Geochemical characteristics of rare earth elements in high-fluoride groundwater in the Guide Basin and its implications

doi:10.13745/j.esf.sf.2022.9.3

Abstract

Abstract:

High-fluoride groundwater is one of the most serious environmental geological problems in China and abroad. Although the formation mechanism of high-fluoride groundwater has been studied extensively by many researchers, it is not completely clear whether chemical speciation and migration characteristics of rare earth elements (REEs) in high-fluoride groundwater are indicative of the fluoride enrichment process. This study focused on the Guide Basin where high fluoride content groundwater is widely distributed, and explored the distribution and migration processes of fluoride and REEs in aquifer by field sampling, laboratory testing and comprehensive geochemical analysis, combined with hydrogeochemical simulation. It was found that the average fluoride concentration in groundwater was 2.67 mg·L^-1—with 75% of samples higher than 1.5 mg·L^-1—and showed an upward trend along the groundwater flow path. PHREEQC calculation results showed that fluoride mainly occurred as free F^- in groundwater (99.5%). XRD and SEM-EDS results showed that the main minerals in aquifer sediments were quartz (52.9%-56.5%) and plagioclase (19.8%-21.8%) that has undergone chemical weathering. REE contents in groundwater samples were low (0.052-0.267 μg·L^-1), and REEs mainly occurred as LnCO₃⁺ and Ln(CO₃)₂^- (>99%)(Ln represents REEs). NASC-normalized REE patterns showed that LREEs were enriched relative to HREEs, with slight negative Ce anomaly and obvious positive Eu anomaly. Migration of fluoride and REEs in groundwater was affected by reductive dissolution of iron oxide minerals and inhomogeneous hydrolysis of feldspar minerals, and, to certain extent, REE enrichment process was indicative of fluoride enrichment in groundwater. This research expanded REE applications in the study of high-fluoride groundwater and provided a reference for identifying high-fluoride groundwater distribution and revealing fluoride enrichment mechanisms.

Key words: high-fluoride groundwater, rare earth elements, Guide Basin, water-rock interaction, elemental migration and enrichment

CLC Number:

P641.3
P595

WANG Zhen, GUO Huaming, LIU Haiyan, XING Shiping. Geochemical characteristics of rare earth elements in high-fluoride groundwater in the Guide Basin and its implications[J]. Earth Science Frontiers, 2023, 30(3): 505-514.

Figures/Tables 10

Fig.1 Location of the study area, distribution of sampling points in the study area, and hydrogeological profile along line AB

Fig.2 Piper plot for groundwater samples from the Guide Basin

Table 1 Summary table of hydrochemical composition of groundwater samples in the study area

水样编号	pH	Eh/ mV	ρ_B/(mg·L^-1)
水样编号	pH	Eh/ mV	TDS	NH₄-N	$H C O 3 -$	F^-	Cl^-	$N O 3 -$	$S O 4 2 -$	K⁺	Ca²⁺	Na⁺	Mg²⁺
4	8.38	110	290	0.15	221	0.77	35.6	0.00	60.6	0.99	23.3	91.8	3.83
5	8.60	145	572	0.04	92.6	3.15	225	0.67	124	2.28	14.3	196	0.07
6	8.79	142	375	0.11	166	2.23	81.4	0.24	79.6	1.47	5.44	140	0.17
8	8.55	147	639	0.21	185	3.59	218	0.42	106	2.37	8.90	236	0.33
9	8.81	99	520	0.42	299	4.08	125	0.35	68.6	2.12	4.51	212	1.11
10	8.60	99	730	0.32	312	3.62	230	0.32	91.5	3.14	7.83	280	5.08
12	9.07	116	325	0.05	117	1.85	81.4	0.32	77.4	1.13	5.86	114	0.17
13	8.97	113	365	0.05	112	1.84	101	0.84	90.8	1.08	8.65	124	0.22
19	8.74	123	482	0.08	134	2.83	155	0.35	98.6	1.69	9.27	176	0.30
20	8.70	152	475	0.09	166	3.47	127	0.23	78.1	1.39	7.66	175	0.19
21	8.90	146	538	0.012	115	2.18	145	0.57	140	1.56	8.87	191	0.42
23	8.99	195	435	0.08	115	1.32	105	0.26	137	1.15	7.85	144	0.26
24	8.95	97	510	0.12	107	2.07	135	0.32	145	1.41	8.02	174	0.40
25	8.80	143	492	0.15	156	1.90	112	0.22	139	1.55	6.62	175	0.31
32	8.87	131	540	0.36	388	5.67	90.3	0.05	104	1.88	3.44	225	0.55
34	8.82	141	572	0.34	305	4.84	98.1	0.38	104	1.78	3.76	226	0.64
35	8.70	86	623	0.585	373	5.02	121	0.40	90.4	1.93	3.97	243	1.48
41	9.08	150	365	0.25	217	1.39	46.0	0.06	86.5	1.05	3.05	127	0.32
43	8.84	29	328	0.25	188	0.86	43.8	0.47	78.7	1.13	5.87	114	0.52
44	8.70	100	315	—	171	0.66	44.2	0.44	73.9	1.21	11.0	105	1.66

Table 1 Summary table of hydrochemical composition of groundwater samples in the study area

水样编号	pH	Eh/ mV	ρ_B/(mg·L^-1)
水样编号	pH	Eh/ mV	TDS	NH₄-N	$H C O 3 -$	F^-	Cl^-	$N O 3 -$	$S O 4 2 -$	K⁺	Ca²⁺	Na⁺	Mg²⁺
4	8.38	110	290	0.15	221	0.77	35.6	0.00	60.6	0.99	23.3	91.8	3.83
5	8.60	145	572	0.04	92.6	3.15	225	0.67	124	2.28	14.3	196	0.07
6	8.79	142	375	0.11	166	2.23	81.4	0.24	79.6	1.47	5.44	140	0.17
8	8.55	147	639	0.21	185	3.59	218	0.42	106	2.37	8.90	236	0.33
9	8.81	99	520	0.42	299	4.08	125	0.35	68.6	2.12	4.51	212	1.11
10	8.60	99	730	0.32	312	3.62	230	0.32	91.5	3.14	7.83	280	5.08
12	9.07	116	325	0.05	117	1.85	81.4	0.32	77.4	1.13	5.86	114	0.17
13	8.97	113	365	0.05	112	1.84	101	0.84	90.8	1.08	8.65	124	0.22
19	8.74	123	482	0.08	134	2.83	155	0.35	98.6	1.69	9.27	176	0.30
20	8.70	152	475	0.09	166	3.47	127	0.23	78.1	1.39	7.66	175	0.19
21	8.90	146	538	0.012	115	2.18	145	0.57	140	1.56	8.87	191	0.42
23	8.99	195	435	0.08	115	1.32	105	0.26	137	1.15	7.85	144	0.26
24	8.95	97	510	0.12	107	2.07	135	0.32	145	1.41	8.02	174	0.40
25	8.80	143	492	0.15	156	1.90	112	0.22	139	1.55	6.62	175	0.31
32	8.87	131	540	0.36	388	5.67	90.3	0.05	104	1.88	3.44	225	0.55
34	8.82	141	572	0.34	305	4.84	98.1	0.38	104	1.78	3.76	226	0.64
35	8.70	86	623	0.585	373	5.02	121	0.40	90.4	1.93	3.97	243	1.48
41	9.08	150	365	0.25	217	1.39	46.0	0.06	86.5	1.05	3.05	127	0.32
43	8.84	29	328	0.25	188	0.86	43.8	0.47	78.7	1.13	5.87	114	0.52
44	8.70	100	315	—	171	0.66	44.2	0.44	73.9	1.21	11.0	105	1.66

Fig.3 Variation trends of ∑REE and water-quality parameters along the flow path (top panel) and percentage variations of different forms of fluoride along the flow path and with pH (bottom panel)

Fig.4 Main minerals identified in aquifer sediments at depths of (a) 18.8 m, (b) 104 m and (c) 362 m under optical microscope, and (d) SEM-EDS analysis results on sediment at depth of 362 m. Pl, Qtz, Ab and Hm represent plagioclase, quartz, albitite and hematite, respectively.

Table 2 Descriptive statistics of raw data on REE contents in groundwater of the Guide Basin

统计量	ρ_B/(ng·L^-1)
统计量	La	Ce	Pr	Nd	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu
最小值	6	9	1.21	4.5	1.18	2.11	2.09	0.18	0.98	0.21	0.76	0.07	0.56	0.00
最大值	50	92	20.7	88.7	14.3	30.5	13.1	1.52	6.87	1.47	3.62	0.73	3.48	0.68
平均值	22	39	6.84	26.2	4.74	10.6	5.37	0.58	3.03	0.65	1.83	0.28	1.57	0.18
标准差	12	21	4.44	19.0	3.11	6.59	2.85	0.36	1.88	0.30	0.82	0.19	0.75	0.15

Fig.5 Scatter plots showing correlation between (a) ∑REE and Eh, (b) ∑REE and Fe, (c) ∑REE and pH, and (d) NH4-N and HCO3-

Fig.6 Changes in the proportion of (a) LnCO3+ and (b) Ln(CO3)2- in groundwater along the flow path

Fig.7 NASC-normalized REE distribution patterns in groundwater samples

Fig.8 Scatter plots showing correlation between (a) ∑REE and Na+, (b) Sr/Ca and HCO3-, (c) Na/Ca and F-, and (d) ∑REE and F-

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