Thioarsenate formation upon dissolution of orpiment and arsenopyrite

Thioarsenates were previously determined as dominant species in geothermal and mineral waters with excess sulfide. Here, we used batch leaching experiments to determine their formation upon weathering or industrial leaching of the arsenic-sulfide minerals orpiment (As₂S₃) and arsenopyrite (FeAsS) under different pH and oxygen conditions. Under acidic conditions, as expected based on their known kinetic instability at low pH, no thioarsenates formed in either of the two mineral systems. Under neutral to alkaline conditions, orpiment dissolution yielded mono-, di- and trithioarsenate which accounted for up to 43-55% of total arsenic. Thioarsenate formation upon arsenopyrite dissolution was low at neutral (4%) but significant at alkaline pH, especially under suboxic to sulfidic conditions (20-43%, mainly as monothioarsenate). In contrast to orpiment, we postulate that recombination of arsenite and sulfide in solution is of minor importance for monothioarsenate formation during alkaline arsenopyrite dissolution. We propose instead that hydroxyl physisorption lead to formation of As-OH-S surface complexes by transposition of hydroxyl anions to arsenic or iron sites. Concurrently formed ironhydroxides could provide re-sorption sites for the freshly released monothioarsenate. However, sorption experiments with goethite showed slower sorption kinetics of monothioarsenate compared to arsenite, but comparable with arsenate. The discovery that thioarsenates are released by natural weathering and industrial leaching processes and that, once they are released, have a higher mobility than the commonly-investigated species arsenite and arsenate requires future studies to consider them when assessing arsenic release in sulfidic natural or mining-impacted environments.     

电解锰渣中锰的浸出条件及特征

采用水洗-酸解法回收电解锰渣中锰,探讨了清水量、酸量以及温度在不同阶段对锰浸(洗)出条件的影响,分析了回收锰的主要因素及浸出特征。实验结果表明,50 g电解锰渣经m渣∶m水=1∶10的清水水洗后,采用10%的硫酸在70℃的水浴温度下酸解2 h,Mn2+浸出量为1.673 g,回收率达到97.3%,而温度和酸度对锰离子的浸出影响明显,酸度调控可有效分离酸浸锰液中金属成分,为减少电解锰渣环境污染的同时,实现电解锰渣资源化利用。     

有机酸土柱淋洗法修复重金属污染土壤

通过室内模拟实验,采用土柱淋洗方法,研究草酸、柠檬酸、乙酸和酒石酸溶液对某电镀厂附近土壤中重金属的去除效果。探讨了淋洗剂浓度、淋洗次数和淋洗时间等对淋洗效果的影响,研究草酸淋洗前后土壤中重金属形态的变化。结果表明,淋洗过程中铬的去除效果明显滞后于铜、锌和镍3种重金属离子。1 mol/L的草酸在土水比为1∶1,淋洗5h,淋洗4次的条件下可以达到最佳淋洗效果,Cu、Zn、Ni和Cr的去除率分别是99.6%、66.98%、88.7%和18.23%。     

Reduced downward mobility of metribuzin in fly ash-amended soils

Metribuzin, a triazine herbicide, is poorly sorbed in the soils, therefore leaches to lower soil profile. Fly ash amendment, which enhanced metribuzin sorption in soils, may play a significant role in reducing the downward mobility of herbicide. Therefore, the present study reports the effect of Inderprastha fly ash amendment on metribuzin leaching in three soil types. Fly ash was amended at 1, 2 and 5% levels in the upper 15 cm of 30 cm long packed soil columns. Results suggested a significant reduction in the leaching losses of metribuzin in fly ash-amended columns of all the three soil types and effect increased with increase in the level of fly ash. Even after percolating water equivalent to 362 mm rainfall no metribuzin was recovered in the leachate of 5% fly ash-amended columns. Fly ash application affected both metribuzin breakthrough time and its maximum concentration in the leachate. Further, it resulted in greater retention of metribuzin in the application zone and better effect was observed in the organic carbon poor soils.     

Field dissipation of oxyfluorfen in onion and its dynamics in soil under Indian tropical conditions

Oxyfluorfen, a diphenyl-ether herbicide is being used to control annual and perennial broad-leaved weeds and sedges in a variety of field crops including onion. The present study was aimed to investigate the dynamics and field persistence of oxyfluorfen in onion plant, bulb and soil under Indian tropical conditions. Application of four rates of oxyfluorfen viz., 200, 250, 300 and 400 g AI ha^?1 as pre-emergence gave good weed control in field experiment with onion. The oxyfluorfen residue dissipated faster in plant than in soil respectively, with a mean half-life of 6.1 and 11.2 days. Dissipation followed first-order kinetics. In laboratory column leaching experiments, 17 percent of the applied oxyfluorfen was recovered from the soil and indicates its solubility in water and mobility in sandy clay loam soil was low. A sorption study revealed that the adsorption of oxyfluorfen to the soil was highly influenced by the soil organic carbon with the K_oc value of 5450. The study concludes that the dissipation of oxyfluorfen in soil and onion was dependent on the physico-chemical properties of the soil and environmental conditions.     

Agricultural Chemicals in the Alluvial Aquifer of a Typical County of the Arkansas Delta

Statistical methods and a Geographic Information System (GIS) were used to investigate potential indicators of ground water vulnerability to agricultural chemical contamination in a representative area of the Mississippi River alluvial aquifer. A total of 47 wells were sampled for analysis of nitrate, phosphorus, potassium, and 13 pesticides commonly-used in the area. Ten soil and hydrogeologic variables and five ground water vulnerability indices were examined to explain the variations of chemical concentrations. The results showed that no individual soil or hydrogeologic variables or their linear combinations could explain more than 25% of the variation of the chemical concentrations. A quadratic response surface model with the values of confining unit thickness, slope, soil permeability, depth to ground water, and recharge rate accounted for 62% of the variation of nitrate, 43% of P, and 83% of K, suggesting that the interactions among soil and hydrogeologic variables were significant. Observed trends of decreasing nitrate and P concentrations with increasing well depth and/or depth to ground water seemed to correlate with carbonate equilibrium in the aquifer and more reduced environment with depth. In view of uncertainties involved, it was recognized that the limitations associated with input data resolution used in GIS and the formulation of leaching indices limited their use for predicting ground water vulnerability. Misuse of pesticides could be another factor that would complicate the relationships between pesticide concentrations and the vulnerability indices.     

南方土壤酸沉降敏感性研究Ⅷ.盐基离子淋溶的多因素分析

在模拟酸雨条件下土壤盐基离子淋溶特性研究的基础上,采用生成分分析及多元回归分析方法研究了土壤盐基淋溶的影响因子．结果表明,通过主成分分析方法可将选取的15个原始变量综合成为2个主成分,为进一步分析盐基释放量与土壤理化性质之间的关系提供了方便．影响盐基释放量的主要因子有土壤原始pH值、可交换性盐基含量、蒙脱石含量、活性氧化物、1.4nm矿物等,它们表现出效应,而高岭石和可交换性铝含量表现出负效应．利用主成分分析的结果进行多元回归分析,可得到土壤累积盐基释放量与2个主成分之间的回归方程．     

Land Cover Changes as a Result of Environmental Restrictions on Nitrate Leaching in Dairy Farming

Nitrate leaching forms an important environmental problem because it causes pollution of groundwater and surface water, and adds to already problematic eutrophication. This study analyses the impact of reductions in nitrate leaching on land cover decisions of dairy farms, of which the activities make an important contribution to nitrate leaching. As the level of nitrate leaching depends on groundwater depth as well as on the supply of nitrogen, spatial variation in groundwater levels will cause a spatial variation in land cover under restrictions on nitrate leaching. A non-linear partial optimisation model for the economic and ecological aspects of the problem were used to show how land cover and dairy farms' financial balances change when nitrate losses are reduced. The model is spatially explicit, and describes nitrate leakage and yields of maize and grass as a function of groundwater depth, including the effects of various grazing systems. The model analyses the decisions of a risk neutral agent who minimises costs under the following constraints: (i) production, feed requirements and mass balances for fodder; (ii) constraints for nitrate leaching. Economic costs are attributed to increased costs of fodder and processing of manure when nitrate restrictions are tightened. An important result of the study is the variation in compliance costs and land cover for maize and grass production brought about by spatial variation in groundwater depth. While the effects are negligible for some shallow groundwater classes, it is extremely difficult in other classes – if not impossible – to obtain the EU standard of maximum admissible losses of 34 kg N ha^–1 at low costs. The study shows an important reduction in land cover by maize.     

Characterizing sources of nitrate leaching from an irrigated dairy farm in Merced County, California

Dairy farms comprise a complex landscape of groundwater pollution sources. The objective of our work is to develop a method to quantify nitrate leaching to shallow groundwater from different management units at dairy farms. Total nitrate loads are determined by the sequential calibration of a sub-regional scale and a farm-scale three-dimensional groundwater flow and transport model using observations at different spatial scales. These observations include local measurements of groundwater heads and nitrate concentrations in an extensive monitoring well network, providing data at a scale of a few meters and measurements of discharge rates and nitrate concentrations in a tile-drain network, providing data integrated across multiple farms. The various measurement scales are different from the spatial scales of the calibration parameters, which are the recharge and nitrogen leaching rates from individual management units. The calibration procedure offers a conceptual framework for using field measurements at different spatial scales to estimate recharge N concentrations at the management unit scale. It provides a map of spatially varying dairy farming impact on groundwater nitrogen. The method is applied to a dairy farm located in a relatively vulnerable hydrogeologic region in California. Potential sources within the dairy farm are divided into three categories, representing different manure management units: animal exercise yards and feeding areas (corrals), liquid manure holding ponds, and manure irrigated forage fields. Estimated average nitrogen leaching is 872 kg/ha/year, 807 kg/ha/year and 486 kg/ha/year for corrals, ponds and fields respectively. Results are applied to evaluate the accuracy of nitrogen mass balances often used by regulatory agencies to assess groundwater impacts. Calibrated leaching rates compare favorably to field and farm scale nitrogen mass balances. These data and interpretations provide a basis for developing improved management strategies.     

Long-term depletion of calcium and other nutrients in eastern US forests

Both harvest removal and leaching losses can deplete nutrient capital in forests, but their combined long-term effects have not been assessed previously. We estimated changes in total soil and biomass N, Ca, K, Mg, and P over 120 years from published data for a spruce-fir site in Maine, two northern hardwood sites in New Hampshire, central hardwood sites in Connecticut and Tennessee, and a loblolly pine site in Tennessee. For N, atmospheric inputs counterbalance the outputs, and there is little long-term change on most sites. For K, Mg, and P, the total pool may decrease by 2%–10% in 120 years depending on site and harvest intensity. For Ca, net leaching loss is 4–16 kg/ha/yr in mature forests, and whole-tree harvest removes 200–1100 kg/ha. Such leaching loss and harvest removal could reduce total soil and biomass Ca by 20%–60% in only 120 years. We estimated unmeasured Ca inputs from rock breakdown, root-zone deepening, and dry deposition; these should not be expected to make up the Ca deficit. Acid precipitation may be the cause of current high leaching of Ca. Although Ca deficiency does not generally occur now in acid forest soils, it seems likely if anthropogenic leaching and intensive harvest removal continue.