Concentrations and Sources of Arsenic and Fluoride in High-Temperature Geothermal Water from Yangbajing, Xizang
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摘要:
砷(As)和氟(F)是西藏羊八井高温地热流体中两种典型的高浓度有害元素，通过地热开发可以进一步促进与加速地热源As和F向地表或近地表环境释放，导致地表水和土壤环境污染。如何从As和F浓度分布特征联系水化学特征从而揭示水体As和F的富集规律，对丰富和认识西藏地区水环境中As和F的环境地球化学行为具有重要意义。本文结合野外调查现场测定了水体常规理化指标，包括水温、pH值、电导率(EC)、总溶解固体(TDS)和盐度(SAL)，采用原子荧光光谱法和X射线荧光光谱法分别测定水体和土壤样品中的As浓度，离子选择性电极法测定水体和土壤样品中的F浓度，评价As和F超标风险，探析其富集机制。结果表明：水化学类型为Na-HCO3∙Cl型，水体Na+浓度高达445.5mg/L，Ca2+浓度低至3.31mg/L，水体pH在7.87～9.42之间，富钠贫钙高pH是羊八井地热水和温泉水最主要的水化学特征。受水汽蒸发浓缩影响，温泉水As和F浓度高于地热水，两元素浓度最高分别达6.50mg/L和17.89mg/L。地热废水的不当处理存在水体和土壤As和F暴露风险，地热水和温泉水As和F浓度显著高于《地热资源评价方法》(DZ40—85)对有害成分规定的最高允许排放浓度(总砷为0.50mg/L，氟化物为10mg/L)。而土壤中总As浓度为79.50～99.08mg/kg，F浓度为1162.70～1285.10mg/kg，显著高于西藏土壤背景值。地热水体和地表土壤As和F富集主要为水-岩浸溶相互作用，独特的水化学特征为水体As和F浸取溶出提供了有利条件。
Abstract:Arsenic (As) and fluoride (F) are two typical harmful elements with high concentrations in Yangbajing high-temperature geothermal water, and the release of As and F from geothermal sources to the surface or near-surface environment can be further promoted and accelerated through geothermal development, causing surface water and soil environmental pollution. To understand the enrichment mechanism of As and F in the geothermal water body, hydrochemical characteristics as well as the concentrations of As and F were investigated by water quality analyzer, atomic fluorescence spectrometry, X-ray fluorescence spectrometry, and ion selective electrode method. The results indicate that the main sources of As and F in geothermal water and surface soil are water-rock leaching interaction. Unique hydrochemical characteristics (Na-HCO3∙Cl) with high concentration Na+ (reach to 445.5mg/L), poor in Ca2+ (as low as 3.31mg/L), and high pH (7.87−9.42) provided a favourable condition for the leaching of As and F in water. Affected by water vapor evaporation, the concentrations of As and F in hot spring water were higher than those in geothermal water and reached 6.50mg/L and 17.89mg/L, respectively. Notably, the total concentrations of As and F in waters were significantly higher than the maximum allowable emission concentrations for harmful components (0.5mg/L for As, and 10mg/L for F) in the Geothermal Resources Assessment Method (DZ40—85). Moreover, the concentrations of total As and F in the soils were 79.50−99.08mg/kg and 1162.70−1285.10mg/kg, respectively, significantly higher than the background values in Xizang soil. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202310260168 . -
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表 1 样品分析方法及测定条件
Table 1. Sample analysis methods and measurement conditions
样品类型和元素 分析方法 检出限 RSD 仪器测定条件 水体As、Hg、Sb、Se AFS As：0.0096μg/L
Hg：0.0017μg/L
Sb：0.01μg/L
Se：0.01μg/L＜5% (1)还原剂：0.5% (m/m) NaOH+2% (m/m) KBH4
(2)载液：5% (V/V)盐酸
(3)载气(Ar)流速0.4L/min土壤As XRF 1mg/kg ＜5% 分析线Kβ；能量11.72keV；电压50kV；分析时间300s；滤光片Ag 土壤和水体F ISE 定量下限0.09mg/L ＜5% 10mL样品+1mL总离子强度调节缓冲溶液(TISAB) 水体Ca2+、K+、Na+、Mg2+、Cl−、NO3 − IC Ca2+：0.011mg/L
K+：0.02mg/L
Na+：0.005mg/L
Mg2+：0.013mg/L
Cl−：0.032mg/L
NO3 −：0.054mg/L＜5% (1) EGC-III淋洗液自动发生器；DS6型电导检测器
阳离子测定条件：CSRS 300-4 mm阳离子抑制器；CS12A型分离柱(4mm×250mm)；淋洗液20mmol/L硫酸；流速1mL/min；进样体积500μL
(2)阴离子测定条件：ASRS 300-4 mm阴离子抑制器；Ion Pac AS19型分离柱(4mm×250mm)；淋洗液：30mmol/L KOH; 流速1mL/min；进样体积500μL水体CO3 2−、HCO3 − 容量法 － ＜1% 5%酚酞-乙醇指示剂；1%溴酚蓝指示剂；双指示剂滴定分析法 水体Ca、K、Na、Mg、Fe、Al、Mn ICP-OES Ca：0.003mg/L
K：0.06mg/L
Na：0.02mg/L
Mg：0.02mg/L
Fe：0.002mg/L
Al：0.03mg/L
Mn：0.005mg/L＜5% (1)射频功率1250W；等离子体气(Ar）流速15L/min；辅助气(Ar）流速0.2L/min；雾化器气体(Ar）流速0.75L/min；样品提升量1.5L/min；观测方式：垂直；冲洗时间30s；积分时间5s；重复测定3次
(2)最佳波长选择：Ca 317.933nm、K 766.49nm、Na 588.995nm、Mg 285.213nm、Fe 238.204nm、Al 396.153nm、Mn 285.213nm水体V、Be、Zn、Cr、Co、Ni、Mn、Pb、Mo、Ti、Cu、Ba、Cd ICP-MS
Zn、Cr、Be、Co、Ni、Mn、Cu、Cd： 1～10ng/L；
Mo、Pb、Ba、Ti、V： 0.1～1ng/L＜5% (1)射频功率1150W；等离子体气(Ar）流速17 L/min；辅助气(Ar）流速1.2 L/min；载气(Ar）流速1.06 L/min；扫描模式为跳峰；重复测定3次
(2)m/z: 51V、9Be、66Zn、52Cr、59Co、60Ni、55Mn、208Pb、98Mo、48Ti、63Cu、115Ba、111Cd
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表 2 水体和土壤中As和F浓度测定准确性验证
Table 2. The accuracy of measuring As and F concentrations in water and soil samples
样品类型 元素 加标值
(mg/L)测定值
(mg/L)回收率
(%)地热水 As 0 3.16±0.10 − 3 6.25±0.12 103.0±2.69 F 0 15.91±0.24 − 15 30.65±0.47 98.2±3.16 温泉水 As 0 4.18±0.07 − 4 8.78±0.12 114.8±2.98 F 0 17.67±0.23 − 20 37.65±0.15 99.9±0.75 土壤样品 元素 标准值
(mg/kg)测定值
(mg/kg)回收率
(%)沉积物GBW07310 As 25±3.0 28.4±0.85 113.5±3.40 F 149±25 138.0±16.57 92.6±11.10
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表 3 水质常规理化参数
Table 3. Conventional physicochemical parameters of the water quality
采样时间 水期 样品类型 采样位置 水温
(℃)pH 电导
(μS/cm)TDS
(mg/L)盐度
(mg/L)2021年6月 丰水期 温泉水 温泉洗浴入口 41.4 9.42 1690 1180 914 地热水 电站钻井口 76.0 9.15 1699 1220 952 2021年11月 平水期 温泉水 温泉洗浴排废口 29.6 7.87 1882 1340 956 地热水 电站钻井口 78.0 8.95 1670 1213 935 2022年4月 枯水期 温泉水 温泉洗浴排废口 28.3 7.93 1783 1238 974 地热水 电站钻井口 77.5 9.14 1678 1126 983
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表 4 地热水和温泉水中主要阴阳离子浓度
Table 4. Concentrations of major anion and cation ions in the geothermal and hot spring waters
样品类型 阳离子浓度(mg/L) 阴离子浓度(mg/L) 阳离子当量浓度
(mmol/L)阴离子当量浓度
(mmol/L)相对误差
(%)Ca2+ Mg2+ K+ Na+ Cl− SO4 2− CO3 2− HCO3 − 地热水
(钻井口)一电厂6.66 0.20 35.19 445.5 331.6 16.79 85.95 546.4 20.63 21.53 2.13 地热水
(废井口)二电厂3.31 0.013 3.42 147.2 59.26 26.30 14.51 260.1 6.66 6.97 2.28 温泉水洗浴
(入口)38.23 10.86 15.91 183.4 72.46 99.9 4.84 262.3 11.19 8.59 13.15 温泉水洗浴
(排废)31.45 5.66 47.02 328.5 91.60 229 ND 428.9 17.53 14.38 9.85 注：“ND”为未检出。
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表 5 地热水和温泉水中金属元素浓度
Table 5. The metal element concentrations in geothermal and hot spring waters
样品类型 金属元素浓度(mg/L) Ca K Mg Na Fe V Be Mn Cr Pb Sb 温泉水 35.74 15.46 10.20 195.4 0.091 0.009 0.002 0.14 0.035 0.0002 0.014 地热水 6.36 36.63 ＜0.013 456.5 0.047 0.013 0.005 0.012 0.049 0.0002 0.027 样品类型 Mo Cd Ti Se Zn Cu Ni Co Ba Hg 温泉水 0.035 0.0002 0.018 ND 0.002 0.0008 0.0032 0.00013 0.16 ＜0.0004 地热水 0.070 0.0001 0.025 ND 0.003 0.0014 0.0029 0.00003 0.090 ＜0.0004 注：“ND”表示未检出。
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