發(fā)布時(shí)間：2018-04-04 14:25

  本文選題：娘子關(guān)巖溶水系統(tǒng)　切入點(diǎn)：采礦活動(dòng)　出處：《中國(guó)地質(zhì)大學(xué)》2017年博士論文

【摘要】：巖溶地下水歷來(lái)是巖溶地區(qū)重要的供水水源,近年來(lái)由于受城鄉(xiāng)經(jīng)濟(jì)的發(fā)展及全球氣候變化的影響,對(duì)地下水的需求量急劇增加。特別是在我國(guó)北方碳酸鹽巖分布地區(qū),地表水資源分布嚴(yán)重不均,污染日趨嚴(yán)重,巖溶水資源的開(kāi)發(fā)利用和合理保護(hù)也就顯得日益重要。娘子關(guān)泉是我國(guó)北方最大的巖溶泉之一,也是陽(yáng)泉市工農(nóng)業(yè)生產(chǎn)和人民生活的重要供水水源,對(duì)地方經(jīng)濟(jì)的可持續(xù)發(fā)展具有至關(guān)重要的作用。然而,自從20世紀(jì)80年代以來(lái),隨著社會(huì)經(jīng)濟(jì)的快速發(fā)展,由于降雨量周期性變化、過(guò)度開(kāi)采地下水和受采煤疏干影響,使得地下水水位持續(xù)下降。更為嚴(yán)重的是在氣候變化和人類活動(dòng)影響下,巖溶水水質(zhì)惡化現(xiàn)象顯著,硬度和硫酸鹽等指標(biāo)嚴(yán)重超標(biāo),同時(shí)伴隨著其它致毒性組分含量升高,生態(tài)環(huán)境惡化。由于地下水水質(zhì)下降導(dǎo)致的可利用水資源量減少,已嚴(yán)重影響了城市工農(nóng)業(yè)的健康發(fā)展。在整個(gè)研究區(qū)內(nèi),由采煤活動(dòng)引起的酸性礦坑排水會(huì)對(duì)地表水和地下水水質(zhì)造成影響。煤系地層富含各種有機(jī)、無(wú)機(jī)成分,在煤礦采掘與空氣接觸后,硫鐵礦等被氧化,使得礦坑水酸化并極大地增強(qiáng)其溶解能力,地層中礦物以及采掘設(shè)備損耗的金屬成分被溶入水中而導(dǎo)致水質(zhì)惡化。礦坑水水質(zhì)總體上有如下特征:(1)pH值偏低,(2)硫酸根離子含量偏高,(3)硬度偏大,(4)溶解性總固體高,(5)鐵離子含量高。本文通過(guò)水文地球化學(xué)、鍶同位素以及室內(nèi)水巖相互作用實(shí)驗(yàn)等方法來(lái)探究人類采礦活動(dòng)影響下娘子關(guān)泉域巖溶水的水質(zhì)演化特征以及礦坑水對(duì)研究區(qū)內(nèi)碳酸鹽巖物理性質(zhì)的影響。文章內(nèi)容可分為以下三個(gè)部分:1.娘子關(guān)巖溶系統(tǒng)水文地球化學(xué)特征以及采煤活動(dòng)對(duì)巖溶水水質(zhì)的影響本文運(yùn)用水文地球化學(xué)分析,多元統(tǒng)計(jì)分析,以及地球化學(xué)模擬等方法對(duì)娘子關(guān)泉域采礦活動(dòng)對(duì)巖溶水水質(zhì)的影響進(jìn)行了評(píng)估。娘子關(guān)泉是中國(guó)北方最大的巖溶泉之一,沿著地下水流動(dòng)的方向出現(xiàn)了嚴(yán)重的水質(zhì)惡化現(xiàn)象,比如巖溶水中硫酸鹽、硝酸鹽和TDS均被檢測(cè)到有明顯的上升。在泉域補(bǔ)給區(qū),所采集的水樣主要為Ca-Mg-HCO3型水,在煤礦開(kāi)采區(qū)域的水樣以Ca-Mg-HCO3-SO4為主,在排泄區(qū)域則以Ca-Mg-SO4-HCO3/HCO3-SO4為主。運(yùn)用主成分分析法(PCA)將所采集的水樣提出4個(gè)主成分,能夠解釋大于82.9%的總變化量。其中,所占的比例最大的因子1為45.33%,說(shuō)明煤礦開(kāi)采活動(dòng)和自然水-巖相互作用是作為最主要的控制喀斯特水質(zhì)量的影響因素。人類活動(dòng)影響被當(dāng)做因子2提出來(lái),其NO3-和Cl-的因子載荷都很高并且偏正。其他兩個(gè)因子分別可以解釋共沉淀去除微量元素以及硅酸鹽礦物溶解,占總變化量的20.96%。由于用硫同位素來(lái)估算礦坑水與巖溶水的混合比會(huì)導(dǎo)致結(jié)果偏高,本文根據(jù)硫酸鹽含量建立一個(gè)雙端元混合模型來(lái)估算礦坑廢水在巖溶水中所占的混合比例。模擬結(jié)果表示,礦坑水對(duì)地下巖溶水的貢獻(xiàn)在1.11-27.05%之間,這比用硫同位素方法得到的結(jié)果要低將近3倍。2.基于D,18O,~(87)Sr/~(86)Sr以及Sr/Ca特征對(duì)娘子關(guān)巖溶地下水污染物來(lái)源再認(rèn)識(shí)本文對(duì)娘子關(guān)泉域所采集的樣品進(jìn)行了水化學(xué)分析和同位素(D,18O和~(87)Sr/~(86)Sr)分析。聯(lián)合研究區(qū)水樣中主要離子的水化學(xué)特征和穩(wěn)定同位素特征可以確定(1)地表水和地下水的化學(xué)組分來(lái)源,(2)巖溶地下水可能經(jīng)歷的水化學(xué)過(guò)程,以及(3)采礦活動(dòng)對(duì)巖溶地下水的影響。就巖溶水、裂隙水和泉水而言,他們的水化學(xué)類型從Ca-HCO3演變?yōu)榻咏乇硭偷V坑水的Ca-SO4,表明沿著地下水流動(dòng)方向從補(bǔ)給區(qū)到煤礦開(kāi)采區(qū),地下水經(jīng)歷了一個(gè)混合過(guò)程。lgCa和lgSr的線性關(guān)系表明在大多數(shù)水樣中鍶的一個(gè)可能性來(lái)源為碳酸鹽巖的溶解。根據(jù)水樣中Sr/Ca和Sr/Mg的比例可以確定兩個(gè)端元水體。端元MW3的特征為Sr/Ca和Sr/Mg的比例都很高,但是端元RW1則具有相當(dāng)?shù)偷腟r/Ca比值。像水樣KW8和Sf8都比較靠近MW3端元,這可以解釋為它們與礦坑水發(fā)生了混合作用。像水樣Sf6、KW17和FW2都很靠近端元RW1,這些水樣可以歸因于大氣降水的輸入。巖溶地下水水樣的穩(wěn)定氫氧同位素組成都分布比較廣,δ18O的分布范圍是-9.93到-6.85,δD的范圍是-69到-50.2。泉水是巖溶地下水的主要排泄方式,其氫氧同位素的分布范圍分別為-69到-50.2和-9.93到-6.85,這比巖溶水的分布范圍要低很多,并接近于雨水樣品的分布范圍。根據(jù)18O和D的分布情況,大部分水樣都分布在全球大氣降水線附近(GMWL,δD=8δ18O+10),表明這些水樣都受大氣降水補(bǔ)給。其中,巖溶水樣的同位素組成分布范圍比較廣并且有輕微的偏離大氣降水線,這反應(yīng)了巖溶水中同位素分布受到蒸發(fā)作用的影響。高~(87)Sr/~(86)Sr以及低Sr/Na比值表明了一些巖溶水樣和礦坑水樣都來(lái)自硅酸鹽礦物的溶解,比如水樣KW21和MW3。低~(87)Sr/~(86)Sr以及高Sr/Na比值則表示巖溶水是碳酸鹽巖來(lái)源的,比如水樣KW8。由于硅酸鹽來(lái)源的水和礦坑水對(duì)巖溶水有共同影響的作用,因此本文建立了一個(gè)三端元混合計(jì)算模型。巖溶地下水主要分布在礦坑水混合比例小于10%的區(qū)域,說(shuō)明采礦活動(dòng)的影響不是很顯著。其中礦坑水混合比例最高的是巖溶水樣KW8,高達(dá)20%。3.酸性礦坑水-碳酸巖含水介質(zhì)水巖作用行為實(shí)驗(yàn)研究碳酸鹽巖礦物的溶解控制著娘子關(guān)巖溶地下水系統(tǒng)中的主要離子組分。由反應(yīng)溶液穿透孔隙介質(zhì)引起的礦物溶解或沉淀經(jīng)常會(huì)使孔隙體積和孔隙比表面積發(fā)生改變,并影響孔內(nèi)流體和運(yùn)移參數(shù),比如飽和/相對(duì)滲透率、孔隙度、反應(yīng)比表面積、毛細(xì)管壓力曲線以及孔徑分布特征。在3組巖心穿透實(shí)驗(yàn)中,Ca、Mg和堿度的升高表明是來(lái)源于白云石和方解石的溶解。在對(duì)巖心RD2進(jìn)行的穿透實(shí)驗(yàn)中,在流出溶液中檢測(cè)到Na+和Si有輕微的上升,表明可能是鈉長(zhǎng)石的溶解。值得注意的是,初始溶液S1中的Fe3+和S2中的Fe2+在穿透實(shí)驗(yàn)后基本下降到儀器檢測(cè)線附近,表明溶液經(jīng)歷了鐵水合物的沉淀過(guò)程。在巖心RD2中,鐵離子濃度的峰形曲線表明經(jīng)過(guò)13天的穿透實(shí)驗(yàn)出現(xiàn)了蟲孔,導(dǎo)致流體在巖心中的駐留時(shí)間變短。然而,優(yōu)勢(shì)流通道不會(huì)一直存在,因?yàn)殍F水合物的沉淀會(huì)堵塞通道,這可以從鐵濃度在后5天中的濃度又逐漸減少得到印證。對(duì)于粗粒白云巖巖心RD1,初始穿透溶液pH為3.27,主要重金屬離子為Fe3+,在15天的穿透實(shí)驗(yàn)后總孔隙度從3.1%減小到1.7%,滲透率只是輕微的從0.7751×10-3μm2減少到0.7469×10-3μm2。對(duì)于白云巖巖心RD2,初始穿透溶液pH為2.3,主要重金屬離子為Fe2+,在20天的穿透實(shí)驗(yàn)后,其總孔隙度從4%減小到2.7%,滲透率從0.~(86)51×10-3μm2下降到0.8471×10-3μm2。這表明當(dāng)實(shí)驗(yàn)室制備的酸性礦坑水與白云巖巖心接觸后,有礦物沉淀在孔隙表面積并且堆積起來(lái)從而導(dǎo)致有效反應(yīng)表面積的減少。除此之外,我們還對(duì)這些穿透實(shí)驗(yàn)前后的巖心進(jìn)行氮?dú)馕綄?shí)驗(yàn)。其熱力學(xué)曲線屬于類型I和IV的結(jié)合。在相對(duì)壓力較低的區(qū)域,熱力學(xué)曲線表現(xiàn)出較高的吸附性,說(shuō)明巖石中主要存在微孔(類型I),在相對(duì)壓力較高的區(qū)域(P/P00.45),其熱力學(xué)曲線呈現(xiàn)一個(gè)滯回環(huán),說(shuō)明在介孔中存在毛細(xì)管冷凝(類型IV)。主要涉及碳酸鹽巖中孔徑分布變化的過(guò)程為為以下兩個(gè):(1)酸性流體穿透碳酸鹽巖可以刺激微孔裂隙的形成,增加介孔數(shù)量;(2)由于pH的升高而導(dǎo)致鐵水合物的納米顆粒形成,這些納米顆�？梢愿街诳紫侗砻娌p小平均孔徑。
[Abstract]:Karst groundwater is always an important water source in karst area in recent years, due to the impact of urban and rural economic development and global climate change, the demand for groundwater increased rapidly. Especially in the distribution area of Northern Rock carbonate in China, the distribution of surface water resources is extremely uneven, serious pollution, water resources development and utilization of the karst reasonable protection will become increasingly important. The Niangziguan Spring is the largest karst spring in North China, Yangquan city is also the important water resource for industrial and agricultural production and people's life, has the vital role in the sustainable development of the local economy. However, since 1980s, with the rapid development of social economy, due to periodic rainfall change, over exploitation of groundwater and coal mining drainage effect, the groundwater level continued to decline. The more serious is the climate change and human activities. Ring, the karst water quality deteriorated significantly, the hardness and sulphate index accompanied by serious exceed the standard, other toxic components content increased, the deterioration of the ecological environment. The groundwater quality decline caused by the reduction of water resources, has seriously affected the healthy development of city industry and agriculture. In the study area, cause by mining activities of acid mine drainage will affect the surface water and groundwater quality. Coal strata rich in organic and inorganic components in coal mine mining and air contact, pyrite is oxidized, the mine water acidification and greatly enhance its ability to dissolve, formation of minerals and mining equipment loss metal components are dissolved in the water due to the deterioration of water quality. The mine has the following characteristics: the overall water quality (1) pH (2) value is low, high sulfate content, (3) greater hardness, total dissolved solids (4), (5) Iron content is high. The hydro geochemistry, strontium isotope and indoor water rock interaction experiment and other methods to explore the impact of human activities under water mining in Niangziguan karst water affect the evolution of characteristics and mine water on the physical properties of the carbonate rocks in the area. The contents of the article can be divided into the following three parts: 1. lady close the karst system hydrogeochemical characteristics and influence of mining activities on karst water quality based on hydrogeochemical, multivariate statistical analysis, and geochemical simulation methods of mining activities off spring snake effect on karst water quality was evaluated. The Niangziguan Spring is the largest karst spring in North Chinese, along the groundwater flow direction appeared serious deterioration of water quality, such as karst water sulfate, nitrate and TDS were significantly increased in spring. Domain recharge area, collected water samples for Ca-Mg-HCO3 water, mainly Ca-Mg-HCO3-SO4 in the coal mining area of water, the discharge area is dominated by Ca-Mg-SO4-HCO3/HCO3-SO4. By using principal component analysis (PCA) collected water samples presented 4 main components, can explain more than 82.9% of the total variation. The factor the largest proportion of the 1 was 45.33%, that of coal mining activities and natural water rock interaction is as the main factors affecting the quality of water control in Karst. The impact of human activities was proposed as the 2 factor, the factor loadings NO3- and Cl- are very high and partial. The other two factors respectively. Explain the removal of trace elements and silicate mineral dissolution precipitation, the total changes in the amount of 20.96%. due to estimate mixed mine water and karst water ratio will lead to the results with high sulfur isotope, according to sulfate The content of building a two endmember mixing model to estimate the mine wastewater for karst water mixing ratio. The results showed that the mine water of underground karst water contribution between 1.11-27.05%, than with sulfur isotope results to low nearly 3 times of.2. based on D, 18O, ~ (87) Sr/~ (86) Sr and Sr/Ca characteristics of Niangziguan karst groundwater pollution source recognition based on Niangziguan water samples were collected for chemical analysis and isotope (D, 18O and ~ (87) Sr/~ (86) Sr) analysis. The main research area in water samples with water chemical characteristics and stable isotope characteristics (1) to determine the chemical composition of groundwater and surface water source, (2) water chemical process of karst groundwater may experience, and (3) the effect of mining activities on the karst groundwater. Karst fissure water and water, water, water chemical type from their Ca-HCO3 Is close to the surface water and mine water Ca-SO4, that along the flow direction of the groundwater from recharge area to coal mining area, groundwater has undergone a mixing process of.LgCa and lgSr showed a linear relationship between the source of the possibility in most samples for strontium carbonate rock dissolution. According to Sr/Ca and Sr/Mg in water ratio can be determined two end water. The characteristics of end member MW3 for Sr/Ca and Sr/Mg were high, but the end is Sr/Ca yuan RW1 ratio is quite low. Like water KW8 and Sf8 are relatively close to the end of MW3 yuan, which may explain the mixing effect for their students with mine water. As the water Sf6, and KW17 FW2 is very close to the end of RW1, these samples can be attributed to the precipitation inputs. Groups of stable hydrogen and oxygen isotope of groundwater in the Chengdu karst distribution is wide, -9.93 to the -6.85 distribution range of delta 18O, -69 to -50.2. range is 5 D Spring is the main discharge of karst groundwater, the distribution range of the hydrogen and oxygen isotopes were -69 to -50.2 and -9.93 to -6.85, the ratio of the distribution range of karst water is much lower, the distribution range and close to the water samples. According to the distribution of 18O and D, the majority of water are located in the vicinity of the global meteoric water line (GMWL, Delta D=8 Delta 18O+10), indicating that these samples are recharged by rain. The karst water isotope composition distribution range is relatively wide and slightly deviate from the atmospheric precipitation, the reaction of karst water isotope distribution affected by evaporation. High ~ (87) Sr/~ (86) Sr and low Sr/Na ratio show some karst water and mine water dissolved from silicate minerals, such as water KW21 and low MW3. (87) Sr/~ ~ (86) Sr and high Sr/Na ratio indicates that karst water is carbonate sources, such as water samples by KW8. In silicate sources of water and the mine water has the common influence on karst water effect, so we set up a three endmember mixing calculation model. The karst groundwater is mainly distributed in the mine water mixing ratio is less than 10% of the area, illustrates the influence of mining activities is not very significant. The ore pit water mixing ratio is the highest in karst water KW8, up to 20%.3. of acid mine water - dissolved carbonate rock aquifer water rock interaction behavior experimental study of carbonate minerals in control of the main ion group Niangziguan karst groundwater system in the reaction solution. The penetration of mineral dissolution and precipitation in porous media which often makes the pore volume and pore specific surface area changed. And the influence of hole and fluid transport parameters, such as saturation / relative permeability, porosity, reaction surface area, pore size distribution and capillary pressure curve characteristics. In 3 groups of core penetration In the experiment, Ca, elevated Mg and alkalinity is dissolved from dolomite and calcite. The penetration experiment was carried out on the core of RD2, the effluent solution was detected in Na+ and Si increased slightly, which may indicate albite dissolution. It is worth noting that the initial solution in S1 and Fe3+ S2 Fe2+ in the experiment after the fall to near penetration instrument detection line, show that the solution subjected to precipitation process of iron hydrate. In the core RD2, peak curves of iron ion concentration showed that after 13 days of the experiment through the wormhole, resulting in Yan Xinzhong's fluid residence time becomes shorter. However, the dominant flow channel not always exist, because of the iron precipitation hydrate will block the channel, it can concentration from iron concentration in 5 days and decreased gradually confirmed. For coarse grained dolomite rock RD1, initial penetration solution pH is 3.27, the main heavy metal ions For Fe3+, the total porosity in the penetration experiment after 15 days decreased from 3.1% to 1.7%, the permeability only slightly from 0.7751 * 10-3 M2 reduced to 0.7469 * 10-3 m2. to dolomite rock RD2, initial penetration solution pH is 2.3, the main heavy metal ions is Fe2+, in the breakthrough experiment after 20 days, the total the porosity decreased from 4% to 2.7%, the permeability from 0.~ (86) 51 * 10-3 M2 down to 0.8471 * 10-3 m2. suggesting that the laboratory preparation of acid mine water and dolomite cores after contact with mineral deposits in the pore surface area and piled up resulting in effective reaction surface area decrease. In addition we have to penetrate these, before and after the experiment of core nitrogen adsorption experiment. The thermodynamic curve belongs to the type I and IV. At a relatively low pressure region, the thermodynamic curve shows better adsorption properties, rock existed in micro hole (type I), In the relatively high pressure region (P/P00.45), the thermodynamic curves show a hysteresis loop, indicating the presence of capillary condensation in mesoporous (type IV). The process mainly involves the change of pore distribution in carbonate rocks as the following two aspects: (1) the formation of acid fluid penetrating carbonate can stimulate the micropore fracture, increase mesoporous number; (2) due to the increase of pH and lead to the formation of hydrate iron nanoparticles, the nanoparticles can be attached to the pore surface and average pore size decreased.

【學(xué)位授予單位】：中國(guó)地質(zhì)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：P641.134

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本文編號(hào)：1710344