulfidation level not only affects the inherent reactivity but also the magnetic-induced heating (MIH) and corrosion (MIC) of nZVI. These collectively influence the degradation efficiency of nZVI under EMF. Sulfidation generally diminished the MIH effect. The low degree of sulfidation (S/Fe = 0.1) slightly reduced the MIC effect by 21.4%. However, the high degree of sulfidation (S/Fe = 0.4) led to significantly enhanced MIC effect by 107.1%. For S/Fe = 0.1 and 0.4, the overall enhancement in the reactivity resulting from EMF was alternately dominated by the contributions of MIH and MIC. This work provides valuable insights into the MIH and MIC effects about the sulfidation level of nZVI, which is needed for further exploration and optimization of this combined technology.

Impact of Flooding-Drainage Alternation on Fe Uptake and Transport in Rice: Novel Insights from Iron Isotopes.

Iron (Fe) isotopes were utilized to provide insights into the temporal changes underlying Fe uptake and translocation during rice growth (tillering, jointing, flowering, and maturity stages) in soil-rice systems under typical flooding-drainage alternation. Fe isotopic composition (δ56Fe values) of the soil solution generally decreased at vegetative stages in flooding regimes but increased during grain-filling. Fe plaques were the prevalent source of Fe uptake, as indicated by the concurrent increase in the δ56Fe values of Fe plaques and rice plants during rice growth. The increasing fractionation magnitude from stem/nodes I to flag leaves can be attributed to the preferred phloem transport of light isotopes toward grains, particularly during grain-filling. This study demonstrates that rice plants take up heavy Fe isotopes from Fe plaque and soil solution via strategy II during flooding and the subsequent drainage period, respectively, thereby providing valuable insights into improving the nutritional quality during rice production.

Soil Humic Acid Stimulates Potentially Active Dissimilatory Arsenate-Reducing Bacteria in Flooded Paddy Soil as Revealed by Metagenomic Stable Isotope Probing.

Dissimilatory arsenate reduction contributes a large proportion of arsenic flux from flooded paddy soil, which is closely linked to soil organic carbon input and efflux. Humic acid (HA) represents a natural ingredient in soil and is shown to enhance microbial arsenate respiration to promote arsenic mobility. However, the community and function profiles of metabolically active arsenate-respiring bacteria and their interactions with HA in paddy soil remain unclear. To probe this linkage, we performed a genome-centric comparison of potentially active arsenate-respiring bacteria in anaerobic microcosms amended with 13C-lactate and HA by combining stable-isotope probing with genome-resolved metagenomics. Indeed, HA greatly accelerated the microbial reduction of arsenate to arsenite. Enrichment of bacteria that harbor arsenate-respiring reductase genes (arrA) in HA-enriched 13C-DNA was confirmed by metagenomic binning, which are affiliated with Firmicutes (mainly Desulfitobacterium, Bacillus, Brevibacillus, and Clostridia) and Acidobacteria. Characterization of reference extracellular electron transfer (EET)-related genes in these arrA-harboring bacteria supports the presence of EET-like genes, with partial electron-transport chain genes identified. This suggests that Gram-positive Firmicutes- and Acidobacteria-related members may harbor unspecified EET-associated genes involved in metal reduction. Our findings highlight the link between soil HA and potentially active arsenate-respiring bacteria, which can be considered when using HA for arsenic removal.

Roles of Chloride and Sulfate Ions in Controlling Cadmium Transport in a Soil-Rice System as Evidenced by the Cd Isotope Fingerprint.

Anions accompanying inorganic fertilizers, such as chloride and sulfate ions, potentially affect the solubility, uptake, and transport of Cd to rice grains. However, the role of anions in controlling Cd transport in the soil-soil solution-Fe plaque-rice plant continuum remains poorly understood. Cd isotope ratios were applied to Cd-contaminated soil pots, hydroponic rice, and adsorption experiments with or without KCl and K2SO4 treatments to decipher transport processes in the complex soil-rice system. The chloride and sulfate ions increased the Cd concentrations in the soil solution, Fe plaque, and rice plants. Accordingly, the magnitude of positive fractionation from soil to the soil solution was less pronounced, but that between soil and Fe plaque or rice plant is barely varied. The similar isotope composition of Fe plaque and soil, and the similar fractionation magnitude between Fe plaque and the solution and between goethite and the solution, suggested that desorption-sorption between iron oxides and the solution could be important at the soil-soil solution-Fe plaque continuum. This study reveals the roles of chloride and sulfate ions: (i) induce the mobility of light Cd isotopes from soil to the soil solution, (ii) chloro-Cd and sulfato-Cd complexes contribute to Cd immobilization in the Fe plaque and uptake into roots, and (iii) facilitate second leaves/node II-to-grain Cd transport within shoots. These results provide insights into the anion-induced Cd isotope effect in the soil-rice system and the roles of anions in facilitating Cd migration and transformation.

Cd isotope fractionation in a soil-rice system: Roles of pH and mineral transformation during Cd immobilization and migration processes.

Cd speciation in soil and its transport to rice roots are influenced by the soil pH, oxidation-reduction potential, and mineral transformation; however, the immobilization and migration of Cd in soil-rice systems with different pH values under distinct water regimes remain unclear. This study used Cd isotope fractionation, soil physical analysis, and root gene quantification to elucidate the immobilization and transport of Cd in different soil-rice systems. In drainage soils, the high soil pH enhanced the transformation and magnitude of negative fractionation of Cd from MgCl2 extract to FeMn oxide-bound pool; however, it favored Cd uptake and root-to-grain transport. Compared with drainage regimes, the flooding regimes shifted fractionation toward heavy isotopes from MgCl2-extracted Cd to FeMn oxide-bound Cd in acidic soils (∆114/110CdMgCl2 extract - FeMn oxide-bound Cd = -0.09 ± 0.03 ‰) and to light isotopes from MgCl2-extracted Cd to carbonate-bound Cd in neutral and alkaline soils (∆114/110CdMgCl2 extract - carbonate-bound Cd = 0.29-0.40 ‰). The submerged soils facilitated the forming of carbonate and poorly crystalline minerals (such as ferrihydrite), which were transformed into highly crystalline forms (such as goethite). These results demonstrated that the dissolution-precipitation process of iron oxides was essential for controlling soil Cd availability under flooding regimes, and the relative contribution of carbonate minerals to Cd immobilization was promoted by a high soil pH. Flooding regimes induced lower expressions of OsNRAMP1 and OsNRAMP5 to limit the uptake of light Cd isotopes from MgCl2-extract pool, whereas a teeter-totter effect on gene expression patterns in roots (including those of OsHMA3 and OsHMA2) limited the transport of heavy Cd isotopes from root to grain. These findings demonstrate that flooding regimes could exert multiple effects on soil Cd immobilization and Cd transport to grain. Moreover, alkaline soil was conducive to forming carbonate minerals to sequester Cd.

Cadmium isotope fractionation and gene expression evidence for tracking sources of Cd in grains during grain filling in a soil-rice system.

Grain filling is the key period that causes excess cadmium (Cd) accumulation in rice grains. Nevertheless, uncertainties remain in distinguishing the multiple sources of Cd enrichment in grains. To better understand the transport and redistribution of Cd to grains upon drainage and flooding during grain filling, Cd isotope ratios and Cd-related gene expression were investigated in pot experiments. The results showed that the Cd isotopes in rice plants were much lighter than those in soil solutions (∆114/110Cdrice-soil solution = -0.36 to -0.63 ‰) but moderately heavier than those in Fe plaques (∆114/110Cdrice-Fe plaque = 0.13 to 0.24 ‰). Calculations revealed that Fe plaque might serve as the source of Cd in rice (69.2 % to 82.6 %), particularly upon flooding at the grain filling stage (82.6 %). Drainage at the grain filling stage yielded a larger extent of negative fractionation from node I to the flag leaves (∆114/110Cdflag leaves-node I = -0.82 ± 0.03 ‰), rachises (∆114/110Cdrachises-node I = -0.41 ± 0.04 ‰) and husks (∆114/110Cdrachises-node I = -0.30 ± 0.02 ‰), and significantly upregulated the OsLCT1 (phloem loading) and CAL1 (Cd-binding and xylem loading) genes in node I relative to that upon flooding. These results suggest that phloem loading of Cd into grains and transport of Cd-CAL1 complexes to flag leaves, rachises and husks were simultaneously facilitated. Upon flooding of grain filling, the positive fractionation from the leaves, rachises and husks to the grains (∆114/110Cdflag leaves/rachises/husks-node I = 0.21 to 0.29 ‰) is less pronounced than those upon drainage (∆114/110Cdflag leaves/rachises/husks-node I = 0.27 to 0.80 ‰). The CAL1 gene in flag leaves is down-regulated relative to that upon drainage. Thus, the supply of Cd from the leaves, rachises and husks to the grains is facilitated during flooding. These findings demonstrate that the excess Cd was purposefully transported to grain via xylem-to-phloem within nodes I upon the drainage during grain filling, and the expression of genes responsible for encoding ligands and transporters together with isotope fractionation could be used to tracking the source of Cd transported to rice grain.

Source and Strategy of Iron Uptake by Rice Grown in Flooded and Drained Soils: Insights from Fe Isotope Fractionation and Gene Expression.

Rice can simultaneously absorb Fe2+ via a strategy I-like system and Fe(III)-phytosiderophore via strategy II from soil. Still, it remains unclear which strategy and source of Fe dominate under distinct water conditions. An isotope signature combined with gene expression was employed to evaluate Fe uptake and transport in a soil-rice system under flooded and drained conditions. Rice of flooded treatment revealed a similar δ56Fe value to that of soils (Δ56Ferice-soil = 0.05‰), while that of drained treatment was lighter than that of the soils (Δ56Ferice-soil = -0.41‰). Calculations indicated that 70.4% of Fe in rice was from Fe plaque under flooded conditions, while Fe was predominantly from soil solution under drained conditions. Up-regulated expression of OsNAAT1, OsTOM2, and OsYSL15 was observed in the root of flooded treatment, while higher expression of OsIRT1 was observed in the drained treatment. These isotopic and genetic results suggested that the Fe(III)-DMA uptake from Fe plaque and Fe2+ uptake from soil solution dominated under flooded and drained conditions, respectively.

Cadmium uptake and transport processes in rice revealed by stable isotope fractionation and Cd-related gene expression.

Multiple processes are involved in Cd transfer in rice plants, including root uptake, xylem loading, and immobilization. These processes can be mediated by membrane transporters and can alter Cd speciation by binding Cd to different organic ligands. However, it remains unclear which processes control Cd transport in rice in response to different watering conditions in soil. Herein, Cd isotope fractionation and Cd-related gene expression were employed to investigate the key regulatory mechanisms during uptake, root-to-shoot, and stem-to-leaf transport of Cd in rice grown in pot experiments with Cd-contaminated soil under flooded and non-flooded conditions, respectively. The results showed that soil flooding decreased the Cd concentration in soil porewater and, thereby, Cd uptake and transport in rice. Cd isotopes fractionated negatively from soil porewater to the whole rice (flooded: ∆114/110Cdrice-porewater = -0.15‰, non-flooded: ∆114/110Cdrice-porewater = -0.39‰), suggesting that Cd transporters preferentially absorbed light Cd isotopes. The non-flooded treatment revealed an upregulated expression of OsNRAMP1 and OsNRAMP5 genes compared to the flooded treatment, which may partially contribute to its more pronounced porewater-to-rice fractionation. Cd isotopes fractionated positively from roots to shoots under flooded conditions (∆114/110Cdshoot-root = 0.19‰). However, a reverse direction of fractionation was observed under non-flooded conditions (∆114/110Cdshoot-root = -0.67‰), which was associated with the substantial upregulation of CAL1 in roots, facilitating xylem loading of Cd-CAL1 complexes with lighter isotopes. After being transported to the shoots, the majority of Cd were detained in stems (44%-55%), which were strongly enriched in lighter isotopes than in the leaves (∆114/110Cdleaf-stem = 0.77 to 1.01‰). Besides the Cd-CAL1 transported from the roots, the expression of OsPCS1 and OsHMA3 in the stems could also favor the enrichment of Cd-PCs with lighter isotopes, leaving heavier isotopes to be transported to the leaves. The higher expression levels of OsMT1e in older leaves than in younger leaves implied that Cd immobilization via binding to metallothioneins like OsMT1e may favor the enrichment of lighter isotopes in older leaves. The non-flooded treatment showed lighter Cd isotopes in younger leaves than the flooded treatment, suggesting that more Cd-CAL1 in the stems and Cd-PCs in the older leaves might be transported to the younger leaves under non-flooded conditions. Our results demonstrate that isotopically light Cd can be preferentially transported from roots to shoots when more Cd is absorbed by rice under non-flooded conditions, and isotope fractionation signature together with gene expression quantification has the potential to provide a better understanding of the key processes regulating Cd transfer in rice.

Water Management Alters Cadmium Isotope Fractionation between Shoots and Nodes/Leaves in a Soil-Rice System.

The drainage of rice soils increases Cd solubility and results in high Cd concentrations in rice grains. However, plant Cd uptake is limited by sorption to iron plaques, and Cd redistribution in the plant is regulated by the nodes. To better understand the interplay of Cd uptake and redistribution in rice under drained and flooded conditions, we determined stable Cd isotope ratios and the expression of genes coding transporters that can transport Cd into the plant cells in a pot experiment. In soil, both water management practices showed similar patterns of isotope variation: the soil solution was enriched in heavy isotopes, and the root Fe plaque was enriched in light isotopes. In rice, the leaves were heavier (Δ114/110Cdleaf-shoot = 0.17 to 0.96‰) and the nodes were moderately lighter (Δ114/110Cdnode-shoot = -0.26 to 0.00‰) relative to the shoots under flooded conditions, indicating preferential retention of light isotopes in nodes and export of heavy isotopes toward leaves. This is generally reversed under drained conditions (Δ114/110Cdleaf-shoot = -0.25 to -0.04‰, Δ114/110Cdnode-shoot = 0.10 to 0.19‰). The drained treatment resulted in significantly higher expression of OsHMA2 and OsLCT1 (phloem loading) but lower expression of OsHMA3 (vacuolar sequestration) in nodes and flag leaves relative to the flooded treatment. It appeared that OsHMA2 and OsLCT1 might preferentially transport isotopically heavier Cd, and the excess Cd was purposefully retranslocated via the phloem under drained conditions when the vacuoles could not retain more Cd. Cd in seeds was isotopically heavier than that in stems under both water management practices, indicating that heavy isotopes were preferentially transferred toward seeds via the phloem, leaving light isotopes retained in stems. These findings demonstrate that the Fe plaque preferentially adsorbs and occludes light Cd isotopes on the root surface, and distinct water management practices alter the gene expression of key transporters in the nodes, which corresponds to a change in isotope fractionation between shoots and nodes/leaves.

[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.

Removal of both cationic and anionic contaminants by amphoteric starch.

A novel amphoteric starch incorporating quaternary ammonium and phosphate groups was applied to investigate the efficiency and mechanism of cationic and anionic contaminant treatment. Its flocculation abilities for kaolin suspension and copper-containing wastewater were evaluated by turbidity reduction and copper removal efficiency, respectively. And the kinetics of formation, breakage and subsequent re-formation of aggregates were monitored using a Photometric Dispersion Analyzer (PDA) and characterized by flocculation index (FI). The results showed that amphoteric starch possessed the advantages of being lower-dosages-consuming and being stronger in shear resistance than cationic starch, and exhibited a good flocculation efficiency over a wide pH range from 3.0 to 11.0.

[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.

Synthesis, characterization, and secondary sludge dewatering performance of a novel combined silicon-aluminum-iron-starch flocculant.

Flocculation is one of the most widely used cost-effective pretreatment method for sludge dewatering, and a novel environmentally friendly and efficient flocculant is highly desired in the sludge dewatering field. In this study, a novel combined silicon-aluminum-ferric-starch was synthesized by grafting silicon, aluminum, and iron onto a starch backbone. The synthesized starch flocculant was characterized using Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy, X-ray powder diffraction, and thermogravimetric analysis. The dewatering performance of secondary sludge was evaluated according to the capillary suction time, settling volume percentage, and specific resistance to filtration. The results indicated that the copolymer exhibited: (1) a good dewatering efficiency over a wide pH range of 3.0-11.0, (2) superior sludge dewatering performance compared to those of polyaluminum chloride (PACl), polyacrylamide (PAM), ferric chloride, and (3) a discontinuous surface with many channels or voids that helps to mobilize the impermeable thin layer of secondary sludge during filter pressing. Such a novel copolymer is a promising green flocculant for secondary sludge dewatering applications.