Spectroscopic study of heavy metals sorption on clinoptilolite

Sorption of heavy metal cations (Pb(II), Cr(III), Cd(II), Ni(II)) from aqueous solutions on natural Na-clinoptilolite was studied using atomic absorption spectrometry (AAS) and FT-IR spectroscopy. It was found that the sorption capacity of clinoptilolite decreases in the following order: Pb(II) (22,600 mg/kg), Cr(III) (21,200 mg/kg), Cd(II) (10,400 mg/kg) and Ni(II) (6,200 mg/kg). In the FT-IR spectra of the samples, in the region of pseudolattice vibrations (500–800 cm^–1), systematic changes connected with the type of cation and its concentration in the initial solution were observed. The proportions of ion exchange and chemisorption in the whole process of sorption were also estimated. It was found that the amount of cations sorbed on clinoptilolite depended on the concentrations and pH of the solutions used as well as on the contact time of zeolite-solution system. After 120 min of the reaction, despite the metal type, 90–100% of the total amount of cations were immobilized.     

Competitive adsorption,release and speciation of heavy metals in the Yellow River sediments,China

The competitive adsorption and the release of selected heavy metals and their speciation distribution before and after adsorption in the Yellow River sediments are discussed. The adsorption of metals onto sediments increases with increasing pH value and decreases with increasing ionic strength. The competitive coefficient K _c and the distribution coefficient K _d are obtained to analyze the competitive abilities of selected heavy metals, which are ranked as Pb > Cu >> Zn > Cd. The competition among selected heavy metals becomes more impetuous with increasing ion concentration in water. Speciation analysis was done by an improved analytical procedure involving five steps of sequential extraction. Cu, Pb and Zn were mainly transformed into the carbonate-bound form (50.8–87.7%) in adsorption. Most of (60.7–77.3%) Cd was transformed into the exchangeable form, and the percentage of carbonate-bound Cd was 19.7–30.4%. The release reaction was so quick that the release capacity of selected heavy metals from sediments to aqueous solution reached half of the maximum value only in 30 s. As opposed to adsorption, the release capacities of selected heavy metals were ranked as Cd > Zn >> Cu > Pb. In this study, Cd produces the most severe environmental hazards, because its concentration in the release solution is 85.8 times more than the human health criteria of US EPA.     

Adsorption characteristics of heavy metals in soil zones developed on spilite

Various soil zones such as Bw, C1, and C3 are developed on spilite. Montmorillonite, vermiculite and chlorite is moderately occurred in the C1 and C3 soil zones, in contrast montmorillonite and vermiculite are absent in Bw soils whereas illite and sesquioxide are relatively increased. The high cation exchange capacity (CEC) of montmorillonite and vermiculte and moderate CEC of chlorite and illite resulted in the high adsorption of heavy metals. The adsorption of the heavy metals on spilite soil zones was studied at different concentrations and pH levels. Heavy metals like lead, cadmium, and copper were selected for adsorption studies considering their contribution as toxic metals in the environment. The initial solute concentrations ranged from 7.0 × 10⁻³ to 1.0 × 10² mg/L. The sorption behavior of Cd²⁺, Pb²⁺, and Cu²⁺ on soil zones of spilite was investigated using the batch equilibrium technique at 25°C. The characteristics of the adsorption process were investigated using Scatchard plot analysis (q/C vs. q) by the batch equilibrium technique at 25°C. In the adsorption of heavy metals, deviation from linearity in the plot of q/C versus q was observed, indicating the presence of multi-model interaction and non-Langmuirean behavior. When the Scatchard plot showed a deviation from linearity, greater emphasis was placed on the analysis of the adsorption data in terms of the Freundlich model, in order to construct the adsorption isotherms of the metal(s) at particular concentration(s) in solutions. The adsorption behavior of these metal ions on spilite soil zones is expressed by the Freundlich isotherms. Adsorption constants and correlation coefficients for the Cd, Pb, and Cu on spilite soil zones were calculated from Freundlich plots.     

松嫩平原黑土区西北部阿荣旗黑土重金属分布特征、评价及预警

近年来,松嫩平原黑土区南部、东北部的一些区域已出现了重金属元素的累积,严重威胁着粮食生产安全和人体健康。为明晰黑土区西北部区域的重金属污染情况,本文以松嫩平原黑土区西北部阿荣旗为研究区,采集了32个表层黑土样品,测定As、Cd、Cr、Cu、Hg、Ni、Pb、Zn等8种重金属元素的含量,利用单因子指数法（P_i）、内梅罗综合污染指数法（NPI）、潜在风险分析法（RI）并引入生态风险预警指数法（IER）对黑土的重金属潜在生态风险进行综合研究,绘制了重金属元素的空间分布图。结果显示：Cd、Pb元素含量分别是内蒙古表层土壤背景值的1.99和1.50倍,其余6种均低于内蒙古表层土壤背景值。8种重金属元素平均含量均低于国家标准（GB15618-2018）中的风险筛值,为清洁无污染。NPI平均值为0.33,为无影响等级;潜在风险结果显示Cd中等潜在风险,RI平均值为115.36,轻微生态风险。生态风险预警结果显示：选用国家标准（GB15618-2018）中的风险筛值做参考时,无风险预警;选用内蒙古表层土壤背景值做参考时显示Cd轻警态势,Pb预警态势,其余6种元素无警态势,IER平均值为0.65,为预警态势,8种元素的RI、IER的空间分布格局相似,Cd元素为研究区黑土中的生态风险元素和预警元素。生态风险预警指数法（IER）在研究区黑土中得到了较好的应用。     

Study on soil heavy metals contamination of a lead refinery

The contents of Pb, Cd, Cr, As, and Hg was investigated in the neighboring areas of a lead smelting enterprise and the metals contamination of soil was evaluated with the methodologies of the single factor index and Nemerow integrated index. It is found that the content of heavy metals in the neighboring areas has no obvious difference from the reference points. And the soil contamination of heavy metals varies by elements, the contamination index follows the pollution order： Cd〉Hg〉Cr〉As〉Pb. The pollution degree of Cd is at high level and Hg at low level, but Cr and As reached the warning level. Therefore, the lead smelting enterprises should not only control lead but also other heavy metals as Cd.     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.     

青海东部地区土壤重金属污染评价

在青海东部地区表层、深层土壤重金属调查基础上,根据国家《土壤重金属污染评价标准》(GB15618-1995),对土壤中重金属污染状况进行评价;重点选择甘河滩地区,对区内单点样、植物样、水样、地球化学剖面结果进行探讨;比较了Cd、Hg在不同时期污染形势的变化。综合分析认为,青海省东部地区重金属污染总体上并不严重,但在甘河滩一带Zn、Cd、Pb在不同介质中形成较为明显的循环污染,污染程度已达深层,不适宜农业发展;时间尺度上,Cd污染有加剧趋势,Hg污染状况有所改善。     

Flocculation of heavy metals during mixing of freshwater with Caspian Sea water

Flocculation of colloidal size fraction for Cu, Zn, Pb, Ni and Mn was investigated on a series of mixtures with water salinities ranging from 1.5 to 9.5‰ during mixing of Haraz River with the Caspian Sea water. The flocculation trend of Zn (85.5%) > Mn (55.2%) > Cu (39.6%) > Pb (33.7%) > Ni (11.3%) indicates that Cu, Zn, Pb and Mn have non-conservative behavior and Ni has relatively conservative behavior during estuarine mixing. Highest flocculation of heavy metals occurs between salinities of 1.5 and 4.5‰. Statistical analysis indicates that the flocculation of Cu, Zn and Ni is governed by pH and total nitrogen.     

斥水性土壤水分入渗试验和模型

为研究斥水性土壤水分入渗规律,并探寻适用于斥水性土壤水分入渗的数学模型,以妫水河流域亲水性和斥水性土壤为研究对象,开展室内一维垂直土柱入渗试验;分别采用Kostiakov分段函数、Fourier级数、一阶Gaussian函数以及Gaussian分段函数对斥水性土壤入渗率进行拟合。试验结果表明:亲水性土壤入渗率随时间呈单调减小变化趋势,斥水性土壤入渗一段时间后累积入渗量会出现翘尾现象,入渗率为先增大后减小的单峰曲线。模型图形分析表明: Kostiakov分段函数入渗率在拐点处同时存在一个极大值和极小值,Fourier级数存在多个波峰,一阶Gaussian函数不能反映入渗率在拐点后大于拐点前的试验现象,因而均难以真实反映斥水性水分入渗过程。忽略水分开始快速入渗过程,Gaussian分段函数模型不仅能够反映入渗率在拐点前的单调增以及拐点后的单调减过程,同时也能够体现入渗率在拐点后大于拐点前的试验现象。     

岩溶铅锌矿区土壤重金属污染特征

以DX、DW铅锌矿区土壤为研究对象,利用原子吸收光谱法（AA800）、原子荧光光谱法（AF-640）测定土壤中铅、铬、镉、铜、锌、镍、汞和砷等重金属的含量,利用单因子污染指数法、N.L.Nemerow综合污染指数法对比分析土壤中重金属的污染特征,采用PCC统计学方法分析矿区土壤中重金属之间的相关性。结果表明:两矿区土壤中除Cu、Cr外,其余重金属均已对土壤造成单一或复合污染,其中Cd污染最为严重,对综合污染贡献最大。DX、DW矿区土壤重金属的Nemerow指数分别为27.61、63.54,均达到极强污染水平,且DW矿区污染较为严重。DX矿区,除Ni外,Pb、Cr等7种重金属元素之间存相关性;DW矿区,除Cr外,Pb、Ni等7种重金属元素之间存相关性,这可能与二矿区均属多金属伴生、共生矿床有关;土壤中各重金属总含量与pH值没有显著的相关性。研究结果将为合理制定矿区土壤污染的修复和治理措施提供依据。      

北京平原区两年内土壤中五种重金属元素化学形态变化及生物有效性

为了监测北京市平原区2015年和2016年土壤中5种重金属As、Cd、Hg、Pb、Zn化学形态的变化趋势,运用Tessier连续提取法对土壤重金属进行了形态分析,并对影响重金属元素生物有效性的因素进行研究。结果表明,2年内研究区表层土壤重金属元素的形态变化微弱,有效态含量以Cd元素最高,达到45.67%,故潜在生态危害性最大;其次为Zn元素,达12.16%,其中碳酸盐结合态占比虽大,但由于研究区土壤呈偏碱性,Zn元素的迁移能力较弱,潜在危害性较小;As、Hg、Pb均以难迁移态存在,故潜在危害性也较小。土壤重金属元素的生物活性系数及迁移系数分别为:CdZnPbAsHg和CdAsZnPb=Hg,其中Cd元素2年的生物活性系数和迁移系数最高,展现出较强的生物活性和迁移能力,其余重金属元素的活性系数和迁移系数较低,潜在危害性较弱。影响重金属元素生物有效性的因素较复杂,以重金属元素全量为主,p H、有机质、CEC等理化性质次之。     

铜陵矿区土壤重金属元素的空间变异及污染分析

运用地统计学分析手段对铜陵矿区土壤中的As、Cd、Hg、Pb和Zn5种重金属元素进行空间变异分析及空间插值,并进行污染分析,以期为铜陵矿区土壤环境评价、土壤污染修复及环境决策提供科学依据。数据来源于"安徽省江淮流域多目标区域地球化学调查"结果,采用Johnson变换进行正态转换,地统计拟合变异函数中,As、Cd元素为球状模型,Pb、Zn元素为五球形模型,Hg元素为指数模型。结果表明,As、Cd、Pb、Zn元素的变异函数表现为各向异性,其方向性可能主要受矿床分布控制;Hg元素块金效应较大,表明其受小     

Distribution and storage of sediment-associated heavy metals downstream of the remediated Rum Jungle Mine on the East Branch of the Finniss River,Northern Territory,Australia

Instream, overbank and cut riverbank exposures along the East Branch of the Finniss River downstream of Rum Jungle Mine, Northern Territory have been analysed for their total metal concentrations using instrumental neutron activation analysis (INAA). Concentration values for the < 62.5 μm and bulk sample fractions are compared to Australian sediment quality guidelines values (ANZECC/ARMCANZ, 2000). The results reveal that channel and overbank environments are contaminated with heavy metals, with many samples exceeding the low and high sediment guidelines values. The < 62.5 μm fraction is consistently more contaminated than bulk samples as are instream environments compared to adjacent overbank environments. Metal concentrations are strongly correlated to sediment pH and Fe values, suggesting that these variables are significant in controlling the spatial distribution of sediment-associated metals. The strong positive correlation between sediment-associated metals and Fe is probably related to the process of metal sequestration by Fe (and Mn) oxyhydroxides. The spatial distribution of sediment-associated metals downstream of the Rum Jungle Mine site does not display a simple distance–metal concentration decay pattern. It is suggested that the non-uniform spatial distribution of sediment-associated metals is a function of local, reach-scale variations in channel geometry and geomorphology, which control sediment storage and transfer patterns. In cut riverbank exposures the vertical of metals distribution is non-uniform and probably reflects differential metal mobility. Despite rehabilitation of the mine site in the 1980s, the elevated sediment-associated metal concentrations that remain within the East Branch of the Finniss River system are likely to render the system contaminated for the foreseeable future and limit the potential for the full recovery of aquatic and terrestrial flora and fauna.     

Adsorption of heavy metals in glacial till soil

The charged sites on soil particles are important for the retention/adsorption of metals. Metallic counterions can neutralize the intrinsic charges on the surfaces of soil particles by forming complexes. In this study, efforts have been made to determine the effect of surface potential, pH, and ionic strength on the adsorption of four metal ions, hexavalent chromium Cr(VI), trivalent chromium Cr(III), nickel Ni(II) and cadmium Cd(II), in glacial till soil. Batch tests were performed to determine the effect of pH (2–12) and ionic strength (0.001–0.1 M KCl) on zeta potential of the glacial till soil. The point of zero charge (pH _PZC ) of glacial till was found to be 7.0±2.5. Surface charge experiments revealed the high buffering capacity of the glacial till. Batch adsorption experiments were conducted at natural pH (8.2) using various concentrations of selected metals. The adsorption data was described by the Freundlich adsorption model. Overall glacial till shows lower adsorption affinity to Cr(VI) as compared to cationic metals, Cr(III), Ni(II) and Cd(II).     

A study on the characteristics of heavy metals in orange ecosystem

An investigation was conducted to identify the characteristics of heavy metals in orange ecosystem in three areas in the Three Gorge Reservoir Region by using the modified Tessier sequential extraction procedure. The contents of Cu and Pb in different speciation fractions of the soils can be ordered as the Residual (F6)>Reducible (F4)>Oxidable (F5)>Water soluble (F1)>Carbonate (F3)>Exchangeable (F2), and the contents of Zn and Ni follow the order of the Residual (F6)>Oxidable (F5)>Reducible (F4)>Water soluble (F1)>Carbonate (F3)> Exchangeable (F2), and those of Cd follow the order of the Reducible (F4)>Oxidable (F5)>Exchangeable (F2)>Carbonate (F3)>Residual (F6)>Water soluble (F1). The concentrations of Cu in the different organs of oranges follow the increasing sequence of pulp>leaf>pericarp, those of Zn and Ni following the increasing sequence of leaf>pulp>pericarp, and those of Pb and Cd follow the increasing sequence of leaf>pericarp>pulp. Correlation degrees of different forms of same heavy metals in soils are according to the order of Cu>Zn>Cd>Pb>Ni. Correlation degrees of different heavy metals in same forms are according to the order that the forms of Reducible (F4), Oxidable (F5) and Residual (F6) are higher than the forms of Water soluble (F1), Exchangeable (F2) and Carbonate (F3). There are either positive or negative correlations between heavy metals in leaves and in pulp, while there are all positive correlations between heavy mentals in leaves and in pericarp. There are significant correlations between the concentrations of some heavy metals in leaves, pericarp or pulp, and those in speciation fractions in the soils.     

德兴铜矿地区土壤的基本特征及其对重金属元素的吸附研究

本文首先分析了江西德兴铜矿区周围土壤的微量元素和矿物组成特征,结果显示该地区重金属元素富集,且表层土中重金属元素含量与粘土矿物相对含量变化具有较好的一致性。室内土柱淋滤实验结果表明,当总淋滤时间为451 h时,土壤对Pb²⁺的总吸附量为2 584.75 mg/kg,淋滤实验的前半期存在多种竞争吸附机制,后半期土壤对Pb²⁺的吸附基本达到动态平衡。淋滤后土壤矿物的相对质量分数发生了改变,粘土矿物有所减少。粘土矿物在不同土壤层对Pb²⁺的吸附能力也各异。     

山东省沂南县东部土壤重金属生态健康风险评价

【研究目的】 山东是中国矿业与农业发达省份、沂南县东部堪称其代表。掌握当地土壤重金属污染及对生态健康风险的影响对生态环境保护有重要意义。【研究方法】 系统调查分析表层土壤样品4779件,获取Hg、Cd、Cr、Ni、As、Cu、Pb、Zn等元素分布最新数据,并用地累积指数法、潜在生态危害指数法和健康风险评估模型等评价研究了生态健康风险及相关问题。【研究结果】 （1）上述重金属均量与临沂市土壤背景值大致相当,仅Hg略偏高且变异系数最大,指示当地土壤Hg受人类活动影响明显。与国家农用地土壤污染风险筛选值相比,Cu、Cr、Ni是相对主要超标元素,As、Cd、Cu、Pb超标倍数大,它们均可能会产生生态健康危害;（2）据地累积指数平均值,该区土壤总体无污染,据单样值,Hg、Cu污染最突出,其他6元素污染较轻;（3）生态风险方面,Hg、Cd是主要生态风险元素,As、Cu次之。高生态风险区为铜井镇南东部、界湖镇西北金场附近以及县城西部主城区3个片区;（4）人体健康风险方面,重金属对成人不具有非致癌风险和致癌风险,极个别地区对儿童具有非致癌风险和致癌风险,Cr、As是主要非致癌风险元素,As致癌风险最大。【结论】 沂南县东部土壤质量总体较好,铜井镇南东部、界湖镇西北金场附近以及县城西部主城区3个片区为高生态风险区,Hg、Cr、As为主要生态健康风险元素。     

Impact of polluted canal water on adjacent soil and groundwater systems

Received, 12 May 1999 · Accepted, 2 August 1999     

内江市双桥乡土壤重金属含量及风险评价

以四川省内江市双桥乡为研究区域,调查分析各类土壤中重金属（Cu、Pb、Zn、Cd、Cr、As、Hg、Ni）含量情况。采用单因子污染指数、内梅罗综合污染指数和富集因子评价方法,对土壤重金属污染状况进行评价。研究结果表明,该地区Cd、Cr、Cu、Ni、Pb、Zn元素平均含量高于成都经济区、四川省、中国土壤背景值,有一定程度的Cd、Cr、Cu、Ni、Pb、Zn富集,Hg元素有个别样点含量偏高,并且单因子重金属的污染程度依次为：Cd〉Ni〉Zn〉Cu〉Cr〉Pb〉As〉Hg,Cd在绝大部份区域存在轻微污染,由内梅罗污染指数和富集因子评价得出区域综合污染程度为轻度。     

安徽省宣城市南部地区土壤重金属元素地球化学特征

利用1∶25万土地质量地球化学调查数据分析和研究了安徽省宣城市南部地区土壤中As、Cd、Cr、Cu、Hg、Ni、Pb、Zn 8种重金属元素的地球化学特征以及重金属异常来源。调查发现地质背景是土壤元素含量的主控因素,调查区表、深层土壤重金属元素含量空间分布特征与地质背景、沉积环境表现出显著的空间一致性,重金属高含量成土母岩(荷塘组、皮园村组、蓝田组等地层)是土壤重金属元素高异常的主要影响因素,此外矿山开采、大气干湿沉降也是土壤重金属高异常的影响因素之一,土壤中Pb、Hg、Cd、Cr元素具有大气干湿沉降的输入来源。调查区土壤重金属污染风险主要影响指标为Cd,土壤Cd超过农用地土壤污染风险管制值的样品比例为2.56%,形态分析结果显示土壤Cd以离子交换态为主,结合农作物调查发现在土壤Cd高异常区存在一定的生态风险。