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随着国家工业化和城市化的发展,农业、工业和交通运输业等人为活动导致重金属在土壤中有较高程度的积累[1−4],导致土壤质量降低。重金属在土壤中具有毒性强、隐蔽性强、生物降解性弱等特点,是环境污染防治的重点和难点[5],同时对食品安全和人类健康构成严重威胁[6−10]。重金属经食物链在生物体内富集[11],导致慢性铅中毒,表现为神经学缺陷、肾机能障碍和贫血,环境中高含量的铅(Pb)在儿童体内积累后会影响智力发育及注意力等[12]。土壤 Pb 来源有自然来源和外源输入。自然来源主要是成土母质,外源输入相对复杂,主要包括大气降尘、汽车尾气排放、燃油燃煤、含铅矿山的开采与冶炼等工业排放[13−14]。
针对污染现状了解污染物来源是防止污染的最根本措施,土壤重金属源解析包括对污染来源的定性分析以及污染源对土壤重金属贡献的定量计算[15−16]。同位素示踪法是源解析的一种有效方法[17−19],精准度和识别能力较高[20−22]。自然界中 Pb 同位素主要由有204Pb、206Pb、207Pb和208Pb等4种。环境样品形成时间的不同导致了 Pb 稳定同位素组成的显著差异[23],因此,利用 Pb 同位素组成特征能很好地区分自然源和外源输入。曾志刚等[24−25]研究表明:在大西洋洋中脊海底表层热液沉积物中,同一热液区的 Pb 同位素组成变化不大,但不同热液区之间有着明显的变化;刘子宁等[26]对珠江三角洲第四纪沉积物 Pb 同位素组成进行分析,结果表明:第四纪沉积物基本不受人为源影响,物质来源稳定;李锋[27]对中国北方沙尘源区风成沙 Pb 同位素分布特征的研究表明:塔克拉玛干沙漠可能是中国黄土、格陵兰冰芯粉尘和北太平洋深海沉积物主要有效源区,对整个亚洲地区有着显著影响。
诸多研究已阐明Pb 在全球范围内的污染分布及危害,但对其污染来源的研究尚未完善,基于 Pb 稳定同位素源解析能够对土壤中 Pb 污染物来源及污染程度进行定性定量分析[28−31]。在中国东部地区广泛分布着新生代玄武岩发育土壤[32−33],在自然来源和外源输入共同作用下,外源输入对土壤 Pb 的贡献尚未得到明确的结论,因此,制定合理的污染防治措施具有重要的理论意义和应用价值[34]。本研究以新嵊盆地为研究对象,分析不同剖面以及环境中潜在污染源的 Pb 同位素组成特征,定量计算外源输入对土壤中 Pb 的贡献率,进行风险评价,并利用 Pb 同位素指纹特征辨识沉积物中 Pb 污染来源,以期为中国东部土壤重金属污染防治提供理论依据。
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新嵊盆地位于中国东部浙江省绍兴市。浙江省地势自西南向东北方向倾斜,以丘陵和低山为主,属亚热带季风区,高温多雨,年平均气温为16.5 ℃,年平均降水量为1 500.0 mm。浙江省广泛分布着以玄武岩为主的火山岩,其中以绍兴市新嵊盆地玄武岩较为典型且分布面积较广。在少有土壤堆积和搬运,且远离交通干线的玄武岩集中分布区台地中央区域布设研究样点,以减少人为活动和侵蚀的影响。以新昌县上市场村(SSC剖面,29°16′27″N, 120°49′02″E),挂帘山村(GLS剖面,29°28′57″N,120°54′09″E)以及嵊州市浦桥村(PQ剖面,29°34′47″N,120°45′55″E)等3个采样点的剖面作为研究对象,所有剖面的母岩均为新鲜拉斑玄武岩,采集深度1 m以上,层次完整,土壤样品按发生层从下到上采集。
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土壤样品在通风无阳光直射处自然风干,挑出砾石并去除枯枝落叶、根系、虫卵等非土壤成分;对土壤样品进行研磨,分别过10、60、100和200目尼龙筛;用孟塞尔比色卡进行比色。土壤的基本理化性质按照常规分析方法测定,具体实验步骤见土壤调查实验室分析方法[35]。痕量元素用Finnigan Element Ⅱ型高分辨率电感耦合等离子质谱仪(HR-ICP-MS)测定,检测限低于0.5×10−9,相对标准偏差小于5%。分析在南京大学内生金属矿床成矿机制研究国家重点实验室完成。
Pb 同位素测定主要分为分解样品、分离纯化过程和质谱测定3个步骤。①对样品带进行预处理。将样品带放入盐酸中浸洗,再用高纯水冲洗至中性,烘干,然后将样品带点焊在插件上,置于高真空设备中,在1 800 ℃除气0.5 h。称取过200目筛的土样0.25 g至聚四氟乙烯坩埚,加入20 mL浓硝酸,在电热板上加热1 h,接着加入30 mL氢氟酸与1 mL高氯酸,蒸干至样品完全溶解,再加入5 mL 硝酸,转移到250 mL容量瓶中,定容后摇匀。②用高纯水溶解已制备好的锶试样,用微量注射器分3~4次,每次2~3 μL将试样溶解液分别滴加于处理好的样品带的中心区域,蒸干并红化样品带,将插件放入质谱计。③待质谱计的真空达到要求后,打开通往分析管道的隔离阀,给蒸发带灯丝加上电流,缓慢升温,当达到1 000~2 000 ℃时,寻找208Pb的电子流,并小心调节加到蒸发带上的电流,使离子流达到足够的强度并保持稳定,质谱分析采用多接受杯同时接收,数据取多次测定的平均值。 Pb 同位素测定在中国科学技术大学壳幔物质与环境重点实验室完成。实验仪器为高分辨率热电质谱仪(TIMS)。由美国国家标准与技术研究院(NIST981)测定的207Pb/206Pb和208Pb/206Pb值分别校准为0.914 7±0.008 4和2.168 3±0.009 9。
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迁移率是土壤中Pb的物质来源的重要指标。研究土壤元素的迁移特征不能直接用元素的绝对质量分数变化,需采用稳定元素作为参照,计算土壤样品中强活动性元素在土壤中的真实迁移或富集程度。铌(Nb)作为土壤中流动性最小的元素[36−37],将其作为计算公式中的指标元素综合估算土壤中 Pb 质量分数变化,探究不同深度 Pb 的迁移率(τPb,h)。计算公式如下:
$$ {\tau }_{\mathrm{P}\mathrm{b},h}=\left[\left(\frac{{C}_{\mathrm{P}\mathrm{b},h}}{{C}_{\mathrm{P}\mathrm{b},\mathrm{p}}}\right)\left/{\left(\frac{{C}_{\mathrm{N}\mathrm{b},h}}{{C}_{\mathrm{N}\mathrm{b},\mathrm{p}}}\right)} \right.\right]-1。 $$ (1) 式(1)中:CPb,h为土壤层 h 中元素Pb的质量分数,CPb,p为母岩中元素Pb的质量分数,CNb,h为土壤层 h 中元素Nb的质量分数,CNb,p为母岩中元素Nb的质量分数。
以估算人为源对土壤中 Pb 的贡献为目的,基于同位素质量平衡构建自然-人为两元模型[28]。计算公式如下:
$$ {f}_{\mathrm{人}\mathrm{为}\mathrm{源}}^{\mathrm{P}\mathrm{b}}=\frac{{R}_{\mathrm{P}\mathrm{b}}^{\mathrm{土}\mathrm{壤}}-{R}_{\mathrm{P}\mathrm{b}}^{\mathrm{自然}\mathrm{源}}}{{R}_{\mathrm{P}\mathrm{b}}^{\mathrm{人}\mathrm{为}\mathrm{源}}-{R}_{\mathrm{P}\mathrm{b}}^{\mathrm{自然}\mathrm{源}}} 。 $$ (2) 式(2)中$ {:f}_{\mathrm{人}\mathrm{为}\mathrm{源}}^{\mathrm{P}\mathrm{b}} $为人为源对土壤中 Pb 的贡献百分比,$ {R}_{\mathrm{P}\mathrm{b}}^{\mathrm{土}\mathrm{壤}} $、${R}_{\mathrm{P}\mathrm{b}}^{\mathrm{自然}\mathrm{源}}$和$ {R}_{\mathrm{P}\mathrm{b}}^{\mathrm{人}\mathrm{为}\mathrm{源}} $分别为土壤、自然源和人为源206Pb/207Pb值,自然源和人为源的206Pb/207Pb值分别为1.196 0和1.172 0[38−39]。
采用ArcGIS、Excel、Origin等软件进行相关分析、统计分析、数据处理和作图等。
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研究区剖面的基本理化性质见表1。土壤剖面自下而上,颜色由7.5YR5/6向7.5YR3/3过渡;土壤结构由块状逐渐变化为团粒结构;根系逐渐增加。研究区土壤样品大部分呈弱酸性,pH为5.59~6.65,且pH随剖面深度的增加而略有升高,最大值出现在PQ剖面的底土层,最低值出现在SSC剖面的表土层。土壤有机质为1.30~49.60 g·kg−1,SSC、GLS、PQ剖面的最大值分别为37.10、27.30、49.60 g·kg−1,最小值分别为4.20、1.30、6.30 g·kg−1,最大值出现在PQ剖面的表土层,最小值出现在GLS剖面的底土层,土壤有机质质量分数沿剖面自下而上呈现增加趋势。
表 1 土壤剖面描述与部分基础理化性质
Table 1. Soil profile description and some basic physical and chemical properties
剖面 地理位置 深度/cm 颜色 pH 有机质/(g·kg−1) 结构 根系 SSC 新昌县上市场村 0~10 7.5YR3/3 5.59 37.1 团粒状 大量 10~25 7.5YR3/4 5.79 28.5 弱块状 中量 25~60 7.5YR4/4 6.11 13.8 弱块状 少量 60~90 7.5YR4/4 6.18 4.2 块状 无 90~120 7.5YR5/6 6.33 5.8 块状 无 GLS 新昌县挂帘山村 0~15 7.5YR3/4 5.79 27.3 团粒状 大量 15~45 7.5YR4/4 6.42 4.9 弱块状 中量 45~75 7.5YR4/6 6.49 1.3 块状 少量 75~110 7.5YR5/6 6.35 5.6 块状 无 PQ 嵊州市浦桥村 0~10 7.5YR3/4 6.49 49.6 团粒状 大量 10~25 7.5YR4/4 6.28 20.2 弱块状 中量 25~65 7.5YR4/6 6.65 6.3 弱块状 少量 65~120 7.5YR5/6 6.52 9.2 块状 无 -
本研究剖面的元素 Nb 和 Pb 质量分数见表2,通过公式(1)计算 Pb 在土壤中的迁移率得到图1。当τPb,h>0时,表示 Pb 在土壤中相对于母岩的富集,当τPb,h<0时,表示 Pb 在土壤中相对于母岩的淋失。研究剖面自上而下,土壤中 Pb 的迁移率由正转负,整体呈逐渐下降的趋势,在底土层趋近于0,研究区表层土壤 Pb 质量分数的富集最高达到母岩的1.5倍以上。
表 2 土壤样品与人为源同位素比值及样品痕量元素质量分数
Table 2. Isotopic ratios of soil samples to anthropogenic sources and trace element contents of samples
剖面 深度/cm Nb/(mg·kg−1) Pb/(mg·kg−1) 208Pb/206Pb 206Pb/207Pb SSC 0~10 31.2±0.2 15.6±0.7 2.103 9±0.006 3 1.176 3±0.003 4 10~25 30.6±0.1 10.6±0.6 2.094 1±0.003 9 1.183 2±0.004 8 25~60 23.4±0.1 3.9±0.5 2.093 9±0.004 6 1.185 5±0.003 9 60~90 18.9±0.1 4.3±0.4 2.100 0±0.003 5 1.185 7±0.002 4 90~120 21.4±0.1 3.2±0.2 2.099 1±0.004 2 1.184 9±0.005 3 GLS 0~15 47.2±0.3 22.4±0.7 2.101 5±0.006 2 1.179 5±0.004 9 15~45 40.0±0.2 10.8±0.5 2.102 3±0.005 7 1.184 8±0.003 3 45~75 37.6±0.1 3.9±0.3 2.099 9±0.005 2 1.185 9±0.006 1 75~110 37.1±0.1 5.0±0.2 2.100 7±0.004 8 1.186 5±0.003 2 PQ 0~10 42.3±0.2 17.3±0.6 2.099 1±0.005 4 1.176 1±0.004 6 10~25 40.2±0.1 7.3±0.5 2.101 0±0.005 8 1.179 4±0.003 6 25~65 38.9±0.1 6.3±0.2 2.100 9±0.004 1 1.179 2±0.005 2 65~120 36.6±0.1 9.9±0.1 2.090 6±0.002 9 1.186 7±0.004 5 母岩(本研究) − 20.0±0.1 3.9±0.1 2.082 0±0.003 1 1.196 0±0.001 5 人为源 − − − 2.112 0±0.048 4 1.172 0±0.031 0 说明:−表示无此项。人为源数据来源于文献[38, 40−42]。 -
研究区土壤样品的206Pb/207Pb和208Pb/206Pb值见表2,206Pb/207Pb的变化范围为1.176 1~1.186 7。本研究母岩206Pb/207Pb均值为1.196 0。人为源206Pb/207Pb值为1.172 0。研究剖面自下而上206Pb/207Pb值均呈递减的趋势,表土层的低206Pb/207Pb值更接近人为源均值,随着剖面深度的不断增加,底土层更靠近自然背景。研究区土壤样品的208Pb/206Pb为2.090 6~2.103 9,且样品的208Pb/206Pb值变化范围在自然源和人为源这2个端元值之间(图2)。
Estimation of Pb provenance contribution in basalt-developed soils in Xinsheng Basin based on Pb isotope
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摘要:
目的 土壤铅(Pb)污染有着严重的生态和健康风险。探究Pb污染来源对防治土壤污染,保障土地资源健康可持续发展意义重大。 方法 以浙江省新嵊盆地为研究区域,采集人为活动较少的乡村地区土壤和母岩样品,测定研究区的痕量元素质量分数,分析Pb质量分数变化及在土壤中的迁移规律,利用Pb同位素示踪方法定性分析研究区的Pb污染来源,并且定量分析污染源对研究区的物源贡献。 结果 研究区土壤Pb质量分数在表土层出现明显富集,最高达到土壤背景值的1.5倍,并随剖面深度的递增而逐渐减小,表明近地表层的外源输入影响显著,且研究区域的Pb质量分数较高时,其206Pb/207Pb值相对较低。研究区土壤样品的206Pb/207Pb和208Pb/206Pb值变化范围分别是1.176 3~1.186 7和2.090 6~2.103 9,206Pb/207Pb值的变化范围越大说明人为活动对土壤Pb质量分数的影响越大。Pb同位素示踪表明:研究区母岩的206Pb/207Pb端元值为1.196 0,人为源的206Pb/207Pb端元值为1.172 0,燃煤是研究区 Pb 污染的主要人为源,人为源贡献率为38.8%~82.9%。 结论 低206Pb/207Pb值表明燃煤对研究区域 Pb 的输入。颗粒污染物通过源源不断的沉降过程进入土壤表层,因此,降低颗粒污染物排放量是减轻当地 Pb 污染的重要途径。图3表2参51 Abstract:Objective Soil lead (Pb) pollution has serious ecological and health risks. This study tries to explore the source of Pb pollution to prevent and control soil pollution and ensure the healthy and sustainable development of soil resources. Method Taking Xinsheng Basin in Zhejiang Province as the research object, soil and parent rock samples were collected from rural areas with less anthropogenic activities. The content of trace elements in the study area was measured, and the changes in Pb content and its migration patterns in soil were analyzed. Pb isotope tracer method was used to qualitatively analyze the Pb pollution sources in the study area, and quantitatively analyze the contribution of Pb to the pollution sources in the study area. Result The Pb content was significantly enriched in the topsoil layer, up to 1.5 times the soil background value, and gradually decreased with the increase of the profile depth, indicating a significant impact of the exogenous input near the surface layer. When the Pb content in the site was high, its 206Pb/207Pb value was relatively low. The variation ranges of 206Pb/207Pb and 208Pb/206Pb values in the soil samples were 1.176 3−1.186 7 and 2.090 6−2.103 9, respectively. The larger the variation range of 206Pb/207Pb value, the greater the impact of human activities on soil Pb content. Pb isotope tracers indicated that the 206Pb/207Pb end member value of the parent rock was 1.196 0, and the 206Pb/207Pb endmember value of anthropogenic source was 1.172 0. Coal burning was the main anthropogenic source of Pb pollution in the study area, with a contribution rate of 38.8%−82.9% from anthropogenic sources. Conclusion The low 206Pb/207Pb value indicates the input of Pb from coal burning to the study area, and particulate pollutants enter the soil surface through continuous deposition process. Therefore, reducing the emission of particulate pollutants is an important way to reduce local Pb pollution. [Ch, 3 fig. 2 tab. 51 ref.] -
Key words:
- lead /
- isotope /
- anthropogenic source /
- Xinsheng Basin
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表 1 土壤剖面描述与部分基础理化性质
Table 1. Soil profile description and some basic physical and chemical properties
剖面 地理位置 深度/cm 颜色 pH 有机质/(g·kg−1) 结构 根系 SSC 新昌县上市场村 0~10 7.5YR3/3 5.59 37.1 团粒状 大量 10~25 7.5YR3/4 5.79 28.5 弱块状 中量 25~60 7.5YR4/4 6.11 13.8 弱块状 少量 60~90 7.5YR4/4 6.18 4.2 块状 无 90~120 7.5YR5/6 6.33 5.8 块状 无 GLS 新昌县挂帘山村 0~15 7.5YR3/4 5.79 27.3 团粒状 大量 15~45 7.5YR4/4 6.42 4.9 弱块状 中量 45~75 7.5YR4/6 6.49 1.3 块状 少量 75~110 7.5YR5/6 6.35 5.6 块状 无 PQ 嵊州市浦桥村 0~10 7.5YR3/4 6.49 49.6 团粒状 大量 10~25 7.5YR4/4 6.28 20.2 弱块状 中量 25~65 7.5YR4/6 6.65 6.3 弱块状 少量 65~120 7.5YR5/6 6.52 9.2 块状 无 表 2 土壤样品与人为源同位素比值及样品痕量元素质量分数
Table 2. Isotopic ratios of soil samples to anthropogenic sources and trace element contents of samples
剖面 深度/cm Nb/(mg·kg−1) Pb/(mg·kg−1) 208Pb/206Pb 206Pb/207Pb SSC 0~10 31.2±0.2 15.6±0.7 2.103 9±0.006 3 1.176 3±0.003 4 10~25 30.6±0.1 10.6±0.6 2.094 1±0.003 9 1.183 2±0.004 8 25~60 23.4±0.1 3.9±0.5 2.093 9±0.004 6 1.185 5±0.003 9 60~90 18.9±0.1 4.3±0.4 2.100 0±0.003 5 1.185 7±0.002 4 90~120 21.4±0.1 3.2±0.2 2.099 1±0.004 2 1.184 9±0.005 3 GLS 0~15 47.2±0.3 22.4±0.7 2.101 5±0.006 2 1.179 5±0.004 9 15~45 40.0±0.2 10.8±0.5 2.102 3±0.005 7 1.184 8±0.003 3 45~75 37.6±0.1 3.9±0.3 2.099 9±0.005 2 1.185 9±0.006 1 75~110 37.1±0.1 5.0±0.2 2.100 7±0.004 8 1.186 5±0.003 2 PQ 0~10 42.3±0.2 17.3±0.6 2.099 1±0.005 4 1.176 1±0.004 6 10~25 40.2±0.1 7.3±0.5 2.101 0±0.005 8 1.179 4±0.003 6 25~65 38.9±0.1 6.3±0.2 2.100 9±0.004 1 1.179 2±0.005 2 65~120 36.6±0.1 9.9±0.1 2.090 6±0.002 9 1.186 7±0.004 5 母岩(本研究) − 20.0±0.1 3.9±0.1 2.082 0±0.003 1 1.196 0±0.001 5 人为源 − − − 2.112 0±0.048 4 1.172 0±0.031 0 说明:−表示无此项。人为源数据来源于文献[38, 40−42]。 -
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