Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid(OA) on the immobilization of Pb(Ⅱ) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(Ⅱ) by KH2PO4, phosphate rock(PR), activated phosphate rock(APR) and synthetic hydroxyapatite(HAP) at different phosphate:Pb(P:Pb) molar ratios(0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or Ca Cl2, Community Bureau of Reference(BCR) sequential extraction and toxicity characteristic leaching procedure(TCLP)methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was 5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

Leaching-induced migration and compositional form change of Cu,Zn, and Cd from sludge to loess

Land utilization of sewage sludge has become one of the major issues in environmental mitigation in China. This is particularly important in the Loess Plateau of Northwest China. Sludge enriched with organic matter and nutrients might effectively help to resolve the problems of silty loess soils as evidenced by porosity defect, structural alterations and absence of fertility. After sludge flows into the loess, irrigation water contains heavy metals that leach and migrate into sludge and consequently related human health risks may occur that raise concerns; and this situation needs to be rectified. The characteristics of the vertical migration and composition form change of Cu, Zn, and Cd from composted sludge to loess, and corresponding influencing factors, were investigated by performing a soil column simulation test under the leaching treatment of a one-year irrigation water capacity. Results demonstrated that: (1) composted sludge significantly improved loess fertility, and irrigation leaching transported only a small quantity of organic matter in sludge in the plough layer; (2) although some of the Cu, Zn, and Cd in composted sludge migrated to and concentrated in the middle and upper layers of the soil column during leaching, these metals were mostly retained in the plough layer; and (3) after the leaching treatment of the one-year irrigation water capacity, the compositions of Cu, Zn, and Cd (particularly Cu and Zn) in both plough layer and loess began to stabilize with low concentrations in the exudate. These findings confirmed the applicability of composted sludge in loess regions. This study provided a new insight into the sludge reuse in alkaline soils in arid and semi-arid region.     

Respective contributions of point and non-point sources of E. coli and enterococci in a large urbanized watershed (the Seine river, France)

Because the large rivers of the Seine watershed have a low microbiological water quality, the main sources of fecal contamination were investigated in the present study. The inputs of the point (wastewater treatment plants (WWTPs) effluents) and non-point sources (surface runoff and soil leaching) of fecal bacteria were quantified for Escherichia coli and intestinal enteroccoci used as bacterial indicators. In order to assess the contamination through non-point sources, fecal indicators abundance was estimated in samples collected in small streams located in rural areas upstream from all point sources; these small rivers were characterized by the land use of their watershed. Bacterial indicator numbers were also measured in effluents of WWTPs, some using classical treatment (settling followed by activated sludge process) and some using an additional disinfection stage (UV irradiation). These data were used to estimate the respective importance of each type of source at the scale of the whole Seine river watershed taking into account the land use and the population density. It shows the predominant importance of the point sources of fecal indicator bacteria at the scale of the whole watershed. In a scenario in which activated sludge treatment would be complemented with UV in all WWTPs located in this watershed, the non-point sources of fecal indicator bacteria would be dominant.     

SnAgCu焊料中Sn元素在模拟土壤溶液中的浸出行为

研究了Sn-3.5Ag-0.75Cu无铅焊料及其与Cu基板的钎焊接头在模拟土壤的NaCl,NaCl-Na2SO4和NaCl-Na2SO4-Na2CO3溶液中Sn元素的浸出行为.结果表明:焊料在NaCl-Na2SO4-Na2CO3溶液中Sn的浸出相对严重;而接头在NaCl溶液中Sn的浸出量最多.在Sn浸出量多的焊料和接头表面形成厚而疏松的腐蚀产物,XRD分析表明其产物主要由SnO,SnO2和Sn4(OH)6Cl2组成.动电位极化测试分析表明接头中Cu基板与焊料合金之间的电偶腐蚀是焊料合金与接头在同种溶液中Sn元素浸出差异的主要原因.     

以印刷电路板废粉末料制取碱式碳酸铜的研究

印刷电路板废粉末料的资源化和无害化问题日益得到重视。以报废印刷电路板经机械粉碎和分选后的非金属粉(铜含量1%～5%)为原料,采用"氨浸—脱氨—干燥"的工艺制备碱式碳酸铜,设计了实验装置,考察了氨浸分离工艺条件,通过实验验证了其可靠性:铜的回收率达到98.8%以上,获得了纯度不小于98.0%的碱式碳酸铜,采用X射线粉末衍射(XRD)﹑扫描电镜(SEM)和能谱(EDS)方法对产品进行了分析和表征。     

零价铁和碱激发矿渣稳定/固定化处理铬渣研究

采用零价铁和碱激发矿渣对铬渣进行稳定/固定化处理,考察了处理后固化体的毒性浸出水平,矿物组成及Cr形态分布变化情况,并对铬渣的处置和利用的有效性进行评价.结果表明,还原固定化处理后的样品硫酸硝酸法浸出毒性可满足作为砖或砌块使用的标准,抗压强度均高于15 MPa,其中Cr主要以Fe/Mn氧化物结合态存在,可被用于采石场修复、封闭泻湖以及作为路基材料等一些特殊用途.     

LED3A土柱淋洗Pb与Zn污染砂土的效果

为探究不同淋洗方式下螯合型表面活性剂LED3A（N-十二酰基乙二胺三乙酸钠盐）对重金属污染土壤的淋洗效果,采用室内土柱淋洗法研究了LED3A在不同流速条件下对Pb、Zn单一污染砂土的淋洗效果,并通过优化的BCR法分析了淋洗前、后土柱中不同深度处Pb、Zn的形态变化特征.结果表明:LED3A对Pb、Zn单一污染砂土的淋洗规律基本类似,淋出液中ρ（Pb）、ρ（Zn）随淋洗液累积孔隙体积数目的增加呈现急剧增大、达到峰值后逐渐降低的趋势;Pb、Zn的淋洗曲线中均存在不同程度的拖尾现象,且对称性较差;淋出液中ρ（Pb）、ρ（Zn）峰值和Pb、Zn最大累积去除率均随流速的增大而减小.随着淋洗深度和流速的增加,各形态Pb、Zn的去除率均呈现减小的趋势,LED3A对酸可提取态Pb、Zn的去除效果最为显著,去除率均大于50%;对氧化物结合态、有机结合态和残渣态Pb、Zn的去除率大小顺序与淋洗深度和流速有关;对比淋洗前、后土柱中重金属的形态分布可知,最易释放和被生物利用的酸可提取态的占比明显减少,不易或不能被生物利用的氧化物结合态、有机结合态和残渣态的占比明显增加.研究显示,LED3A低流速淋洗不仅能够去除一定量的土壤重金属,同时可有效降低残留重金属对环境的潜在风险.      

Differential leaching of nutrients from soluble vs. controlled-release fertilizers

Extremely sandy soils and poorly distributed high annual rainfall in the state of Florida contribute to significant leaching losses of nutrients from routine fertilization practices. A leaching column experiment was conducted to evaluate the leaching losses of nutrients when using currently available N, P, K blend fertilizers for young citrus tree fertilization. Fertilizer blends included NH₄NO₃, Ca(NO₃)₂, IBDU, IBDU plus Escote, Nutralene, Osmocote, and Meister. Following leaching of 1000 ml of water through soil columns, which simulates leaching conditions with 26 cm of rainfall, the amount of NO₃ and NH₄ recovered in the leachate from soil columns amended with an NH₄NO₃ blend accounted for 37% and 88% of the respective nutrients contained in the quantity of blend per column. The corresponding values for soil columns amended with a Ca(NO₃)₂ blend were 48% and 100%. Leraching losses of both NO₃ (<3%) and NH₄ (<4%) were drastically decreased when using controlled-release fertilizers. The recoveries of P and K in 1000 ml of leachate were 1.3% and 8%, respectively, of the nutrients added as Osmocote, which contained coated P and K sources. In the case of the rest of fertilizer blends, the recoveries of P and K in 1000 ml of leachate were as high as 52%–100% and 28%–100%, respectively. Therefore, controlled-release technology offers an important capability for minimizing leaching losses of nutrients.     

Anthropogenic nitrogen sources and exports in a village-scale catchment in Southeast China

An experimental village-scale catchment was selected for investigation of nitrogen (N) sources and exports. The mean N application rate over the catchment was 350.2 kg N ha⁻¹, but this rate varied spatially and temporally. The N leaching loss rate varied from 8.1 to 52.7 kg N ha⁻¹ under different land use regimes. The average N leaching loss rate was 13.4 kg N ha⁻¹ over the whole catchment, representing about 3.8% of the total N inputs. The N export rate through stormflows was 28.8 kg N ha⁻¹, about 8.2% of the total N inputs. Seasonal patterns showed that 95% of N exports through stormflows occurred during July to September in 2002. Overall, the maximum riverine N exports were 12.1% of total N inputs and 15.5% of the inorganic fertilizer N applied. Understanding N sources and exports in a village-scale catchment can provide a knowledge base for amelioration of diffuse agricultural pollution.     

Leaching of atrazine, metolachlor and diuron in the field in relation to their injection depth into a silt loam soil

A field experiment was conducted on a Calcaric Cambisol soil to study the consequences of the penetration depth and properties of pesticides on the risk of subsequent leaching. Three pesticides with different mobility characteristics and bromide were injected at 30 cm (where soil organic matter (OM) was 2%) and 80 cm (soil OM 0.5%) on irrigated plots without a crop. The migration of injected solutes was assessed for two years by sampling the soil solution using six porous cups installed at 50 and 150 cm depth and by relating solute contents to drainage water flux estimated by the STICS model (Simulateur mulTIdisciplinaire pour les Cultures Standard). Pesticides injected at 30 cm were strongly retained so that no metolachlor or diuron was detected at 50 and 150 cm. The ratio of atrazine peak concentration in the soil solution to concentration in the injected solution (C/C₀) was 1 × 10⁻³ and 0.2 × 10⁻³, respectively, at 50 and 150 cm. When injected at 80 cm, (C/C₀) of atrazine, metolachlor and diuron were 10 × 10⁻³, 1 × 10⁻³ and 0.3 × 10⁻³ at 150 cm, respectively; 1/(C/C₀) was correlated with K_oc values reported from databases. The ratio of drainage volume to the amount of water at field capacity in the soil layer between the injection point at 30 cm and the water sampling level (V/V₀) at 50 and 150 cm was 0.6 and 0.9, respectively, for bromide and 1.6 and 1.0 for atrazine. V/V₀ of the injected solutes at 80 cm was for bromide, atrazine, metolachlor and diuron 0.6, 0.9, 1.2 and 1.7, respectively; pesticide V/V₀ was correlated with K_oc. The retardation factor was a good indicator of migration risk, but tended to overestimate retardation of molecules with high K_oc. Atrazine desorption represented an additional leaching risk as a source of prolonged low contamination. The large variability in soil solution of bromide and pesticide concentrations in the horizontal plane was attributed to flow paths and clods in the tilled soil layer. This heterogeneity was assumed to channel water fluxes into restricted areas and thereby increase the risk of groundwater contamination. The methodology used in the field proves to provide consistent results.