长春市城区土壤中Pb、Cu、Zn、Cd及Cr化学形态特征

为弄清长春市城市土壤中Pb、Cu、Zn、Cr及Cd的化学形态分布特征,系统采集了26件城市表层(0~20 cm)土壤样品,采用连续提取法对重金属各化学形态含量进行了测定。结果表明:Pb、Zn、Cu及Cr主要以残渣态存在,其次是铁锰氧化物结合态、腐殖酸结合态和强有机结合态占有次要地位,离子交换态和水溶态所占比例均较低;Cd则主要以碳酸盐结合态存在,同时,水溶态和离子交换态所占比例较高。残渣态Pb和Zn在城区表层土壤中所占比例较近郊土壤中略有下降,但幅度不大,除Cu外,其余各元素易迁移、高生物有效性的水溶态在城区表层土壤中所占比例略有上升。Pearson相关分析结果表明,各元素残渣态与全量均呈极显著正相关,其它各活性态与全量间的相关程度与重金属种类有关。土壤pH值和Fe、Mn含量对重金属的化学形态的影响也与重金属种类有关,而且,同一重金属的不同存在形态受土壤pH值和Fe、Mn含量的影响程度也不同。     

Solubility control of Cu, Zn, Cd and Pb in contaminated soils

We developed a semiempirical equation from metal complextion theory which relates the metal activity of soil solutions to the soil's pH, organic matter content (OM) and total metal content (MT). The equation has the general form: where pM is the negative logarithm (to base 10) of the metal activity, and a, b and c are constants. The equation successfully predicted free Cu²⁺ activity in soils with a wide range of properties, including soils previously treated with sewage sludge. The significant correlation of pCu to these measured soil properties in long-contaminated soils suggests that copper activity is controlled by adsorption on organic matter under steady state conditions. An attempt was made from separate published data to correlate total soluble Cu, Zn, Cd and Pb in soils to soil pH, organic matter content and total metal content. For Cu, the total Cu content of the soil was most highly correlated with total soluble Cu. Similarly, total soluble Zn and Cd were correlated with total metal content, but were more strongly related to soil pH than was soluble Cu. Smaller metal solubility in response to higher soil pH was most marked for Zn and Cd, metals that tend not to complex strongly with soluble organics. The organic matter content was often, but not always, a statistically significant variable in predicting metal solubility from soil properties. The solubility of Pb was less satisfactorily predicted from measured soil properties than solubility of the other metals. It seems that for Cu at least, solid organic matter limits free metal activity, whilst dissolved organic matter promotes metal solubility, in soils well-aged with respect to the metal pollutant. Although total metal content alone is not generally a good predictor of metal solubility or activity, it assumes great importance when comparing metal solubility in soils having similar pH and organic matter content.     

工业型城乡交错区农业土壤Cu、Zn、Pb和Cd的空间分布及影响因素研究

在江苏省无锡市工业型城乡交错区，选择8km2区域，采集119个土壤样品，对土壤Cu、Zn、Pb,Cd及其有效态含量的空间分布和影响因素进行探讨。结果表明：该区土壤Cu、Zn、Pb、Cd含量和变异系数都明显增加，土壤有效态重金属含量与相应的全量重金属含量具有显著相关性。土壤Cu、Zn、Cd空间变异主要受到工业影响，但由于该区工业类型的多样性和工厂分布的分散性，Cu、Zn、、Cd空间分布模式并不相同。本区土壤Pb的分布与工厂分布的相关性不大，但随与城市距离增加而降低。公路和土地利用与土壤重金属含量的关系表现不明显。该区工业污染对土壤重金属空间变异的影响可能掩盖了公路和土地利用等的影响，建议在城乡交错区合理安排工业布局以控制土壤受重金属污染的范围。     

长期秸秆还田对德阳地区稻田土壤镉赋存形态的影响

明确长期秸秆还田对稻田土壤Cd污染阻控或促进效应,有利于制定针对性的农田Cd污染治理措施,对保障粮食安全生产具有重要意义。以四川省德阳市旌阳区Cd污染稻田为研究对象,通过田间实地调查与采样分析,探讨了秸秆还田不同年限(0 a、1 a、4 a、8 a)对农田土壤Cd赋存形态及其生物有效性的影响。结果表明,研究区稻田土壤Cd形态含量分布为:残渣态铁锰氧化物结合态有机结合态碳酸盐结合态可交换态;秸秆还田(4 a以上)显著增加了土壤有机质含量,进而促进了稻田耕作层(0~20 cm)土壤有机结合态Cd含量水平显著上升(以秸秆还田4 a,其含量增加了45%为最高),对土壤可交换态Cd含量略有增加效应;土壤p H则随秸秆还田年限的延长呈先升高后缓慢下降趋势,主要影响土壤碳酸盐结合态Cd含量水平的变化。从土壤Cd形态的生物利用性角度评价,随秸秆还田年限延长(1~4 a),能减轻稻田耕作层(0~20 cm)土壤有效态Cd的分配,促进其向潜在态Cd转移;而对犁底层(20~40 cm)土壤Cd形态的生物有效利用性的影响未达显著水平。总体来看,秸秆还田(1~4 a)提高了土壤有机质含量,显著增加了耕作层(0~20 cm)土壤有机结合态Cd含量水平,促进了耕作层(0~20 cm)稻田土壤Cd由有效态向潜在态转化,降低稻田土壤Cd污染状况;持续长期的秸秆还田(连续秸秆还田8 a以上),则可能因土壤p H下降而促进土壤Cd由潜在态向有效态转化,增加稻田土壤Cd的生物吸收累积效率。     

地质统计学评估伊朗伊斯法罕城市采矿过渡区近地表土壤上铅锌镉的污染

Due to the lack of regulation and environmental education and awareness, Sepahanshahr located in vicinity of Isfahan City, central Iran, is now a rapid growing residential area suffering from the considerable consequences of poorly regulated mining activities operating in its vicinity. A survey was carried out on soil Pb, Zn and Cd concentrations around Sepahanshahr Town to explore the spatial structure of Pb, Zn and Cd distribution and to map their concentrations using geostatistical techniques. 100 near-surface soil samples were collected and analyzed for Pb, Zn and Cd and some related soil physical and chemical variables such as pH, organic matter content, electrical conductivity, and clay, silt and sand contents. The variography results showed a strong spatial dependency in heavy metals concentration due to the dilution effects of natural factors including atmospheric dispersion and precipitation. The almost same range values calculated for both ln-transformed Pb and sand data suggested presence of spatial co-regionalization. However, ln-transformed Zn data showed a shorter spatial dependency among the three tested heavy metals. Kriged maps of all three heavy metals showed a strong gradient of contamination around the three mining sites activating in the area. The results of this study provide insight into identification of the extent and spatial variability of Pb, Zn and Cd pollution in the mining sites and surrounding urban areas.     

The flux of Cd,Cu, Pb and Zn in mining polluted soils

The monitoring of heavy metal deposition onto soils surrounding old Pb-Zn mines in two locations in the UK has shown that relatively large amounts of Cd, Pb, Zn and, in one case, Cu are entering the soil annually. Small particles of ore minerals in windblown mine tailings were found to be contributing up to 1.46 g m^?2 yr^?1 of Pb, 1.41 g m^?2 yr^?1 of Zn and 0.027 g m^?2 yr^?1 of Cd. However, when these inputs from bulk deposition are compared with the concentrations of the same metals within the soil profiles it is apparent that relatively little long-term accumulation is occurring. Metals are being lost from the soil profiles, probably through leaching. A calculated relative retention parameter gave values that ranged from 0.01 to 0.17 for Cd, 0.11 to 0.19 for Zn, 0.32 to 0.63 for Cu and over 1 for Pb. These relative retention values were found to follow the order of electronegativity of the elements concerned: Pb>Cu>Zn>Cd. Distribution coefficient (Kd) values quantifying the adsorptive capacity of the mine soils for Cd and Pb showed marked differences for the two metals (12 to 69 cm³ g^?1 for Cd and 14 to 126 cm³ g^?1 for Pb) and may, in part, account for the two to one hundred-fold variation in the relative retention parameter for the different metals within these soils.     

用突变点检测方法预测木生境下污染土壤中的可提性镉、铅和锌

Accumulation of heavy metals in soils poses a potential risk to plant production, which is related to availability of the metals in soil. The phytoavailability of metals is usually evaluated using extracting solutions such as salts, acids or chelates. The purpose of this study was to identify the most significant soil parameters that can be used to predict the concentrations of acetic and citric acid-extractable cadmium (Cd), lead (Pb) and zinc (Zn) in contaminated woody habitat topsoils. Multiple linear regression models were established using two analysis strategies and three sets of variables based on a dataset of 260 soil samples. The performance of these models was evaluated using statistical parameters. Cation exchange capacity, CaCO3, organic matter, assimilated P, free Al oxide, sand and the total metal concentrations appeared to be the main soil parameters governing the solubility of Cd, Pb and Zn in acetic and citric acid solutions. The results strongly suggest that the metal solubility in extracting solutions is extractable concentration-dependent since models were overall improved by incorporating a change point. This change point detection method was a powerful tool for predicting extractable Cd, Pb and Zn. Suitable predictions of extractable Cd, Pb and Zn concentrations were obtained, with correlation coefficient (adjusted r) ranging from 0.80 to 0.99, given the high complexity of the woody habitat soils studied. Therefore, the predictive models can constitute a decision-making support tool for managing phytoremediation of contaminated soils, making recommendations to control the potential bioavailability of metals. The relationships between acetic and/or citric acid-extractable concentrations and the concentrations of metals into the aboveground parts of plants need to be predicted, in order to make their temporal monitoring easier.     

土壤中木质素磺酸盐对土壤溶液化学和磷脂脂肪酸组成的影响

An incubation experiment （Exp. 1） with three soils, two from Australia and one from Norway, was carried out to investigate the fate of dissolved BorreGro （a lignosulfonate, produced by Borregaard LignoTech Company, Norway） at different concentrations （0, 10 and 100 mg C L-1） in soil solutions. A rhizobox experiment （Exp. 2） was also done in a Norwegian clay soil, mixed with four levels of BorreGro-carbon （BG-C） added （0, 2, 20 and 200 mg BG-C kg-1） to test the impact of BorreGro on root growth, rhizosphere chemistry （pH, metals and dissolved organic carbon （DOC）） and the composition of phospholipid fatty acids （PLFAs）. The BorreGro addition increased the concentration of Mn due to the high concentrations in BorreGro. The BorreGro addition to soil had an indirect but significant impact on the rhizosphere chemistry and PLFAs. The lowest amounts of added BorreGro facilitated the DOC excretion at plant roots, and thereby increased the bacterial and fungal biomass, likely as an effect of increased Mn solubility from BorreGro in the root zone.     

长三角和珠三角农业土壤中铅、铜、镉的化学形态与转化

研究了重金属Pb、Cu、Cd在长江三角洲和珠江三角洲土壤中的转化及不同Pb、Cu、Cd负荷水平对土壤重金属形态的影响。结果表明:未明显污染土壤中重金属主要以残余态为主,可提取态组分的比例Cd>Cu>Pb,但不同土壤之间有较大变化;随着土壤重金属负荷的提高,土壤中交换态重金属的比例增大,残余态比例下降,有效性提高,对环境威胁增大;当重金属加入量较低时,重金属优先向氧化物结合态、有机质结合态转化,而当加入量较高时,向交换态和碳酸盐结合态转化的比例明显增加;pH和土壤组分对重金属在土壤中的转化有显著影响,土壤pH下降可使交换态Cd、Cu、Pb的比例递增。     

Variability and relationships between Pb,Cu, and Zn concentrations in soil solutions and forest floor leachates at heavily polluted sites

Seasonal variability of Cu, Pb, and Zn concentrations in litter leachates and soil solutions was examined in an afforested zone surrounding a copper smelter in SW Poland. Litter leachates (with zero‐tension lysimeters) and soil solutions (with MacroRhizon suction‐cup samplers, installed at a depth of 25–30 cm) were collected monthly at three sites differing in contamination levels in the years 2009 and 2010 (total Cu: 2380, 439, and 200 mg kg^–1, respectively). Concentrations of Cu in the litter leachate were correlated with dissolved organic C (DOC), whereas Zn and Pb were mainly related to leachate pH. Metal concentrations in the soil solution were weakly influenced by their total content in soils and the monthly fluctuations reached 300, 600, and 700% for Cu, Pb, and Zn, respectively. Metal concentrations in soil solutions (Cu 110–460 μg L^–1; Zn 20–1190 μg L^–1; Pb 0.5–36 μg L^–1) were correlated with their contents in the litter leachates. Chemical speciation, using Visual Minteq 3.0, proved organically‐complexed forms even though the correlations between metal concentrations and soil solution pH and DOC were statistically insignificant. The flux of organically‐complexed metals from contaminated forest floors is believed to be a direct and crucial factor affecting the actual heavy metal concentrations and their forms in the soil solutions of the upper mineral soil horizons.     

施用碱稳定固体的酸性土壤的Cu和Zn的形态分布

Fractionation of metals in a granite-derived acid sandy loam soil amended with alkaline-stabilised sewagesIudge biosolids was conducted in order to assess metal bioavailability and environmental mobility soil solution was extracted by a centrifugation and filtration technique. Metal speciation in the soil solution wasdetermined by a cation exchange resin method. Acetic acid and EDTA extracting solutions were used forextraction of metals in soil solid surfaces. Metal distribution in different fractions of soil solid phase was determined using a three-step sequential extraction scheme. The results show that the metals in the soilsolution existed in different fractions with variable lability and metals in the soil solid phase were also presentin various chemical forms with potentially different bioavail ability and environmental mobility Alkaline-stabilised biosolids could elevate solubility of Cu and proportion of Cu in organically complexed fractionsboth in soil liquid and solid phases, and may therefore increase Cu mobility. In contrast, the biosolids lowered the concentrations of water-soluble Zn (labile fraction) and exchangeable Zn and may hence decrease bioavailability and mobility of Zn. However, Fe and Mn oxides bound and organic matter bound fractions are likely to be Zn pools in the sludge-amended soil. These consequences possibly result from the liming effect and metal speciation of the sludge product and the difference in the chemistry between the metals in soil.     

洞庭湖区典型蔬菜土壤镉、铜、锌、铅含量状况及评价

采用单项污染指数和综合污染指数法对湖南洞庭湖区典型蔬菜土壤Cd,Cu,Zn,Pb含量状况进行了评价。结果表明,与湖南省潮土土壤背景值相比,土壤Cd,Cu和Zn含量明显富集,Pb含量总体不高。与国家土壤质量二级标准(GB15618-1995)相比,洞庭湖区蔬菜土壤以Cd污染为主,其次是Zn和Cu。Pb含量没有超标,其中湘阴县、沅江市、资阳区和赫山区蔬菜土壤环境质量为轻度污染,华容县处于警戒水平,需要修复治理或者改变土地利用方式。君山区和南县蔬菜土壤为清洁水平,适宜发展无公害蔬菜。污染风险高的区域土壤Cd,Cu和Zn之间存在极显著或显著正相关关系,但相关性弱。     

Partition of Cd,Cu, Pb and Zn among mineral particles during their sorption in soils

Journal of Soils and Sediments - Heterogeneity of soil mineral particles may lead to the misinterpretation of bulk sorption data on their role in metal sorption, which may be resolved through the...     

云南省呈贡县蔬菜地表层土壤Pb Cu和Zn的小尺度空间分布特征

应用地统计学对云南省呈贡县蔬菜生产基地2个典型区域（湖滨区和平坝区）3种微量元素（Pb、Cu和Zn）含量和土壤理化参数（CEC、〈0.01 mm粘粒和有机质含量）进行了空间结构分析。结果表明：（1）Pb、Cu和Zn含量在湖滨区低于平坝区, 湖滨区Pb含量的变异系数较大, 达到88.7%;（2）Pb、Cu和Zn含量在不同方向上呈带状各向异性,方向都为WS-NE和SE-NW;（3）Pb、Cu和Zn含量表现出强烈的空间变异,空间相关度介于25%和75%之间。在湖滨区Pb的变异强度高,Cu和Zn在平坝区的变异强度大于湖滨区;（4）CEC在湖滨区受到随机因素引起的变异强度大于平坝区,而粘粒含量和有机质含量的空间相关度均介于25%和75%之间。Pb、Cu和Zn含量与CEC之间呈显著的负相关性;（5）5个相邻的温室大棚湖滨区Pb含量高度变异,Cu和Zn的变异系数小。平坝区各指标的变异系数接近。呈贡县蔬菜生产基地表层土壤Pb、Cu和Zn含量在小于1 km^2的尺度上表现出明显的空间变异性,空间变异与土壤结构、灌溉、耕作活动、管理水平、施肥水平、大棚蔬菜生产年限、地下水位、农田道路网络和城市排污沟渠的分布等有关。     

绿化植物废弃物对土壤中Cu Zn Pb和Cd形态的影响

利用自制的Cu、Zn、Pb和Cd污染的灰潮土和黄泥土,通过室内培养实验研究了不同绿化植物废弃物添加量和不同培养时间对这两种污染土壤中这4种重金属形态的影响。结果表明,绿化植物废弃物的加入抑制了Cu的活化,且添加60%绿化植物废弃物时有机结合态Cu的含量最高;绿化植物废弃物与污染土培养2～3个月时,残余态Zn的含量最高,对植物的毒害最小;绿化植物废弃物添加量为60%时灰潮土中有效态Pb含量较低,而添加量为30%时黄泥土中有效态Pb含量最低;绿化植物废弃物添加量的多少对灰潮土Cd形态的影响较小,但黄泥土中的Cd则随绿化植物废弃物量的增加活性逐渐减弱,且两种土壤均在培养2～3个月时可交换态Cd的含量最低。     

Adsorption density,mobility and limit values of Cd,Zn, Cu and Pb in acid forest soils

To investigate Cd, Zn, Cu and Pb adsorption in acidified forest soils, six soil samples of the aluminium buffer range were selected and analyzed for their physical and chemical properties. Determination of the specific surface area using ethylene glycol monoethyl ether (EGME) adsorption yielded a characteristic value of the solid phases, which can parameterize the major properties of the various soil constituents with sufficient accuracy.

Traditional adsorption isotherms reveal the relation between the amount of a heavy metal adsorbed and the heavy metal concentration in the soil solution only for the soil under study and can therefore not be applied to other soils. To meet the aim of modelling heavy metal adsorption and mobility also for soils differing greatly in their properties, it was attempted to establish a generalizing adsorption isotherm for soils of entirely different composition of the solid phase. The generalizing adsorption density isotherms introduced in the following provide a useful mathematical model for the quantity/intensity relation of heavy metals in soils that differ greatly in their specific surface area and their composition.

It is also shown that limit values which take into account the major quantities influencing heavy metal adsorption and mobility in acid soils can be established from the regression equation between the adsorption density of a heavy metal (ions/m² specific surface area) and its concentration in the soil solution. In particular in view of the groundwater contamination to be expected if acid rain and, as a result, soil acidification continues, these limit values seem to provide considerably more information than the European limit values, given in mg heavy metal /kg soil, which are presently valid for any soil condition and property.     

绿化植物废弃物对重金属迁移的影响

采用土柱模拟实验,比较研究了覆盖绿化植物废弃物与土壤之上和绿化植物废弃物与土壤混合处理对城市绿地土壤中重金属淋溶的影响。结果表明,Zn、Pb和Cd均在80天后淋溶完全,而Cu有所不同,在80天后又有增加的趋势,原因可能跟重金属与有机质的结合能力有关。此外,绿化植物废弃物与土壤相混合能抑制Cu、Zn、Pb和Cd向下淋溶,而绿化植物废弃物覆盖于土壤之上则有促进Cu、Zn、Pb和Cd淋溶的趋势,且不论是混合处理还是覆盖处理,20cm厚绿化植物废弃物的处理均比10cm厚绿化植物废弃物处理对Cu、Zn、Pb和Cd的促进或抑制作用大。研究还得知,Cu、Zn、Pb和Cd的迁移还与土壤pH有关,低pH土壤有利于重金属的淋溶。     

铅-锌-镉复合污染物在土壤-芥菜/油菜系统中的迁移及交互作用

了解重金属复合污染物在土壤-植物系统中的迁移分配情况对污染土壤的安全利用、土壤环境质量标准的修订以及重金属污染土壤的植物修复具有重要意义。通过盆栽试验,以芥菜和油菜为例,研究了铅-锌-镉复合污染物在土壤-植物系统中的迁移分配情况。结果表明：与对照相比,复合污染条件下,芥菜和油菜体内重金属含量显著提高,且Cd含量的提高程度要远远高于Pb和Zn;芥菜和油菜对Cd的吸收达到了100 m g/kg以上,表现出超富集植物的吸收水平。重金属的富集系数大小依次为Cd〉Zn〉Pb,地下部富集系数要高于地上部,转运系数大小为Cd≈Zn〉Pb。Pb、Zn、Cd的富集系数均随各自元素在土壤中含量增大而减小,而且表现为低含量时显著减小,高含量时缓慢减小;重金属在土壤-植物系统的迁移分配深受共存元素的影响,且在不同元素之间和不同浓度范围内表现出不同的特点。Pb、Zn、Cd在芥菜和油菜体中积累量,均与其各自在土壤中的含量成正相关;Zn和Cd对Pb的吸收积累以及Pb对Zn的吸收积累具有明显的抑制作用;Zn-Cd对Zn的吸收积累具有正的交互作用,而对Cd的吸收积累具有负的交互作用。     

铅-锌-镉复合污染物在土壤-芥菜/油菜系统中的迁移及交互作用

了解重金属复合污染物在土壤-植物系统中的迁移分配情况对污染土壤的安全利用、土壤环境质量标准的修订以及重金属污染土壤的植物修复具有重要意义。通过盆栽试验,以芥菜和油菜为例,研究了铅-锌-镉复合污染物在土壤-植物系统中的迁移分配情况。结果表明:与对照相比,复合污染条件下,芥菜和油菜体内重金属含量显著提高,且Cd含量的提高程度要远远高于Pb和Zn;芥菜和油菜对Cd的吸收达到了100 m g/kg以上,表现出超富集植物的吸收水平。重金属的富集系数大小依次为Cd>Zn>Pb,地下部富集系数要高于地上部,转运系数大小为Cd≈Zn>Pb。Pb、Zn、Cd的富集系数均随各自元素在土壤中含量增大而减小,而且表现为低含量时显著减小,高含量时缓慢减小;重金属在土壤-植物系统的迁移分配深受共存元素的影响,且在不同元素之间和不同浓度范围内表现出不同的特点。Pb、Zn、Cd在芥菜和油菜体中积累量,均与其各自在土壤中的含量成正相关;Zn和Cd对Pb的吸收积累以及Pb对Zn的吸收积累具有明显的抑制作用;Zn-Cd对Zn的吸收积累具有正的交互作用,而对Cd的吸收积累具有负的交互作用。     

Suitability of inorganic and organic amendments for in situ immobilization of Cd,Cu, and Zn in a strongly contaminated Kastanozem of the Mashavera valley,SE Georgia. I. Effect of amendments on metal mobility and microbial activity in soil

The aim was to find an adequate, cost‐efficient in situ remediation technique for the Mashavera valley, a mining area in SE Georgia heavily contaminated with Cd, Cu, and Zn. A 12‐month experiment was conducted to test: iron grit, natural zeolite, biochar, and Divergan® (a scavenger) for soil melioration. The amendments were added in different concentrations to the topsoil of a Kastanozem. Mobile metal concentrations decreased with increasing concentrations of amendments in the sequence Divergan® >> iron grit ≈ natural zeolite > biochar. In the same order amendments enhanced activities of soil microbial respiration, alkaline phosphatase, and dehydrogenase; microbial C also followed this trend. A sequential extraction confirmed a shift from easily mobilized to heavily bound fractions. The addition of 2% (w/w) of Divergan® was sufficient to lower mobile trace metal concentrations below German thresholds by chemisorption, and soil microbial activity was significantly increased. The effects of all other treatments were at a much lower level and not found suitable due to needed application rates.