锰工业聚集区水化学特征及其污染分析

龚效宇; 张重乾; 黎伟; 谢蔚嵩; 朱令; 徐磊; 叶樑锴; 张少剑; 王程程; 朱彬; 安思危; 黄代宽

doi:10.11932/karst20250302

锰工业聚集区水化学特征及其污染分析

doi: 10.11932/karst20250302

贵州省环境科学研究设计院, 贵州贵阳 550009

基金项目: 贵州省科技计划项目（黔科合基础—ZK【2022】一般238）；贵州省科技计划项目（黔科合支撑[2023]一般182）；贵州省科技厅环境科技项目（2121-03）

详细信息

作者简介:
龚效宇（1994-)，女，工程师，硕士研究生，长期从事水文地球化学及水环境污染研究。E-mail：15387497230@163.com

通讯作者:
黄代宽(1981-)，男，正高级工程师，博士研究生，长期从事环境污染治理。E-mail：63523227@qq.com。

中图分类号: X52
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出版历程
- 收稿日期: 2024-02-27
- 录用日期: 2024-07-31
- 修回日期: 2024-03-22
- 网络出版日期: 2025-09-03
- 刊出日期: 2025-06-25

Analysis of hydrochemistry and pollution characteristics in manganese-related industrial watersheds

Guizhou Institute of Environmental Science Research and Designing, Guiyang, Guizhou 550009,China

摘要

摘要: 文章以地处“锰三角”的松桃河流域为研究对象，分别采集丰水期（5月）和平水期（9月）流域内可能的污染源及污染受体进行水样分析，通过因子分析探究影响松桃河流域地表水水化学特征的控制因素。结果表明：（1）EC和TDS呈现渣库渗滤液＞垃圾填埋场渗滤液＞“两井”＞表层岩溶泉＞地表水，Mn浓度总体呈现渣库渗滤液＞“两井”＞垃圾填埋场渗滤液＞地表水＞表层岩溶泉；地表水和表层岩溶泉中的氮素主要以${\rm{NO}}_3^{-} $-N的形式存在，“两井”、渣库和垃圾填埋场渗滤液氮素均以NH$_4^{+} $-N为主。地表水中氨氮超标率达到13%，Mn超标率为9.6%。（2）垃圾填埋场水化学类型呈SO₄·Cl-Na·K，锰渣库渗滤液水化学类型呈SO₄-Mg型，地表水和表层岩溶泉水化学类型呈HCO₃-Ca·Mg型，“两井”地下水受到渣库渗滤液的影响，水化学类型向渣库渗滤液的方向演变，呈现出SO₄-Mg·Ca型。（3）地表水在丰水期表现出明显的雨季稀释作用，垃圾渗滤液部分指标表现出明显的淋滤作用，其他水体丰平两季水化学指标差异性较小。（4）影响研究区水化学特征的主要因素为地球化学作用、锰工业及生活污染，其中地球化学作用的影响最大，贡献率在53%左右，锰工业及生活污染占39%左右。虽然PCA和PMF分析尚不能准确区分锰工业和生活污染对研究区水环境污染的贡献率，但通过与表层岩溶泉水化学特征的结合比对以及松桃河Mn和氨氮沿程变化，指示地表水仍然受到锰渣库和生活污染，对松桃河流域涉锰工业企业、渣库和生活污染的治理工作仍需继续。
- 松桃河流域 /
- 锰 /
- 氨氮 /
- 渣库渗滤液 /
- 水化学 /
- PCA分析 /
- PMF分析
Abstract: The counties of Xiushan in Chongqing, Songtao in Guizhou, and Huayuan in Hunan are home to the enterprises producing Electrolytic Manganese Metal (EMM) in China and form China’s "Manganese Triangle". Although the development of the manganese industry has driven economic growth, it has also caused significant ecological and environmental damage. Statistically, the production of 1 ton of EMM generates 6 tons to 10 tons of electrolytic manganese slag. The leachate from fresh slag is acidic (pH≈5) and contains high concentrations of ammonia nitrogen (565 mg·L⁻¹ to 792 mg·L⁻¹), manganese (936 mg·L⁻¹ to1,460 mg·L⁻¹), and sulfate (9,250 mg·L⁻¹ to 11,400 mg·L⁻¹). Additionally, the leachate contains high levels of ions such as nitrogen (N), phosphorus (P), potassium (K), and magnesium (Mg). Rainfall and surface water can dissolve these soluble components, facilitating their migration into the environment. However, due to inadequate anti-seepage measures and complex geological conditions, the leachate has not been fully collected and treated, leading to contamination of surrounding soils and surface water bodies. Hence, to better understand the impact of the manganese industry on the environment, this study investigated the hydrochemical characteristics and pollution patterns in the Songtao River Basin. Water samples from potential pollution sources and receptors were collected during both the rainy season (May) and the dry season (September), respectively. Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF) were used to identify the controlling factors affecting the hydrochemical characteristics of surface water in the study area.The findings are as follows:(1) Electrical Conductivity (EC) and Total Dissolved Solids (TDS) exhibited the following decreasing trend: leachate from manganese slag yard > landfill leachate > polluted groundwater from two wells > surface karst spring > surface water. Mn concentrations generally followed the order: leachate from manganese slag yard > polluted groundwater from two wells > landfill leachate > surface water > surface karst spring. The nitrogen in surface water and surface karst springs primarily existed in the form of NO$_3^{-}$-N, while in other instances, nitrogen mainly appeared as NH$_4^{+}$ -N. In surface water, NH$_4^{+}$ and Mn concentrations exceeded 13% and 9.6% of the permitted levels, respectively. (2) the pH of the landfill leachate had a pH above eight, and the chemical composition included SO₄ ·Cl-Na·K. In contrast, the leachate from the manganese slag yard exhibited a pH value ranging from weakly acidic to neutral (pH 4.64 to 7.17), with a chemical composition of SO₄-Mg. The surface water and surface karst spring water were dominated by HCO₃-Ca·Mg type water. Interestingly, the polluted groundwater from two wells, although classified as groundwater, exhibited a SO₄ -Mg·Ca type due to the influence of the leachate from manganese slag. (3) in the rainy season, surface water demonstrated substantial dilution effects, whereas specific indicators within waste leachate exhibited a significant percolation. Meanwhile, chemical indicators in other water bodies exhibited minimal variation between the rainy and dry seasons.(4) both PCA and PMF extracted four main influencing factors, identifying geochemical processes, the manganese industry, and domestic pollution as the primary contributors to the hydrochemical characteristics. Factor 1 (F1) in PCA and Factor 4 (F4) in PMF exhibited consistent patterns, primarily associated with HCO$_3^{-}$, Ca²⁺, Mg²⁺, and TDS. These factors represent the combined effects of geochemical processes, with an average contribution rate of 52.99%. F4 in PCA aligned closely with Factor 3 (F3) in PMF, where Mn as the dominant loading variable, indicated pollution from the manganese industry, contributing an average of 5.06%. F3 in PCA and F1 in PMF, characterized by K⁺, Cl⁻, and Na⁺, represented domestic pollution, with an average contribution rate of 16.44%. However, due to the overlapping signatures of pollutants from both manganese industrial emissions and domestic sources, neither method can accurately quantify the individual contribution rates of these two pollution sources to the contamination of the water environment in the study area. By comparing the chemical compositions of surface karst springs, and according to the synchronous trends of manganese and ammonia nitrogen concentrations along the Songtao River, it can be inferred that surface water continues to be affected by both manganese slag storage and domestic pollution.This highlights the need to sustain and strengthen remediation efforts targeting manganese-related industrial activities, slag yards, and domestic pollution in the Songtao River Basin. Additionally, localized monitoring of manganese and ammonia nitrogen should be enhanced to identify pollution pathways and prevent untreated leachate from slag yards and other pollution sources from being directly discharged into surface water. Furthermore, stricter supervision and regulation of domestic pollution discharges are essential to ensure that domestic sewage and pollutants are not released untreated into surface water.
- the Songtao River Basin /
- manganese /
- ammonia nitrogen /
- leachate from slag yards /
- hydrochemisty /
- PCA analysis /
- PMF analysis

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图 1 研究区及采样点分布图

Figure 1. Distribution of sampling sites

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图 2 Piper三线图

Figure 2. Hydrochemistry diagram of Piper

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图 3 垃圾填埋场渗滤液（LJ）及渣库(BTW、HF、XH、LGW）渗滤液水质指标

Figure 3. Parameters of water quality (LJ, BTW, HF, XH, and LGW) of the leachate from the landfill and the slag yard

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图 4 地下水主要阴阳离子图（左：阳离子；右：阴离子）

Figure 4. Main anion and cation of groundwater (Left: cation; Right: anion)

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图 5 地表水${\rm{NO}}_3^{-}$-N、NH$_4^{+}$-N、Mn浓度图

Figure 5. Concentrations of ${\rm{NO}}_3^{-}$-N, NH$_4^{+}$-N, and Mn in surface water

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图 6 地表水主要阳离子浓度图

Figure 6. Concentrations of main cation in surface water

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图 7 地表水主要阴离子浓度图

Figure 7. Concentrations of main anion in surface water

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图 8 PCA解析的地表水污染源贡献结果

Figure 8. Contributions of pollution sources to groundwater based on PCA

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图 9 PMF解析的地表水污染源贡献结果

Figure 9. Contributions of pollution sources to groundwater based on PMF

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表 1 采样点基本信息

Table 1. Basic information of sampling sites

序号	名称		概况
1	地表水	松桃河	共计12个采样点。松桃河是流域内最大的河流，主要受大路河、大坝河、道水河、老卜茨小溪、镇江河以及地下水补给，河床平均高程355 m。
		道水河	共计5个采样点。道水河是松桃河的重要支流，上下游共分布有5个渣库，两家电解锰企业，是受涉锰行业污染较为严重的支流。
		大坝河	共计2个采样点。大坝河上游为九龙湖，下游横穿松桃县城，两岸分布有商铺、集市、饭店等，存在生活垃圾和污水乱扔乱排现象。
		镇江河	共计2个采样点。镇江河流域分布有一个渣库，污染相对较小。
		九龙湖	共计2个采样点。九龙湖受ZK3的影响，湖底靠近ZK3附近的土壤及水体受到污染。
		其他河流	其他采样点共计3个，是松桃河上游三条支流汇入口，未发现受锰行业污染。
2	表层岩溶泉		表层岩溶泉共计4个，主要分布在松桃河右岸，平均出露高程395 m，经调查与渣库和电解锰企业无直接水力联系。
3	污染地下水（简称“两井”）	LPC（老卜茨岩溶泉）	岩溶泉出露在老卜茨小溪左岸，出露高程350 m，比附近河床高4 m，与老卜茨小溪汇合后最终排泄至松桃河，已查明受ZK2、ZK4渗滤液的污染。
3	污染地下水（简称“两井”）	WS（文山水井）	文山岩溶系统是道水河流域最为复杂的地下水系统，文山水井是文山岩溶系统地下暗河的出口，出露在道水河右岸，出口高程380 m，最终排泄至道水河。勘查发现文山岩溶系统受周边渣库的污染，其氨氮和锰超标严重。
4	垃圾填埋场渗滤液	LJ(垃圾填埋场)	占地面积约80 hm²，日产污水量120 m³·d⁻¹，埋填时间＞5年，持续有新堆存垃圾（主要为城市生活垃圾），是研究区生活污染的集中体现。填埋场部分位于老卜茨岩溶系统内，渗滤液往下渗漏向老卜茨小溪排泄。
5	锰渣库渗滤液	BTW(ZK1 渣库）	2018年投入使用，堆渣约90万m³，渗滤液收集池混有生活污水和雨水，日收集渗滤液约500 m³·d⁻¹，运行过程中发现渗滤液通过库区底部的岩溶裂隙和管道向道水河排泄。
		HF(ZK2 渣库）	2010年建成并投入使用，产生渗滤液约30 m³·d⁻¹，库区地下水位标高363.37~424.35 m，渣库原始地形为冲沟，淋滤液收集池位于冲沟底部。因底部未铺设防渗膜，淋滤液主要垂向向下和沿断层、节理裂隙的侧向渗漏，进入岩溶漏斗中天然发育的垂向溶隙进入岩溶主管道，通过老卜茨水井地下河出口排出地表。
		XH(ZK3 渣库）	2014年建成投入使用，目前该库实际堆存锰渣约101万m³，坝高40 m。由于建设需要，其渗滤液收集池由敞开式的3500 m³·d⁻¹变为地埋式的400 m³·d⁻¹（埋藏于九龙湖底），经过勘查发现渣库防渗层、渗滤液收集池和附属管道均出现破坏，导致渗滤液混入九龙湖，对九龙湖造成污染。
		LGW(ZK4 渣库）	2004年建成使用，2013年2月堆满，堆渣96万m³，汛期渗滤液产生量为20~50 m³·d⁻¹，枯水期10 m³·d⁻¹以下，渗滤液经裂隙进入断层集中径流带，分别向北污染老卜茨上游暗河和向南污染老卜茨小溪。

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表 2 松桃河流域主要水质指标统计

Table 2. Statistics of main indexes for water quality in the Songtao River Basin

时间	样品编号	测试项目
时间	样品编号	DO	pH	EC	TDS	NH$_4^{+}$-N	${\rm{NO}}_3^{-}$-N	${\rm{SO}}_4^{2-}$	Cl⁻	${\rm{HCO}}_3^{-}$	Ca²⁺	K⁺	Mg²⁺	Na⁺	Mn
5月	地表水（n=26））	7.19	7.69	0.28	0.18	0.44	1.64	32.15	5.02	130.15	35.41	2.00	13.62	4.32	0.46
	表层岩溶泉（n=4）	5.63	7.72	0.48	0.31	0.00	3.82	19.70	4.91	255.25	64.35	1.35	30.03	1.77	0.05
	“两井”（n=2））	2.40	7.09	1.93	1.25	49.05	13.07	937.50	22.05	220.50	107.55	6.98	142.00	13.60	28.38
	垃圾填埋场（n=1）	2.04	8.04	17.30	11.25	694.68	34.32	5370.00	2740.00	123.00	222.00	1010.00	282.00	1550.00	3.04
	渣库（n=4））	5.41	6.62	19.63	12.76	967.18	28.60	19573.50	24.25	94.50	227.23	41.68	2196.23	129.43	2434.30
9月	地表水（n=26））	7.54	8.21	0.37	0.18	0.45	1.61	37.68	6.45	146.96	44.18	2.18	15.79	6.44	0.54
	表层岩溶泉（n=4）	4.68	7.30	0.59	0.29	0.00	3.09	17.93	5.60	333.25	70.53	2.20	27.58	2.90	0.02
	“两井”（n=2））	2.08	7.07	2.42	1.25	57.59	23.73	949.00	17.95	205.00	151.50	4.45	156.50	16.30	52.53
	垃圾填埋场（n=1）	＜LD	8.03	20.77	12.41	699.46	1.10	6640.00	3260.00	1770.00	316.00	1730.00	382.00	2650.00	2.38
	渣库（n=4））	4.01	6.17	33.71	22.31	2330.68	40.75	45612.50	45.03	83.50	446.25	99.99	9647.75	426.20	8817.78
注：“＜LD”为检出线以下；单位：pH/无量纲，Ec/mS·cm⁻¹，TDS/g·L⁻¹，其他/mg·L⁻¹。

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表 3 地下部分水质指标参数

Table 3. Parameters of groundwater quality

采样时间	样品类型	样品名称	DO/mg·L⁻¹	pH	Ec/mS·cm⁻¹	TDS/g·L⁻¹	NH$_4^{+}$-N /mg·L⁻¹	${\rm{NO}}_3^{-}$-N /mg·L⁻¹	Mn /mg·L⁻¹
5月	“两井”	LPC	2.96	7.00	2.03	1.32	44.49	7.72	10.41
	“两井”	WS	1.84	7.18	1.82	1.18	53.60	18.43	46.34
	表层岩溶泉	YGQ	7.05	7.63	0.42	0.27	<LD	3.57	0.15
		ZDG	5.88	7.89	0.50	0.33	0.00	1.03	0.01
		DW	5.09	7.85	0.49	0.32	0.01	1.36	0.01
		PL	4.51	7.49	0.52	0.34	<LD	9.30	0.02
9月	“两井”	LPC	0.38	7.18	2.28	1.17	53.61	7.72	1.06
	“两井”	WS	3.77	6.96	2.55	1.32	61.56	39.74	104.00
	表层岩溶泉	YGQ	4.28	7.28	0.62	0.30	＜DN	1.07	0.07
		ZDG	5.68	7.51	0.54	0.26	＜DN	5.17	0.02
		DW	5.84	7.20	0.60	0.29	＜DN	1.54	＜0.01
		PL	2.93	7.19	0.60	0.29	0.01	4.56	＜0.01

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表 4 解释的总方差

Table 4. Explanation of total variance and variance

成分	初始特征值			提取载荷平方和			旋转载荷平方和
成分	总计	方差 %	累积 %	总计	方差 %	累积 %	总计	方差 %	累积 %
1	5.981	54.372	54.372	5.981	54.372	54.372	3.468	31.525	31.525
2	2.007	18.248	72.62	2.007	18.248	72.62	3.435	31.23	62.755
3	1.499	13.625	86.244	1.499	13.625	86.244	2.205	20.048	82.803
4	0.71	6.452	92.696	0.71	6.452	92.696	1.088	9.893	92.696
5	0.5	4.546	97.242
6	0.151	1.377	98.619
7	0.073	0.663	99.282
8	0.036	0.331	99.613
9	0.028	0.259	99.872
10	0.01	0.091	99.962
11	0.004	0.038	100

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