便携式XRF在污染地块土壤金属元素调查中的应用

研究了便携式X荧光光谱仪（PXRF）测定土壤中砷、铅、铬、铜、锌和镍的性能，评估其检出限、精密度和准确度，探索了土壤水分和粒径对测定结果的影响程度，并与常规实验室分析方法测定结果进行比对。结果表明，PXRF测定土壤中砷、铅、铬、铜、锌和镍的检出限为5~15mg/kg，标准物质测定结果的相对标准偏差（RSD）≤8.6%，相对误差在±15%以内。随着土壤水分含量的增加，各金属元素测定结果均呈下降趋势，而RSD有上升趋势。土壤粒径对测定结果的影响较小，随着土壤粒径减少，各金属元素测定结果的RSD略有下降趋势。PXRF可以简单、快速地测定多种重金属元素，适用于污染地块重金属元素的现场实时监测。     

偏振能量色散X-射线荧光光谱法测定土壤中Ni、Cu、Zn、Pb四种重金属元素

以土壤和水系沉积物标准物质为校准样品,采用粉末样品压片制样,建立了偏振能量色散X-射线荧光光谱仪测定土壤中Ni、Cu、Zn、Pb四种重金属元素的方法。该方法分别采用Ge,Zn,Zr等3个不同二次靶对被分析元素进行选择性激发和测定,利用经验系数和康普顿散射线作内标校正基体效应,优化了元素校准曲线方程,实验结果表明,土壤和水系沉积物标准物质准确度实验结果符合定值要求,方法精密度RSD在1.12%~6.09%之间(n=10),Ni、Cu、Zn、Pb四种重金属元素的检出限分别达到2.54、0.93、0.96、0.98 mg/kg。土壤样品测定值与原子吸收法测定结果一致,该方法准确度、精密度、检出限均能满足土壤检测的需要。     

便携式XRF土壤重金属检测仪在环境应急监测中的应用探讨

系统评估了便携式XRF重金属检测仪的精密度、准确度及测定影响因素,开展了该方法测定土壤中Cu、Zn、As、Pb、Cr与国标分析方法的系统比对。结果表明:上述5种元素的方法检出限为5.7 mg/kg~16.0 mg/kg,土壤标准样品测定6次结果的RSD为1.0%~4.7%,Zn、Pb和As测定结果的相对误差10%;与国标法相比,便携式XRF重金属检测仪测定Cu、Zn、As、Pb的准确度较好,测定Cr的准确度波动较大。将该方法用于应急污染事故监测,可迅速锁定污染物及污染区域,实现野外分析的预判。     

电感耦合等离子体发射光谱法与原子吸收光谱法测定土壤中重金属元素的比较

文章采用电感耦合等离子体光谱法测定土壤中As、Cd、Cu、Cr、Hg、Ni、Pb、Zn共8种重金属元素,与传统标准方法原子吸收光谱法进行了结果比对、并且通过加标回收率以及标准物质的测试进行验证,得出:电感耦合等离子体光谱法满足HJ/T166-2004《土壤环境监测技术规范》以及GB15618-2018《土壤环境质量农用地土壤污染风险管控标准》中对重金属检测的要求,并且该方法的检出限较低,满足土壤中重金属污染风险筛选值的要求;标准曲线测量范围宽,达到两个数量级,可满足各种含量土壤中重金属的测试;精密度均小于1%,重复性好,结果稳定可靠;线性拟合系数R=0.999～0.99999;与原子吸收法检测结果比对良好,加标回收率以及标准物质测试准确度高。该方法一次进样同时得到所需元素的结果,极大地提高检测工作效率,降低检测工作成本,适用于大批量检测土壤中重金属的含量。     

复杂污染源下采煤沉陷区土壤重金属分布及行为特征

采用数理统计学、克里金插值等方法研究安徽淮北采煤沉陷区土壤中Cu、Zn、Cd、Cr、Ni、Pb、As和Hg等元素空间分布及其行为特征.结果表明:土壤中Zn平均值是农用地土壤污染风险筛选值的1.1倍,其他元素未超过筛选值.Cu富集在工业园区南部,Zn、As富集在两河交汇处、工业园区南部,Cd、Pb和Hg富集在沉陷区西部,Cr、Ni富集在沉陷区东部、西部;土壤剖面上Cu最大值出现在80 cm处,Ni最大值在40 cm处,其他元素最大值均在20 cm处.土壤中元素迁移程度为Cu最高,Zn、Cr、Hg和As最低;土壤中Cd活化率较高,达到27.1％,易被植物吸收富集.     

石油化工业对周边土壤中金属元素的影响分析

在黄岛石油化工区周边采集土壤样品27个，测定土壤中As、Cd、Cr、Cu、Hg、Ni、Pb、Zn等元素，并运用统计分析、土壤质量综合指数法对测定结果做系统分析。结果表明，除As外，黄岛石油化工区周边土壤中Cd、Cu、Cr、Hg、Ni、Pb、Zn的测定均值均超过青岛市土壤背景值。Cd、Pb、Zn空间分布大体一致，测定值最高的地方均是离石油化工区最近的地方。Cr、Cu、Ni离石油化工区越远，测定值越低。而Hg则相反，离石油化工区越远测定值越高。黄岛石油化工区周边土壤不宜用作农用地，除1处不宜用作建设用地Ⅰ类外，其他均可作为建设用地Ⅰ类和Ⅱ类。     

煤矿周边土壤重金属影响评价及来源分析

在麟游县郭家河煤矿下风向500 m范围内布设10个土壤采样点,测定其表层土中Zn、Cr、Pb、Cu、Cd、Hg和As7种元素的质量比,利用土壤综合质量影响指数法和富集因子法评价该煤矿周边土壤重金属影响状况,并应用Spearman相关分析法和主成分分析法分析污染来源。结果表明:Cu、Pb、Zn和Hg 4种重金属的平均质量比均高于陕西省土壤(A层)背景值和麟游县土壤环境背景值;距矿区10 m~150 m范围内7种元素富集状况受人类活动的影响较大;矿区Cu、Zn、Pb、Cd、As和Hg元素均来自煤矿开采导致的"三废"污染及农药、化肥的使用,Cr主要受成土母质的控制。     

湖南省某冶炼厂周边农田土壤重金属污染及生态风险评价

利用野外采样与实验室分析相结合的方法,以湖南省某冶炼厂周边农田土壤(0~20 cm)为研究对象,监测了Cd、As、Pb、Cr、Cu、Zn、Hg等7种重金属的含量,并对重金属污染程度与潜在生态风险进行了评价。结果表明,7种重金属都存在不同程度的超标或污染,其中Cd、As、Pb等的污染较为严重。统计学分析结果表明,Pb、As、Hg、Zn、Cd等来源相同,可能主要都来自于人为污染,即冶炼作业造成的污染。7种重金属化学形态不尽相同:在重金属有效态中,Cd的水溶态和可提取态较高;Pb、Cu、Zn可还原态、可氧化态这两部分含量较高。而Hg、As、Cr的残渣态含量较高。风险评价代码评价结果表明,Cd的生态风险较高,4.5%的样点Cd为极高生态风险,52.8%的样点Cd为高生态风险,42.7%的样点Cd为中度生态风险;100%的样点Zn为中度生态风险;Cu有60.1%的样点属于低生态风险,39.9%的样点属于中度生态风险;As、Pb主要以低生态风险为主(所占比例分别为77.2%、80%);Hg主要以无生态风险为主(所占94.3%)。Hakanson潜在生态风险指数法计算的综合潜在生态风险指数(RI)的范围为46.4~1 627.5,表明研究区域农田土壤存在很高的生态风险。上述各项结果综合表明,研究区农田土壤受到了严重的重金属污染,由此引起的重金属生态风险应引起高度关注。     

典型涉污企业周边土壤重金属污染特征及潜在生态风险评价

分析和评价典型涉污企业周边土壤环境质量,对于加强企业用地环境风险管控,实施土壤重金属污染精准防控,进一步保障农产品质量安全具有重要意义。以18类典型涉污企业周边土壤为研究对象,对475家企业周边的2 017个监测样点进行土壤重金属Cd、As、Pb、Hg、Cr、Cu、Zn和Ni元素含量测定,并采用主成分分析法、Hakanson 潜在生态风险指数法进行分析及评价。结果表明:典型涉污企业周边土壤重金属污染以Cd、Pb和As元素为主,各元素含量超过土壤污染风险筛选值的样品比例为9.82%~31.0%,超过土壤污染风险管控值的样品比例为4.46%~13.1%,其次是Zn、Cu、Hg和Ni,Cr无明显污染;主要污染元素Cd、Pb、As、Zn和Cu来自相同污染源且主要分布在有色金属矿采选业(B9)、黑色金属冶炼和压延加工业(C31)、有色金属冶炼和压延加工业(C32)、生态保护和环境治理业(N77)等行业企业周边;黑色金属冶炼和压延加工业(C31)、有色金属矿采选业(B9)、有色金属冶炼和压延加工业(C32)等行业企业周边土壤重金属潜在生态风险等级较高,中等风险及以上比例分别为76.0%、53.0%和54.1%。可见,典型涉污企业周边土壤重金属存在一定程度的污染,尤其是有色金属矿采选业(B9)等采矿业以及黑色金属冶炼和压延加工(C31)等制造业等,污染程度高,潜在生态风险大,需要加强监测和管控。     

典型铝塑厂周边土壤重金属分布特征与健康风险评价

为探究铝塑园区周边土壤重金属污染情况,选取山东省某城市塑料开发区为研究区,按照分层采样方式获取到80个土壤样品,分别测定土壤中As、Cd、Hg、Cr、Cu、Ni、Pb、Zn含量,运用统计分析法探讨土壤重金属等的分布特征和来源,并利用健康风险评价模型确定了土壤重金属对周边居民的健康风险。结果表明:As、Cd、Hg、Cr、Cu、Ni、Pb和Zn均超出山东省土壤背景值,其中Cd、Hg、Cu和Pb分别超出背景值48. 15%、106. 90%、62. 04%和39. 96%,表明土壤中存在一定程度的重金属积累,在周边140～210 m处最为严重,且受人类活动影响强烈,与风向关系不大;土壤重金属垂直分布特征大致呈现随着深度的增加不断增加,在20 cm深度附近达到最高值,其后不断降低并趋于平稳,Cd、Hg、Cu、Pb和Zn变异幅度大,受到人为干扰较大,As、Cr和Ni主要受成土母质控制,属于自然来源,变动幅度较小;研究区内8种元素不存在非致癌风险,Cr、As、Ni和Cd产生的致癌风险处在可接受范围内,但存在的潜在致癌风险应引起足够的重视。     

环境污染事故中重金属优先快速监测方法研究

在国内外重金属监测技术的基础上对环境污染事故中重金属（铜、铅、锌、砷、汞、铬、镉）的两种主要快速监测方法进行了研究。研究结果表明：比色法可测试铜、铅、锌、镉、六价铬5种重金属，且精密度与准确度均较好；阳极溶出伏安法（ASV）可测试铜、铅、锌、镉、砷、汞6种重金属，但测定六价铬时偏差较大；除六价铬和铜外，阳极溶出伏安法的测试范围较比色法宽，且检出限较低；阳极溶出伏安法可同时测定镉、铅、铜3种金属，具有较好的适用性。     

Monitoring of total and bioavailable heavy metals concentration in agricultural soils

The aim of this paper is to evaluate total and bioavailable concentration of heavy metals in agricultural soils in order to estimate their distribution, to identify the possible correlations among toxic elements and the pollution sources, to distinguish the samples in relation to sampling site or to sampling depth, and to evaluate the available fraction providing information about the risky for plants. In particular, we reinvestigated total concentrations of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V, and Zn and available concentrations of As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, and Zn in soil from Apulia (Southern Italy). Analytical results showed that total concentrations, for all soils, are in the range permitted by regulations in force in Italy, but some soils evidence slight enrichment of Cd, Cr, Cu, Pb, and Zn. All the heavy metals in the available fraction were below the detection limits of the analytical techniques used except Cu, Ni, Pb, and Zn.     

某铀尾矿库周围农田土壤重金属污染潜在生态风险评价

为能够定量评价铀尾矿库周围农田土壤重金属污染程度及其潜在生态危害性,采用Hakanson潜在生态风险指数法对土壤中重金属进行综合污染评价。结果表明,铀尾矿库周围部分农田土壤中重金属Cd、Ni、As、Cu、Hg、Zn含量存在积累和超标情况,尤以Cd的污染最严重,Ni、As次之;Pb、Cr含量能够满足标准限值要求。潜在生态风险评价结果显示,铀尾矿库周围农田土壤重金属潜在生态风险较高,主要潜在生态风险因子为Cd,其次是Hg、As,Cr、Pb、Ni、Cu、Zn并不构成潜在生态风险。铀尾矿库周围农田土壤中较高水平的Cd在构成环境污染的同时,也构成了较严重的生态危害,应加强对重金属Cd、Hg的生态风险防治。     

Monitoring of labile metals in turbid coastal seawater using diffusive gradients in thin-films

Diffusive gradients in thin-films (DGT) have been investigated for in situ monitoring of labile metals in north Australian coastal seawater. Field and experimental data showed that DGT devices provided adequate detection limits, accuracy and precision for monitoring of near-pristine levels of labile Mn, Co, Cu, Cd and Pb when deployed for periods of 3 days. However, Zn could not be adequately determined due to high blank levels. The ratio of DGT-labile to 0.45 microm-filtered metal levels in natural seawater ranged from 0.44-0.63 for Cu but was close to unity for Co and Cd. Elevated levels of suspended particulate matter up to 57.3 mg l(-1) did not have an adverse effect on the performance of DGT.     

菏泽市不同类型村庄土壤主要无机元素的监测与评价

为揭示土壤主要无机元素积累成因,制定科学防控措施,以菏泽市养殖型、蔬菜型、粮食型、工业型4种类型村庄为研究对象,分析了11个典型村庄8种土壤主要无机元素含量、分布特征及污染风险。结果表明,土壤镉、汞、砷、铅、铬、铜、镍、锌的质量分数分别为0. 01～0. 53、0. 002～0. 145、5. 51～15. 20、17. 6～75. 8、14. 5～69. 9、13. 3～33. 8、18. 8～46. 9、41. 5～96. 4 mg/kg。蔬菜型村庄镉、汞、铅元素含量最高;粮食型村庄铬、铜、镍含量最高;养殖型村庄砷、锌元素含量最高;工业型村庄铬、铜、镍元素含量较高,其余元素的含量都较低。各主要无机元素平均值均未超过农用地土壤污染筛选值,但除汞外,均超过了黄河故道区域土壤环境背景值,尤以镉最显著。     

Heavy metal contamination in soil alongside mountain railway in Sichuan, China

Heavy metal concentration in soil was investigated at three sites with different topography (cut slope, flat and embankment) within the vicinity of Chengdu-Kunming railway in Sichuan, China. Surface soil was sampled at certain distances from the track at each site and was analyzed for Cu, Mn, Pb, Zn, Cd by atomic absorption spectrometry. Cu, Cd and Zn concentrations in some soil exceeded the thresholds for non-polluted soil following the soil quality standard set by the State Environmental Protection Agency of China. Compared to local background values, the highest enrichment factor values of Cu, Mn, Zn and Cd were 2.7, 3.4, 3.7 and 7.7, respectively, indicating a moderate or significant enrichment of these metals in soil closest to the railway. Pb showed little accumulation with the EF values generally nearer 1 at the chosen sites. Topography profile was found to influence metal levels and distribution in soil alongside railway. At the cut slope site, Mn, Zn, Cd showed the highest concentrations and the smallest dispersion distance of 2 m, while Cu showed further dispersion distance of 25 m due to a main Cu emission source, the head-over traction cable, being located higher than any other metal emission source (wheels and tracks). Heavy metal concentrations decreased conversely as compared to distance from the track, peak values occurring at locations closest to the tracks, whilst embankment site soil Cd concentrations peaked at distances of 25 m. Significant correlation was found amongst Mn, Cu, Zn and Cd, which indicates that these metals have the same anthropogenic origin there. Organic matter content had no significant correlation to the elements Mn, Cu and Zn, which implies relatively high mobility to those metals.     

Assessment of heavy metals in sediments from a typical catchment of the Yangtze River, China

An intensive investigation was conducted to study the accumulation, speciation, and distribution of various heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) in sediments from the Yangtze River catchment of Wuhan, China. The potential ecological risks posed by these heavy metals also were estimated. The median concentrations of most heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) were higher than the background values of soils in Wuhan and were beyond the threshold effect level (TEL), implying heavy metal contamination of the sediments. Carbonate-bound Cd and exchangeable Cd, both of which had high bioavailability, were 40.2% and 30.5% of the total for Cd, respectively, demonstrating that Cd poses a high ecological risk in the sediments. The coefficients of the relationship among Pb, Hg, and Cu were greater than 0.797 using correlation analysis, indicating the highly positive correlation among these three elements. Besides, total organic carbon content played an important role in determining the behaviors of heavy metals in sediments. Principal component analysis was used to study the distribution and potential origin of heavy metals. The result suggested three principal components controlling their variability in sediments, which accounted for 36.72% (factor 1: Hg, Cu, and Pb), 28.69% (factor 2: Cr, Zn, and Ni), and 19.45% (factor 3: As and Cd) of the total variance. Overall, 75% of the studied sediment samples afforded relatively low potential ecological risk despite the fact that generally higher concentrations of heavy metals relative to TEL were detected in the sediments.