福建龙海市土壤与稻米铅地球化学特征分析

中国南方红壤区铅的分布特征、运移规律及生物效应尚不明确。本文以福建龙海市土壤和稻米为研究对象,系统分析了土壤铅的分布特征、形态组成、生物富集能力及影响机理,总结了铅在母岩-土壤-稻米迁移过程的富集分配规律。结果表明,龙海市中部区域表层土壤的铅含量高,其余区域较低,92.5%样点值在10~90 mg/kg,对应p H为4.0~7.5,强酸性和碱性土壤铅含量略低;稻米铅(0.018~0.398 mg/kg)超标率仅4.1%,对土壤铅的富集能力较弱(富集系数0.23%±0.16%),所以研究区土壤铅超标时稻米不一定超标。影响土壤铅的主要因素是成土母岩和土壤类型,不同成土母岩区的土壤铅含量规律为:第四纪海积物第四纪残坡积物花岗岩和酸性火山岩佛昙组基性玄武岩,不同土壤类型的铅含量规律为:潮土滨海盐土水稻土红壤赤红壤滨海风沙土。土壤铅有效态(离子交换态、水溶态)仅占铅全量的4.95%,强有机态和残渣态等其余形态合计占94.99%,说明土壤铅主要以稳定态存在,难于被植物吸收,进一步为合理解释"土壤铅超标而稻米不超标"这一现象提供了调查依据。研究还表明,稻米铅与表层土壤铅之间无明显相关性,保持土壤p H值在弱酸性至弱碱性范围可降低土壤铅活性。     

福建铁观音茶园生态地球化学特征

东南沿海是铅等重金属的地球化学高背景区。该地区广泛分布酸性红壤,酸雨沉降、不适当施肥导致土壤酸化以及由此引发土壤重金属生态风险令人关注。以福建省铁观音主产区为研究区,采集了79个茶园的表层和亚表层土壤样、茶叶样品,测定了重金属元素以及土壤常量元素和理化指标。研究表明,福建铁观音茶园土壤中Hg、Pb、Se、Zn高含量主要由地质背景所引起,土壤常量组分、有机质、酸碱度等理化条件对土壤元素含量有一定的影响;铁观音茶树老叶中As、Cd、Cr、Hg、Se、Pb、F等非植物营养元素含量明显高于嫩叶,显示这些元素随植物生长逐渐累积的特征,而嫩叶中植物生长必需的营养元素Cu、(Ni)、Zn则高于老叶,反映出微量营养元素在茶叶生长部位相对富集的特征;多数情况下土壤与茶叶间元素含量相关性差,说明茶树对土壤元素的吸收累积受到多种复杂因素的影响。研究表明茶叶与土壤Pb、Cr具有显著正相关性,为建立铅污染土壤生态效应预测评价模型提供了基础依据。     

贵州省正安县茶园土壤细菌群落的敏感性分析

本研究主要对正安县某两处茶园的土壤和茶树样品检测,探究影响茶叶元素含量的原因。利用16S rRNA基因高通量测序技术,解析茶园土壤细菌群落结构,结合土壤理化性质探究影响茶园土壤细菌群落的主要环境因子。研究结果如下:1SO42-是影响茶园土壤细菌群落的主要因素。茶园土壤细菌群落结构与SO42-含量的冗余分析表明,SO42-对茶园土壤细菌群落组成具有显著影响(p＜005)。2茶叶内重金属含量受细菌类群影响。茶树嫩叶更易受土壤细菌影响,假单胞菌属、热酸菌属、Subgroup_2、楸子岛杆菌属(Chujaibacter)和芽孢杆菌属等对嫩叶重金属含量影响显著。为茶叶品质检测提供新的评判依据,为通过SO42-调整茶园土壤细菌群落结构,降低茶叶内重金属元素含量提供新的研究思路。     

西湖茶园茶叶铅污染铅同位素示踪

通过对西湖茶园的植物和土壤样品进行一系列的调查,以着力寻找茶叶的铅污染源。利用铅同位素技术对西湖茶园的土壤、茶叶和城区的燃煤、大气气溶胶、汽车尾气进行铅同位素示踪研究。研究表明,茶园土壤铅物质的可溶相具同源性和残查态偏于多源性。清洗后的茶叶铅含量显著降低,但其同位素组成不发生明显改变,显示出茶叶中的铅与叶面空气沉降物中的铅同源。不同介质铅同位素对比值平均值呈现表土、大气(气溶胶)、煤的w(²⁰⁶Pb)/w(²⁰⁷Pb)与茶叶趋于相近,汽油低之;表土、大气(气溶胶)、汽油的w(²⁰⁸Pb)/〔w(²⁰⁶Pb)+w(²⁰⁷Pb)〕与茶叶趋于相近,煤略高之。不同区域茶叶铅物质具同源性,与种植的农业地质背景无关。在煤燃烧、气化过程中,Pb进入大气,通过大气沉降或被茶树吸收或附着在茶叶叶面;汽车尾气的排放是茶树铅污染的重要原因之一。     

陕西紫阳地区茶园土壤氟形态测定及影响茶叶氟含量主要因素

氟在人体生长发育和骨骼代谢中起着重要作用,近年来通过饮茶摄入氟与人体健康的关系受到较大关注。本文以大巴山区紫阳县茶园土壤为研究对象,采集64组茶园土壤和对应茶叶样品,测定土壤理化性质、土壤氟形态、茶叶氟含量,通过多元回归分析建立了影响大巴山区茶叶氟含量的Freundlich模型,并检验了模型的预测精度。结果显示：(1)研究区茶园表层土壤氟含量范围为487.37～1120.78mg/kg,平均值为730.63mg/kg;研究区茶叶氟含量为31.23～112.49mg/kg,平均值为57.58mg/kg,所有样品均未超过农业标准(NY659—2003)限值;(2)研究区茶园土壤氟的形态分布为：残渣态>水溶态>有机态>铁锰结合态>可交换态,水溶态氟含量范围为5.27～23.15mg/kg,平均值为9.72mg/kg,远高于中国地氟病发生区水溶态氟的平均含量2.5mg/kg,说明研究区存在一定生态风险。土壤水溶态氟与茶叶氟含量有显著相关性(n=64,r=0.82,p<0.01),其余形态与茶叶氟含量无显著相关性;(3)以水溶态氟、CEC、交换性铝、有机质、pH五个...     

杭州市土壤铅污染的铅同位素示踪研究

根据杭州市40个土壤全铅和38个可溶相铅的统计分析,土壤中全铅平均含量为49.6×10^-6,可溶相铅平均为21.4×10^-6,城区表土的全铅高达76.1×10^-6,显著高于全国土壤平均值。分析结果还显示,从农村→远郊→近郊→公路旁,土壤可溶相铅含量逐渐增加,且土壤的可溶相铅含量与深度具明显的负相关关系。表明杭州市土壤受到了不同程度的铅污染,污染程度由农村→远郊→近郊→公路旁→城区有明显的增高趋势。通过对茶园土壤中可溶相铅、残渣态铅及城区表土全铅的同位素组成对比分析发现,从土壤残渣态(代表土壤背景)→土壤可溶相→城区表层土壤全铅²⁰⁶Pb/²⁰⁷Pb比值有明显的降低。²⁰⁸Pb/(²⁰⁶Pb+²⁰⁷Pb)也有类似的变化趋势。将土壤与杭州市的汽车尾气、大气等环境样品进行对比发现,随着土壤受污染程度的增加,铅同位素组成逐渐向汽车尾气铅漂移,表明汽车尾气排放的铅为其主要污染源。     

土壤中铅的可溶态与地表植物铅含量线性相关性研究

土壤中铅的可溶态根据常用提取剂主要分为:弱酸可溶态、络合可溶态和盐可溶态。在研究土壤中铅的植物有效态过程中,常常采用混合提取剂来分析铅对植物有效性的相关可溶态。本文通过采用单一提取剂,计算土壤中铅的单一提取可溶态与地表植物中铅含量的线性相关系数,研究铅的弱酸可溶态、络合可溶态和盐可溶态对于地表植物有效态的线性相关性,确认铅环境影响评价过程中主要相关的形态。从实验的结果看,土壤中铅的总量、弱酸可溶态、络合可溶态和盐可溶态含量都与地表植物中铅的含量没有形成极显著的相关性。土壤中铅的弱酸可溶态与土壤表面生长植物(主要是禾草类植物的叶)中铅含量具有一定的线性相关性。而这种线性相关性受土壤的p H和土壤类型的影响而有所变化。     

南方某工业区周边土壤和蔬菜中铅的健康风险评估

在南方某城市工业区周边采集了蔬菜样品100个、土壤样品145个,分析了土壤和蔬菜中铅的含量水平,对其健康风险进行了评估;并通过计算富集系数筛选出抗铅污染能力较强的蔬菜品种。研究区土壤中铅累积明显,共有135个土壤样品中的铅含量超过了二级土壤环境质量标准。蔬菜样品中铅含量范围为1.41～303.10mg·kg-1,均超过食品中污染物限量标准,超标率达到100%。其中,叶类蔬菜的铅含量明显高于根茎类和瓜果类蔬菜;瓜果类蔬菜的铅富集系数最低,抗污染能力最强,而根茎类和叶类蔬菜对人群健康存在严重的健康风险。     

河北中南部平原土壤重金属元素存在形态及生物有效性分析

本文以河北省中南部平原农田表层土壤为研究对象,对表层土壤中7种重金属元素的形态含量进行了统计和分析,对重金属元素的生物有效性进行了评价,并运用相关分析法,对影响重金属元素生物有效性的因素进行了研究。结果表明,研究区表层土壤7种重金属元素的有效态含量以Cd最高,达36.83%,潜在生态危害性较大;其次为Pb,达13.37%,其中碳酸盐结合态达到12.38%,由于土壤呈中性或偏碱性,Pb元素的迁移能力较弱,其潜在危害性较小;Cu、Hg、Cr、As、Zn重金属元素含量均以稳定态的含量存在,之和均在90%以上,表明其潜在危害性较小;研究区土壤重金属元素的活性系数和迁移系数大小顺序为:CdPbHgCuZnAsCr和CdHgAsCuPbZnCr,其中Cd的活性系数和迁移系数平均值分别达到0.330和0.160,展现出较强的生物活性、不稳定性和迁移能力,其他重金属元素在土壤中活性系数(Pb除外)和迁移系数均较小,生物活性较弱,在土壤中稳定存在,由土壤中向植物中的迁移能力弱;研究区不同的重金属的生物有效性与其影响因素的关系不尽相同,其主要因素是土壤重金属元素全量,其次为p H、TOC、CEC、粘粒含量等,二者关系复杂。     

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。     

Synvolcanic mixing of ore lead and the development of lead isotopic provinces in the Skellefte district,Sweden

Ore lead isotope ratios have been analysed in galenas and sulphosalts from nineteen massive sulphide deposits hosted by Svecofennian (1.9 Ga) supracrustals in the Skellefte ore district, northern Sweden. The ore lead data can be grouped on the basis of their geographical distribution. Most probably, this feature is reflecting a number of lead isotopic provinces which correspond to crustal blocks. The obtained ore lead data define linear trends in conventional Pb-Pb plots. The ore lead signatures are due to synvolcanic mixing processes as lead was leached from mafic and acid volcanic sources. The relationships inferred for initial ratios in source rocks at 1.89 Ga require a pre-Svecofennian crustal history. It is suggested that magmatic processes at c. 2.0 Ga involved recycling of Archean sedimentary material into the mantle and the formation of a crystalline, felsic basement. The metasomatized mantle and the basement melted at the time of Svecofennian magmatism (1.89 Ga) which created mafic and acid magma sources. Subsequently, basalts and rhyolites were extruded onto the sea floor. Ore was formed as hot solutions penetrated isotopically different levels of the volcanic pile.     

Present-day precipitation of lead and zinc from groundwaters

Small quantities of galena and sphalerite are currently precipitating 26m below the surface, at the Vinemount quarry, Ontario, Canada from sulfurous spring waters, issuing from carbonates of the Lockport Formation. At the spring orifices, these sulfides are present in both fracture coatings and an associated black sludge. These precipitates are overlain by a crust rich in native sulfur. The mineralogy of the precipitates, and the chemistry of waters taken from three consistent spring horizons, indicates that downward-moving meteoric groundwaters leach metals from the host rocks and precipitate galena and sphalerite on encountering H₂S-rich waters at the water table. While our observation of the transport and deposition of lead and zinc by shallow groundwaters lends support to intra-karstic models for the direct precipitation of galena and sphalerite, it also enables us to propose that many carbonate-hosted Pb-Zn deposits, of differing theories of origin, may have been enriched during periods of uplift.     

Determination of cadmium and lead in human milk

The objectives of this study were to determine cadmium and lead concentrations in the breast milk of healthy lactating women who were living in Zarrinshahr, an industrial area of Iran and to investigate the effect of mother’s age, parity and smoking habits in families living in the vicinity of areas contaminated with heavy metals. Cadmium and lead concentrations were determined by graphite furnace atomic absorption spectrometry in 44 milk samples from healthy lactating women collected on first to sixth postpartum week. Accuracy of the analysis was checked by various methods including the use of reference material. The mean ± standard deviation of cadmium and lead concentrations in human milk were 2.44 ± 1.47 μg/L (range 0.62–6.32 μg/L) and 10.39 ± 4.72 μg/L (range 3.18–24.67 μg/L), respectively. There was a positive correlation between the concentrations of lead in milk samples and mother’s age and parity (P < 0.05). Also the concentration of cadmium in breast milk significantly increased (P < 0.05) in mothers who were actively and/or passively exposed to smoking. The results of this study showed that lead and cadmium concentrations in milk samples from lactating women in Zarrinshahr were high. This can be a major public health hazard for the inhabitants living in this industrial region of Iran.     

Isotopic evolution of common lead

The isotopic composition of lead from galenas and feldspars of granitic rocks covering a time span of 3600 m.y. is reviewed. Hew data are combined with data from the literature, all ratios being normalized to a fixed value for the isotopic composition of lead in an inter-laboratory reference sample. Comparison of feldspar and galena results show that the isotopic composition of initial lead in granitic rocks may be identical to, or more radiogenic than, that in coeval stratiform (or ‘single stage’) ore deposits. The isotopic evolution of terrestrial lead over the past 3600 m.y. deduced from the stratiform ore data does not fit the closed system source. The data are best fitted to evolution models in which the value of μ (U²³⁸/Pb²⁰⁴ normalized to the present day) in the source has increased either over approximately the past 3.6 billion years or since the time of formation of the Earth. A limited number of high precision data for strontium likewise indicate open system isotopic evolution. In this system the Rb/Sr ratio appears to have decreased as a function of time. Physical models that explain the data are presented. Either mantle differentiation or crustal contamination processes could account for the change in μ in the source for the lead. The strontium data and some detailed studies of the isotopic composition of lead in oceanic volcanic rocks support mantle differentiation rather than crustal contamination. The exact nature of the mantle differentiation process cannot be specified, although empirical data favoring the existence of such a process are given. The best estimate of the age of the Earth, calculated with the data from 2750 and 3290 m.y.-old lead ores, is 4660 m.y.     

Contemporary lead concentration and stable lead isotope ratio distribution in forest moss across the Czech Republic

Lead concentrations and stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about ²⁰⁴Pb/²⁰⁶Pb = 0.0550, ²⁰⁶Pb/²⁰⁷Pb = 1.167, ²⁰⁶Pb/²⁰⁸Pb = 0.478 and ²⁰⁷Pb/²⁰⁸Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km²) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.     

Solid solution between lead fluorapatite and lead fluorvanadate apatite: mixing behavior,Raman feature and thermal expansivity

The solid solution between lead fluorapatite and lead fluorvanadate apatite, Pb₁₀[(PO₄)_6-x (VO₄) _x ]F₂ with x equal to 0, 1, 2, 3, 4, 5 and 6, was synthesized by solid-state reaction at 1 atm and 700°C for 72 h and characterized by scanning electronic microprobe, electronic microprobe analysis, micro-Raman spectroscopy, and powder X-ray diffraction. The volume-composition relationship at ambient temperature does not show significant deviation from the Vegard’s Law. The Raman spectrum data suggest that both P and V are identical on a C _s site and both end-members show no apparent factor-group effect. The Raman frequency shift of the symmetric stretching vibration is linearly dependent on the composition. High temperature X-ray diffraction data, up to 600°C, suggest that the thermal expansion coefficients α _a , α _c , and α _V also vary linearly with the compositions of the apatites.     

Stable lead isotopes reveal a natural source of high lead concentrations to gasoline-contaminated groundwater

Concentrations of total lead as high as 1,600 g/L were detected in gasoline-contaminated and uncontaminated groundwater at three gasoline-release sites in South Carolina. Total lead concentrations were highest in turbid groundwater samples from gasoline-contaminated and uncontaminated wells, whereas lower turbidity groundwater samples (collected using low-flow methods) had lower total lead concentrations. Dissolved lead concentrations in all wells sampled, however, were less than 15 g total lead/L, the current United States Environmental Protection Agency (US EPA) maximum contaminant level (MCL). Because many total lead concentrations exceeded the MCL, the source of lead to the groundwater system at two of the three sites was investigated using a stable lead isotope ratio approach. Plots of the stable isotope ratios of lead (Pb) in groundwater as ²⁰⁷Pb/²⁰⁶Pb versus ²⁰⁸Pb/²⁰⁶Pb, and ²⁰⁸Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb were similar to ratios characteristic of lead-based minerals in local rocks of the southeastern US, and were not similar to the stable lead isotopes ratios characteristic of distant lead ore deposits such as Broken Hill, Australia, used to produce tetraethyl lead in gasoline products prior to its phase-out and ban in the United States. Moreover, the isotopic composition of dissolved lead was equivalent to the isotopic composition of total lead in turbid samples collected from the same well, suggesting that the majority of the lead detected in the groundwater samples was associated with sediment particulates of indigenous aquifer material, rather than lead associated with spilled leaded gasoline. The results of this investigation indicate that (1) lead detected at some gasoline-release sites may be derived from the local aquifer material, rather than the gasoline release, and consequently may affect site-specific remediation goals; (2) non-low flow groundwater sampling methods, such as a disposable bailer, may result in turbid groundwater samples and high total lead concentrations, and; (3) stable lead isotopes can be used to clarify the source of lead detected above permissible levels in gasoline-contaminated groundwater systems.     

Quantitative determination of cerussite (lead carbonate) by X-ray powder diffraction and inferences for lead speciation and transport in stream sediments from a former lead mining area in Scotland

Most current investigations of sites contaminated with heavy metals (e.g. Pb, Zn, Cu) emphasise the importance of determining the amounts of physical and chemical forms of metals rather than just the total amounts present. Chemical extraction techniques used for this purpose are inevitably operationally defined. A more direct approach to the identification of crystalline forms can be made by mineralogical techniques such as X-ray powder diffraction (XRPD), but quantitative determination of a particular form is not often attempted. Recent advances in methods of analysis and sample preparation for XRPD mean that it is now a relatively simple matter to obtain quantitative XRPD data. Here, it is applied to the quantitative determination of the forms of Pb in different size-fractions of stream sediment samples from Leadhills/Wanlockhead, SW Scotland, an historic Pb mining area. Comparison of the XRPD analyses with determinations of Pb by atomic absorption spectrophotometry demonstrates that a large proportion of the Pb present in the stream sediments is in the form of cerussite (PbCO₃). Furthermore, the cerussite tends to be concentrated in the silt fraction and is even a minor component of the clay-size fraction. However, quantitative analysis of fractions <6 μm indicates that cerussite alone cannot account for all the Pb in this size range. Indirectly, this result suggests that Pb adsorbed to clay minerals, organic matter and/or amorphous Fe and Mn oxides may be proportionally more important for the <6 μm materials. Sediment in this size range, however, typically accounts for no more than 1% by weight of the total stream bed sediment samples collected in the study area. In relation to its size distribution, the mobility of Pb within the wider environment is most likely to occur principally through physical transport of fine particles.     

滇东南白牛厂多金属矿床铅同位素组成及铅来源新认识

白牛厂矿床位于滇东南锡多金属成矿带中部,是一个Ag、Pb、Zn、Sn等共生的多金属矿床,但成因争议较大.前人引用早期矿床矿石矿物铅同位素数据得出矿石铅主要来源于基底岩石淋滤,矿床经历了热水沉积+岩浆热液叠加两个成矿阶段的结论.本文采用最新铅同位素数据系统研究了白牛厂矿床的铅同位素组成,其中,白牛厂矿床矿石矿物的铅同位素组成206Pb/204Pb、207Pb/204Pb和208Pb/204Pb分别为17.264～18.537、14.843～15.862和38.481～39.424;薄竹山花岗岩长石铅同位素组成206Pb/204Pb、207Pb/204Pb和208Pb/204Pb分别为18.301～18.387、15.611～15.670和38.677～38.904;薄竹山岩体接触带型矿床(点)矿石矿物铅同位素组成206Pb/204Pb、207Pb/204Pb和208Pb/204Pb分别为18.302～18.417、15.603～15.692和38.596～38.868;区域地层及矿区地层钻孔样品铅同位素组成206Pb/204Pb、207Pb/204Pb和208Pb/204Pb分别为18.307～19.206、15.622～15.809和38.436～39.932.对比四者铅同位素组成特征,白牛厂矿床矿石矿物、薄竹山花岗岩长石、薄竹山岩体接触带型矿床(点)矿石矿物具有一致的铅同位素组成,与地层铅同位素组成相差甚远,表明白牛厂矿床铅主要来自岩浆作用,在侵入的过程中可能受到了地层的轻度混染.矿床地质特征及近期地球化学和年代学研究成果表明,白牛厂矿床的形成主要受岩浆作用影响,沉积成矿作用在白牛厂矿床很可能是不存在的.     

Geology and structural features of vein-type lead and zinc deposits

The geological and structural position and localization conditions of the vein-type Pb-Zn deposits of the Sadon (North Ossetia) and East Karamazar (North Tajikistan) ore districts are considered. The leading role of long-lived deep faults in the control of large deposits is emphasized. Examples of such deposits in different provinces are given. The study of fractures and faults at Pb-Zn deposits is important for understanding of the formation conditions of other hydrothermal deposits.