Selective and efficient immobilization of cadmium in soil by layered double hydroxides intercalated with the mercaptosuccinic acid.

Cadmium (Cd) contamination in cropland poses a significant threat to the quality of agricultural products, but even though in-situ remediation has been extensively applied, non-selective immobilization remains an issue. In order to develop a material that specifically immobilizes Cd in soil, a layered double hydroxide, intercalated with mercaptosuccinic acid (MSA-CFA), was synthesized through co-precipitation. In this case, the MSA-CFA's maximum adsorption capacity was increased from the 513.8 mg·g-1 for unintercalated hydrotalcite CFA to 692.6 mg·g-1. Besides, MSA-CFA efficiently removed 99.25 % of Cd from soil water-extract solution and immobilized up to 70.03 % of bio-available Cd. However, interestingly, its immobilization effects on beneficial metal elements Fe, Mn and Zn were milder, being equivalent to 2/7, 5/7 and 1/2 that of lime, respectively. Moreover, XRD and XPS techniques revealed isomorphous substitution with calcium and sulfhydryl complexation during the Cd adsorption by MSA-CFA. Compared with CFA, the increased adsorption capacity of MSA-CFA for Cd was due to intercalated MSA acting as a new adsorption site, while the enhanced selectivity was contributed by sulfhydryl's affinity for Cd. Altogether, MSA-CFA showed great promise as a competitive and highly efficient candidate amendment in Cd-contaminated soil remediation.

[Combined Effect of Weathered Coal Based Amendments and Soil Water Management on Methylmercury Accumulation in Paddy Soil and Rice Grains].

A pot experiment and field experiment were designed to study the changes in the grain methyl mercury content in paddy soil and rice yield by sowing soil amendments that contained weathered coal, CaCO3, and Na2SeO3 as the main raw materials, combined with water management in a paddy field (80% field capacity after the heading and flowering periods). The results showed that:① In pot experiment, the content of methylmercury in rice rhizosphere soil decreased by 86.6% and the content of methylmercury in the rice grains decreased by 65.2% compared with that of the control. In field experiment, the content of methylmercury in rice rhizosphere soil decreased by 77.4% and the content of methylmercury in rice grains decreased by 60.6% upon adding the amendment+water management compared with that of CK. ② The soil pH increased by more than 0.3 in the pot experiment and 0.2 in the field experiment compared with that of the control. Furthermore, rice yield and plant biomass did not decrease in the two parts of the experiment. It can be inferred that the soil amendment and agronomic regulation measures (water management) used in this study have the advantages of quick effects, convenient use, and remarkable control effects and without secondary pollution. More, they can effectively reduce the risk of rice methylmercury exposure.

Health Assessment of Trace Metal Concentrations in Organic Fertilizer in Northern China.

The application of organic fertilizer could be accompanied by potential hazards to soil and humans caused by trace metals. A wide survey of organic fertilizers was carried out in northern China. A total of 117 organic fertilizer samples were collected to analyze the concentrations of seven trace metals. Simulation models were used to estimate the trace metal accumulation risk in soil and non-carcinogenic and carcinogenic risks to the human body. The concentrations of trace metals varied widely (Cr: 2.74⁻151.15; Ni: 2.94⁻49.35; Cu: 0.76⁻378.32; Zn: 0.50⁻1748.01; As: 1.54⁻23.96; Cd: 2.74⁻151.15; and Pb: 1.60⁻151.09 mg·kg-1). Chinese organic fertilizer standard limits were exceeded by0.85% for Cr, 5.98% for As, 1.71% for Cd, and 4.27% for Pb. Monte Carlo simulations showed that repeated application of organic fertilizer likely significantly increased the concentrations of Zn, Cd, and As in soil compared with the soil background levels according to the Soil Environmental Quality Standards of China. As and Cr pose high risks to human health, especially as carcinogenic risk factors with a skin exposure pathway. Reducing the content of Cr, Cu, Zn, As, and Cd in organic fertilizer would be of great significance for minimizing the damage caused by trace metals.

Evaluation of leafy vegetables as bioindicators of gaseous mercury pollution in sewage-irrigated areas.

Mercury (Hg) can evaporate and enter the plants through the stomata of plant leaves, which will cause a serious threat to local food safety and human health. For the risk assessment, this study aimed to investigate the concentration and accumulation of total gaseous mercury (TGM) in five typical leafy vegetables (Chinese chives (Allium tuberosum Rottler), amaranth (Amaranthus mangostanus L.), rape (Brassica campestris L.), lettuce (Lactuca sativa L.), and spinach (Spinacia oleracea L.)) grown on sewage-irrigated areas in Tianjin, China. The following three sites were chosen to biomonitor Hg pollution: a paddy field receiving sewage irrigation (industrial and urban sewage effluents) for the last 30 years, a vegetable field receiving sewage irrigation for 15 years, and a grass field which did not receive sewage irrigation in history. Results showed that the total Hg levels in the paddy (0.65 mg kg-1) and vegetation fields (0.42 mg kg-1) were significantly higher than the local background level (0.073 mg kg-1) and the China national soil environment quality standard for Hg in grade I (0.30 mg kg-1). The TGM levels in ambient air were significantly higher in the paddy (71.3 ng m-3) and vegetable fields (39.2 ng m-3) relative to the control (9.4 ng m-3) and previously reported levels (1.45 ng m-3), indicating severe Hg pollution in the atmospheric environment of the sewage-irrigated areas. Furthermore, gaseous mercury was the dominant form of Hg uptake in the leaves or irreversibly bound to leaves. The comparison of Hg uptake levels among the five vegetables showed that the gradient of Hg accumulation followed the order spinach > red amaranth > Chinese chives > rape > lettuce. These results suggest that gaseous Hg exposure in the sewage-irrigated areas is a dominant Hg uptake route in leafy vegetables and may pose a potential threat to agricultural food safety and human health.

[Simulation study on the effect of salinity on the adsorption behavior of mercury in wastewater-irrigated area].

This study was designed to pinpoint the impact of salinity ( NaCl and Na2SO4, added at salinity levels of 0-5%, respectively) on the adsorption behavior of mercury in wastewater-irrigated areas of Tianjin City by batch and kinetic experiments. The results showed that, the Langmuir isotherm and the Elovich equation can well fitted batch and kinetic experimental data, respectively. As NaCI spiked in soil, Hg( II) adsorption capacity and strength had marked decreases, from 868.64 mgkg-1 and 1. 32 at control to 357.48 mgkg-1 and 0.63 at 5% salinity level of NaCI, respectively. As Na2SO4 spiked in soil, Hg(II) adsorption capacity (parameter qm in Langmuir isotherm) and strength (parameter k in Langmuir isotherm) changed slightly, from 868.64 mg kg-1 and 1.32 at control to 739.44 mg.kg-1 and 1. 18 at 5% salinity level of Na2 SO4, respectively. Kinetic data showed that, Hg( II) adsorption rate (parameter b in Elovich equation) in soil was not influenced by Na2SO, addition. However, the addition of NaC1 had a great effect on mercury adsorption rate. Hg(II ) adsorption capacity as a function of CI- or SO(2-)(4) content in soil could be simulated by the natural logarithm model, while Hg( II ) adsorption rate as a function of CI- content in soil could be simulated by the linear model. The study manifested that NaCI can significantly increase migration of Hg( II ) in the soil irrigated with wastewater, which may enhance Hg( II) bioavailability in the soil and cause a hazard to surface water. Especially, it will be harmful to human body through the food chain.

[Concentrations of mercury in ambient air in wastewater irrigated area of Tianjin City and its accumulation in leafy vegetables].

Gaseous Hg can evaporate and enter the plants through the stomata of plat leaves, which will cause a serious threat to local food safety and human health. For the risk assessment, this study aimed to characterize atmospheric mercury (Hg) as well as its accumulation in 5 leafy vegetables (spinach, edible amaranth, rape, lettuce, allium tuberosum) from sewage-irrigated area of Tianjin City. Bio-monitoring sites were located in paddy (wastewater irrigation for 30 a), vegetables (wastewater irrigation for 15 a) and grass (control) fields. Results showed that after long-term wastewater irrigation, the mean values of mercury content in paddy and vegetation fields were significantly higher than the local background value and the national soil environment quality standard value for mercury in grade I, but were still lower than grade II. Soil mercury contents in the studied control grass field were between the local background value and the national soil environment quality standard grade I . Besides, the atmospheric environment of paddy and vegetation fields was subjected to serious mercury pollution. The mean values of mercury content in the atmosphere of paddy and vegetation fields were 71.3 ng x m(-3) and 39.2 ng x m(-3), respectively, which were markedly higher than the reference gaseous mercury value on the north sphere of the earth (1.5-2.0 ng x m(-3)). The mean value of ambient mercury in the control grass fields was 9.4 ng x m(-3). In addition, it was found that the mercury content in leafy vegetables had a good linear correlation with the ambient total gaseous mercury (the data was transformed into logarithms as the dataset did not show a normal distribution). The comparison among 5 vegetables showed that the accumulations of mercury in vegetables followed this order: spinach > edible amaranth > allium tuberosum > rape > lettuce. Median and mean values of mercury contents in spinach and edible amaranth were greater than the hygienic standard for the allowable limit of mercury in food. Spinach appeared to accumulate more mercury than the other four vegetables, in which the median and mean mercury content were both higher than 20 µg x kg(-1). The mercury concentrations in rape, lettuce and allium tuberosum were lower than the standard. Moreover, test results indicated that the Hg content in leafy vegetables was mainly the gaseous mercury through leaf adsorption but not the Hg particulates. This study clearly manifested that there should be a great concern on the pollution risk of both air-and soil borne mercury when cultivating leafy vegetables in long-term wastewater-irrigated area.

[Polycyclic musks exposure affects gene expression of specific proteins in earthworm Eisenia fetida].

To investigate the changes in gene expression of earthworm specific proteins following long-term exposure to low-dose polycyclic musks in soil, the mRNA expression levels of the four representative protein-coding genes (HSP70, CRT, cyPA, TCTP) were examined in earthworm Eisenia fetida exposed to polycyclic musks using real-time quantitative PCR (RT-qPCR). The purpose of this study was to investigate mRNA expression profiles of test protein genes in response to sublethal galaxolide (HHCB) and tonalide (AHTN) for 28 d exposure. The analysis results of both sequence alignment and melting curves of RT-qPCR reactions showed that the selected primers were appropriately qualified for quantitative mRNA analysis. mRNA expressions of HSP70 gene were not significantly changed in Eisenia fetida exposed to low concentrations of AHTN (less than 30 microg x g(-1)) and HHCB (less than 50 microg x g(-1)). But HSP70 gene expressions were significantly down-regulated at concentrations of AHTN or HHCB equal to or greater than 30 or 50 microg x g(-1). However, up-regulation of CRT gene expressions was induced in response to all test concentrations of AHTN and HHCB. Both cyPA and TCTP gene expressions were not varied compared to control groups after 28 days of exposure. Overall, the results indicated that HSP70 and CRT genes expression patterns might be potential early molecular biomarkers for predicting the harmful exposure level and ecotoxicological effects of polycyclic musks contaminated soil.

[Aging process of Cr(III) in 22 typical soils of China and influence factors Analysis].

Aging process is a key factor influencing the availability and toxicity of heavy metals in soil. However, the aging of chromium (Cr) in soils and its influence factors are still unclear, as a result of complexity of soils in China. This study was conducted to investigate the aging process of Cr(Ill) in 22 typical soils of China by using 0.01 mol.L-1 CaCl2 as the extractant for available Cr. The results manifested that Cr spiked in the soil was time-dependently transferred from the available fraction into less labile fractions. Two regions could be distinguished: the first one for short extraction time (t <21 days), corresponding to a faster transformation of metals and the second for longer extraction time (t >21 days) where the transformation was relatively slower. The decrease of Cr in available fraction during the incubation could be simulated by the Elovich equation, and decrease rates were applied to reflect the transformation rates of aging process among various soils. Multiple regression analysis showed that decrease rates might be related to the organic matter, pH and amorphous Fe oxides of soil, and organic matter was the key factor to the aging process.

Leaching behavior of heavy metals and transformation of their speciation in polluted soil receiving simulated acid rain.

Heavy metals that leach from contaminated soils under acid rain are of increasing concern. In this study, simulated acid rain (SAR) was pumped through columns of artificially contaminated purple soil. Column leaching tests and sequential extraction were conducted for the heavy metals Cu, Pb, Cd, and Zn to determine the extent of their leaching as well as to examine the transformation of their speciation in the artificially contaminated soil columns. Results showed that the maximum leachate concentrations of Cu, Pb, Cd, and Zn were less than those specified in the Chinese Quality Standards for Groundwater (Grade IV), thereby suggesting that the heavy metals that leached from the polluted purple soil receiving acid rain may not pose as risks to water quality. Most of the Pb and Cd leachate concentrations were below their detection limits. By contrast, higher Cu and Zn leachate concentrations were found because they were released by the soil in larger amounts as compared with those of Pb and Cd. The differences in the Cu and Zn leachate concentrations between the controls (SAR at pH 5.6) and the treatments (SAR at pH 3.0 and 4.5) were significant. Similar trends were observed in the total leached amounts of Cu and Zn. The proportions of Cu, Pb, Cd, and Zn in the EXC and OX fractions were generally increased after the leaching experiment at three pH levels, whereas those of the RES, OM, and CAR fractions were slightly decreased. Acid rain favors the leaching of heavy metals from the contaminated purple soil and makes the heavy metal fractions become more labile. Moreover, a pH decrease from 5.6 to 3.0 significantly enhanced such effects.