Relations Between Soil Properties and Selected Heavy Metal Concentrations in Spring Wheat (Triticum aestivum L.) Grown in Contaminated Soils

Spring wheat was grown in soils near a non-ferrous metals mining and smelting base in Baiyin city, Gansu province, P.R. China. The area studied is 501 km². Some of the croplandshad been contaminated by heavy metals mainly through wastewaterirrigation or aerial deposition. The soil samples were analyzedfor pH, organic matter and available phosphorous (P); also fortotal cadmium (Cd), lead (Pb), copper (Cu) and zinc (Zn) contents. Spring wheat grains were also analyzed for heavy metals. The results were interpreted using multiple linear correlation and stepwise regression analyses. The increment oftotal soil contents of selected heavy metals could enhance grain Cd accumulation, and the increment of total Zn content of soil could lower the grain Pb accumulation. The correlationswere markedly increased by including other soil properties forgrain Cd and Pb. Stepwise regression analyses indicated that the effect of soil pH and available P on the uptake of grain Cd were greater than that of the other total soil contents ofheavy metals. Grain Cd and Pb could be reliably predicted bythe total soil contents of Cd and Pb while the uptake of grainZn and Cu were not satisfactorily predicted.     

酸雨地区蔬菜对重金属的吸收及重金属健康风险基准的估算

通过盆栽实验,以小白菜(上海青)、大白菜和萝卜为指示作物,研究了酸雨作用下Cu,Zn,Pb,Cd,Cr和Ni复合污染物在土壤-作物系统中的吸收与富集情况。结果表明,酸雨-重金属复合污染处理使Cu,Pb,Cr和Ni在蔬菜中积累量明显高于对照处理;Zn和Cd一般只有在复合污染处理中外源Zn或Cd含量较高时才明显高于对照处理。与对照相比,酸雨-重金属复合污染处理使Pb和Ni的富集系数增大,Cu的富集系数多数情况下增大,Cd的富集系数多数情况下减小,Zn和Cr富集系数的变化在不同蔬菜之间存在较明显的差异;重金属在不同蔬菜中的富集系数一般表现为萝卜>上海青>大白菜,蔬菜中不同重金属富集系数一般表现为Zn>Cd>Ni>Cu>Pb>Cr。酸雨-重金属复合污染条件下蔬菜中重金属积累量与其在土壤中总量之间的相关性均达到显著或极显著水平。以大宗蔬菜上海青、大白菜和萝卜为指示作物对酸雨地区蔬菜地中重金属的健康风险基准进行了估算,这对开展酸雨地区土壤重金属环境容量评价、重金属污染修复目标及地方性土壤环境质量标准的制订提供了参考依据。     

水稻子实对不同形态重金属的累积差异及其影响因素分析

在分析成都平原核心区土壤重金属(Cd、Cr、Pb、Cu、Zn)全量、各形态含量及相应点位种植的水稻子实重金属含量的基础上,通过统计分析、空间插值及线性回归方程的模拟,研究了土壤Cd、Cr、Pb、Cu、Zn全量的空间分布状况、各形态重金属含量统计特征,以及水稻子实对重金属各形态的累积差异及其影响因素。结果表明,成都平原水稻土重金属污染较轻,除Cd外,均低于国家土壤环境质量二级标准。土壤中重金属的可交换态含量均较低,Cd主要以铁锰氧化态存在,Cr、Cu、Zn、Pb主要以残渣态存在。水稻子实对5种重金属的累积效应顺序为:Cd>Zn>Cu>Pb>Cr。与水稻重金属累积关系密切的重金属活性形态(可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态)主要有:Cd的碳酸盐结合态、Cr的可交换态、Pb的有机物结合态和Cu的碳酸盐结合态含量;Zn各活性形态对水稻子实含量的影响不明显。土壤理化性质对不同活性形态重金属元素的影响效应各不相同。活性态Cd主要受有机质、pH和容重的影响;活性态Cr与pH、有机质、CEC和容重密切相关;活性态Pb与有机质、容重、中细粉粒、砂粒等均有密切的关系;Cu的活性主要受粘粒、有机质含量的影响;Zn的有效性主要受pH、有机质、砂粒、容重的影响。总的看来,对土壤Cd、Cr、Pb、Cu、Zn各活性形态含量影响效应较强的是有机质、pH、容重,而与土壤吸附性能密切相关的颗粒组成、CEC的影响不甚明显。     

Effect of pH on chemical forms and plant availability of cadmium,zinc, and lead in polluted soils

The effect of pH on chemical forms and plant availability of heavy metals in three polluted soils was investigated. The soils were adjusted to pH values of 7.0, 6.0, and 4.5, then sequentially extracted so that Cd, Zn, and Pb could be partitioned into five operationally defined chemical fractions: exchangeable, carbonate, Fe-Mn oxide, organic, and residual. Kidney beans were grown in the soils to investigate plant availability of the metals in relation to changes of their levels in chemical forms resulting from alteration of soil pH. Alteration of pH resulted in changes of chemical forms of the metals in the soils, and at lower pH the changes were more significant. When soil pH values were decreased from 7.0 to 4.55, levels of Cd, Zn, and Pb in exchangeable form increased, decreased in carbonates and decreased slightly in Fe-Mn oxide forms. Their levels in organic and residual forms were unchanged. Although concentration of metals in plants increased with reduction in soil pH values, dry matter yields were also restricted, so that the amount of metal uptake were almost similar. The uptake rate of the metals in the exchangeable + carbonate forms was the same for the three elements in all the cases.     

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。     

添加物对镉、锌、铅污染土壤上小白菜的生长和养分吸收的影响

A pot experiment was carried out to study the effects of two amendments, lime and calcium magnesium phosphate, on the growth and Cd,Pd,Zn,Cu,Mn,Fe,N,P and K uptake of pakchoi (Brassica chinensis) in a Cd,Pb and Zn polluted acid soil in the southern part of China. The growth of pakchoi was apparently improved by lime and calcium magnesium phosphate application, the uptake of Cd,Pb,Cu and Zn by pakchoi was significantly depressed and the symptom caused by heavy metals pollution was eliminated. Meanwhile, the absorption of N,K and Mn was also inhibited by these amendments. Soil pH was the main factor controlling the uptake of the heavy metals by pakchoi. This suggests that lime and calcium magnesium phosphate could be used as effective amendments for eliminating the toxicity of heavy metals to the vegetable and inhibiting their absorption by the crop.     

海泡石改良土壤效果研究

通过连续三季盆栽试验研究海泡石提高油菜生物量,降低油菜Cd、Pb、Cu、Zn浓度及土壤Cd、Pb、Cu、Zn有效态浓度的效果。结果表明:海泡石在不同程度上提高了三季油菜的生物量,适量的海泡石可降低油菜中Cd、Pb、Cu、Zn浓度及土壤Cd、Pb、Cu、Zn有效态浓度。海泡石降低油菜中重金属浓度效果,第一季,Zn>Pb>Cd>Cu,第二季,Pb>Zn>Cd>Cu,第三季,Zn>Cd>Pb>Cu;降低有效态浓度的效果,第一季,Cd>Cu>Pb>Zn,第二季,Cu>Cd>Zn>Pb,第三季,Pb>Cd>Cu>Zn。因此,海泡石可用于土壤改良,提高油菜生物量,降低油菜中Cd、Pb、Cu、Zn浓度及土壤中Cd、Pb、Cu、Zn有效态浓度。海泡石降低油菜中重金属浓度总效果为Zn>Pb>Cd>Cu;降低土壤重金属有效态浓度总效果为Cd>Cu>Pb>Zn。     

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.     

耕作方式对稻-油轮作系统土壤理化性质及重金属有效性的影响

为探明不同耕作方式下稻-油轮作系统中土壤重金属有效性的变化规律,测定了21年长期定位试验稻-油轮作系统中土壤及其剖面的主要理化性质和重金属有效含量,分析了二者间的关系。结果表明,与翻耕相比,垄作免耕使各土层土壤有机质含量和阳离子交换量显著提高,并具有明显的表层聚集现象,土壤pH值明显降低。耕层土壤Cd、Cu和Zn有效量以垄作免耕处理最高,土壤Pb的有效量则以常规平作处理最高,不同耕作方式下,土壤有效Cd和Pb出现表聚现象,但有效Zn和Cu随土壤深度的变化无明显规律。相关分析表明,土壤有机质含量与土壤Cd、Zn有效量呈极显著正相关关系,与土壤Pb、Cu有效量呈显著正相关,土壤pH值与土壤Pb有效量呈显著正相关,而土壤阳离子交换量与4种重金属有效量间的相关性不显著。由此推测,耕作方式主要是通过影响土壤有机质含量而影响重金属元素的有效性,垄作免耕较翻耕在改良土壤理化性质上有较大优势,却使0-20cm和20-40cm土层重金属有效量显著增加,表现出明显的表层富集趋势。     

北京市朝阳区(五环内)绿地土壤重金属分布特征及其影响因素

为了研究和分析北京市朝阳区（五环内）土壤重金属的分布特征及影响因素,通过居住绿地、公园绿地、街旁绿地以及附属绿地（包括公共设施用地、对外交通用地和市政设施用地）4种土壤利用类型分别进行了土壤重金属铜（Cu）、锌（Zn）、镉（Cd）、铅（Pb）以及土壤pH值、有机质的测定。结果表明:表层土壤中的重金属平均含量,除Pb外,均高于中国土壤背景值,尤其是重金属Cd,已达到0.26 mg/kg,超过了国家土壤环境质量1级标准;从土壤利用类型上来看,Cu在附属绿地土壤含量最高,达到33.576 mg/kg,Zn在居住绿地土壤含量最高,达到80.636 mg/kg,Cd在街旁绿地土壤含量最高,达到0.296 mg/kg,Pb在公园绿地土壤含量最高,达到24.706 mg/kg;在空间分布上,重金属Cu和Zn空间分布格局相类似,整体呈由西北向东南递减趋势,而Cd高值区在中部,整体北部高于南部,重金属Pb整体上呈由西南向东北递减趋势;通过相关性分析可知,土壤pH值对土壤重金属含量没有明显的影响,而土壤有机质与重金属Zn,Cd和Pb的含量有明显的相关性;4种重金属呈显著正相关（p<0.01）。     

泉州走马埭典型土壤重金属的赋存形态分析

采用改进的Tessier连续萃取方法研究了泉州走马埭国家农田示范保护区典型土壤中重金属(Cr、Ni、Cu、Zn、Cd、Pb)的化学形态分布,通过土壤重金属的赋存形态分析比较了6种重金属的生物可利用性。研究结果表明,土壤中不同重金属元素化学形态分布具有不同的特点:Cr和Ni主要以残渣态存在,其余形态所占的比例很小;Cu以残渣态含量最高,碳酸盐结合态含量最低;Zn以残渣态为主,可交换态含量最低;Cd以可交换态和碳酸盐结合态为主,水溶态含量最低;Pb以残渣态和铁锰氧化物结合态为主,水溶态含量最低。土壤中除Cd外,Zn、Cu、Cr、Pb、Ni在正常自然条件下相对比较稳定。     

不同pH值混合螯合剂对土壤重金属淋洗及植物提取的影响

为了得出混合螯合剂（MC）淋洗去除重金属的最佳pH值以及对后续植物提取重金属的影响,用Ca(OH)2将pH值为2.75的MC提高至pH值5、7和9,对重金属污染土壤进行了盆栽淋洗试验,而后种植东南景天（Sedum Alfredii）,测定淋出液及植物重金属含量。另外,通过浸提试验研究了含有不同阳离子的MC对重金属淋洗效果的影响。结果表明,pH值为5和7的MC显著提高了Cd、Pb和Cu的淋出率。与Na+、K+离子相比,Ca2+的存在能够提高MC对重金属的淋洗去除。pH值7和9的MC淋洗土壤后提高了东南景天的生物量,但是降低东南景天中Cd和Zn的浓度,导致其植物提取率低于无淋洗剂对照。在化学淋洗+植物提取联合技术中,Cd和Zn主要靠植物提取去除,植物提取率分别可达土壤Cd的30%～40%和土壤Zn的6.5%～6.9%;而Pb和Cu主要靠混合螯合剂淋洗去除,去除率分别为2.3%～2.6%和1.6%～2.0%。综合来说,如果需要同时去除Cd、Zn、Pb和Cu,降低土壤重金属有效态含量,用pH值9的MC淋洗土壤联合植物提取较为合适。     

Fractionation and Prediction of Copper,Lead, and Zinc Uptake by Two Leaf Vegetables from Their Geochemical Fractions in Urban Garden Fields in Northern Nigeria

The bioavailability and mobility of heavy metals in soil are strongly influenced by the chemical or geochemical species of the metals in soils. We determined the geochemical fractions of copper (Cu), lead (Pb), and zinc (Zn) in garden soils, using the seven-step Zeien and Bruemmer fractionation scheme in relation to metal uptake by two leaf vegetables (lettuce, Latuca sativa, and amaranthus, Amaranthus caudatus). Our objective was to develop predictive models for assessing the lability of these metals from the soil metal fractions. The sums of fractions of Cu, Pb, and Zn did not differ by more than 10% from the “pseudo” total concentrations of the metals determined independently by aqua regia digestion. The general distribution of Cu and Pb among the soil fractions was in the order organic-matter-bound > Fe_o and Fe_c > Mn_ox > exchangeable > residual > mobile, except for Cu, where residual and the exchangeable were reversed. Zinc was fairly evenly distributed among organic matter (20%), Fe_o (22%), Fe_c (20%), and residual (21%). Averaged across sites, Cu, Pb, and Zn concentrations in the lettuce were almost twice as great as the concentrations in amaranthus even though they were raised in the same fields. The variance in Cu, Pb, and Zn uptake by amaranthus was predicted up to 51–99% from soluble, exchangeable, organic matter, and Fe_o-bound fractions; the variance in metal uptake by lettuce was best predicted from Fe_c- and Fe_o-bound fractions up to 76–90%. Our results indicated differential accessibility to metal fractions by lettuce and amaranthus grown in the same field.     

From soil to rice – a typical study of transfer and bioaccumulation of heavy metals in China

For the purpose of studying the contamination, bioaccumulation and transfer of heavy metals and understanding the effects of soil properties on these, the work was carried out on a regional scale. A total of 30 sets of soil and pairing rice tissues samples (root, straw and grain) were collected in Xiangzhou of Guangxi, China; soil properties and Cd, Cu, Pb and Zn of different rice tissues were analyzed. The mobility and bioaccumulation of Cd, Cu, Pb and Zn were assessed by transfer coefficients and bioaccumulation factors of them. The results indicated that the excess proportions of Cd and Pb were 50%, 3.33% and 30%, 6.67% in soil and rice grain, respectively, according to Chinese maximum permitted concentrations of heavy metals. Cd and Zn showed stronger bioaccumulation and mobility capability; the bioaccumulation and transfer of Cu were slightly lower than Cd and Zn; Pb had the weakest mobility. The bioaccumulation and mobility of heavy metals from soil to rice were restrained by soil pH, CaO, SOC, Fe oxides and Mn.     

施污土壤与污泥中Cu、Pb、Cd、Zn的形态分布

污泥中的重金属元素是限制其大规模农田利用的重要因素。施污土壤和污泥中重金属的形态研究可以用来评价土壤中重金属的生物有效性以及它们在土壤中的移动性。用修正BCR三步连续提取法进行分步提取研究了污水污泥和施污后的西红柿地土壤中Cu、Pb、Cd、Zn的形态分布状况。施用污泥堆肥10t hm-2后的土壤中Cu、Pb、Cd、Zn的全量与各种形态含量无明显增加,Cu、Pb、Zn含量远低于国家土壤环境质量标准。土壤中Cu的各种形态分布关系是:残渣态>可还原态=可氧化态>可交换态和弱酸溶解态,Cu在土壤中的存在是以最稳定的残渣态为主。堆肥污泥与干化污泥相比,残渣态Cu的比例明显增加。土壤中Pb的各种形态分布关系是以残渣态和可还原态为主,但可氧化态的分布比例最小。土壤中Cd的可交换态、可还原态和残渣态各占据相等的含量,但可氧化态Cd的含量几乎为零。Zn在土壤中的各种形态分布关系是:可交换态和弱酸溶解态>可氧化态>可还原态>残渣态,Zn在土壤中的存在是以最易迁移的可交换态和弱酸溶解态为主。这些金属元素在土壤中的相对稳定性顺序为:Cu>Pb>Cd>Zn。Zn在土壤中的移动性要远高于Cu。     

6种固化剂对土壤Pb Cd Cu Zn的固化效果

通过在重金属污染土壤中分别施加沸石、石灰石、硅藻土、羟基磷灰石、膨润土和海泡石6种固化剂,研究了这6种固化剂对土壤中Pb、Cd、Cu、Zn的固化效果,筛选出几种效果较好的固化剂。实验结果表明：沸石、石灰石和羟基磷灰石均能够有效地降低土壤中交换态Pb、Cd的含量,并且明显减少了土壤中Pb、Cd的毒性浸出量,其中沸石最多降低土壤中交换态Pb、Cd含量分别达到48.7%和56.2%,减少土壤中Pb、Cd的毒性浸出量达到37.1%和30.1%;沸石、石灰石均能够有效降低土壤中交换态Cu的含量,降低量分别高达68.1%和85.2%,膨润土能有效减少土壤中Cu的毒性浸出量,减少量最高达到66.51%;石灰石对土壤中Zn有着良好的固化效果。     

石灰及其后效对玉米吸收重金属影响的田间实例研究

通过田间试验方法,研究了在铅锌矿废水污染的土壤上施用石灰1 a后,继续施用石灰和石灰后效处理对后续第1、2季低累积玉米（Zea mays）的产量以及重金属Cd、Pb、Zn和Cu含量的影响,并分析了土壤pH、土壤DTPA提取态重金属含量和土壤重金属全量的变化。结果表明,连续施用石灰和石灰后效均显著提高玉米产量,其中连续施用石灰处理效果最佳,第1季籽粒产量是对照（无石灰）的6倍,第2季是对照的3.8倍。与对照相比,连续施用石灰处理显著降低了2季玉米籽粒Cd、Pb、Zn和Cu含量,石灰后效只能降低第2季玉米茎叶Cd、Pb和Cu含量,而籽粒Cd、Pb含量与对照相比略有升高,说明石灰后效能维持一年半左右。对照处理土壤Cd和Zn全量显著低于石灰处理,可能是土壤中Cd和Zn随着雨水的淋洗向下层迁移造成的。施用石灰可防止Cd和Zn对地下水的污染。     

Effect of Organic Materials on Partitioning,Extractability and Plant Uptake of Metals in an Alum Shale Soil

Soils developed on sulphide-bearing shale (alum shale) in Norway contain naturally high amount of heavy metals. We conducted a greenhouse pot experiment to study the effect of four rates (0, 2, 4, and 8%) and three sources (cow manure, pig manure and peat soil) of organic matter in partitioning and distribution, extractability and plant uptake of Cd, Cu, Ni and Zn in an alum shale soil. Sequential extraction scheme was used to determine the distribution patterns of metals in the soil. DTPA was used for extracting the metals from the soil. Wheat (Triticum aestivum) was used as a test crop to study the plant uptake of metals. The highest amount of Cd was present in the exchangeable fraction, irrespective of the rate and source of organic matter applied. Copper, Ni, and Zn, on the other hand, were present only in small quantities in this fraction. The largest fraction of Cu was associated with organic matter and the amounts present in the oxide, carbonate and exchangeable fractions were very small. Nickel and Zn were found mainly in the residual fraction. Increasing rates of cow and pig manure decreased the amounts of Cd and Ni associated with the exchangeable fraction whereas, the addition of peat soil at the same rate increased the amounts of these metals associated with this fraction. This effect of organic matter was primarily associated with the change in soil pH caused by different organic matter sources. The DTPA-extractable metals were decreased with increasing rates of organic matter application, irrespective of its source. Grain and straw yields of wheat were decreased with increasing rates of organic matter. The application of organic matter increased the Cu and Zn concentrations in both grain and straw. The concentration of all metals was lower in plants grown in the cow manure amended soil as compared to those grown in the soil amended with either pig manure or peat soil. These results sugggest that the source of organic matter was a determining factor for metal distribution in the soil and for metal uptake by plants. In this study cow manure slightly increased the soil pH and thus was more effective than either pig manure or peat soil in reducing the plant uptake of metals but in general the efficiency of the organic material in reducing heavy metal uptake was small.     

黔产薏苡仁及其产地土壤重金属污染的特征

[目的]探明黔产薏苡仁及其产地土壤重金属污染特征,为黔产薏苡仁产业可持续发展及其产地土壤重金属防控提供科学依据。[方法]以黔西南薏苡仁及其产地土壤为供试样品,分析测定土壤pH值、有机质、阳离子交换量(CEC)和5种重金属元素镉(Cd)、铅(Pb)、锌(Zn)、铜(Cu)、镍(Ni)的含量,运用GIS和单因子污染风险评价等方法,探讨土壤重金属空间分布和土壤重金属污染对薏苡仁品质安全的影响。[结果]①土壤中5种重金属Cd,Pb,Zn,Cu和Ni含量范围分别为0.01~1.35,10.09~34.70,80.39~236.36,22.54~131.42,26.75~137.76 mg/kg,其中,Cd,Cu和Ni的最大值均高于国家现行标准(GB15618-2018),表明研究区土壤中主要存在一定范围的Cd,Cu和Ni污染风险;综合污染指数为1.94,污染等级为轻度污染。②薏苡仁中Cd,Pb,Zn,Cu和Ni含量范围分别为未检测到~0.027,0.179~1.348,42.615~58.961,10.028~16.244,0.552~5.045 mg/kg,Cd未超标,而Pb,Zn,Cu和Ni均有不同程度的超标,超标率依次为90%,25%,75%和30%;薏苡仁对Pb具有很强的累积效应。[结论]通过同步采集土壤样品和对应的薏苡仁样品,分析结果能更好地评估土壤重金属污染对薏苡仁品质安全的影响。