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.     

Seasonal bioconcentration of heavy metals in Onchidium struma （Gastropoda： Pulmonata） from Chongming Island, the Yangtze Estuary, China

The seasonal concentration changes of selected heavy metal Cd, Cr, Cu, Fe, Mn, Pb, and Zn in five tissues of marine gastropod Onchidium struma were studied in the Chongming Island, the Yangtze Estuary on July 2006, September 2006, and November 2006, April 2007, respectively. The results demonstrated that the bioconcentration factor of Cu (biomass/water) in all selected tissues was about 104 magnitudes, Fe and Cd were 103, Zn was 102, and Mn, Pb, and Cr were 101. Hepatopancreas was proven to be the dominant storage tissue of Cr, Cu, Mn, and Zn, whereas Fe and Pb were mainly stored in muscle and digenetic gland, and Cd was stored in vitelline gland and albumen gland. Additionally, it was found that Cu, Fe, Mn, and Zn were concentrated significantly by O. struma (whole-body) in summer or autumn, and Cd, Cr, and Pb increased slightly in spring and winter. Furthermore, the bioconcentration of Cr was nearly 2-fold higher and Zn was 1.6-fold higher in the water compared with the Water Quality Standard for Fisheries. With view of excessive amount of Pb, Cd, and Cu according to seafood standard, the consumption of O. struma might have the risk of health hazard.     

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.     

Efficiency of white lupin in the removal of mercury from contaminated soils： Soil and hydroponic experiments

This study examined the ability of the white lupin to remove mercury (Hg) from a hydroponic system (Hg concentrations 0, 1.25, 2.5, 5 and 10 μmol/L) and from soil in pots and lysimeters (total Hg concentration (19.2 ± 1.9) mg/kg availability 0.07%, and (28.9 ± 0.4) mg/kg availability 0.09%, respectively), and investigated the accumulation and distribution of Hg in different parts of the plant. White lupin roots efficiently took up Hg, but its translocation to the harvestable parts of the plant was low. The Hg concentration in the seeds posed no risk to human health according to the recommendations of the World Health Organization, but the shoots should not be used as fodder for livestock, at least when unmixed with other fodder crops. The accumulation of Hg in the hydroponically-grown plants was linear over the concentration range tested. The amount of Hg retained in the roots, relative to the shoots, was almost constant irrespective of Hg dose (90%). In the soil experiments, Hg accumulation increased with exposure time and was the greater in the lysimeter than in the pot experiments. Although Hg removal was the greater in the hydroponic system, revealing the potential of the white lupin to extract Hg, bioaccumulation was the greatest in the lysimeter-grown plants; the latter system more likely reflects the true behaviour of white lupin in the field when Hg availability is a factor that limits Hg removal. The present results suggest that the white lupin could be used in long-term soil reclamation strategies that include the goal of profitable land use in Hg-polluted areas.     

Non-point source analysis of a railway bridge area using statistical method：Case study of a concrete road-bed

In an effort to protect the quality of the water system, interest in non-point source pollution is increasing. Recently, studies of non-point sources pollution are continuing in relation to various land- use areas, but such studies have not been fully conducted in railway facility sites. Using monitoring data of railway bridge area with concrete road-bed, the runoff characteristics, pollutant unit loads, and first flush criteria were assessed. Railway bridge area with concrete road-bed typically show the first flush effect, and the pollutant unit load was determined to be higher than other public facilities areas. Further, the first flush criteria show an effective rainfall amount of 7 mm. In other words, from the runoff of railway facilities, considerable amounts of non-point source pollutants are occurred, indicating the need to create best management practices which are adequate for railway facility sites.     

连续4 a施有机肥降低紫泥田镉活性与稻米镉含量

商品有机肥由于可能含镉(Cd),并在施入后对水稻土中Cd的有效性具有"抑制"和"激活"的双重作用,导致施有机肥的稻米降Cd效应目前仍存在较大不确定性.通过选取湘东地区典型水稻土(紫泥田土种),连续4 a定位监测了大田施用商品有机肥对双季稻稻米的降Cd效应,探索稻米Cd含量与双季稻不同生育期土壤Cd有效性、土壤因子(pH、土壤活性有机碳组分与铁氧化物)的关系.结果表明,施有机肥降低双季稻糙米Cd含量28%～56%,且晚稻糙米Cd含量降幅(43%～56%)高于早稻糙米Cd含量的降幅(28%～45%),降幅的年际波动小.一方面,施有机肥也导致双季稻某些生育期(分蘖盛期自齐穗期)土壤有效态Cd含量平均下降6%～7%;土壤交换态Cd含量降低11%,土壤有机结合态Cd含量提高14%,直接反映土壤Cd有效性的降低.另一方面,施有机肥也稳定提升土壤pH值0.1～0.3个单位,促进土壤环境由酸性向微酸性发展,土壤活性有机碳组分(轻组有机碳、粗颗粒有机碳和细颗粒有机碳)含量大幅提升(53%、 77%和107%),间接反映土壤Cd有效性的降低.本研究表明,紫泥田连续施有机肥后,土壤Cd有效性下降是双季稻米C...     

Combined toxicity of copper and cadmium to six rice genotypes （Oryza sativa L.）

Accumulation of copper (Cu) and cadmium (Cd) in six rice cultivars (94D-22, 94D-54, 94D-64, Gui630, YY-1 and KY1360) was evaluated through exposure to heavy metal contamination (100 mg/kg Cu, 1.0 mg/kg Cd, and 100 mg/kg Cu + 1.0 mg/kg Cd) in a greenhouse. The dry weight of shoot and root, concentrations of Cu and Cd in plant tissues and the Cu, Cd, P, Fe concentrations in the root surface iron plaques were analyzed eight weeks later after treatment. The results indicated that the plant biomass was mainly determined by rice genotypes, not Cu and Cd content in soil. Separated treatment with Cu/Cd increased each metal level in shoot, root and iron plaques. Soil Cu enhanced Cd accumulation in tissues. In contrast, Cu concentrations in shoot and root was unaffected by soil Cd. Compared to single metal contamination, combined treatment increased Cd content by 110.6%, 77.0% and 45.2% in shoot, and by 112.7%, 51.2% and 18.4% in root for Gui630, YY-1 and KY1360, respectively. The content level of Cu or Cd in root surface iron plaques was not affected by their soil content. Cu promoted Fe accumulation in iron plaques, while Cd has no effect on P and Fe accumulation in it. The translocation of Cu and Cd from iron plaques to root and shoot was also discussed. These results might be beneficial in selecting cultivars with low heavy metal accumulation and designing strategies for soil bioremediation.     

郑汴路不同运营路段路旁土壤重金属分布及污染分析

选择运营时间不同的杏花营和圃田路段分别布设1800 m长的采样断面,按距离路基远近不同布设土壤采样点38个,对照采样点2个,在距路基25 m处挖掘土壤剖面2个,共采集土壤样品50个.在室内试验的基础上,对路旁土壤重金属(Pb、Cd、Ni、Cu、Zn、Cr)空间分布特征与污染状况进行了研究.结果表明,公路两侧300 m范围内的土壤重金属含量明显高于对照区和中国潮土背景值,尤其土壤中Cd、Cr和Pb积累明显.路北土壤重金属含量高于路南.对于运营时间长的杏花营断面,土壤重金属含量高于圃田断面.大多数重金属在土壤中的含量随离公路距离的增加在距路基10～50 m处出现积累峰值,然后逐渐下降,在300 m附近接近于对照值.重金属主要累积在土壤深0～40 cm范围内.杏花营路段两侧200 m范围内为重金属轻度污染带,200～300 m之间为警戒带.圃田路段北侧30 m范围内为轻度污染带,30～200 m为警戒带,200～300 m为清洁带;而其南侧15 m范围内为轻污染带,15～80 m为清洁带,80～300 m为警戒带.     

畜禽粪便有机肥中重金属在水稻土中生物有效性动态变化

通过土壤淹水培养试验和土壤淹水培养不同时间后同时开始的水稻生物盆栽试验,研究不同畜禽粪便有机肥中Cu、Zn、Cd、Pb在水稻土中生物有效性动态变化以及与等量重金属无机盐的差异,明确不同畜禽粪便有机肥中不同重金属生物有效性差异及动态变化规律.结果表明,水稻土施入畜禽粪便有机肥后30~60 d内,畜禽粪便有机肥处理土壤溶液中重金属含量显著低于等量重金属无机盐处理,重金属无机盐处理土壤溶液中Cu、Zn、Cd、Pb的含量分别是鸡粪处理的2.4倍、3.1倍、3.9倍和327.3倍,分别是猪粪处理的2.0倍、2.2倍、15.6倍和4.0倍.60d后畜禽粪便有机肥处理和对应等量重金属无机盐处理土壤溶液中Cu、Zn、Cd、Pb的含量变的无差异.不同施用时间的畜禽粪粪便有机肥处理水稻体内Cu、Zn、Pb含量均显著低于对应的等量重金属无机盐处理,施用畜禽粪肥处理降低了土壤中Cu的生物有效性.畜禽粪便有机肥中重金属的生物有效性随施用后不同时间的变化呈现先升高后降低再升高规律,在施用后2个月时畜禽粪便有机肥中重金属的生物有效性最低,只相当于对应的等量重金属无机盐的13.0%~30.0%.     

Source attributions of heavy metals in rice plant along highway in Eastern China

Air and soil pollution from traffic has been considered as a critical issue to crop production and food safety, however, few efforts have been paid on distinguish the source origin of traffic-related contaminants in rice plant along highway. Therefore, we investigated metals (Pb, Cd, Cr, Zn and Cu) concentrations and stable Pb isotope ratios in rice plants exposed and unexposed to highway traffic pollution in Eastern China in 2008. Significant differences in metals concentrations between the exposed and unexposed plants existed in leaf for Pb, Cd and Zn, in stem only for Zn, and in grain for Pb and Cd. About 46% of Pb and 41% of Cd in the grain were attributed to the foliar uptake from atmosphere, and there were no obvious contribution of atmosphere to the accumulations of Cr, Zn and Cu in grain. Except for Zn, all of the heavy metals in stem were attributed to the root uptake from soil, although significant accumulations of Pb and Cd from atmosphere existed in leaf. This indicated that different processes existed in the subsequent translocation of foliar-absorbed heavy metals between rice organs. The distinct separation of stable Pb isotope ratios among rice grain, leaf, stem, soil and vehicle exhaust further provided evidences on the different pathways of heavy metal accumulation in rice plant. These results suggested that further more attentions should be paid to the atmospheric deposition of heavy metals from traffic emission when plan crop layout for food safety along highway.     

The chemical stability of heavy metals in a natural water system

A comprehensive investigation of heavy metal pollutants in Xiangjiang river was accomplished to evaluate their chemical stability through three different ways: (1) Chemical speciation by direct measurements; (2) Chemical equilibrium model simulation; (3) Sediment extraction experiments. All the results demonstrated that the directly bioavailable fraction was in a very limited amount. The metal bound to organic ligands, adsorbed particles and precipitated species presented a buffer for solution species. The majority of metals occured in the residues as solid particulates. It was inferred that the heavy metal pollutants in this aquatic system exhibited a high chemical stability. The critical limits of discharging load and pH values were suggested.     

污水污泥中重金属的细菌淋滤效果研究

通过驯化分离和加富培养源自污泥自身的氧化亚铁硫杆菌，采用序批式试验，初步研究了其对污泥中重金属生物淋滤的效果。研究表明，污泥起始驯化阶段大约需要16天，随后采用选择性培养基对氧化亚铁硫杆菌进行2次共1周的分离与加富培养即可获得活性较高的硫杆菌菌液。采用此菌液对供试厌氧消化污泥中重金属进行生物淋滤，通过8天时间，污泥中Cu和Zn的去除率分别达93％和85％。     

Microbial diversity of soil bacteria in agricultural field contaminated with heavy metals

In this study we evaluated the bacterial diversity in a soil sample from a site next to a chemical industrial factory previously contaminated with heavy metals. Analysis of 16S rDNA sequences amplified from DNA directly extracted from the soil revealed 17 different bacterial types （genera and/or species）. They included Polyangium spp., Sphingomonas spp., Variovorax spp., Hafina spp., Clostridia, Acidobacteria, the enterics and some uncultured strains. Microbes able to tolerate high concentrations of cadmium （500μmol/L and above） were also isolated from the soil. These isolates included strains of Acinetobacter （strain CD06）, Enterobacter sp. （strains CD01, CD03, CD04 and CD08） （similar strains also identified in culture-independent approach） and a strain of Stenotrophomonas sp. The results indicated that the species identified from direct analysis of 16S rDNA of the soil can be quite different from those strains obtained from enrichment cultures and the microbial activities for heavy metal resistance might be more appropriately addressed by the actual isolates.     

Chelation of heavy metals by potassium butyl dithiophosphate

Potassium butyl dithiophosphate (PBD) was developed and introduced as a new chelating agent for heavy metal removal. The synthesized PBD were characterized by IR and NMR. The e ects of pH, chelating agent dosage, and other heavy metal ions on the performance of PBD in Cd2+ removal from water are investigated. Experimental results showed that the chelating agent could be used to treat acidic heavy metal wastewater. The Cd2+ removal was not a ected by solution pH value within the range of 2 to 6. The Cd2+ removal rate could reach over 99%. Therefore, the deficiency of the precipitation process using hydroxide under alkaline condition can be overcome.Without the need for pH adjustment, the method could save on costs. If Cd2+ co-exists with Pb2+ and Cu2+, the a nity of the chelating agent with these three heavy metal ions was in the order of: Cu2+ > Pb2+ > Cd2+. Through PBD chelating precipitation, all the contents of Pb2+, Cd2+, and Cu2+ in wastewater met the standard levels through a one-step treatment. The one-step treatment process was superior to the process (sectional treatment is required) of precipitation with hydroxide. When the pH was between 3 and 11, the amount of leached chelated Cd2+ was much lower than that obtained by precipitation with hydroxide. Therefore, the risk of environmental pollution could be further reduced.     

提高植物修复效率的技术途径与强化措施

通过物理、化学或生物学手段,从土壤、植物及其生境3个方面着手来提高植物去除土壤重金属能力是植物修复技术应用研究的重要方向.对国内外植物修复过程中所应用的强化手段与辅助措施进行了一定的研究,分别阐述了施肥、水分管理、耕作栽培、修复剂、生物技术等方法的作用机制及应用效果.今后,植物修复技术需针对有应用前景的超富集植物进行生境特征的系统研究,并着重开发高效、低风险的土壤修复剂,注重植物修复成套技术的工程应用研究.     

矿山公园土壤重金属的生态与健康风险评价—以湖南M矿为例

矿山公园建设是矿山生态环境修复治理的重要途径,评估土壤修复效果对矿山公园建设运营及游客旅游安全具有重要意义。在湖南M矿山公园非硬化地面采集地表0~30 cm旱土土壤样品66个,测定其中重金属Mn、Cr、Zn、Pb、As、Cu、Ni、Hg的浓度,采用综合污染指数法、潜在生态危害指数法及健康风险评估模型对矿山公园土壤修复后污染状况、潜在生态风险和人类健康风险三方面进行评价。结果表明：M矿山公园土壤中各金属浓度平均值从高到低依次为Mn>Cr>Zn>Pb>As>Cu>Ni>Hg,其中,Cr、Mn、Cu、As和Pb的平均值分别是湖南省土壤背景值的1.23、1.80、1.12、2.05和1.34倍。土壤重金属污染指数为0.51,处于安全级别。各重金属元素单因子潜在风险指数均处于低生态风险级别,重金属综合潜在风险指数均值为81.64,处于低生态风险级别,不存在潜在生态风险。儿童和成人的非致癌风险总值分别为2.46×10⁻¹和7.43×10⁻²,不会造成非致癌风险;总致癌风险指数为1.38×10⁻⁷,不存在致癌风险。经过生态修复后的M矿山公园不存在土壤重金属生态健康风险,适于各类人群开展旅游休闲活动。

     

我国西南三市家庭灰尘重金属水平及差异

以西南3个省会城市(直辖市)贵阳、南宁和重庆为研究对象,研究城市家庭灰尘中Ca、Fe、Cd、Cr、Cu、Ni、Pb和Zn的含量及累积状况.结果显示3个城市的家庭灰尘中Ca、Fe含量的空间变异度较小,其他元素空间变异度较大.贵阳与重庆家庭灰尘重金属水平较为接近,南宁相对略低.贵阳市家庭灰尘中Ca(10.1%)含量高于南宁市,Cd(1.18mg/kg)、Cu(207mg/kg)、Ni(87.3mg/kg)和Pb(259mg/kg)含量均高于重庆市和南宁市,其中贵阳市家庭灰尘中Ca、Cd和Cu含量显著高于南宁市.与3城市土壤重金属背景值相比,6种有毒重金属中,Zn、Pb和Cd在家庭灰尘中累积相对较重;3城市中,南宁市家庭灰尘重金属累积相对较重;贵阳、南宁和重庆家庭灰尘重金属累积较重的元素分别是Zn和Pb、Zn和Pb、Cd和Zn.