Forms Distribution of Heavy Metals and Their Ecological Risk Evaluation in Soils of Ion Adsorption Type in the Rare Earth Mining Area of Southern Jiangxi, China
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摘要: 稀土矿的露天开采易造成土壤重金属污染等环境问题。已有研究表明赣南离子吸附型稀土矿区土壤存在以Cd、Pb为主的轻、中度重金属污染。常见环境质量评价以主要污染因子(如重金属总量)作为衡量污染程度的指标,仅能反映重金属的富集程度。为查明赣南稀土矿区土壤重金属的赋存状态、迁移能力以及生物有效性,本文在利用电感耦合等离子体质谱法(ICP-MS)测定土壤重金属各形态含量的基础上,采用地累积指数法、潜在生态危害指数法及RAC风险评价法对赣南稀土矿区土壤重金属的生态风险进行评价。结果表明:①研究区土壤重金属主要以残渣态存在,占总量的65.5%。②土壤样品中Cd、Pb含量平均值分别是江西省土壤背景值的1.72倍和2.14倍;流域内位于矿山下游河流沿岸农田土壤Cd的平均值、尾矿库附近农田Pb的平均值分别是土壤背景值的2.33倍和3.06倍,22.7%样品的Cd或Pb含量超过风险筛选值,其中可交换态所占比例仅次于残渣态,分别占总量的47.1%和13.5%。③地累积指数与潜在生态风险评价结果表明Cd、Pb累积程度及生态风险水平较高,Co、Ni、Cu、Zn较低;RAC风险评价结果显示Cd生态风险较高,Co、Zn、Pb生态风险中等,Cu、Ni生态风险低。④针对矿区农田土壤的三种评价方法各有侧重,其评价结果异中有同,均表明研究区土壤Cd具有较高的污染程度和迁移活性,生态风险较高。本研究结果将为识别稀土矿周边农田土壤的潜在环境风险,提出有效的防范、应急与减缓措施提供科学依据。Abstract: BACKGROUND: The open-pit mining of rare earth mines easily causes heavy metal pollution problems. Studies have shown that the soil of the rare earth mining area in southern Jiangxi has been polluted by heavy metals of Cd and Pb in low and moderate degrees. Environmental quality assessment usually uses pollution factors (total heavy metal content) as indicators of the degree of pollution, which can only reflect the degree of enrichment of heavy metals.
OBJECTIVES: To investigate the forms of heavy metals in the soil of the rare earth mining area in southern Jiangxi Province, migration ability and bioavailability.
METHODS: Based on the forms analysis of soil heavy metals measured by inductively coupled plasma-mass spectrometry (ICP-MS), the ecological risk of soil heavy metals in the rare earth mining area was evaluated using the geoaccumulation index method, potential ecological hazard index method and RAC risk assessment.
RESULTS: The heavy metals in the soil in the study area mainly existed in the residual form, accounting for 65.5% of the total. The average content of Cd and Pb in the soil samples was 1.72 times and 2.14 times the soil background value of Jiangxi Province, respectively. The average value of Cd in the soil in the farmland along the river downstream of the mine and the average value of Pb in the farmland near the tailing pond were 2.33 times and 3.06 times background value, respectively. The Cd or Pb content of the 22.7% samples exceeded the risk screening value. Among them, the exchangeable form of Cd and Pb accounted for 47.1% and 13.5% of the total amount, respectively, secondary to the residual form. Geoaccumulation index and potential ecological risk assessment results show that the accumulation degree and ecological risk level of Cd and Pb were higher, and Co, Ni, Cu, and Zn were lower. RAC risk assessment results show that Cd ecological risk was higher, whereas Co, Zn, and Pb was medium and Cu and Ni was low. Although the focal point and some results of the three evaluation methods were also different, the comprehensive conclusion showed that the soil Cd pollution and migration activities in the mining area were high, and the ecological risk was high.
CONCLUSIONS: The research results provide scientific basis for identifying the potential environmental risks of farmland soil in rare earth mining areas and propose effective prevention, emergency response and mitigation procedures. -
重晶石是重要的含钡矿物,主要用于油气钻井中泥浆的加重剂,也是制备含钡化工产品的重要矿物原料[1]。硫酸钡是评价重晶石质量的主要指标,含量范围在46%~96%之间。重晶石常与石英、方解石、白云石、菱铁矿、菱锰矿、天青石、萤石、硫化矿物(黄铁矿、方铅矿、闪锌矿、黄铜矿)及其氧化物伴生,一般含二氧化硅、钙、锶、铅等。目前重晶石中硫酸钡的主要测定方法有:硫酸钡重量法、铬酸钡容量法。硫酸钡重量法以称重反应生成的硫酸钡的方式测定硫酸钡量;铬酸钡容量法通过滴定铬酸根离子间接测定硫酸钡量;两种方法检测流程均繁琐、复杂,且容量法分析条件不易控制,铅、锶在两种方法中都会与钡共沉淀,导致硫酸钡的测定结果偏高,样品中含锶时需要用其他方法测定锶进行差减校正。应用电感耦合等离子体发射光谱法(ICP-OES)测定硫酸钡含量的方法已有报道[2],分析流程需要两次高温熔样,两次过滤,流程仍较复杂。采用熔融制样X射线荧光光谱法(XRF)测定地质样品中的组分较为快速、简便[3-9],该法用于测定钡含量已有文献报道[10-13],例如仵利萍等[10]和曾小平等[11]以熔融制样XRF法测定重晶石中的主次量元素,可以快速测定总钡量,样品中碳酸钡的钡量会计入硫酸钡量,测定方法中未除去碳酸钡,不能准确测定其中的硫酸钡量。因此,采用XRF法测定重晶石中的硫酸钡时,样品需要进行酸处理以除去碳酸钡、铅等干扰,但样品经酸处理后不同样品的剩余量不同,造成熔剂与样品的比例不确定,仍然不能准确测定硫酸钡的含量。
本文优化了样品前处理条件、XRF分析中熔片条件和仪器工作条件等因素,取一定量样品以10%的盐酸和10%的硝酸溶解过滤除去碳酸钡、硫酸钙及铜、铅、锌等有色金属元素,未溶解的样品在700℃下灼烧,灼烧后将样品量以氧化铝补充到初始取样量,以重晶石国家标准物质、岩石国家标准物质、高纯硫酸钡及人工混合的校准样品制作标准曲线,实现了XRF熔片法准确测定重晶石中的硫酸钡,对需要样品前处理XRF测定组分的分析方法提供了解决方案。
1. 实验部分
1.1 仪器及工作条件
Axios顺序扫描式波长色散X射线荧光光谱仪(荷兰PANalytical公司),陶瓷薄铍端窗(75 μm)超尖锐铑钯X射线管,SuperQ 4.0定量分析软件。
已有文献对XRF法测定钡的分析参数作了系统的研究[10-13],本实验根据钡元素的性质,选择低电压,高电流;粗准直器;无滤光片;背景点选择在长波侧。重晶石中钡及主要元素的测量条件见表 1。
表 1 XRF仪器测量条件Table 1. Measurement parameters of XRF instrument元素 谱线 晶体 准直器
(μm)探测器 滤光片 管电压
(kV)管电流
(mA)2θ(°) 脉冲高度分析器 测量时间(s) 峰值 背景 LL PL 峰值 背景 Rh Kα-C LiF 200 150 Scint. Al(200 μm) 60 60 18.4386 - 26 78 20 10 Sr Kα LiF 200 300 Scint. Al(200 μm) 60 60 25.1190 0.6602 22 78 20 10 Ba Lα LiF 200 300 Flow None 40 90 87.1708 1.3070 33 66 20 10 S Kα Ge 111 300 Flow None 30 120 110.6960 1.6632 35 65 20 10 Ca Kα LiF 200 300 Flow None 30 120 113.1450 -1.0626 32 73 20 10 Fe Kα LiF 200 15 Flow None 60 60 57.5264 -0.9716 15 68 20 10 Ti Kα LiF 200 300 Flow None 40 90 8601904 -1.1912 28 71 20 10 SQP电子分析天平(赛多利斯科学仪器有限公司,北京)。
HMS-Ⅱ-MXZ型高频熔样机(成都多林电器有限公司),可同时熔融2个样品,铂黄合金坩埚。
1.2 主要试剂
盐酸、硝酸、氯化铵、三氧化二铁、氧化镁、氧化铝、硝酸铵、溴化锂、碘化铵(分析纯)。
四硼酸锂+偏硼酸锂混合熔剂(分析纯,质量比67:33),600℃灼烧2 h,冷却后置于干燥器中备用。
1.3 实验方法
准确称取在105℃干燥2 h的样品0.2000 g,置于50 mL烧杯中,加10 mL 10%的盐酸、4 mL 10%的硝酸,盖上表面皿,于低温电热板上加热微沸30 min(随时加水控制体积10 mL),取下,用水吹洗表面皿及杯壁,冷却至室温,用慢速滤纸定量过滤,将全部未溶解的样品移至定量中速滤纸上,水洗至无氯离子,将沉淀连同滤纸一起置于50 mL瓷坩埚中,置于高温炉中低温烘干后升温灰化,于700℃灼烧30 min,取出,冷却至室温,转移到称量皿称量灼烧物质量,以氧化铝补加到0.2000 g,置于原坩埚中,称取6.0000 g四硼酸锂+偏硼酸锂混合熔剂(质量比67:33) 和0.5 g硝酸铵于坩埚中,搅匀,转移到铂黄合金坩埚中,加饱和溴化锂溶液0.4 mL,于高频熔样机上650℃预氧化3 min,1075℃熔融2 min,加碘化铵20 mg,摇动熔融4.5 min,再加碘化铵20 mg,摇动熔融1.5 min后倒入已预热的铂金合金模具中,冷却后倒出,1 h后置于XRF仪器进样交换器中测定。
1.4 校准样品
以7个重晶石国家标准物质GBW07811~GBW07817、2个岩石国家标准物质GBW07111和GBW07132、高纯硫酸钡以及人工配制的校准样品做标准系列,所选的标准物质不经酸处理,全样熔片,以标准物质中的全钡量换算为全硫酸钡量。
2. 结果与讨论
2.1 样品前处理方法研究
2.1.1 样品酸处理方法的选择
重晶石矿石中除含有硫酸钡外,伴生矿物可能含有碳酸钡、硫酸钙、铅、锌等成分,影响硫酸钡的测定结果,毛香菊等[2]以10%的盐酸溶解样品、过滤除去干扰组分,ICP-OES法测定重晶石选矿样品中的硫酸钡,其结果与重量法一致。对于XRF法测定重晶石中的硫酸钡,应除去样品中的碳酸钡以及铜、铅、锌等对铂黄合金坩埚造成腐蚀的组分,熔融过程中预氧化难以消除其影响,样品前处理应考虑将这些组分尽量除去,以满足对样品熔融的要求。
硫酸钡不溶于酸,选择盐酸、盐酸+氯化铵、盐酸+硝酸体系处理样品,以硫化物型重晶石标准物质GBW07816和多金属矿标准物质GSO-2考察样品的处理效果,以选定的处理方法溶解样品,过滤后的滤液定容、摇匀后以火焰原子吸收光谱法测定滤液中的铜、铅、锌,计算方法的溶出率,结果见表 2。表 2结果表明:单独使用盐酸或盐酸+氯化铵、盐酸+硝酸均可以较好地溶解铅;盐酸、盐酸+氯化铵体系对铜、锌的溶解效果不佳,盐酸+硝酸体系对铜、铅、锌的溶出效果均较好。本法选择以10%盐酸10 mL+10%硝酸4 mL体系前处理样品。
表 2 样品前处理方法及铜铅锌的溶出率Table 2. Sample pretreatment methods and dissolution rate of Cu, Pb, Zn样品编号 前处理方法 溶出率(%) Pb Cu Zn GBW07816 10%盐酸10 mL 97.56 - 40.96 GSO-2 10%盐酸10 mL 99.08 40.95 41.78 GBW07816 10%盐酸10 mL+0.5 g氯化铵 99.76 - 67.82 GSO-2 10%盐酸10 mL+0.5 g氯化铵 100.0 41.9 40.14 GBW07816 10%盐酸10 mL+1 g氯化铵 99.76 - 86.17 GSO-2 10%盐酸10 mL+1 g氯化铵 99.96 29.52 46.01 GBW07816 10%盐酸10 mL+10%硝酸2 mL 99.94 - 96.01 GSO-2 10%盐酸10 mL+10%硝酸2 mL 100.0 89.52 95.31 GBW07816 10%盐酸10 mL+10%硝酸4 mL 99.92 - 99.73 GSO-2 10%盐酸10 mL+10%硝酸4 mL 100.0 91.43 98.84 注:“-”表示标准物质无标准值,未计算溶出率。 2.1.2 样品与熔剂稀释比的选择
样品的熔融程度是影响方法准确度的重要因素[14-15],样品充分熔融,方法的精密度、准确度高。仵利萍等[10]以样品与熔剂1:30的稀释比制作熔片测定重晶石中的总钡量,熔片效果较好。本文以样品与熔剂的稀释比为1:10、1:15、1:20、1:30、1:40,各稀释比制作6个玻璃样片进行实验,上机测定钡的谱线强度,计算标准偏差,结合熔片质量情况确定最佳稀释比。结果表明:样品与熔剂稀释比为1:30时样片清亮,熔融物流动性好,6个样片的钡强度标准偏差小,因此本实验选择样品与熔剂稀释比为1:30。
2.1.3 样品量对分析结果的影响
样品经稀酸处理后,碳酸盐、硫化物等易溶于酸的物质被溶解分离除去,样品量减少,不同样品剩余量不同。剩余样品按原样品量与熔剂1:30的比例熔融后测定,标准物质硫酸钡的测定值偏高;剩余样品以熔剂补加到原取样量再按样品量与熔剂1:30的比例熔融测定,标准物质测定结果偏低。证明样品经酸处理后,不能直接加熔剂熔融后XRF法测定其中的组分,其原因为样品经处理后样品量减少,熔剂与样品比例不确定,导致分析结果出现较大偏差。
研究以化学性质稳定的氧化物将剩余样品补充到样品的初始取样量。选取的氧化物在样品熔融过程中应无挥发,对钡的基体效应小,贮存过程中不发生吸水潮解、反应等现象。氧化铝、三氧化二铁、氧化镁是可选择的补加剂,过高的铁组分会增加熔融体的黏度,不宜单独使用,选择以三氧化二铁+氧化镁(质量比70:30) 混合物、氧化铝为补加剂,熔融制片测定,标准物质测定值见表 3。结果表明:将灼烧物量补加到初始取样量后,样品与熔剂比例一致,标准物质的检测结果基本满足规范要求。三氧化二铁是钡元素的基体校正组分,三氧化二铁+氧化镁(70:30) 混合物补加到不同样品中的量不同,硫酸钡测定结果的准确度较氧化铝为补加成分的结果略差,因此选择以氧化铝为补加成分。
表 3 不同补加成分的标准物质中硫酸钡的测定值Table 3. Analytical results of BaSO4 in standards materials adding different ingredients标准物质
编号补加剂 BaSO4含量 标准值
(%)测量值
(%)相对误差
(%)允许相对误差
(%)GBW07811 三氧化二铁+
氧化镁(70:30)42.32 42.23 -0.21 1.37 GBW07815 三氧化二铁+
氧化镁(70:30)67.04 66.83 -0.31 0.84 GBW07816 三氧化二铁+
氧化镁(70:30)18.87 18.66 -1.11 2.39 GBW07811 氧化铝 42.32 42.41 0.21 1.37 GBW07815 氧化铝 67.04 66.91 -0.19 0.84 GBW07816 氧化铝 18.87 19.02 0.79 2.39 2.1.4 熔片温度的选择
仵利萍等[10]于1050~1150℃、曾小平等[11]于1050℃熔融重晶石样品,熔片效果较好。熔片温度过低,熔融物流动性差,样片效果差,所制样片中有微小不熔颗粒,分析结果精密度差;熔片温度过高,熔融物挥发严重,黏度增大而粘连坩埚,造成不易脱埚。实验证明当温度为1075℃时,钡的谱线强度值相对稳定,测量值的标准偏差和相对标准偏差小且趋于稳定;当高于此温度,熔融物挥发量大,熔融物黏度高,不易脱埚。因此,本实验选择熔片温度为1075℃。
2.1.5 硝酸铵用量的选择
样品中含有还原性物质会对坩埚造成腐蚀,加入氧化剂可以防止还原性物质对坩埚的损坏,由于取样量小,样品经过了稀酸处理、高温灼烧,样品中的还原性物质较少,氧化剂的加入量不必太多。以硝酸铵作氧化剂,过多的硝酸铵会增大熔融物的黏度,需提高碘化铵的加入量以利于脱模。实验选择加入0.25、0.50、0.75、1.0 g硝酸铵,根据熔片情况确定硝酸铵最佳加入量。实验结果表明:硝酸铵加入量小于0.50 g时熔融物的流动性较好;但加入量为0.25 g时熔好的样片脆性较大,冷却过程中部分样片会出现爆裂现象;加入量大于0.75 g时高温熔融物流动性差、黏度大、脱模剂需要量大,熔片效果变差。因此,本实验选择硝酸铵选择加入量为0.50 g。
2.2 基体效应校正
基体效应[16]是试样中元素间吸收、增强效应和物理化学效应对待测元素特征X射线强度的影响。经验系数法是目前XRF分析中准确定量分析的重要基体校正方法,本方法选择经验系数法进行校正。以Fe2O3、SiO2、CaO含量对钡含量进行校正后,硫酸钡的曲线离散度等参数明显改善,GBW07811的硫酸钡的测量误差<0.24%,故选择参与基体校正。
2.3 方法技术指标
2.3.1 方法检出限
根据XRF法检出限计算公式:
$\frac{{3\sqrt 2 }}{m}\sqrt {\frac{{{I_{\rm{b}}}}}{{{t_{\rm{b}}}}}} $ (式中:m为单位含量的计数率,94.3642;Ib为背景计数率,1.5345;tb为峰值和背景总计数时间,60 s),计算得到硫酸钡检出限为72 μg/g,满足对重晶石中硫酸钡的检测要求。本法检出限略高于ICP-OES法,但远低于重晶石10%的边界品位,完全可以满足重晶石中硫酸钡的测定要求。2.3.2 方法精密度
按实验方法对标准物质GBW07815重复制备12个样片,按确定的测量方法测定硫酸钡,计算平均值为66.94%,相对标准偏差(RSD)为0.36%,与仵利萍等[10]采用熔融制样XRF法报道的氧化钡的精密度(RSD为0.36%)相近,优于毛香菊等[2]采用ICP-OES法的精密度(RSD为0.39%~4.1%)。这些对比表明本方法重现性较好,满足DZ/T 0130—2006《地质矿产实验室质量管理规范》的要求。
2.4 与经典化学方法的比对
选取不同硫酸钡含量的重晶石样品10件,以本法及硫酸钡重量法(由国土资源部保定矿产资源监督检测中心检测)测定,进行方法比对。测定结果(表 4)表明:本法与硫酸钡重量法结果相符,表明适用于重晶石中硫酸钡的测定。
表 4 本方法与经典化学分析方法比较Table 4. A comparison of analytical results by this method and traditional chemical methods样品
编号重量法测定值
(%)本法测定值
(%)平均值
(%)相对偏差
(%)允许相对偏差
(%)1 11.40 11.21 11.31 0.84 4.38 2 59.12 58.97 59.05 0.13 1.39 3 34.58 35.64 35.11 -1.51 2.26 4 67.44 68.70 68.07 -0.93 1.16 5 71.16 71.52 71.34 -0.25 1.09 6 51.80 52.84 52.32 -0.99 1.59 7 5.52 5.69 5.61 -1.52 5.85 8 44.29 44.28 44.29 0.01 1.87 9 61.02 60.73 60.88 0.24 1.34 10 87.49 87.32 87.41 0.10 0.77 3. 结论
采用XRF法分析重晶石中的硫酸钡时,样品需要前处理导致样品量减少,无法准确测定其中的待测组分。本研究提出了以对钡基体效应小的氧化铝补充到初始取样量的方法,较好地解决了问题,在样品处理过程中,以稀酸溶解过滤除去重晶石中的干扰组分,消除了锶、铅等元素的干扰,提高了XRF法的准确度。
本方法在样品灰化后直接熔片即可进行XRF测定,而ICP-OES法在样品灰化后需要碱熔、过滤、酸溶解钡、上机测定,分析周期较长。总体上,较容量法、重量法、ICP-OES法的干扰少、分析流程短,提高了分析测试效率。
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