大同盆地高砷地下水稀土元素特征及其指示意义

谢先军; 王焰新; 李俊霞; 苏春利; 吴亚; 余倩; 李梦娣

doi:10.3799/dqkx.2012.046

大同盆地高砷地下水稀土元素特征及其指示意义

doi: 10.3799/dqkx.2012.046

谢先军^{1, 2,},
王焰新^{1, 2},
李俊霞^{1, 2},
苏春利^{1, 2},
吴亚^{1, 2},
余倩^{1, 2},
李梦娣^{1, 2}

1.
中国地质大学环境学院, 湖北武汉 430074
2.
中国地质大学生物地质与环境地质国家重点实验室, 湖北武汉 430074

基金项目:

国家自然科学基金项目 40830748

国家自然科学基金项目 40902071

教育部博士点基金 20090145120004

详细信息

作者简介:
谢先军(1979-), 男, 副教授, 主要从事地下水污染与防治及环境地球化学研究.E-mail: xianjun.xie@gmail.com

中图分类号: X523
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出版历程
- 收稿日期: 2010-08-12
- 刊出日期: 2012-03-15

Characteristics and Implications of Rare Earth Elements in High Arsenic Groundwater from the Datong Basin

XIE Xian-jun^{1, 2
,},
WANG Yan-xin^{1, 2},
LI Jun-xia^{1, 2},
Su Chun-li^{1, 2},
WU Ya^{1, 2},
YU Qian^{1, 2},
Li Meng-di^{1, 2}

1.
School of Environmental Studies, China University of Geosciences, Wuhan 430074, China
2.
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074, China

摘要

摘要: 对大同盆地典型高砷地下水开展了稀土元素地球化学研究.研究表明: 高砷地下水具有低∑REE含量及富集重稀土(HREEs)特征.地下水中低含量∑REE与含水层沉积物中Fe-Mn氧化物/氢氧化物对REEs的吸附有关.地下水中重稀土元素相对于轻稀土元素的富集可能是吸附作用和碳酸根离子同REEs发生络合作用的共同结果.采用平均大陆上地壳标准化的地下水稀土元素分布表现出显著的Ce及Eu正异常.地下水Ce/Ce^*值及Eu含量与Fe+Mn具有显著相关性, 表明铁锰氧化物还原性溶解是控制Ce/Ce^*值及Eu含量特征的主要因素.Ce/Ce^*值及Eu含量与As浓度的关系表明, Ce异常及Eu含量特征能对地下水中As的富集进行有效指示.
- 水污染 /
- 砷 /
- 稀土元素 /
- 氧化还原反应 /
- 水文地质 /
- 大同盆地
Abstract: In order to better understand the occurrence of high arsenic groundwater, rare earth elements (REEs) analyses were conducted for groundwater from the Datong basin. The results indicate that high arsenic groundwater usually has low ∑REE concentration and enriches in HREEs relative to LREEs. The low concentration of ∑REE in groundwater samples could be due to the scavenging of REEs onto the surface of solid phase Fe-Mn oxides/hydroxides within aquifer sediment. The enrichment of HREEs can be attributed to the combined result of complexation, and desorption and readsorption. The average up crust normalized REEs patterns clearly exhibit significant positive Ce and Eu anomalies in high arsenic groundwater. The observed good correlation between Ce/Ce^* values and Eu and Fe+Mn could be related to the reductive dissolution of Fe and Mn oxides/hydroxides. The relationship between As and Ce/Ce^* value and Eu suggests that Ce/Ce^* value and Eu concentration are useful indicators of arsenic mobilization in groundwater system.
- water pollution /
- arsenic /
- rare earth elements /
- redox reactions /
- hydrogeology /
- Datong basin

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图 1 研究区及采样点位置示意

Fig. 1. Study area and sampling sites

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图 2 大同盆地地下水中∑REE与U(a)、Mo(b)和HCO₃^-(c)关系图及(La/Yb)_N和HCO₃^-(d)关系

Fig. 2. Relationship between ∑REE and U (a), Mo (b), HCO₃^- (c) and (La/Yb)_N and HCO₃^- (d) in groundwater from Datong basin

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图 3 地下水平均大陆上地壳标准化的稀土元素配分模式

Fig. 3. Average upper crust (AUC)-normalized REEs patterns in groundwater from Datong basin

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图 4 大同盆地地下水中Eu/Eu^*与Ba/Sm比值关系

Fig. 4. Correlation between Eu/Eu^* and Ba/Sm of the groundwater from Datong basin

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图 5 地下水中Fe+Mn与Eu及Ce/Ce^*关系

Fig. 5. The relationship between Fe+Mn and Eu and Ce/Ce^* values in groundwater from Datong basin

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图 6 地下水中As与Eu含量及Ce/Ce^*值之间的关系

Fig. 6. The relationship between As and Eu concentration and Ce/Ce^* values in groundwater from Datong basin

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表 1 大同盆地高砷地下水水化学组成特征

Table 1. Chemistry of high arsenic groundwater from the Datong basin

样号	点位	pH	Cl^-(mg/L)	SO₄^2-(mg/L)	HCO₃^-(mg/L)	K(mg/L)	Na(mg/L)	Ca(mg/L)	Mg(mg/L)	Ba(mg/L)	Mn(μg/L)	Fe(μg/L)	As(μg/L)	Mo(μg/L)	U(μg/L)
SHY-29	112°39.77′E39°16.80′N	8.18	21.6	1.2	436	0.45	78.69	10.65	12.18	0.73	69.68	348.48	179.10	12.10	0.07
SHY-33	112°38.83′E39°17.89′N	7.75	100.9	204.7	495	0.72	136.53	33.65	56.91	1.44	53.03	229.52	1.55	50.21	24.72
SHY-34	112°41.37′E39°18.29′N	8.24	105.3	71.2	328	1.58	82.87	22.18	26.44	0.80	82.65	187.82	73.07	10.41	0.34
SHY-35	112°42.85′E39°18.62′N	8.13	44.4	49.6	473	0.71	88.37	16.43	29.93		89.44	158.25	585.10	22.04	3.19
SHY-37	112°45.32′E39°19.11′N	7.65	497.4	515.3	825	32.09	357.73	95.78	182.79	0.47	78.10	455.97	3.70	20.03	44.88
SHY-45	112°47.14′E39°19.74′N	8.05	44.9	24.8	416	0.43	79.80	12.12	25.86	0.91	36.49	146.99	572.00	3.80	4.41
SHY-46	112°48.46′E39°20.19′N	8.18	21.1	1.4	341	1.47	57.50	16.35	20.91	1.84	127.52	250.04	119.90	12.14	7.66
SHY-47	112°49.72′E39°20.57′N	8	19.8	1.9	303	0.20	40.21	13.88	21.66	0.61	83.12	134.35	284.90	10.66	0.66
SHY-55	112°51.22′E39°21.10′N	7.97	13.2	1.4	289	0.12	34.44	13.66	18.67	1.10	78.12	125.07	348.50	0.38	0.03
SHY-57	112°51.06′E39°20.48′N	7.64	6.6	7.8	222	0.90	17.82	34.37	6.35	1.05	279.85	218.23	14.01	9.64	2.25
SHY-58	112°51.94′E39°22.21′N	7.82	55.7	3.6	362	0.37	52.09	16.85	27.50	0.41	156.86	1 791.48	565.80	0.38	0.02
SHY-59	112°52.90′E39°22.45′N	7.73	658.4	613.7	750	1.89	521.16	27.47	91.54	0.32	198.3	182.03	499.70	9.85	6.64
SHY-60	112°54.13′E39°22.54′N	7.88	13.5	2.0	359	0.43	31.30	17.19	33.02	0.56	5.82	196.57	417.10	0.74	0.06
SHY-61	112°54.27′E39°23.20′N	7.93	12.0	＜0.1	317	0.24	38.35	14.00	16.78	1.20	4.02	187.35	135.20	0.64	0.02
SHY-63	112°54.61′E39°24.21′N	7.8	492.3	516.6	847	3.55	416.29	32.07	122.59	0.58	14.48	202.25	83.48	12.57	3.09
SHY-70	112°56.30′E39°26.34′N	8.13	15.9	1.3	364	0.29	48.41	11.41	23.55	0.42	18.32	140.27	280.80	0.59	0.04
SHY-71	112°58.66′E39°26.48′N	8.1	14.4	2.9	303	0.42	31.83	22.98	19.45	0.25	2.86	222.97	2.21	16.77	15.3
SHY-72	112°59.40′E39°27.11′N	7.96	17.5	1.3	275	0.29	38.48	13.60	14.20		2.93	168.77	274.80	4.37	0.04
SHY-73	112°59.23′E39°28.42′N	8.34	17.9	1.5	398	0.22	58.88	13.39	22.27	0.82	3.02	168.14	247.80	1.15	0.06
SHY-74	113°0.24′E39°29.03′N	7.8	229.4	255.2	1 012	3.17	334.45	13.52	40.37	0.21	59.76	122.54	43.33	148.96	12.99
SHY-76	112°57.89′E39°28.04′N	8.02	16.7	1.6	393	0.25	61.37	11.91	21.58		4.17	91.09	434.90	0.87	0.02

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表 2 大同盆地高砷地下水稀土元素含量特征(单位：μg/L)

Table 2. Concentration of REEs (μg/L) in high arsenic groundwater from the Datong basin

样号	La	Ce	Pr	Nd	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu	∑REE	Ce/Ce^*	Eu/Eu^*	(La/Yb)_N
SHY-29	0.017 6	0.080 1	0.003 5	0.022 1	0.010 5	0.015 1	0.005 5	0.001 6	0.005 9	0.001 9	0.006 9	0.001 0	0.004 5	0.000 8	0.177 0	0.37	0.95	0.29
SHY-33	0.027 0	0.073 7	0.005 7	0.035 1	0.017 7	0.011 1	0.006 3	0.001 6	0.007 3	0.002 3	0.006 0	0.001 5	0.007 6	0.001 5	0.204 5	0.13	0.65	0.26
SHY-34	0.023 5	0.070 0	0.006 7	0.026 0	0.012 4	0.019 1	0.007 5	0.000 9	0.004 6	0.002 2	0.006 9	0.000 9	0.003 0	0.001 1	0.184 8	0.10	0.96	0.58
SHY-35	0.018 8	0.063 7	0.004 9	0.021 4	0.014 5	0.006 2	0.003 5	0.000 7	0.005 0	0.001 5	0.008 6	0.001 0	0.004 2	0.001 1	0.155 2	0.18	0.54	0.33
SHY-37	0.028 8	0.120 8	0.007 7	0.035 9	0.015 1	0.013 2	0.007 3	0.002 7	0.010 9	0.003 3	0.015 6	0.002 1	0.007 9	0.000 9	0.272 2	0.27	0.76	0.27
SHY-45	0.025 8	0.077 5	0.006 5	0.020 7	0.008 4	0.006 5	0.004 7	0.001 4	0.005 5	0.001 1	0.008 8	0.001 1	0.005 5	0.000 5	0.173 9	0.14	0.68	0.34
SHY-46	0.027 2	0.196 7	0.007 1	0.024 3	0.005 9	0.009 7	0.009 4	0.001 1	0.005 0	0.001 3	0.018 9	0.000 9	0.007 2	0.001 2	0.315 9	0.51	0.76	0.28
SHY-47	0.015 6	0.046 8	0.004 3	0.013 2	0.005 6	0.004 8	0.006 5	0.000 9	0.004 0	0.001 2	0.005 1	0.000 8	0.003 4	0.001 4	0.113 7	0.11	0.56	0.34
SHY-55	0.018 2	0.045 5	0.004 1	0.021 7	0.010 6	0.009 9	0.010 7	0.000 8	0.003 3	0.001 0	0.007 1	0.001 1	0.002 5	0.000 4	0.136 7	0.08	0.64	0.54
SHY-57	0.018 2	0.054 5	0.003 9	0.013 7	0.008 7	0.012 1	0.008 7	0.000 8	0.007 7	0.000 6	0.005 7	0.000 9	0.004 6	0.000 7	0.140 8	0.17	0.82	0.29
SHY-58	0.032 2	0.087 7	0.008 9	0.023 6	0.014 8	0.014 9	0.007 8	0.001 0	0.007 1	0.001 7	0.010 6	0.001 2	0.003 6	0.001 0	0.216 1	0.07	0.80	0.66
SHY-59	0.020 3	0.058 3	0.006 0	0.023 6	0.011 8	0.010 0	0.010 7	0.001 5	0.012 7	0.005 4	0.007 8	0.002 2	0.009 4	0.002 2	0.1819	0.08	0.62	0.16
SHY-60	0.037 0	0.150 2	0.010 2	0.034 8	0.016 7	0.012 6	0.016 7	0.002 4	0.010 1	0.002 1	0.032 2	0.001 2	0.006 4	0.001 1	0.333 7	0.25	0.55	0.42
SHY-61	0.040 8	0.118 4	0.009 8	0.045 3	0.014 8	0.010 4	0.008 8	0.002 0	0.006 6	0.002 3	0.017 8	0.000 5	0.008 9	0.001 1	0.287 5	0.13	0.62	0.34
SHY-63	0.028 3	0.096 8	0.008 4	0.027 5	0.008 4	0.020 7	0.010 4	0.001 9	0.012 0	0.005 1	0.014 2	0.001 6	0.008 2	0.001 4	0.245 0	0.15	1.01	0.25
SHY-70	0.026 6	0.067 4	0.005 5	0.023 9	0.006 5	0.010 1	0.005 6	0.002 0	0.004 9	0.001 1	0.007 4	0.000 9	0.003 6	0.000 4	0.165 8	0.10	0.90	0.54
SHY-71	0.040 3	0.081 0	0.008 4	0.035 3	0.016 4	0.009 3	0.014 8	0.000 9	0.006 4	0.001 7	0.009 5	0.001 5	0.007 0	0.001 9	0.234 4	0.00	0.45	0.42
SHY-72	0.032 1	0.073 7	0.008 7	0.028 7	0.009 8	0.009 9	0.014 9	0.000 9	0.010 3	0.001 8	0.008 7	0.001 2	0.003 3	0.001 5	0.205 3	0.00	0.57	0.72
SHY-73	0.032 9	0.080 2	0.005 6	0.038 6	0.015 5	0.011 5	0.016 8	0.002 1	0.011 1	0.002 3	0.012 5	0.000 7	0.010	0.001 1	0.241 1	0.12	0.52	0.24
SHY-74	0.020 6	0.077 2	0.004 9	0.022 2	0.010 5	0.013 7	0.009 8	0.001 3	0.006 5	0.002 9	0.012 4	0.001 1	0.007 6	0.000 7	0.191 3	0.24	0.80	0.20
SHY-76	0.011 3	0.017 0	0.001 9	0.011 1	0.002 8	0.007 3	0.004 9	0.000 7	0.005 3	0.001 1	0.004 1	0.000 6	0.003 5	0.000 9	0.072 4	-0.08	0.94	0.23
注：下标N表示上地壳标准化值；(La/Yb)_N=(La_N/Yb_N)；Ce/Ce^=log[Ce_N/(La_N+Pr_N)]；Eu/Eu^=log[Eu_N/(Sm_N+Gd_N)].

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