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The problem of mine water pollution from abandoned mines after integration is becoming increasingly serious with the integration of coal resources and the merger and reorganisation of coal companies. An accurate understanding of the development mechanism of mine water quality in abandoned coal mines is an important prerequisite for the protection and use of mine water and the effective prevention and control of groundwater pollution. The leaching behaviour of Fe3+ and Mn2+ and the changes of related water quality indices were investigated by the long-term indoor water-coal immersion test based on the project practice of Shendong mining area. The results show that the solubility of Fe3+ is “wave-like”, and the solubility of both samples reaches the lowest value at the 84th day after immersion, while the solubility of Mn2+ remains relatively stable after a rapid reaction (the first day). The causes of solubility variations were further analysed by ion ratio coefficient method and Pearson correlation coefficient method, and it was found that mine water in goaf may be affected by mining activities, and the water quality of mine water is strongly influenced by the dissolution of silicate rocks and gypsum. The main water-rock interactions in mine water in the goaf area include the dissolution of silicate rocks and evaporative rocks and the alternating adsorption of cations. For the rational development and utilisation of mine water in China, it is of great importance to study the characteristic pollutant ion change law of mine water in the goaf area.

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随着煤炭资源的大力整合与煤炭企业的兼并重组,整合后遗留的废弃矿山所产生的矿井水污染问题日趋严峻。准确掌握废弃煤矿矿井水水质演化成因机制,是目前矿井水保护和利用、地下水污染有效防控的重要前提,基于神东矿区项目工程实践,通过室内长期水煤浸泡试验,探究了Fe3+和Mn2+的浸溶行为及相关水质指标变化规律。研究结果表明:Fe3+的浓度呈“类波浪状”变化,两种煤样浸泡后均在第80天浓度达到最低值,而Mn2+的浓度经快速反应(第1天)后并保持相对稳定;通过离子比例系数法及Pearson相关系数法进一步分析其浓度变异成因,发现采空区矿井水可能因采矿活动影响,矿井水水质受硅酸盐岩和石膏的溶解作用强烈;采空区矿井水中主要发生的水岩相互作用有硅酸盐岩和蒸发盐岩的溶解及阳离子交替吸附作用。研究采空区矿井水中特征污染离子变化规律对中国废弃矿井水合理开发与利用具有重要的意义。

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徐东晶(1986—),男,汉族,山东青岛人,博士,副教授。研究方向:矿井水害防治。E-mail:

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徐东晶(1986—),男,汉族,山东青岛人,博士,副教授。研究方向:矿井水害防治。E-mail:

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徐东晶(1986—),男,汉族,山东青岛人,博士,副教授。研究方向:矿井水害防治。E-mail:

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journalId=1146123166801305609, articleId=1156908297648431980, language=CN, orderNo=5, keyword=水岩相互作用)], refs=[Reference(id=1205909311763574913, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908297648431980, doi=null, pmid=null, pmcid=null, year=2021, volume=21, issue=4, pageStart=1237, pageEnd=1248, url=null, language=null, rfNumber=[1], rfOrder=0, authorNames=王晓蕾, 王晶, 姬治岗, journalName=科学技术与工程, refType=null, unstructuredReference=王晓蕾, 王晶, 姬治岗, 等. 中国煤矿资源勘察及开采过程中的物探技术现状及发展趋势[J]. 科学技术与工程, 2021, 21(4): 1237-1248., articleTitle=中国煤矿资源勘察及开采过程中的物探技术现状及发展趋势, refAbstract=null), Reference(id=1205909311847460994, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908297648431980, doi=null, pmid=null, pmcid=null, year=2021, volume=21, issue=4, pageStart=1237, pageEnd=1248, url=null, language=null, rfNumber=[1], rfOrder=1, authorNames=Wang Xiaolei, Wang Jing, Ji Zhigang, journalName=Science Technology and Engineering, refType=null, 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废弃煤矿矿井水水质演化成因机制:以神东矿区项目工程为例
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徐东晶 , 马如月 , 张智超
科学技术与工程 | 论文·环境科学、安全科学 2025,25(1): 430-438
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科学技术与工程 | 论文·环境科学、安全科学 2025, 25(1): 430-438
废弃煤矿矿井水水质演化成因机制:以神东矿区项目工程为例
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徐东晶 , 马如月, 张智超
作者信息
  • 山东科技大学地球科学与工程学院, 青岛 266590
  • 徐东晶(1986—),男,汉族,山东青岛人,博士,副教授。研究方向:矿井水害防治。E-mail:

Evolutionary Mechanism of Mine Water Quality in Abandoned Coal Mine:Take Shendong Mining Area Project as an Example
Dong-jing XU , Ru-yue MA, Zhi-chao ZHANG
Affiliations
  • College of Earth Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China
出版时间: 2025-01-08 doi: 10.12404/j.issn.1671-1815.2400923
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随着煤炭资源的大力整合与煤炭企业的兼并重组,整合后遗留的废弃矿山所产生的矿井水污染问题日趋严峻。准确掌握废弃煤矿矿井水水质演化成因机制,是目前矿井水保护和利用、地下水污染有效防控的重要前提,基于神东矿区项目工程实践,通过室内长期水煤浸泡试验,探究了Fe3+和Mn2+的浸溶行为及相关水质指标变化规律。研究结果表明:Fe3+的浓度呈“类波浪状”变化,两种煤样浸泡后均在第80天浓度达到最低值,而Mn2+的浓度经快速反应(第1天)后并保持相对稳定;通过离子比例系数法及Pearson相关系数法进一步分析其浓度变异成因,发现采空区矿井水可能因采矿活动影响,矿井水水质受硅酸盐岩和石膏的溶解作用强烈;采空区矿井水中主要发生的水岩相互作用有硅酸盐岩和蒸发盐岩的溶解及阳离子交替吸附作用。研究采空区矿井水中特征污染离子变化规律对中国废弃矿井水合理开发与利用具有重要的意义。

废弃矿山  /  矿井水  /  水污染  /  特征离子  /  水岩相互作用

The problem of mine water pollution from abandoned mines after integration is becoming increasingly serious with the integration of coal resources and the merger and reorganisation of coal companies. An accurate understanding of the development mechanism of mine water quality in abandoned coal mines is an important prerequisite for the protection and use of mine water and the effective prevention and control of groundwater pollution. The leaching behaviour of Fe3+ and Mn2+ and the changes of related water quality indices were investigated by the long-term indoor water-coal immersion test based on the project practice of Shendong mining area. The results show that the solubility of Fe3+ is “wave-like”, and the solubility of both samples reaches the lowest value at the 84th day after immersion, while the solubility of Mn2+ remains relatively stable after a rapid reaction (the first day). The causes of solubility variations were further analysed by ion ratio coefficient method and Pearson correlation coefficient method, and it was found that mine water in goaf may be affected by mining activities, and the water quality of mine water is strongly influenced by the dissolution of silicate rocks and gypsum. The main water-rock interactions in mine water in the goaf area include the dissolution of silicate rocks and evaporative rocks and the alternating adsorption of cations. For the rational development and utilisation of mine water in China, it is of great importance to study the characteristic pollutant ion change law of mine water in the goaf area.

abandoned coal mines  /  mine water  /  water pollution  /  characteristic ions  /  water-rock interaction
徐东晶, 马如月, 张智超. 废弃煤矿矿井水水质演化成因机制:以神东矿区项目工程为例. 科学技术与工程, 2025 , 25 (1) : 430 -438 . DOI: 10.12404/j.issn.1671-1815.2400923
Dong-jing XU, Ru-yue MA, Zhi-chao ZHANG. Evolutionary Mechanism of Mine Water Quality in Abandoned Coal Mine:Take Shendong Mining Area Project as an Example[J]. Science Technology and Engineering, 2025 , 25 (1) : 430 -438 . DOI: 10.12404/j.issn.1671-1815.2400923
中国现有“富煤、贫油、少气”的基本能源结构,其中煤炭资源储量大,同时也是煤炭消耗大国[1],在未来较长时间里煤炭将依然是中国的主体能源以及开发利用的主要对象。中国大约有80万座矿山,其中约有40万座矿山因生态环境破坏而需要被修复[2],“十三五”期间,全国累计退出煤矿5 500处左右、退出落后煤炭产能10亿t/a以上。据中国工程院研究,预计到2030年,中国关闭或废弃矿山将达到1.5万处,不但影响生态环境,同时也闲置了大量土地资源[3]。中国矿井水类型大致分为高矿化度矿井水、高硫酸盐矿井水、高氟矿井水、酸性矿井水、常见组分矿井水及含特殊组分的矿井水这6大类型。地表水受矿业活动影响较大[4],水污染对人类生产生活造成了巨大的影响,相比于主动处理技术,被动处理技术在针对矿区用水方面展现出更大的优势,在煤矿如果能就地取材,该技术不需要频繁维护,仅依靠矿区可用的矿物岩石来净化水质,采空区矿井水中特征污染因子在自然条件下就能得到较好的平衡和缓解,从而减少废弃矿井水中的部分污染因子。在双碳目标的背景下,合理、有效、安全地对煤矿进行开采,对中国采空区矿井水污染控制、治理具有积极推动作用和科学意义,同时缓解了矿山生产与采矿区矿井水利用之间的矛盾,具有深远的影响意义和更为广泛的应用空间。
20世纪90年代后期,随着发达国家较早进入工业化进程,煤炭的开采量在长时间增加后出现大量废弃煤矿以及污染废水,发达国家开始寻找解决问题的方法。受地质条件及周边环境因子的影响,水化学特征演变也不尽相同。21世纪以来,随着国外对废弃矿井水研究逐渐深入,各种解决方案也逐渐成熟,污染治理手段相对成型;中国地质条件及水文条件差异巨大,加之技术起步时间晚,发展时间较短,但国内学者也尤其认识到废弃煤矿及矿井水对环境和人类会引起较大危害。陈永亮等[5]以神东矿区工程实践为例,发现了矿井水中氟化物含量过高的现象,同时分析了其来源和形成机制,对生态用水灌溉提出了适宜性评价。王鹏等[6]以甘肃陇南市西和县废弃矿山为研究对象,在调查和测绘的基础上分析了废弃矿山存在的问题,提出了以削坡和地形整饰为基础,以挡墙工程、截排水工程以及绿化工程技术为辅助的绿色生态修复措施。袁亮等[7]提出了考虑关闭/废弃矿井水文地质条件,分析地下水系统和环境特征并基于应力场-裂隙场-渗流场的耦合演化规律,实现对矿井水进行智能精准开发;刘敏等[8]以峰峰矿区矿井水污溉的农田土壤为例,分析了其中重金属的污染来源,并进行了环境重金属评估。国内学者的现阶段研究多关注于矿井水的开发与环境中污染现状的评价,研究中对采空区矿井水中特征污染因子来源以及通过其自相反应达到净水效果的研究较少。
鉴于此,现通过乌兰木伦煤矿新鲜煤样与采空区现场水样168 d的浸泡试验,开展矿井水定期取样、常规水质指标及特征离子铁锰浓度的测定工作,首先利用实验结果探寻废弃矿山采空区矿井水中影响特征污染因子铁锰离子变化规律的主控因素;然后利用离子比例系数法和Pearson相关系数法分析并揭示矿井水水质演化的形成机制;最终在矿井水污染上提供原位处理建议,进而减少煤矿开采过程中造成的人为污染问题,为中国废弃煤矿矿井水污染控制及矿井水利用提供一定的参考依据。
神东矿区位于陕西省北部和内蒙古鄂尔多斯市南部,常年气候干燥且降水稀少,水资源匮乏。神东矿区地表水系统发达,其典型的浅埋深、薄基岩、富含水的厚松散层条件易诱发矿井水害的发生。神东矿区的主要水害威胁是具有灾害影响大、破坏范围广等特点的突水溃砂型水害,对煤矿的安全、有效开采有较大的危害。乌兰木伦煤矿位于内蒙古自治区鄂尔多斯市伊金霍洛旗境内,隶属于中国神华能源股份有限公司。其西北距伊金霍洛旗约30 km,行政区划隶属于乌兰木伦镇。西邻乌兰木伦河,东北边界靠近考考赖沟,西北界靠近公捏尔盖沟,北界靠近淖尔壕八社村庄。
选取2种典型新鲜煤样和1类采空区矿井水水样,通过电镜扫描、X射线荧光(X-ray fluorescence,XRF)、X射线衍射(X-ray diffraction,XRD)检测后,控制温度、压力和固液比等参数最大程度模拟采空区环境,每一类煤样充分混合并研磨至40目(≤0.45 mm),最大程度模拟煤炭行业中的“细粉”,并将其标记为CYM、BNM;将煤样破碎成一定粒径大小,以观察其表面形态结构的变化;选取采空区矿井水水样,将其作为浸泡试验用水。在室内对煤样进行浸泡试验,水样采集后,将其置于黑暗环境中并在25~30 ℃条件下密封保存,最大程度还原采空区真实情况,在实验室经0.45 μm玻璃纤维滤膜过滤后检测其中各组分的含量,提取上清液并进行过滤,使用Hydrolab多参数水质分析仪测定水质参数及电感耦合等离子体质谱仪(inductively coupled plasma mass spectrometry,ICP-MS)测定铁、锰离子的浓度。
为保证实验环境接近煤矿地下水库实际条件,瓶口密封并置于25~30 ℃恒温培养箱静置浸泡,分别称取定量的煤样和水样置于浸泡瓶中,随后调节试验箱体的温度和压力。平行试验设置3组,以1、2、4、7、14、21、42、84、168 d的时间间隔取样,共计288组,进行批量浸出试验。
通过SEM-EDS扫描电子显微镜、XRD及XRF观察煤样浸泡前后表面的形态结构并测定煤中的主要化学成分组成,对过滤并烘干后的煤块进行矿物成分、主量元素及微量元素的检测;过滤浸泡煤样后的水样,同时检测常规水质指标及特征污染因子浓度。采用离子比例系数方法分析其水化学组分的形成以及来源,并利用Pearson相关系数法分析离子之间的来源关系。
煤样的矿物组成是探究煤-水相互作用的重要前提。如图1所示,利用XRF对长焰煤、不粘煤的化合物组成分析得知:长焰煤中SiO2、Al2O3占氧化物总量的90%,而不粘煤中CaO占较大比重。
图2所示,通过XRD对长焰煤、不粘煤的矿物组成分析得知:长焰煤的主要矿物成分为高岭石(70.40%)、石英(25.80%)、方解石(2.60%)、黄铁矿(1.40%);不粘煤的矿物组成主要为高岭石(49%)、方解石(9.9%)、石英(17.9%)、黄铁矿(1.8%),二者主要矿物均为高岭石,但不粘煤中高岭石含量更高。
实验采用扫描电镜(scanning electron microscope,SEM)+能谱仪(energy dispersive spectrometer,EDS)进行表面分析,放大倍数为25万~100万倍,分辨率为1.0 nm(15 kV)/1.4 nm(1 kV),最大可测200 mm直径。将筛选出来的煤样放至镜下观察,放大直径控制在30~100 μm,如图3所示,长焰煤煤样较为致密,浸泡前为处理过的平整煤块,有一定量的铸膜孔出现,孔洞不具有明显形态变化,裂隙之间相互沟通,并伴有少量结晶矿物出现;浸泡后的煤样表面较之前光滑,煤样破碎程度更高,裂隙被岩溶矿物充填覆盖,有明显的溶蚀痕迹,同时吸附质自矿物表面向裂隙中扩散。
在水化学分析中,通常使用pH、总溶解固体(total dissolved solids,TDS)、氧化还原电位(oxidation-reduction potential,ORP)、溶解氧(dissolved oxygen,DO)作为基本水质指标,其与水样中常规离子的化学浓度有关,同时水质指标的变化趋势也可以反映水样总体变化规律。分别选取浸泡1、2、4、7、14、21、42、84、168 d作为取样时间,通过两种煤样水质指标的变化进行对比分析并归纳其规律,结果如图4所示。
(1)与不粘煤相比,长焰煤TDS在4 d和14 d出现明显的波动,最终两种煤样均呈现低于初始值的终值。峰值在4 d出现,达到712.00 mg/L,经短暂下降后14 d达到次峰值(696.00 mg/L),说明此时溶液中析出的沉淀最多,煤-水反应相对较弱,矿物溶解量小于矿物沉淀量。通过两种煤样含量变化图像的斜率得出,长焰煤与溶液反应更为剧烈。在浸泡过程中,阳离子可能发生反应最终生成沉淀,使TDS终值减少。不粘煤终值(641.22 mg/L) 略低于长焰煤(650.67 mg/L),说明不粘煤的煤-水反应更加强烈。
(2)两种煤样的ORP趋势大致相同,均在42 d时达到最低点,长焰煤达到117.00 mg/L,不粘煤达到123.30 mg/L,42 d之后出现回升趋势,在实验过程中,溶液还原作用强于氧化作用,终值较初始值出现降低。
(3)两种煤样的DO在小幅变化后最终略低于初始值,整体变化趋势较为稳定。说明溶液在进行缓慢长过程的氧化反应。
(4)两种煤样的pH均在一定的变化后出现上升的趋势。长焰煤的pH在4 d达到最低值(7.65),7 d达到最高值(8.05),变化幅度较为明显。两种煤样均在14 d时达到稳定值7.9,略高于初始值7.72,反映两种煤样在浸泡液中,均具有维持溶液酸碱平衡的能力。
地下水水化学特征是水文地质长期作用的结果,通过分析水中存在的特征离子对于探究煤-水相互作用过程具有重要的意义。铁、锰元素在自然界中广泛存在,他们原子序数相邻且核外电子排布相似,都具有一定的还原性且均可以以多种价态存在,但是过量的铁、锰在生产生活中有诸多危害,会影响生态环境、改变农作物生长周期,还会对人体造成伤害。因此,通过剖析Fe3+和Mn2+两种具有代表性特征离子在煤-水相互作用过程中的变化规律,来探究废弃煤矿矿井水水质演化成因机制,结果如图5所示。
1)Fe3+浓度变化分析
两种煤样在浸泡过程中变化趋势大致相同,经小幅下降后在4 d达到最高值,经过一定的波动后在42 d达到较高值,在84 d时达到最低值,证明此时沉淀析出量最大之后浓度又出现小幅上升,终值与初始值大致相同。
Fe3+浓度变化的主要原因在于,在实验初期1 d存在较高浓度的氧气,会加快黄铁矿的氧化,Fe3+大量释放,但随着浸泡时间延长至4 d,氧被消耗殆尽,其释放效率也逐渐降低。除此之外,黄铁矿水解产出的氢氧化铁沉淀,也使其后期生产沉淀,进而减少其溶解的浓度。
2)Mn2+浓度变化分析
Mn2+在不粘煤浸泡开始时的滤液中浓度迅速下降,在1 d时Mn2+浓度已经趋于0,说明溶液浸泡过程中有与Mn2+发生强烈反应的物质,浸泡后迅速析出沉淀,最终几乎全部析出。长焰煤中Mn2+浓度1 d时出现一定减少,值在4 d时达到次高值,而后小幅下降,浸泡168 d后相对于1 d时的值出现小幅增长。
在不同成因和条件下所形成的地下水化学组分,其各组分的某些比例系数有明显不同[10],不同水中离子毫克当量浓度在数值上也会存在明显差异,因此,利用离子比例系数方法对地下水化学组分的形成以及来源[12]做了进一步分析,结果如图6所示。
Na+/Cl-系数是表征地下水中钠离子富集程度的一个重要水文地球化学参数[12]。若Na+/Cl-值接近于1,则表明Na+、Cl-的主要来源为岩盐的溶解[式(1)]。根据图6(a)可知,样点均分布在Na+/Cl-=1线之下,说明岩盐的溶解并非反应后水溶液中Na+和Cl-的唯一来源,多出的Na+还可能来源于煤中硅酸盐等含钠矿物的溶解,如钠长石的溶解[式(2)]。此外,水溶液中发生的阳离子交替吸附作用[式(3)]对Na+的浓度也有影响,水中的Ca2+不断和Na+发生交换。反应式如下。
$\mathrm{NaCl} \longrightarrow \mathrm{Na}^{+}+\mathrm{Cl}^{-}$
$\begin{array}{l} 2 \mathrm{NaAlSi}_{3} \mathrm{O}_{8}(\text { 钠长石 })+2 \mathrm{CO}_{2}+11 \mathrm{H}_{2} \mathrm{O} \longrightarrow \\ 2 \mathrm{Na}^{+}+\mathrm{Al}_{2} \mathrm{Si}_{2} \mathrm{O}_{5}(\mathrm{OH})_{4}+3 \mathrm{H}_{4} \mathrm{SiO}_{4}+2 \mathrm{HCO}_{3}^{-} \end{array}$
$\mathrm{Ca}^{2+}+2 \mathrm{NaX}=\mathrm{CaX}_{2}+2 \mathrm{Na}^{+}$
同样,Ca2+/S O 4 2 -系数接近1通常反映水体中Ca2+、S O 4 2 -主要来源于硫酸盐矿物的溶解,如石膏[式(4)]。根据图6(b)可知,样点均分布在C a 2 +  /S O 4 2 -=1线之上,可能是石膏的溶解促使溶液中Ca2+由液相转入固相,如形成碳酸钙的沉淀;或者由于阳离子交换作用使溶液中Ca2+的毫克当量浓度降低。
$\mathrm{CaSO}_{4}+2 \mathrm{H}_{2} \mathrm{O} \longrightarrow \mathrm{Ca}^{2+}+\mathrm{SO}_{4}^{2-}+2 \mathrm{H}_{2} \mathrm{O}$
Ca2+/HC O 3 -=1表明Ca2+、HC O 3 -主要来源于碳酸盐矿物的溶解,如方解石[式(5)、式(6)]。由图6(c)可知,两种浸溶液Ca2+/HC O 3 -大部分沿着Ca2+/HC O 3 -=1分布,长焰煤浸溶液Ca2+/HC O 3 -呈离散状态分布,不粘煤浸溶液Ca2+/HC O 3 -呈聚集状态分布。
$\mathrm{CaCO}_{3}+2 \mathrm{H}^{+} \longrightarrow \mathrm{Ca}^{2+}+\mathrm{H}_{2} \mathrm{O}+\mathrm{CO}_{2} \uparrow$
$\mathrm{CaCO}_{3}+\mathrm{H}_{2} \mathrm{O}+\mathrm{CO}_{2} \longrightarrow \mathrm{Ca}^{2+}+2 \mathrm{HCO}_{3}^{-}$
水体中的Ca2+、Mg2+的来源主要是碳酸盐、硅酸盐及蒸发岩。根据(Ca2++Mg2+)/(S O 4 2 -+HC O 3 -)的毫克当量比值可以进一步探明Ca2+、Mg2+的主要来源[13]。若比值大于1表明Ca2+、Mg2+主要来源于碳酸盐的溶解,若比值小于1表明Ca2+、Mg2+主要来自硅酸盐与蒸发岩的溶解[14]图6(d)显示样点全部分布在(Ca2++Mg2+)/(S O 4 2 -+HC O 3 -)=1比例线的下方,表明Ca2+、Mg2+主要来自硅酸盐与蒸发岩的溶解。
浸泡液中各离子之间、水质指标之间的相关性受到离子的物理、化学性质及离子间相互作用的影响。水化学之间的相关性分析常用来揭示离子之间的来源关系[15]。选取研究区水样水化学数据中的Fe3+、Mn2+、Na+、Mg2+、Ca2+、K+、Al3+、F-、N O 3 -、S O 4 2 -、HC O 3 -、pH、ORP、TDS、DO共15个水化学参数进行相关性分析,利用SPSS软件[16-17]统计计算得到地下水水化学参数的Pearson相关系数[18]
图7所示,长焰煤浸溶液中Fe3+与Ca2+呈强正相关,由式(5)、式(6)可知方解石的溶解过程中会伴随pH的变化,根据黄铁矿的溶解过程[式(7)、式(8)]推测方解石溶解影响到浸溶液的pH,进而影响到黄铁矿的氧化,所以Fe3+与Ca2+呈明显正相关关系。Fe3+与各水化学参数间无显著负相关性。
$2 \mathrm{FeS}_{2}+7 \mathrm{O}_{2}+2 \mathrm{H}_{2} \mathrm{O} \longrightarrow 2 \mathrm{Fe}^{2+}+4 \mathrm{SO}_{4}^{2-}+4 \mathrm{H}^{+}$
$4 \mathrm{Fe}^{2+}+\mathrm{O}_{2}+4 \mathrm{H}^{+} \longrightarrow 4 \mathrm{Fe}^{3+}+2 \mathrm{H}_{2} \mathrm{O}$
Mn2+与DO呈较强的正相关关系(R=0.824),DO是指溶解于水中的分子状态的氧,溶解氧的含量能够反映出水体的污染程度。由前文得知浸泡过程中Mn2+与DO的浓度较初始值均变小,反映了污染物在水体中进行自我净化时消耗了溶解氧,故Mn2+与DO呈正相关。
图8所示,不粘煤浸溶液中Fe3+与Ca2+也呈强正相关关系,推测和长焰煤浸溶液一样受到方解石溶解的显著影响。Fe3+与各水化学参数间无显著负相关性。
与长焰煤浸溶液相比,Mn2+与HC O 3 -正相关性增强、与pH负相关性增强。一般来说,HC O 3 -主要来自方解石、白云石的溶解,而方解石的溶解会消耗部分H+[式(5)]而使溶液中OH-增多,可溶性的锰盐在此时的碱性环境下与OH-发生沉淀反应[式(9)],OH-被消耗,pH降低,生成的Mn(OH)2很快被氧化成水合的二氧化锰[式(10)],而四价锰盐不稳定,在还原性介质存在的条件下容易被还原成Mn2+,这也使得浸泡液中Mn2+增多。
$\mathrm{Mn}^{2+}+2 \mathrm{OH}^{-} \longrightarrow \mathrm{Mn}(\mathrm{OH})_{2}(\text { 白 }) \downarrow$
$2 \mathrm{Mn}(\mathrm{OH})_{2}+\mathrm{O}_{2} \longrightarrow 2 \mathrm{MnO}(\mathrm{OH})_{2}$
基于神东矿区乌兰木伦煤矿新鲜长焰煤与不粘煤浸泡实验,在实验前对煤样进行XDR、XDF检测,获得其矿物组成及主要化学成分;进行168 d跟踪浸泡试验,测得两种煤样在采空区矿井水浸泡下Fe3+、Mn2+浓度变化规律,发现Fe3+的变化成“类波浪状”,两种煤样在变化中出现趋势一致、范围不同的特点;Mn2+浓度在两种煤样中趋势和范围均大致相同;经离子比例系数法及Pearson分析法进一步分析变化原因得出,采空区矿井水中主要发生的水岩相互作用有硅酸盐岩和蒸发盐岩的溶解及阳离子交替吸附作用。
(1)由于采矿活动的影响,采空区矿井水受硅酸盐岩和石膏的溶解作用强烈;两种浸溶液水化学参数间的相关性均受到碳酸盐岩溶解的影响,而不粘煤浸溶液受到方解石溶解作用的影响更为显著。
(2)采空区矿井水中主要发生的水岩相互作用有硅酸盐岩和蒸发盐岩的溶解及阳离子交替吸附作用;以煤矿采空区现场矿井水为例研究废弃矿山矿井水水质演化,以期改善矿井水污染实现绿色矿山的目标。
(3)长焰煤和不粘煤的主要矿物均为高岭石,高岭石具有一定的吸附作用,受矿井水及煤样相关组分影响,矿井水中Fe3+的浓度明显高于Mn2+,其对水环境污染潜在风险更大。
(4)在整个研究周期中,Fe3+的浓度呈“类波浪状”变化,Mn2+的浓度短时间内变化较快,矿井水中的Fe3+和Mn2+在长期水-煤相互作用下均会在特定时间内达到最低值。
(5)合理调控采空区煤-水相互作用时间,可满足不同领域的不同的矿井水水质需求,进一步提高矿井水利用效率和效益。
(6)由于水煤相互作用是一个较为复杂的过程,Fe3+、Mn2+与其他离子之间的关系有待进一步深入研究。
  • 山东省自然科学基金(ZR2022MD101)
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doi: 10.12404/j.issn.1671-1815.2400923
  • 接收时间:2024-02-01
  • 首发时间:2025-07-29
  • 出版时间:2025-01-08
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  • 收稿日期:2024-02-01
  • 修回日期:2024-10-10
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山东省自然科学基金(ZR2022MD101)
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    山东科技大学地球科学与工程学院, 青岛 266590
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2种不同金属材料的力学参数

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Percentage of
total species (%)

Genus
种数
Number of
species
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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