固相萃取法测定气溶胶中~(210)Pb的可行性分析

采集大气气溶胶中的~(210)Pb,气溶胶滤膜样品经高温灰化后加入~(206)Pb作为~(210)Pb分析的稳定同位素载体,用强碱性阴离子交换树脂在盐酸体系下吸附铅,将洗脱出的铅以硫酸铅沉淀形式称重。放置6个~(210)Bi(T_(1/2)=5 d)的半衰期后,至~(210)Pb和~(210)Bi平衡,在低本底α/β计数器上测定其子体~(210)Bi的计数,计算得出原始样品中~(210)Pb的活度浓度。该方法已广泛应用于四川省内环境质量监测和铀矿冶污染源监测等项目。     

电感耦合等离子体质谱法测定海产品中铅及其同位素比值

采用微波消解,电感耦合等离子体质谱法测定海产品中铅含量及其同位素比。通过选择本底铅浓度低的硝酸降低背景值,选择合适内标以减少仪器波动带来的误差,使得该方法在0μg/L~100μg/L范围内线性良好,~(204)Pb、~(206)Pb、~(207)Pb和208Pb的方法检出限为0.041μg/L~0.180μg/L。用该方法测定有证标准物质,结果在标准值范围内,海产品样品6次测定结果的RSD为3.1%~8.6%,加标回收率为89.9%~96.3%。26种海产品中总铅质量比为0.018 mg/kg~2.32 mg/kg,铅同位素~(207)Pb/~(206)Pb值为0.783 55~0.881 61。     

铅锌冶炼厂周边土壤铅源的铅同位素示踪

以某铅锌冶炼厂周边土壤为研究对象,通过对其原料及周边土壤中铅含量的检测,结果显示：该冶炼厂周边土壤铅质量比在22.73mg/kg～126.51mg/kg之间,平均值为42.68mg/kg,是当地土壤铅背景值的1.85倍.采用铅质量比空间分布分析和同位素混合模型计算分析了冶炼厂周边土壤中铅的可能来源,分析表明：土壤铅质量比的空间分布及铅同位素比值与冶炼厂的焦化原料煤相近,焦化原料煤对周边土壤铅污染贡献最大.     

渤海大气气溶胶元素组成及物源分析

利用电感耦合等离子体-光发射光谱法(ICP-OES)分析了2000年夏季渤海大气气溶胶样品,给出了渤海气溶胶污染物浓度分布特点,结合气象资料和富集因子进行了元素物源分析.分析结果表明,辽东湾的污染程度高于其他海区,气溶胶中含量最高的元素是Zn(1638ng/m3),含量最低的是V(2ng/m3).渤海气溶胶中Pb、Zn、Cu和Ni等具有较高的富集因子.辽东湾Pb的富集因子达4000以上,Zn的富集因子普遍大于其他海区.Pb、Mn、Cu、V等含量的相对大小与同期北京的分析结果一致.综合分析表明,渤海大气严重受到陆地人为排放污染物的影响.     

大气乙醛碳同位素分析方法的研究

利用气相色谱/燃烧/同位素比值质谱(GC/C/IRMS)分析技术,采用NaHSO3与半胱胺衍生化方法,测定了气态乙醛在衍生化反应过程中的碳同位素效应,探讨了采用该方法测定大气乙醛碳同位素组成的可行性。试验测定了乙醛、衍生剂半胱胺及相应衍生物的碳同位素比值,结果表明,乙醛衍生物的δ13C测量值与理论值的偏差范围为0.11‰～0.35‰,在仪器精密度范围内(<0.50‰),即在衍生化过程中基本不会发生碳同位素分馏。采用该方法初步测定了大气中乙醛的碳同位素组成,实测数据显示,广州地化所和肇庆鼎湖山大气乙醛δ13C平均值分别为(-34.21±0.27)‰和(-31.23±0.16)‰,相同采样点的大气乙醛碳同位素组成基本不变,可见该方法可作为研究大气乙醛不同排放源的一种有效方法。     

石家庄市春季大气颗粒物的铅污染特征

为了解石家庄市2016年春季大气颗粒物的铅污染特征及来源,利用单颗粒气溶胶质谱仪(SPAMS),分析了大气中含铅颗粒的化学成分。结果表明: 研究期间大气环境中含铅颗粒数浓度共出现11次跳跃式升高,跳跃时间段内石家庄均处于轻度污染过程。从成分分析来看,含铅颗粒分为纯铅颗粒、Pb与K(Pb-K)、OC(Pb-OC)、Cl(Pb-Cl)、混合颗粒等八大类。观测结果表明:Pb-K颗粒最多,占到含铅颗粒的84.4%；其次为纯铅颗粒,占比为13.0%。与石家庄市污染源谱库比对进行来源解析,得到Pb-K颗粒主要来自生活垃圾焚烧源, 纯铅颗粒主要来自工业源。结合石家庄市大气污染源排放清单和后向气流轨迹分析,推测含铅颗粒可能来自市区西南方向某区县的生活垃圾焚烧企业。     

大气颗粒物中铅污染来源解析技术

近年来,我国大气颗粒物中铅的污染比较严重,其来源比较复杂.大气颗粒物中铅污染来源的解析比较成熟的主要有同位素丰度比、无机多元素分析、质子微探针技术等方法,而序列提取、化学形态分析等技术还处于探索阶段.     

ICP—MS法测定饮用水中的铅

采用ICP—MS法对饮用水中的铅进行了分析测定。并进行了载气流量的选择、定量离子质荷比的选择和内标的选择等实验．本实验铅的质荷比选用206，207和208三个加在一起计算。方法的检测限为0．5×10-3mg／L，精密度实验的变异系数为3．25％～7．63％。     

青岛市大气铅与其它污染物及气象因素的相关性分析

对青岛市大气中铅进行了调查 ,在监测时间里大气铅的小时浓度值范围为 0 .0 1～ 1 .67μg/ m3,日均值在 0 .0 6～0 .33μg/ m3之间。同期监测了总悬浮颗粒物、二氧化硫、氮氧化物和一氧化碳等污染物 ,并讨论其相关性 ,同时结合气象因素简单分析其对铅浓度的影响     

铅冶炼企业周边大气降尘中铅、镉、砷量及其对土壤的影响

通过在2012年5月-2013年4月1个周期年内，对修复基地和对照点每月大气降尘中铅、镉、砷沉降量的监测，结果表明：修复基地大气降尘中铅、镉、砷含量明显较对照点高，年总沉降量分别是对照点的17．6倍、16．3倍和14．1倍，表明铅冶炼企业对基地大气降尘中铅、镉、砷含量影响显著；大气降尘中铅、镉、砷沉降量受位置和时间影响较大，在相距不到100 m的测点间，沉降量相差1倍以上，冬季主导风明显、地面植被少、二次扬尘大，使处于铅冶炼企业下风向的基地降尘中铅、镉、砷沉降量较大。沉降量时空不均匀与土壤污染不均匀现状一致，也验证了铅冶炼企业是基地大气和土壤重金属污染的主要来源。以降尘缸模拟土壤进行测算，结果表明大气降尘中镉对土壤污染速度最快，风险最大。     

The potential of elemental and isotopic analysis of tree bark for discriminating sources of airborne lead contamination in the UK

Samples of tree bark, which accumulate airborne material, were collected from seven locations in the UK to provide an indication of the magnitude and source of lead pollution. Measurement of the Pb content and 206/207Pb stable isotope ratio by inductively coupled plasma mass spectrometry revealed significant differences between the sites. The concentration of Pb varied over almost four orders of magnitude from 7.2 to 9,600 micrograms g-1, the maximum values being found near a 'secondary' Pb smelter. The 206/207Pb isotope ratios varied from 1.108 +/- 0.002 to 1.169 +/- 0.001. The lowest Pb concentrations and highest isotope ratios were detected in bark samples from the Scilly Isles, reflecting the low-level of industry and road traffic. In contrast, samples obtained from a city centre (Sheffield) and near a motorway (M1) contained 25-46 micrograms g-1 Pb and recorded the lowest 206/207Pb ratios. Higher concentrations in the vicinity of a coal-fired power station recorded a 206/207Pb ratio of 1.14, suggesting a significant contribution from fly-ash. The relative contribution of lead from petrol (206/207Pb = 1.08) and other sources such as coal (206/207Pb = 1.18) were thus estimated using mass balance equations. Tree bark near the lead smelter recorded an intermediate 206/207Pb ratio of 1.13 reflecting the processing of material of mixed origin.     

Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios

This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the ²⁰³Tl/²⁰⁵Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios (²⁰⁷Pb/²⁰⁶Pb) found were 0.85073?±?0.0004~0.85373?±?0.0003 for the main stream, while they were 0.83736?±?0.0010 for the tributary and 0.84393?±?0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60 %. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.     

Roadside Rhododendron pulchrum leaves as bioindicators of heavy metal pollution in traffic areas of Okayama, Japan

The leaves of roadside Rhododendron pulchrum Sweet were examined as a bioindicator of traffic-related heavy metal pollution in Okayama. Total contents of heavy metals in roadside soil and the R. pulchrum leaves were determined. Results of correlation analyses showed significant correlations among Pb, Ni, and Zn contents of roadside soil and leaf samples. These results suggest that R. pulchrum is a useful bioindicator of heavy metal pollution in traffic areas. To identify traffic-related heavy metal pollution sources, traffic-related materials such as tires, asphalt pavement, and road paint were collected and analyzed. The results of analyses of our data show that Zn is emitted mainly from the abrasion of tires; Cr is emitted mainly from wear of the asphalt pavement. Furthermore, the respective lead isotope ratios in R. pulchrum leaves, soil, roadside dust, and traffic-related materials were measured using inductively coupled plasma mass spectrometry. The isotopic compositions of lead in R. pulchrum leaves were 207Pb/206Pb = 0.861-0.871 and 208Pb/206Pb = 2.093-2.127, which agrees well with ratios in automobile wheel balance weights, suggesting that lead-containing products associated with automobiles, such as wheel balance weights, contribute to traffic-related lead pollution.     

Suitability of selected bioindicators of atmospheric pollution in the industrialised region of Ostrava,Upper Silesia,Czech Republic

This study is a continuation of our preceding research identifying suitable environmental samples for the tracing of atmospheric pollution in industrial areas. Three additional types of environmental samples were used to characterise contamination sources in the industrial area of Ostrava city, Czech Republic. The region is known for its extensive metallurgical and mining activities. Fingerprinting of stable Pb isotopes was applied to distinguish individual sources of anthropogenic Pb. A wide range of ²⁰⁶Pb/²⁰⁷Pb ratios was observed in the investigated samples: ²⁰⁶Pb/²⁰⁷Pb = 1.168–1.198 in mosses; ²⁰⁶Pb/²⁰⁷Pb = 1.167–1.215 in soils and ²⁰⁶Pb/²⁰⁷Pb = 1.158–1.184 in tree cores. Black and brown coal combustion, as well as metallurgical activities, is the two main sources of pollution in the area. Fossil fuel burning in industry and households seems to be a stronger source of Pb emissions than from the metallurgical industry. Concentration analyses of tree rings showed that a significant increase in As concentrations occurred between 1999 and 2016 (from 0.38 mg kg^?1 to 13.8 mg kg^?1). This shift corresponds to the use of brown coal from Bílina, Czech Republic, with an increased As concentration. The burning of low-quality fuels in households remains a problem in the area, as small ground sources have a greater influence on the air quality than do industrial sources.     

Lead isotope ratios in lichen samples evaluated by ICP-ToF-MS to assess possible atmospheric pollution sources in Havana,Cuba

Epiphytic lichens, collected from 119 sampling sites grown over “Roistonea Royal Palm” trees, were used to assess the spatial distribution pattern of lead (Pb) and identify possible pollution sources in Havana (Cuba). Lead concentrations in lichens and topsoils were determined by flame atomic absorption spectrophotometry and inductively coupled plasma (ICP) atomic emission spectrometry, respectively, while Pb in crude oils and gasoline samples were measured by ICP-time of flight mass spectrometry (ICP-ToF-MS). Lead isotopic ratios measurements for lichens, soils, and crude oils were obtained by ICP-ToF-MS. We found that enrichment factors (EF) reflected a moderate contamination for 71% of the samples (EF > 10). The ²⁰⁶Pb/²⁰⁷Pb ratio values for lichens ranged from 1.17 to 1.20 and were a mixture of natural radiogenic and industrial activities (e.g., crude oils and fire plants). The low concentration of Pb found in gasoline (<7.0 μg L^?1) confirms the official statement that leaded gasoline is no longer used in Cuba.     

Origin of lead associated with different reactive phases in Scottish upland soils: an assessment made using sequential extraction and isotope analysis

Soil samples (0-25 cm) have been taken annually since 1991 from three protected plots set up at an upland location at Glensaugh in Aberdeenshire, Scotland. The soils were analysed using the original BCR sequential extraction procedure and the lead isotopic composition was determined in each of the fractions, as well as the unfractionated soil using thermal ionisation mass spectrometry (TIMS). The lead concentrations in all the soils, including those well away from the road, were much higher than typical background values indicating that the whole area has been subject to deposition of anthropogenic lead. The distribution of lead between the different fractions was similar for the two non-roadside soils with most lead present in the oxidizable fraction. Although most lead in the roadside soil was also present in the oxidizable fraction, a substantial proportion (about 10%) was in the easily soluble fraction suggesting that roadside lead could be more mobile than lead in the other soils. Good reproducibility was obtained for the isotope analyses in all the fractions. The ratios calculated for the bulk soil from the ratios in the individual fractions agreed very closely with those measured directly in the unfractionated soil thereby demonstrating both reproducibilty and accuracy. The lowest (206)Pb/(207)Pb ratios were found in the roadside soil consistent with the recent deposition of petrol lead. The (206)Pb/(207)Pb ratios in all fractions of the other soils fell into a narrow band and it was necessary to use (204)Pb ratios to differentiate between lead in the extractable fractions and lead in the residual component. It is probable that lead in the non-roadside soils was deposited a considerable time ago and is characterised by a relatively high (206)Pb/(207)Pb ratio. Use of the (204)Pb ratios showed that the residual components in each of the three soils were isotopically distinct.     

The changing nature of the 206Pb/207Pb isotopic ratio of lead in rainwater, atmospheric particulates, pine needles and leaded petrol in Scotland, 1982-1998

The inductively coupled plasma-mass spectrometry (ICP-MS)-determined 206Pb/207Pb ratio of 145 samples of rainwater collected at 25 locations around Scotland during December 1997 and January 1998 and at three longterm monitoring stations in the northeast, central belt and southeast of the country from November 1997 to December 1998 averaged 1.144+/-0.017 (1 s). This represents a significant increase from the mean value of 1.120+/-0.016 recorded for the long-term sites in 1989 1991, only partly attributable to a concomitant increase in the 206Pb/207Pb ratio of leaded petrol from 1.075+/-0.013 to 1.088+/-0.007. The rainwater 206Pb/207Pb data for the late 1990s also contrast markedly with the lower 206Pb/207Pb ratios found for pine needle and atmospheric particulate samples from Scotland (e.g. Glasgow: 1.085+/-0.012 in 1985-1986, 1.099+/-0.007 in 1991-1992), England and Western Europe in this study for the period 1982-1992 when emissions of lead to the atmosphere from petrol-engined vehicles in the UK were approximately 2-9 times higher. The observed change in the lead isotopic signature of rainwater predominantly reflects the impact of measures, such as the introduction and growing uptake of unleaded petrol, to reduce car exhaust emissions of lead to the atmosphere in the UK. Based on the rainwater data, source apportionment calculations suggest a general decline in the contribution of leaded petrol to atmospheric lead in Scotland from 53-61% in 1989-1991 to 32-45% in 1997-1998, with a corresponding decline in the urban environment from 84-86% to 48-58%.     

Chronological trends in trace metals recorded by a tree bark pocket in Yakushima Island, Japan

Bark included within the trunk of a 200-year-old Japanese cedar tree harvested in Yakushima Island, Japan, a World Natural Heritage Site located 150 km south of mainland Japan and 800 km east of Shanghai, China, was analysed for trace metals by ICP-MS providing a chronology of atmospheric pollution. The concentration of V, As and Pb in decadal sections of the bark pocket increased 30 to 50 fold from 1900-09 to 1960-69, indicating increased atmospheric deposition of these metals. The trend coincided with the establishment and expansion of heavy industries in Kyushu, Japan, resulting in locally high levels of air pollution. V, As and Pb subsequently declined, reflecting lower industrial emissions following air pollution control legislation from the late 1960's and decline in heavy industries. Ni, Cu and Zn showed a relatively small, 7 to 10 fold increase over time. Lead isotope ratios in the bark pockets shifted from about 0.84 to 0.86 for 207Pb/206Pb and from 2.04 to 2.10 for 208Pb/206Pb, showing that the origin of atmospheric lead changed over time from coal to more diverse sources.     

A 300 year history of lead contamination in northern French Alps reconstructed from distant lake sediment records

Lead concentrations and isotopic ratios were measured along two well-dated sediment cores from two distant lakes: Anterne (2100 m a.s.l.) and Le Bourget (270 m a.s.l.), submitted to low and high direct human impact and covering the last 250 and 600 years, respectively. The measurement of lead in old sediment samples (>3000 BP) permits, in using mixing-models, the determination of lead concentration, flux and isotopic composition of purely anthropogenic origin. We thus show that since ca. 1800 AD the regional increase in lead contamination was mostly driven by coal consumption ((206)Pb/(207)Pb approximately 1.17-1.19; (206)Pb/(204)Pb approximately 18.3-18.6), which peaks around 1915 AD. The increasing usage of leaded gasoline, introduced in the 1920s, was recorded in both lakes by increasing Pb concentrations and decreasing Pb isotope ratios. A peak around 1970 ((206)Pb/(207)Pb approximately 1.13-1.16; (206)Pb/(204)Pb approximately 17.6-18.0) corresponds to the worldwide recorded leaded gasoline maximum of consumption. The 1973 oil crisis is characterised by a drastic drop of lead fluxes in both lakes (from approximately 35 to <20 mg cm(-2) yr(-1)). In the late 1980s, environmental policies made the Lake Anterne flux drop to pre-1900 values (<10 mg cm(-2) yr(-1)) while Lake Le Bourget is always submitted to an important flux (approximately 25 mg cm(-2) yr(-1)). The good match of our distant records, together and with a previously established series in an ice core from Mont Blanc, provides confidence in the use of sediments as archives of lead contamination. The integration of the Mont Blanc ice core results from Rosman et al. with our data highlights, from 1990 onward, a decoupling in lead sources between the high elevation sites (Lake Anterne and Mont Blanc ice core), submitted to a mixture of long-distance and regional contamination and the low elevation site (Lake Le Bourget), where regional contamination is predominant.     

Lead in grass in the Scottish uplands: deposition or uptake?

If it is assumed that the Pb collected in grass samples is derived mainly from atmospheric deposition then grass samples can be used as a convenient and easily analysed monitor for Pb deposition, in particular to establish the isotopic composition of current deposition in remote locations. As some studies have demonstrated a strong correlation between soil and grass Pb concentrations, it was considered important to establish the proportion of soil Pb in the grasses used to monitor atmospheric deposition at upland locations in Scotland. Consideration of earlier studies provided evidence that very little, if any, Pb in grass was derived from soil. Lead isotope analysis, by thermal ionisation mass spectrometry, of grasses grown on soils spiked with enriched (207)Pb in the field situation allowed the relative contribution of atmospheric deposition and soil to the grass Pb to be calculated. In most cases, >80% of Pb in grass was derived from atmospheric deposition and in recent years this value was >90%. Recalculation of the (206)Pb/(207)Pb ratio in grass samples showed that there was very little error in the results, published previously, which were based on the assumption that all the Pb collected with grass was derived from the atmosphere. The trends established by measuring the (206)Pb/(207)Pb ratio in grasses were confirmed and remain valid.