ICP-OES同时测定土壤中多种重金属可给态的研究

研究了以HNO3-HCl为提取剂、电感耦合等离子发射光谱法（ICP-OES）同时测定土壤中重金属As、Pb、Cr、Cu、Zn、Cd、Ni共7种元素的可给态的方法。实验结果表明,土壤中重金属可给态经HNO3-HCl提取后完全分解,采用内标法可以提高测定的准确度和精密度,该方法加标回收率为90.9%～106.3%,精密度〈3%,具有较好的准确度和精密度,是一种快速、高效的分析方法。     

有机螯合剂对城市生活垃圾焚烧飞灰中重金属的稳定化试验研究

选取乙二胺四乙酸二钠(EDTA)和亚硫基二乙酸(TDGA)两种有机稳定剂药剂,研究其对焚烧飞灰重金属的稳定化效果。实验表明,焚烧飞灰浸取液中重金属浓度依次为:Zn (124. 2mg/L) Pb (27. 98mg/L) Cu(15. 29mg/L) Cd (7. 68mg/L) TCr (1. 16mg/L),重金属Pb、Cd、Cu超出标准;在用EDTA和TDGA处理的稳定化样品浸出液中Pb、Cd、Cu、TCr的浓度随着有机螯合剂投加量的增加而减小,并且TDGA的处理效果优于EDTA;在TDGA投加量相同,且浸取剂p H在3到9的范围内时,随着p H的升高,Pb、Zn、Cu、TCr的浸出浓度逐渐减小,其中p H升高对Cd的浸出浓度影响较小;若有机螯合剂溶液与飞灰搅拌均匀,液固比的增加对螯合反应没有产生影响。     

6种芽苗菜微量元素的测定与比较

采用微波消解样品、电感耦合等离子发射发光法测定了红豆、绿豆、黄豆、黑豆、青豆和豌豆6种芽苗菜中的Mg、Ca、Fe、Zn、Mn、Cu、Se、Cr、As、Pb、B、Cd 12种微量元素的含量.该方法的加标回收率为93.24％-108.09％,RSD值小于3％.结果表明,6种芽苗菜中含有多种微量元素,其中Mg、Ca相对含量较高,Fe、Zn、Mn、Cu、Se、Cr含量较小,As、Se和Cd未能检测出.实验结果为芽苗菜进一步合理开发提供科学依据.     

攀枝花市攀钢工业区土壤重金属污染特征及评价

本文对攀枝花市攀钢工业区土壤中五种重金属元素（Cu、Pb、Zn、Cr、Cd）的空间的分布特征、形态分布特征进行了研究，并应用污染负荷指数法对各重金属的污染程度进行了评价。研究发现，Cu、Pb、Zn、Cr的最大值与最小值分别相差2．98、3．4、5．2、2．7倍，cd的最大值与最小值甚至相差15．7倍。重金属元素相关性特征可分为Cd—Pb—Zn和Cu—Cr两组。形态分布特征表现在Cu、Zn、Pb、Cr主要以稳定的残渣态存在，Cd主要以可利用性最强的可交换态和碳酸盐结合态存在。污染较严重的是攀钢机关、攀钢原料场。     

ASD-ICP-MS联合快速测定《土壤环境质量标准》中的金属元素简

采用HNO3-HCl-HF-HClO4体系在全自动消解仪消解土壤样品,以50.0μg/L的Rh作内标,用电感耦合等离子体-质谱仪同时测定《土壤环境质量标准》的7种元素Cd、 As、Cu、 Pb、 Cr、 Zn、 Ni。结果表明,土壤标样的测定值与标准值吻合,各元素对应的检出限和相对标准偏差分别为： Cd：0.002 mg/kg和3.6%, As：0.05 mg/kg和5.5%, Cu：0.10 mg/kg和2.9%, Pb：0.18 mg/kg和4.7%, Cr：0.25 mg/kg和2.2%, Zn：0.40 mg/kg和3.4%, Ni：0.20 mg/kg和3.8%。该方法简便快捷,灵敏度高,重现性好。     

南京市PM_(2.5)中重金属含量分布及溶出规律研究

自2017年1～10月,采集南京市PM_(2.5)样品共计42批次,分析了Cu、Zn等9种重金属的含量分布及其溶出规律。结果表明,PM_(2.5)质量浓度呈现明显季节特征,冬季高,夏季低,年均值为41μg/m~3,与国家二级标准比超标17%。南京市PM_(2.5)中重金属总量高低顺序为Fe Zn Pb Mn Cu Cr As Ni Cd,其中As超出推荐限值19%。在模拟酸雨提取PM_(2.5)中重金属时,淋溶液pH是决定释放率的最主要因素,pH越低,释放率越高。用pH 5. 6的模拟酸雨淋溶液提取南京市PM_(2.5)样品,Cd、Zn、Mn的释放率超过60%,而Fe、Cr、Pb的释放率低于30%。     

柴窝堡湖表层底泥重金属污染评价

研究了乌鲁木齐市柴窝堡湖表层底泥的重金属含量,并采用Hakanson潜在生态危害指数法对底泥中的重金属潜在生态风险进行评价。结果表明:底泥中Cu、Zn、Pb、Cd含量均超出乌鲁木齐市土壤背景值。除湖心区外,Cd在5个监测区域中的潜在生态危害均为中等;其它重金属在5个采样点的潜在生态危害均为轻微。各重金属间的相关性分析表明,Zn与Cu,Pb与Cd、Cu呈显著正相关,说明这4种元素污染源可能相同。柴窝堡湖表层底泥受到Cu、Zn、Pb、Cd污染,需采取相应措施防止重金属由底泥进入水相。     

ASD-ICP-MS联合快速测定《土壤环境质量标准》中的金属元素

采用HNO3-HCl-HF-HClO4体系在全自动消解仪消解土壤样品,以50.0μg/L的Rh作内标,用电感耦合等离子体-质谱仪同时测定《土壤环境质量标准》的7种元素Cd、As、Cu、Pb、Cr、Zn、Ni。结果表明,土壤标样的测定值与标准值吻合,各元素对应的检出限和相对标准偏差分别为:Cd:0.002 mg/kg和3.6%,As:0.05 mg/kg和5.5%,Cu:0.10 mg/kg和2.9%,Pb:0.18 mg/kg和4.7%,Cr:0.25 mg/kg和2.2%,Zn:0.40 mg/kg和3.4%,Ni:0.20 mg/kg和3.8%。该方法简便快捷,灵敏度高,重现性好。     

氢化物发生原子荧光法测定钻井废水中的铅

目前测定铅的分析方法主要有分光光度法、阳极溶出伏安法、示波极谱法、原子吸收法等。针对比色法灵敏度低,试剂不稳定;电化学法干扰严重;而原子吸收法,线性范围窄,样品用量大等问题,江苏油田采用氢化物发生原子荧光法测定钻井废水中的铅。样品经HNO3-HClO4消解,3％～4％KBH4还原,以0.8％～1.5％的HCl为介质,加入10％K3Fe(CN)6和2％H2C2O4基体改进剂,用原子荧光法连续测定钻井废水中的铅。铅的检测限为0.61ng/mL,回收率为87.4％～146％,变异系数＜4.2％。该方法操作简单,灵敏度高。     

四川省马边磷矿区水环境中典型重金属污染分析

马边磷矿区磷矿资源丰富,区内磷矿开采企业较多。在开采的过程中难免会对当地的河水造成一定的影响。为了进一步了解马边磷矿区的环境影响问题,本文通过对磷矿区采集的水体样品和同一地点的水系沉积物样品进行分析测试,共检测了Cd、As、Cu、Cr、Pb、Zn六种重金属元素的含量,采用潜在生态危害指数法对沉积物中的重金属污染程度进行了综合评价。结果如下:马边磷矿区河水中的重金属元素的浓度较低,6种重金属元素含量均低于国家标准(GB3838-2002)。水系沉积物中的重金属元素含量较高,其中:Cd、Pb、Zn分别为2. 06mg/kg、182. 39mg/kg、479. 13 mg/kg。与四川省土壤元素背景值相比:Cd元素超标25. 7倍,Pb元素超标5. 9倍,Zn元素超标5. 5倍,其余元素未超标。与马边地区1∶20万区域水系沉积物背景值相比:Cd元素超标3. 12倍,Pb元素超标3. 3倍,Zn元素超标2. 5倍,As元素超标1. 6倍,Cu、Cr元素含量在背景值以内。与“中国土壤元素背景值”相比:Cd元素超标29. 4倍,Pb元素超标7. 7倍,Zn元素超标7. 1倍。潜在生态危害指数法评价结果表明:Cd的生态危害指数最大,其次为Pb和As,其余Cu、Cr、Zn等元素属于轻微生态风险。     

不同酸消解方法在土壤重金属测定中的比较研究

分别用三种不同的酸消解方法进行土壤标准样品的前处理,用原子吸收分光光度法测定其中铜、铅、锌、镉、镍、锰、总铬元素的含量。结果表明,电热板/硝酸-过氧化氢-氢氟酸消解方法耗酸量少,消解时间短,适用于土壤中铜、铅、锌、镉、镍、锰元素的前处理,相对标准偏差为1.0%～5.0%;而使用电热板/硝酸-硫酸-氢氟酸方法针对土壤中总铬元素进行消解前处理,准确度更高,相对标准偏差为2.7%～5.1%。     

Fate of biosolids trace metals in a dryland wheat agroecosystem

Biosolids land application for beneficial reuse applies varying amounts of trace metals to soils. Measuring plant-available or total soil metals is typically performed to ensure environmental protection, but these techniques do not quantify which soil phases play important roles in terms of metal release or attenuation. This study assessed the distribution of Cd, Cr, Cu, Mo, Ni, Pb, and Zn associated with soluble/exchangeable, specifically adsorbed/carbonate-bound, amorphous Mn hydroxyoxide-bound, amorphous Fe hydroxyoxide-bound, organically complexed, and residual inorganic phases. Biosolids were applied every 2 yr from 1982 to 2002 (except in 1998) at rates of 0, 6.7, 13.4, 26.8, and 40.3 dry Mg biosolids ha(-)(1) to 3.6- by 17.1-m plots. In 2003, 0- to 20-cm and 20- to 60-cm soil depths were collected and subjected to 4 mol L(-1) HNO(3) digestion and sequential extraction. Trace metals were concentrated in the 0- to 20-cm depth, with no significant observable downward movement using 4 mol L(-1) HNO(3) or sequential extraction. The sequential extraction showed nearly all measurable Cd present in relatively mobile forms and Cr, Cu, Mo, Ni, Pb, and Zn present in more resistant phases. Biosolids application did not affect Cd or Cr fractionation but did increase relatively immobile Cu, Mo, and Zn phases and relatively mobile Cu, Ni, and Pb pools. The mobile phases have not contributed to significant downward metal movement. Long-term, repeated biosolids applications at rates considered several times greater than agronomic levels should not significantly contribute to downward metal transport and ground water contamination for soils under similar climatic conditions, agronomic practices, and histories.     

湘中某工业区农田重金属污染的初步研究

通过2年的定点调查,研究了湘中某工业区附近农田土壤、糙米中重金属含量状况;并对重金属在水稻植株中的含量分布,以及影响糙米中重金属含量的土壤因素进行了探讨。     

Sorption of hazardous metals from single and multi-element solutions by saltbush biomass in batch and continuous mode: interference of calcium and magnesium in batch mode

Batch studies were performed to determine the interference of calcium (Ca) and magnesium (Mg) on the sorption of Cu(II), Cd(II), Cr(III), Cr(VI), Pb(II), and Zn(II) [from CuSO(4), K(2)Cr(2)O(7), Pb(NO(3))(2), Cr(NO(3))(3), ZnCl(2), and Cd(NO(3))(2)] by saltbush (Atriplex canescens) biomass. The results demonstrated that Ca and Mg at concentrations of at least 20 times higher than the concentration of most of the target metals did not interfere with the metal binding. The data show that the batch binding capacity from a multimetal solution at pH 5.0 was (micromol/g) about 260 for Cr(III) and Pb, and about 117, 54, and 49 for Cu, Zn, and Cd, respectively. The use of 0.1M HCl allowed the recovery of 85-100% of the bound Cu, Cr(III), and Pb, and more than 37% of the bound Cd and Zn. The column binding capacity for Pb was about 49 micromol/g from both the single and multimetal solutions, while it was, respectively about 35 and 23 micromol/g for Cr(III). The binding capacity for Cu and Zn from the single and multimetal column experiments was 35 micromol/g and less than 10 micromol/g, respectively. The stripping data from the single column experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and Zn, 90% and 74% of the bound Pb and Cr(VI), respectively, and less than 25% of the bound Cd and Cr(III), while the stripping from the multimetal experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and about 74%, 54%, 43%, and 40% of the bound Pb, Zn, Cd, and Cr(III), respectively.     

Concentration and chemical speciation for the determination of Cu,Zn, Ni,Pb and Cd from refuse dump soils using the optimized BCR sequential extraction procedure

The optimized BCR sequential extraction procedure (proposed by the Standards, Measurements and Testing Programme (SM&T) of the European Union) was applied to seven topsoil samples from refuse dump sites for the determination of Cu, Zn, Ni, Pb and Cd. The metals were partitioned into four operationally defined chemical fractions: acid extractable, reducible, oxidizable and residual, and analysed using flame atomic absorption spectrophotometry, FAAS. The results were compared with total metal concentrations obtained using HNO₃, HClO₄ and HF digestion procedures. Results for total metal analysis ranged from - 15.55 to 43.45 for Cu, 37.15 to 222.35 for Zn, 5.15 to 12.10 for Ni, 10.30 to 93.05 for Pb and 0.35 to 3.75 for Cd in μgg⁻¹ dry weight. The results of the partitioning study showed that zinc prevailed in the more soluble fractions and was distributed between the acid-extractable (32.4%) and the reducible (40.3%) fractions, whereas Pb was distributed mainly in the reducible fraction. Copper and nickel were predominantly associated with the reducible and residual fractions - 53.4, 33.3 and 51.1, 24.1% respectively. The ranking of the four fractions for the partitioning of cadmium was: reducible > residual > oxidizable > acid extractable. The percentage recovery for all metals when comparing total metal concentration with the fractional sum of the optimized BCR procedure, were of the order: Zn(93%) > Pb(83%) > Cu(78) > Cd > (68%) > Ni(63%).     

Heavy metal release from contaminated soils: comparison of column leaching and batch extraction results

Heavy metals in soils may adversely affect environmental quality. In this study, we investigated the release of Zn, Cd, Pb, and Cu from four contaminated soils by column leaching and single and sequential batch extractions. Homogeneously packed soil columns were leached with 67 mL/g 10(-2) M CaCl2 to investigate the exchangeable metal pool and subsequently with 1400 mL/g 10(-2) M CaCl2 adjusted to pH 3 to study the potential of metal release in response to soil acidification. In two noncalcareous soils (pH 5.7 and 5.1), exchange by Ca resulted in pronounced release peaks for Zn and Cd that were coupled to the exchange of Mg by Ca, and 40 to 70% of total Zn and Cd contents were rapidly mobilized. These amounts compared well with exchangeable pools determined in single and sequential batch extractions. In two soils with near-neutral pH, the effluent concentrations of Zn and Cd were several orders of magnitude lower and no pronounced elution peaks were observed. This behavior was also observed for Cu and Pb in all four soils. When the soils were leached at pH 3, the column effluent patterns reflected the coupling of CaCO3 dissolution (if present) and other proton buffering reactions, proton-induced metal release, and metal-specific readsorption within the soil column. Varying the flow rate by a factor of five had only minor effects on the release patterns. Overall, Ca exchange and subsequent acidification to pH 3 removed between 65 and 90% of total Zn, Cd, Pb, and Cu from the four contaminated soils.     

湘江株洲段表层水重金属含量及存在形态分布研究

以国家Ⅲ类水质限值为标准,总体来讲,湘江株洲段河水中Cu、Pb、Zn和Cd的总量均不超标,Cd的污染较重。霞湾断面的污染最重,清水塘工业区铅锌冶炼和化工企业是其污染的主要来源。采用化学分析的方法,对湘江株洲段水体中的Cu、Pb、Zn和Cd进行了形态分析,Cu、Zn溶解态在各断面均大于50%;Pb、Cd的形态在不同的断面其所占比例不一样。监测了各水质参数,pH大都在7.5左右,Eh在200~300mv之间,为氧化的环境,COD大部分断面均在15~20mg/L以下。     

Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.