微波消解电感耦合等离子体质谱法测定土壤中稀土金属元素

建立了一种电感耦合等离子体质谱测定土壤中微量稀土金属的方法.分析了土壤标准样品中的微量稀土元素,结果与标准值一致.土壤实际样品分析也得到可靠结果.该方法样品采用微波溶样,灵敏度高,是一种比较可靠的微量稀土元素分析新方法.     

超声波萃取-GC/MS法测定土壤中多氯联苯

建立了超声波萃取、氟罗里硅土柱净化、气相色谱/质谱联用选择离子扫描模式测定土壤样品中多氯联苯Arochlor系列的方法.方法线性良好,灵敏度高,RSD为9.5%～12.2%,加标回收率为65.0%～105%,标准土壤样品的测定结果也符合要求.     

污染土壤重金属检测标准样品在能力验证工作中的应用研究

标准样品在能力验证工作中的使用越来越广泛,但是由于能力验证对样品验证结果评价方式的不同,环境基体标准样品在能力验证工作中的应用还需进一步研究。考察了一种新研制的重金属污染地区土壤标准样品在能力验证工作中的应用。结果表明,能力验证的指定值与标准样品的标准值一致,说明能力验证统计数据无显著偏离;标准样品的均匀性和稳定性引入的不确定度小于0. 3σ(σ为能力评定标准差),不会对参加实验室的能力评定产生影响;该次能力验证参加实验室的满意率约为80%,与测试背景土壤的满意率接近,说明实验室检测污染土壤中铅、镉、镍、铜、铬的水平和检测背景土壤的能力水平相当。     

加速溶剂萃取-高效液相色谱法测定土壤中的苯并[α]芘

采用加速溶剂萃取-高效液相色谱法测定土壤中的苯并[α]芘,优化了色谱条件和萃取池清洗试剂。结果表明,标准曲线线性关系良好,方法检出险为0.26μg/kg,标准样品的测定结果在真值范围内,实际土壤样品的测定回收率为63.4%~77.7%,该方法灵敏度、准确度高,精密度好,适用于环境土壤样品中苯并[α]芘的检测。     

铋磷钼蓝分光光度法测定土壤中磷含量

土壤中磷含量的分析是土壤环境监测的主要项目之一.建立了铋磷钼蓝分光光度法测定土壤中磷含量的新方法,与现有的《土壤全磷测定方法》(GB 9837-88)和土壤总磷快速检测仪方法进行了比较讨论.方法的检出限为5.0 mg/kg,对磷含量为475 mg/kg和292 mg/kg的标准土壤样品进行测定,结果与标准值吻合,其相对...     

固体进样-冷原子吸收法直接测定土壤中总汞

应用固体测汞仪,采用多标准土壤样品(n20)绘制校准曲线法和单一标准土壤样品绘制校准曲线法,分别对土壤中的汞进行测定。结果表明,两者的方法检出限分别为0.30、1.49 ng,平行样(n=6)的相对标准偏差分别为3.6%~4%、5.4%~9.0%,90 d内的重复性精密度为4.1%,对国家土壤标样进行测定,结果与标准值相符。表明与单一标准土壤样品绘制校准曲线法相比,多标准土壤样品绘制标准曲线法具有更好的精密度、更低的检出限,更强的适用性,并且由于校准曲线长期稳定性,有效缩短土壤中汞的检测周期。     

CRC-ICP-MS在重金属突发环境事件中的半定量方法研究

采用非反应性的He碰撞模式和动能歧视与ICP-MS的联用技术,建立了一套在重金属环境突发事件中的半定量检测方法.通过对三江口表层水样加标回收及ESS-2标准土壤样品的半定量分析,结果显示,该方法能够有效消除各种来源和各种活性的多原子离子干扰,实现多种重金属元素的一次性快速测定,水样的回收率85.5%～09%,标准土壤样品的回收率84%～107%.该方法已成功应用于两次突发环境事件中,为快速处理提供了科学依据.     

典型地区农用地污染调查及风险管控标准探讨

针对《土壤污染风险管控标准——农用地土壤污染风险管控标准》(GB 15618—2018),提出以土壤中全量浓度筛选值和管控值作为衡量农用地土壤污染风险管控的标准,对湖南省部分稻田农用地土壤及点对点稻米样品中镉、铅、砷、汞的总量和有效态浓度及稻米中含量进行监测,根据重金属总量浓度分为低风险、中风险、高风险3组。结果显示:(1)土壤及稻米中镉含量基本为随着风险级别的升高而增加,铅、砷在土壤和稻米中含量无规律性结果,汞监测结果均为未检出。(2)低风险组稻米镉超标率为12. 0%,高风险组稻米镉达标率为33. 3%,表明利用总量浓度对农用地土壤潜在风险进行分组存在一定的局限性。(3)依据4种重金属在土壤中总量及稻米(早稻)中含量情况,对风险级别进行调整并综合判断:有58个样品为低风险组,占样品总数的68. 2%,超标率为零;有15个样品为中风险组,占样品总数的17. 7%,超标率为80. 0%;有12个样品为高风险组,占样品总数的14. 1%,超标率为100. 0%。调整后评价结果与上述标准的划分目标更接近,能够提高上述标准的准确性和实用性。     

土壤中镉元素测定精密度评价标准研究

以来自全国31个省份的共31种类型993个实际土壤样品为主要研究对象,经全国67个实验室分析测试,统计分析土壤中镉(Cd)元素测定精密度控制结果,同时将其与现行标准与规范进行比对分析。结果表明,推荐的精密度控制评价标准为:样品ω(Cd)0. 4 mg/kg时,实际样品明码样或标准样品测试实验室内相对偏差(RD)≤30%、实验室间相对标准偏差RD’≤35%,实际样品盲样测试RD≤35%、RD’≤40%;样品ω(Cd)≥0. 4 mg/kg时,实际样品明码样或标准样品测试RD≤25%、RD’≤30%,实际样品盲样测试RD≤30%、RD’≤35%。此外,土壤类型也会影响精密度控制结果。     

微库仑法和离子色谱法测定土壤中可吸附有机卤素

采用振荡吸附处理土壤样品,用微库仑法和离子色谱法分别测定土壤中的可吸附有机卤素(AOX)。通过优化样品前处理条件以提高AOX的提取效率,上述两种方法检出限分别为15.3 mg/kg和16.3 mg/kg, 4-氯苯酚作为标准物质的加标回收率分别为92.2%～95.0%和77.7%～80.2%。两种方法测定实际土壤样品中AOX,6次测定结果的RSD为5.4%～19.2%。GSS系列标准土壤试验结果表明,振荡吸附处理样品,用微库仑法和离子色谱法在测定样品中AOX时测定结果区别不大,土壤中AOX含量与卤素含量无直接关系。     

Bioaccumulation of Trace Elements in a Wild Grass Three Years After the Aznalcóllar Mine Spill (South Spain)

In this paper, we surveyed the concentration of nine trace elements (As, Cd, Cu, Fe, Mn, Ni, Pb, Tl and Zn) in bermudagrass (Cynodon dactylon) 3 years after the mine spill in Aznalcóllar (south Spain). The results were compared with those that had been obtained for the same species in a previous study, 18 months after the accident. Three types of soil condition were determined: i) unaffected soils (UN, control); ii) cleaned up and amended soils (A, amended); and (iii) non-amended soils, inaccessible to the clean-up and remediation operations (NA, non-amended). The trace element concentrations in the plants were lower than those reported in the first sampling for both washed (plant tissues) and unwashed plants (as consumed by herbivores). Apart from Cd, trace elements concentrations (plant tissues) were similar in the A and the UN soils. In the NA soils, the Cd, Fe, Mn, Zn and Pb levels in unwashed plants were excessive for animal consumption. This wild grass seems to be suitable as a soil stabilizer for spill affected soils and as a biomonitor for soil pollution by some trace elements (As, Cu and Zn); however, its potential for phytoextraction is negligible.     

Trace metal (Cd,Cu, Pb,Zn) fractionation in urban-industrial soils of Ust-Kamenogorsk (Oskemen), Kazakhstan—implications for the assessment of environmental quality

Ust-Kamenogorsk is one of the largest cities and industrial centers in Kazakhstan. Non-ferrous metallurgy (Zn–Pb smelter) has acted as a predominating industrial branch in the city since late 1940s. The industrial plants are situated directly adjacent to the residential area of the city which creates grievous ecotoxicological hazard. In the present paper, we aimed at assessing the trace metal pollution of top soils in Ust-Kamenogorsk and its potential threats to the local population. The top soils were sampled at 10 sites throughout the city center. We determined the physical and chemical properties of soils as well as the contents of Cd, Cu, Pb, and Zn. In addition, the soil samples were subjected to a five-step sequential extraction to ascertain the fractionation of trace metals. On this basis, we calculated the geoaccumulation index (I_geo) and pollution load index (PLI) and assessed bioavailability of the elements. From our data, it emerged that the soils displayed a strong polymetallic pollution. PLI was as high as 33.4. Throughout the city, the trace metal contents exceeded the geochemical background and allowable values for residential, recreational, and institutional areas. The I_geo obtained were 3.7–6.5 for Cd, 1.5–4.7 for Cu, 2.8–5.7 for Pb, and 2.6–4.6 for Zn. The soils in Ust-Kamenogorsk displayed extremely high contamination with Cd, moderate to strong contamination with Pb and Zn, and low to moderate contamination with Cu. Cd and Pb were found to be the most bioavailable elements. The mobility of trace metals in the soils changed in the order Cd > Pb > Zn > Cu.     

Biogeochemical assessment of the urban area in Moscow

The biogeochemical and ecological assessment of the industrial city territory including urban soils and trees was carried out. Chemical (macroelement and microelement) composition of the city soils, morphological and biochemical properties of the linden leaves, possible impact of de-icing salts on soil and tree state, the correlation between the content of trace elements, and the S-containing plant compounds (phytochelatins) were included in the assessment. It was found that concentrations of trace elements in the soils near road with intensive traffic are changed from the soils, located at a distance of 40–50 m from the road. They have higher concentrations of As, Fe, Mn, Se, and Sr and lower concentration of Zn. The linden leaves from the roadside were characterized by the increase in As, Cu, Fe, Zn, and Cr and sharp decrease in the Mn and Sr concentrations. The analysis of soil water extracts showed a slight decrease of pH and low content of Ca, Mg, K, and Na for the distant sites. The phytochelatin test of linden leaves was weakly effective as well as asymmetry degree study of leaf lamina. The main differences were observed in the damage symptoms of leaves (chlorosis and necrosis) and the content of pigments (chlorophyll and carotenoids). The biochemical and ecological assessment of soils and trees showed relatively satisfactory ecological state of the investigated area in Moscow. The data obtained shows the weak local impact of the application of de-icing salts and automobile emissions.     

Trace metals content in soils along the state road 51 (northeastern Poland)

The aim of the study was to determine concentrations of some trace elements (lead, cadmium, chromium, and nickel) in soils along State Road 51 leading from Olsztyn to Olsztynek, northeastern Poland. The traffic flow had a significant effect on the content of heavy metals in soils lying along the road. Further away from the road, and under a lower traffic flow intensity, the amounts of contaminants originating from the motor traffic decreased. There was a pine forest growing by the road near Olsztyn, which served as a buffer zone for all the analyzed heavy metals. At all the sampling locations, the content of chromium was approximately the same as its natural concentration. The statistical analysis demonstrated that there was a strong negative correlation between the concentrations of nickel, lead, chromium, and cadmium in soils and the distance from the road. The biggest differences in the content of an individual element were determined for lead and the smallest ones—for cadmium. Emissions of trace elements depended on the differences in the traffic flow intensity, number, type, and speed of vehicles and on the atmospheric conditions as well as the distribution of buildings.     

大气痕量有机硫化物的光电离色谱法测定及硫酸铵在湿浸土壤中释放有机硫化物的研究

采用国产光电离色谱仪(GC-PID)对有机硫化物:乙基硫醇,二甲基硫,二甲基二硫进行了分离分析,其最小检知量在亚微克/升级,并对北京郊区的某些天然源环境样品进行了有机硫化物浓度的测定,实验数据证实,在鸡场,猪场,水稻田与塑料蔬菜大棚等环境大气中含有机硫化物。研究了硫酸铵作为氮肥加入到水浸土壤中后,由于缺氧而生成有机硫化物的现象,观察了其对有机硫化物的释放规律及硫酸铵与葡萄糖分别作为硫源与碳源对有机硫化物生成的影响,实验结果认为:硫酸铵在五种不同类型的水浸土壤中(环境温度25℃),均可解离释放出有机硫化物,随其在土壤中加入量的增多,释放气中的有机硫浓度增加,二甲基硫的释放量最大。     

Baseline concentrations of trace elements in residential soils from Southeastern Missouri

Anthropogenic sources of pollution can significantly contribute to elevated concentrations of toxic elements in soils. A preliminary survey of trace elements content and their availability in residential soils from New Madrid County, Missouri was undertaken. Mean elemental concentrations (mg kg⁻¹, dry wt) of sixty two soil samples were: As 6.6, Be 0.8, Cd 1.6, Co 9.7, Cr 24.5, Cu 18.1, Fe 9951, Mn 298, Ni 15.6, Pb 48.8, V 42.1, Zn 95.5 and Hg 0.05. The US EPA preliminary remediation goals (PRGs) was only exceeded by As (7 % of samples) and V (8% of samples). The Missouri average background values were exceeded by Pb (69%), Zn (31%), Cu (27%), As (23%), Be (19%), Co (18%), Ni (16%), V (8%) and Mn (2%). Crustal enrichments (EF_c) for As (97), Cr (6), Cu (10), Pb (121), V (7), and Hg (17) were highest for North Lilbourn soils. Fractionation experiment revealed that Fe (54–79%) was in the residual phase while Zn (70–90%), Mn (88–92%), As (59–81%) and Pb (63–79%) were potentially available in soils. Factor loadings of the element concentrations on principal components 1, 2 and 3 accounted for over 81% variance of the data set. The factor loadings suggested that apart from natural contributions of trace elements to the soils, human activities possibly accounted for other inputs in soils.     

Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS)

Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied.     

Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments

Several leaching tests were applied and compared to study metal remobilisation on various unpolluted and contaminated soils and on several contaminated sediments. The trace elements considered were Cd, Cr, Cu, Ni, Pb and Zn, and leaching tests consisted of the application of reagents with contrasting characteristics and strengths in order to assess the information provided. An extraction with aqua regia permitted the estimation of the pseudo-total metal content in the sample. Mild extractants such as H2O, CaCl2 and NaNO3 showed low and similar leaching capacities. Acid (CH3COOH) and complexing (EDTA) agents were more effective in remobilising trace metals from soils and sediments. Cd and Zn showed similar extraction characteristics under both extractant solutions, whereas Cu and Pb were more sensitive to complexation, and Ni and Cr to acidification processes. Sequential chemical extractions provided additional information on the association of the trace elements with the different soil and sediment phases. Cd and Zn showed the highest mobility, Pb was associated to reducible solid phases, Cu and Ni to oxidisable phases, and Cr remained mostly in the residual fraction. The results obtained in this paper provided valuable information for choosing a leaching test, which is an instrument of environmental analysis for the estimation of trace metal mobility.     

A proposed methodology to determine accuracy of location and extent of geographically isolated wetlands

The disposal of industrial and sewage water is a problem of increasing importance throughout the world. In India, and most of the developing countries untreated sewage and industrial wastes are discharged on land or into the running water streams which is used for irrigating crops. These wastes often contain high amount of trace elements which may accumulate in soils in excessive quantities on long term use and enter the food chain through absorption by the plants. Among the trace metals, Cd has received the greater attention because of its easy absorption and accumulation in plants and animals to levels toxic for their health. The objective of this study conducted in three industrially different cities viz., Ludhiana, Jalandhar and Malerkotla was to monitor the extent of Cd accumulation in soils and plants receiving untreated sewage water. Plant and soil samples were collected from sewage and tubewell irrigated areas. Soil samples were analysed for texture, pH, EC, organic carbon (OC), CaCO(3), bioavailable DTPA-Cd and plant samples were analysed for total Cd. In sewage irrigated soils, the mean values of pH were lower but organic carbon and electrical conductivity were generally higher both in surface and sub-surface layers of all the three cities as compared to tubewell irrigated soils. The mean DTPA- extractable Cd in sewage irrigated soil was 6.3- and 4.36-fold in Ludhiana, 3.38- and 1.71-fold in Jalandhar and 3.35- and 6.67-fold in Malerkotla in 0-15 and 15-30 cm soil depth, respectively, compared with the values in tubewell irrigated soils. The accumulation of DTPA-Cd in sewage irrigated soils was restricted to 30 cm depth after which the values were generally close to values in tubewell irrigated soils. Soil pH, OC, CaCO(3), clay and silt collectively accounted for 37.1%, 65.1% and 53.9% DTPA-extractable bioavailable Cd in soils of Ludhiana, Jalandhar and Malerkotla, respectively. Lower R(2) values in Ludhiana suggest that factors other than the ones mentioned may be affecting Cd availability. At all sites plants receiving sewage irrigation had elevated levels of Cd as compared to the plants receiving tubewell irrigation. The mean Cd content of sewage irrigated plants irrespective of the city was 5.96 microg g(-1) dry matter as compared to 0.98 microg g(-1) dry matter in tubewell irrigated plants. The results suggest that the intake of Cd obtained from consumption of crops grown on sewage irrigated soils would be much higher than the tolerable limits set by WHO and may, therefore, prove potentially toxic leading to various health ailments to humans and animals.     

土壤背景值数据差异的来源分析及土壤类型对背景值的影响

本文阐述了在我国共８６０多个土壤样品、４１种土类中的４８种元素背景值调查研究中，元素含量差异的来源并估计了各部分来源的差异所占比例；同时采用单因素方差分析法，研究了土壤类型对４８种元素背景值的影响。结果表明，土壤背景值数据的伯差主要来源于样品本身固有的差异；常量元素的采样偏差大于分析测试过程产生的偏差；而微量元素的分析测试偏差大于采样偏差。