Chemodynamics of heavy metals in long-term contaminated soils：Metal speciation in soil solution

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. The soil solution was extracted at 70% maximum water holding capacity (MWHC) after equilibration for 24 h. The free metal concentrations (Cd2+, Cu2+, Pb2+, and Zn2+) in soil solution were determined using the Donnan membrane technique (DMT). Initially the DMT was validated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predicted using MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2 and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used in the DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively. This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cation adsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd2+ (3%–52%) and Zn2+ (11%–72%) in soil solutions were generally higher than those of Cu2+ (0.2%–30%) and Pb2+ (0.6%–10%). Among the key soil solution properties, dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showed only a weak relationship with free metal ion partitioning coefficients (Kp) and dissolved organic carbon did not show any significant influence on Kp.     

Influence of Indian mustard （Brassicajuncea） on rhizosphere soil solution chemistry in long-term contaminated soils： A rhizobox study

This study investigated the influence of Indian mustard (Brassica juncea) root exudation on soil solution properties (pH, dissolved organic carbon (DOC), metal solubility) in the rhizosphere using a rhizobox. Measurement was conducted following the cultivation of Indian mustard in the rhizobox filled four di erent types of heavy metal contaminated soils (two alkaline soils and two acidic soils). The growth of Indian mustard resulted in a significant increase (by 0.6 pH units) in rhizosphere soil solution pH of acidic soils and only a slight increase (< 0.1 pH units) in alkaline soils. Furthermore, the DOC concentration increased by 17–156 mg/L in the rhizosphere regardless of soil type and the extent of contamination, demonstrating the exudation of DOC from root. Ion chromatographic determination showed a marked increase in the total dissolved organic acids (OAs) in rhizosphere. While root exudates were observed in all soils, the amount of DOC and OAs in soil solution varied considerably amongst di erent soils, resulting in significant changes to soil solution metals in the rhizosphere. For example, the soil solution Cd, Cu, Pb, and Zn concentrations increased in the rhizosphere of alkaline soils compared to bulk soil following plant cultivation. In contrast, the soluble concentrations of Cd, Pb, and Zn in acidic soils decreased in rhizosphere soil when compared to bulk soils. Besides the influence of pH and DOC on metal solubility, the increase of heavy metal concentration having high stability constant such as Cu and Pb resulted in a release of Cd and Zn from solid phase to liquid phase.     

Spatial variability of organochlorine pesticides （DDTs and HCHs） in surface soils from the alluvial region of Beijing, China

The spatial variability in the concentrations of 1,2,3,4,5,6-hexachlorocyclohexane (HCH) and 1,1,1-trichloro-2,2-bis-(p-chlorophenyl) ethane (DDT) in surface soils was studied on the basis of the analysis of 131 soil samples collected from the surface layer (0-20 cm depth) of the alluvial region of Beijing, China. The concentrations of total HCHs (including α-, β-, γ-, and δ-isomers) and total DDTs (i ncluding p,p'-DDT, p,p'-DDD, p,p'-DDE, and o,p'-DDT) in the surface soils tested were in the range from nondetectable to 31.72 μg/kg dry soil, with a mean value of 0.91, and from nondetectable to 5910.83 μg/kg dry soil, with a mean value of 32.13,respectively. It was observed that concentrations of HCHs in all soil samples and concentrations of DDTs in 112 soil samples were much lower than the first grade (50 μg/kg) permitted in "Environment quality standard for soils in China (GB15618-1995)". This suggests that the pollution due to organochlorine pesticides was generally not significant in the farmland soils in the Beijing alluvial region. In this study, the spatial distribution and trend of HCHs and DDTs were analyzed using Geostatistical Analyst and GS (513).Spatial distribution indicated how these pesticides had been applied in the past. Trend analysis showed that the concentrations of HCHs,DDTs, and their related metabolites followed an obvious distribution trend in the surface soils from the alluvial region of Beijing.     

Sources of nitrous and nitric oxides in paddy soils：Nitrification and denitrification

Rice-paddies are regarded as one of the main agricultural sources of N 2O and NO emissions. To date, however, specific N2O and NO production pathways are poorly understood in paddy soils. ^15N-tracing experiments were carded out to investigate the processes responsible for N2O and NO production in two paddy soils with substantially different soil properties. Laboratory incubation experiments were carried out under aerobic conditions at moisture contents corresponding to 60% of water holding capacity. The relative importance of nitrification and denitrification to the flux of NaO was quantified by periodically measuring and comparing the enrichments of the N2O, NH~-N and NO3-N pools. The results showed that both N2O and NO emission rates in an alkaline paddy soil with clayey texture were substantially higher than those in a neutral paddy soil with silty loamy texture. In accordance with most published results, the ammonium N pool was the main source of N2O emission across the soil profiles of the two paddy soils, being responsible for 59.7% to 97.7% of total N2O emissions. The NO3-N pool of N2O emission was relatively less important under the given aerobic conditions. The rates of N2O emission from nitrification （N2On） among different soil layers were significantly different, which could be attributed to both the differences in gross N nitrification rates and to the ratios of nitrified N emitted as NzO among soil layers. Furthermore, NO fluxes were positively correlated with the changes in gross nitrification rates and the ratios of NO/N2O in the two paddy soils were always greater than one （from 1.26 to 6.47）. We therefore deduce that, similar to N2O, nitrification was also the dominant source of NO in the tested paddy soils at water contents below 60% water holding capacity.     

Can phosphate compounds be used to reduce the plant uptake of Pb and resist the Pb stress in Pb-contaminated soils？

The effects of di erent phosphate-amendments on lead (Pb) uptake, the activities of superoxide dismutase (SOD) and the level of malondialdehyde (MDA) in cauliflower (Brassica oleracea L.) in contaminated soils with 2500, or 5000 mg P2O5/kg soil of hydroxyapatite (HA), phosphate rock (PR), single-superphosphate (SSP) and the mix of HA/SSP (HASSP) were evaluated in pot experiments. Results showed that the Pb concentrations in shoots and roots decreased by 18.3%–51.6% and 16.8%–57.3% among the treatments respectively compared to the control samples. The e ciency order of these phosphate-amendments in reducing Pb uptake was as follows: HASSPt HA > SSP t PR.With the addition of SSP, HA and the mix of HA/SSP, the SOD activity in shoot was reduced markedly (P < 0.05) compared with that in the control group. For example, the SOD activities in shoot by the treatments of HASSP, SSP, and HA in 5000 mg P2O5/kg were found to be only 51.3%, 56.2%, and 56.7%, respectively. Similar e ects were also observed on the level of MDA in the shoots with a decrease in 24.5%–56.3%. The results verified the inference that phosphate compounds could be used to reduce the plant uptake of Pb and resist the Pb stress in the plant vegetated in Pb-contaminated soils.     

Chemical fractionations and bioavailability of cadmium and zinc to cole （Brassica campestris L.） grown in the multi-metals contaminated oasis soil, northwest of China

A pot experiment was conducted to study the relationship between distribution of cadmium (Cd) and zinc (Zn) and their availability to cole (Brassica campestris L.) grown in the multi-metal contaminated oasis soil in northwest of China. The results showed that Cd and Zn in the unpolluted oasis soil was mainly found in the residual fractionation, however, with increasing contents of Cd and Zn in the oasis soil, the distribution of Cd and Zn changed significantly. The growth of cole could be promoted by low Cd and Zn concentration, but significantly restrained by high concentrations. There was antagonistic e ect among Cd and Zn in the multi-metals contaminated oasis soil. Stepwise regression analysis between fractionations distribution coe cients of the two meals in the soil and their contents in cole showed that both Cd and Zn in the exchangeable fractionation in the oasis soil made the most contribution on the uptake of Cd and Zn in cole. The bio-concentration factor (BCF) of Cd was greater than Zn in cole, and BCFs of the two metals in leaves were greater than those in roots. The translocation factors of the two metals in cole were greater than 1, and the two metals mainly accumulated in the edible parts in cole. Therefore, cole is not a suitable vegetable for the oasis soil because of the plants notable contamination by heavy metals.     

Polycyclic aromatic hydrocarbons in soils of Beijing and Tianjin region： Vertical distribution, correlation with TOC and transport mechanism

The contents and distribution of 20 polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic hydrocarbons (HAHs) were investigated in 16 soil profiles of Beijing and Tianjin region. Transport of high molecular weight PAHs (HMWPAHs) and the correlation between total organic carbon (TOC) and their concentrations were also discussed. The results indicated that highly contaminated sites were located at urban or wastewater irrigation areas and pollutants mainly accumulated in topsoil (< 40 cm), with a sharp content decrease at the vertical boundary of 30–40 cm. Total PAHs/HAHs concentrations in soils from Tianjin were markedly greater than those from Beijing. Even the contents at bottoms of soil profiles in Tianjin were higher than those in topsoils of Beijing soil profile. HMWPAHs dominated the PAH profiles, exhibiting a uniform distribution of pyrogenic origin between topsoils and deep layers. Furthermore, the percentages of HMWPAHs remained relative constant with the depth of soil profiles, which were consistent with the distribution of particulate matter-associated PAHs in the local atmospheric environments. Therefore, HMWPAHs transport with particulates might be the predominant source found in soil profiles.     

Storage and sequestration of organic carbon in major paddy soils of China： Mechanism, stability and the impact on global change——A key project funded by the National Natural Science Foundation of China（2003-2005）

Chinapaddysoilsoccupyalandareaofabout3×107hm2andproduce44%oftotalcerealsofthestatewithalandportionof25%.Managementofpaddysoilscanbetracedbackto7000yearsB.P.andhaveledtoaparticularsoiltypeofanthropogenicwetlandsoilswithenhancedCstorageincomparisonwiththeu…     

Adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ) in paddy soils cultivated for various years in the subtropical China

The adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ) on upland red soil,and paddy soils which were originated from the upland soil and cultivated for 8,15,35 and 85 years,were investigated using the batch method.The study showed that the organic matter content and cation exchange capacity (CEC) of the soils are important factors controlling the adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ).The 15-Year paddy soil had the highest adsorption capacity for Pb(Ⅱ),followed by the 35-Year paddy soil.Both the 35-Year paddy soil and 15-Year paddy soil adsorbed more Cu(Ⅱ) than the upland soil and other paddy soils.The 15-Year paddy soils exhibited the highest desorption percentage for both Cu(Ⅱ) and Pb(Ⅱ).These results are consistent with the trend for the CEC of the soils tested.The high soil CEC contributes not only to the adsorption of Cu(Ⅱ) and Pb(Ⅱ) but also to the electrostatic adsorption of the two heavy metals by the soils.Lower desorption percentages for Cu(Ⅱ) (36.7% to 42.2%) and Pb(Ⅱ) (50.4% to 57.9%) were observed for the 85-Year paddy soil.The highest content of organic matter in the soil was responsible for the low desorption percentages for the two metals because the formation of the complexes between the organic matter and the metals could increase the stability of the heavy metals in the soils.     

Distribution and health risk assessment of organochlorine pesticides （OCPs） in industrial site soils： A case study of urban renewal in Beijing, China

A field survey was conducted in a contaminated industrial site of southern Beijing,China to investigate the contents and distribution of the organochlorine pesticides(α-,β-,γ-,δ-HCH,p,p-DDT,p,p-DDE,p,p-DDD and o,p-DDT) in the profiles of soil,and a health risk assessment was carried out with CalTOX multimedia exposure model.Results showed that mean concentrations of total hexachlorocyclohexane isomers(HCHs) and total dichlorodiphenyltrichloroethane isomers(DDXs) in soils were in the range of 13.20-148.71 mg...     

Effects of mercury contaminated rice from typical chemical plant area in China on nitric oxide changes and c-fos expression of rats brain

IntroductionMercury(Hg) ,asoneoftheprioritypollutantandhottopicinthefrontofenvironmentalresearchinmanycountries ,hasbeenpaidhigherattentionintheworldsincethemiddleoflastcentury .Chinaisthethirdlargestmercuryproducer,GuizhouProvince(2 4°3 0′— 2 9°13′N     

典型化工废渣污染土壤中汞的空间分布规律研究

为阐明氯碱厂废渣堆积遗留场地中汞的空间分布规律,在某典型场地设置313个表层（0.5 m）、79个深层（0.5～13.5 m）土壤采样点位及6个地下水采样点位,分析所有土壤样品的总汞浓度、表层土壤的理化性质及地下水总汞浓度.结果显示：（1）该场地土壤汞污染严重,313个表层土壤样点汞检出浓度为0.002～579.14 mg·kg^-1,平均为8.43 mg·kg^-1,高于《土壤环境质量农用地土壤污染风险管控标准（试行）》中的风险管控值(6 mg·kg^-1).反距离权重法（IDW）及自然邻域法（NNI）对该场地的汞水平浓度分布的插值更为准确.（2）79个深层点位土壤垂向检测结果显示,土壤上层区域（0.5、1.5、2.5 m）汞污染浓度更高,3个深度层的汞浓度平均值分别为7.3、5.5、3.1 mg·kg^-1,2.5 m以下7个深度层的汞浓度平均值仅为（1.02±0.15）mg·kg^-1;汞垂向富集因子为0.4～32,大多数（66%）采样点位汞的富集因子（EF）随着土壤深度增加显著下...     

贵州汞污染地区大米神经毒性基因水平研究

为从分子基因水平探讨汞污染地区大米的神经毒性,用贵州 2 个汞污染区(万山汞矿和清镇化工厂)产的大米喂养大鼠,分别于20d 和30d 后,用 RT-PCR 方法检测脑中即刻早期基因 c-fos mRNA 表达变化,并以非污染区作对照.结果表明,汞污染大米能够极显著诱导大鼠脑c-fos mRNA 表达,并且该表达是持续的.应用 c-fos mRNA 表达变化早期预报汞神经毒性是有可能的.     

汞在喜鹊组织和器官中的分布规律

为了确定汞在喜鹊体内8种组织和器官中详细的分布规律,对采自太原南郊区７只喜鹊不同组织和器官中汞的含量进行了测定,并对其分布规律进行了研究。汞在喜鹊体内的分布规律为：肾＞股肌＞肝＞肺＞心＞胸肌＞胸骨＞股骨。经方差分析,组织间及个体间汞的含量均存在显著的差异。汞在喜鹊体内的分布为不均匀分布。肝和心中汞,肺和肾中汞等均具有明昱的正相关。同时,对喜鹊组织和器官中汞含量进行了生态和生理的比较。     

矿山强酸性多金属污染土壤修复及麻疯树植物复垦条件研究

采用温室盆栽实验,研究了在不同剂量(质量分数分别为0、0.10%、0.25%、0.5%和1.0%)石灰石改良条件下,大宝山矿强酸性多金属不同污染程度土壤中麻疯树的生长状况和吸收金属特征,并探讨了麻疯树在酸性土壤中生长的抑制因素和石灰石改良适宜剂量.研究表明,在低污染酸性土壤中,Cu和Pb的高活性可能是抑制麻疯树生长的主要因素;而在高污染酸性土壤中,Cd、Cu、Zn等金属的高活性及由强酸引起的Al毒也可能是抑制麻疯树生长的主要因素;石灰石通过提高土壤pH值和降低多金属的生物有效态含量,促进了麻疯树在低污和高污土壤中的生长,其最佳剂量分别为0.25%和0.5%;石灰石可以不同程度地降低麻疯树地上部和地下舔的Cd、Cu、Pb、Zn和Al含量,同时随石灰石用量的增加,其金属含量基本呈降低趋势;麻疯树地下部金属含量高于地上部,且石灰石对麻疯树地下部金属(除Cd外)含量降低幅度较地上部大.因此,种植麻疯树与石灰石改良是联合修复大宝山矿酸性多金属污染土壤的有效措施之一.     

烟气单质汞氧化去除过程络合反应机理

湿法氧化去除烟气Hg⁰过程中产物Hg²⁺易发生络合反应,络合产物可能改变氧化体系形成新反应机制,这一现象尚未被认识研究.为获得Hg²⁺络合物生成及其对烟气脱汞影响机理,研究了配体阳离子、配体浓度、反应pH值、反应温度和摩尔比等对Hg²⁺络合反应的影响和氧化去除烟气Hg⁰的络合反应机理.结果表明MgCl₂、KCl、NiCl₂和BaCl₂配体均能与HgCl₂形成络合物,而CuCl₂和SnCl₄则不能生成络合物.络合物生成量随配体浓度的增加先升高然后趋于平衡;络合反应在酸性环境下发生且不受pH值变化影响;碱性环境下络合反应不能进行;反应温度基本不影响络合反应效应;增加配体浓度可提高络合物产量,不同配体络合效应不同,但最大吸光度基本相同,为（4.20±0.03）A.配体对络合反应有响应区间,低于区间下限值时不能形成络合物,高于上限制值时络合物产量不随配体浓度而变化.HgCl₂络合反应累积稳定常数β₄=10^15.07;[HgCl₄]^2-可螯合Hg（aq）和O₂（aq）使其与ClO^-和Hg₂Cl₂反应,形成氧化-络合氧化反应新机理.     

污灌区盐分累积对污染土壤汞释放通量的影响

采用优化设计的动态通量箱,对不同盐分（NaCl和Na₂SO₄）和盐度（0~5%）的盐渍化土壤土-气界面的汞交换通量进行动态监测,研究盐渍化对污灌区土壤汞和大气释放的影响.结果表明：（1）两种盐分类型对土壤Hg释放的影响呈相反趋势.与未发生盐渍化的对照土壤相比,随着NaCl盐度梯度的上升,土壤Hg释放通量呈现上升趋势,5%盐度处理下,Hg通量均值与对照相比提高了48.94%;而随着Na₂SO₄盐度梯度的上升,土壤Hg释放通量呈现下降趋势,5%盐度处理下,Hg通量均值与对照相比降低了20.62%.（2）土壤盐分含量与土壤汞释放通量均值之间呈线性关系.对于NaCl,含量x（g/kg）与汞通量y [ng/（m²·h）]之间的模型为y=0.8258x+86.709（R²=0.9734）,对于Na₂SO₄,模型为y=-0.3354x+85.997（R²=0.9581）.从研究结果来看,高浓度的NaCl环境对土壤汞释放通量有显著影响,土壤的盐渍化趋势会使汞释放及作物吸收风险更趋严重.     

Effect of organic matter and pH on mercury release from soils

An investigation was conducted on the effect of organic matter(OM)and pH on mercury(Hg)release from soils.Hg release flux was measured using the dynamic flux chamber(DFC)combined with the Lumex multifunctional mercury analyzer in both laboratory experiment and field monitoring.The results showed that Hg emission from the OM-added soils was apparently low because of the high affinity of OM to Hg,resulting in the reverse order as the amount of OM addition.Meanwhile,Hg release flux from different pH value soils exhibited the same trend for both Hg~(2 )and Hg_2~(2 )treatment,increasing the Hg flux with pH value of soils increasing.The trend of Hg release in the pH dependence experiment has been well in agreement with that from the field test.In addition,Hg release seemed to be related to its species in the soil,the flux from Hg~(2 )-added soil was obviously higher than that of Hg_2~(2 )-added soil by the laboratory experiment.     

二乙烯三胺接枝螯合絮凝剂的制备及其除汞性能

以聚丙烯酰胺（PAM）、甲醛、二乙烯三胺(DETA)为原料,按照Mannich反应机理制备部分胺化接枝型螯合絮凝剂(CFA),并对其去除水中汞的性能进行了研究.同时,实验考察了螯合絮凝剂合成及从含汞废水中除汞的最佳条件.结果表明,基于在聚丙烯酰胺分子长链上引入具有螯合作用的基团,所得的螯合絮凝剂既具有捕捉Hg2+的螯合作用又具有絮凝作用,对含汞8.1mg·L-1的模拟废水,按0.020%的投加量(絮凝剂与废水质量比),在搅拌速度80~100r·min-1、搅拌时间15min、沉降时间10min的条件下,进行絮凝沉淀处理后,可去除99.5%的汞,除汞效果明显,处理后的水可达到国家排放标准.因此,螯合絮凝剂可用于低浓度含汞废水的处理.同时,该螯合絮凝剂具有合成工艺简单、除汞快速、操作简便等特点,可望成为一种新型、低成本含汞废水处理材料.     

Electrokinetic removal of chromium and copper from contaminated soils by lactic acid enhancement in the catholyte

The electrokinetic removal of chromium and copper from contaminated soils by adding lactic acid in cathode chamber as an enhancing reagent was evaluated. Two sets of duplicate experiments with chromium contaminated kaolinite and with a silty soil sampled from a supeffund site in Califomia of USA and polluted by Cr and Cu, were carried out in a constant current mode. Changes of soil water content and soil pH before and after the electrokinetic experiments, and variations of voltage drop and electroosmosis flow during the treatments were examined. The results indicated that Cr, spiked as Cr(Ⅵ) in the kaolinite, was accumulated mainly in the anode chamber, and some of Cr and metal hydroxides precipitated in the soil sections in contact with the cathode, which significantly increased electrical energy consumption. Treatment of the soil collected from the site showed accumulation of large amounts of Cr and Cu in the anode chamber while none was detected in the cathode one. The results suggested that the two metals either complexed with the injected lactic acid at the cathode or existed as negatively charged complex, and electromigrated toward the anode under a voltage gradient.