蒙陕接壤区煤矿采空区水-岩系统中氟来源及释放规律

采空区是高氟矿井水形成的关键区域,其水-岩系统中氟的来源与溶解释放决定了矿井水中氟的富集或贫化。针对蒙陕接壤区3-1煤采空区矿井水氟来源及释放规律不清晰问题,采用水化学测试、岩石矿物成分分析、矿物扫描电镜与能谱检测,以及室内水-岩作用仿真模拟试验,查明矿井水氟物质来源与赋存载体,揭示岩石中氟释放规律。结果表明：研究区3-1煤矿井水水化学类型主要为HCO₃-Na与SO4-Na型,3-1煤采空区矿井水氟浓度高于3-1煤生产工作面的矿井水浓度,且采空区矿井水pH、Na⁺/Ca²⁺浓度比均大于工作面矿井水。3-1煤采空区矿井水F-的物质来源为泥岩与粉砂岩,2种岩石中氟平均含量分别为741、610 mg/kg,氟在固相中的主要赋存载体为蒙脱石、高岭石、伊利石及绿泥石。采空区水-岩系统中氟的释放受岩性、粒径、pH、温度及Na⁺/Ca²⁺浓度比5个因素影响。其中,泥岩及粉砂岩中的氟比细砂岩中的更容易释放进入水中;无论何种岩性,随着粒径的减小,氟释放F-的浓度增大;此外,碱性、高温及高钠低钙的...     

内蒙古托克托县潜水与承压水中氟化物的空间分布特征及形成机理

氟是维持人体健康所必需的微量元素,过多或过少的摄入都会造成相应的健康问题。本研究从氟的来源、迁移和富集等角度,揭示了内蒙古呼和浩特市托克托县高氟地下水的空间分布规律及其在潜水和承压水中富集的原因。对研究区60个水样(30个潜水和30个承压水)进行了统计分析、水化学特征研究、聚类分析以及相关性分析。结果表明：潜水中F^- 浓度为0.40~7.20(2.30±1.80) mg/L,承压水中F^- 浓度为0.29~12.70(1.67±2.48) mg/L;地下水中F-浓度与HCO^-₃、Na⁺、溶解性总固体(TDS)和电导率(EC)呈正相关,与Ca²⁺呈一定的负相关关系。高氟水的水化学类型主要为HCO₃·Cl-Na型。受地下水流场的控制,高氟潜水(>5 mg/L)主要分布在地下水的排泄区;承压水中F^- 的富集主要受含水层岩性的影响,氟高浓度(>1.5 mg/L)分布区主要集中在研究区南部的湖积台地区域。     

基于水化学及稳定同位素的西藏察雅地下热水成因研究

西藏察雅分布有两处地下热水,其中娘曲热水流量达23 356 m ³/d,温度达36 ℃,掌握其成因以及地下水循环模式对铁路隧道的规划建设具有重要意义。为查明地下热水水化学特征及其成因模式,采用同位素水文地球化学方法进行研究。结果表明:两处地下热水主要阳离子为Ca ²⁺和Mg ²⁺,主要阴离子为SO₄^2-和HCO₃^-,溶解性总固体含量为1 255~2 051 mg/L,水化学类型分别为SO₄·HCO₃-Ca·Mg型和SO₄-Ca·Mg型。氢氧同位素分析结果表明,地下热水补给来源主要为大气降水,并具有 ¹⁸O漂移现象,反映了热水与围岩的氧同位素交换效应。地下热水的补给高程为4 146~4 185 m,热储温度为53.1~61.0 ℃,循环深度为1 409~2 020 m。其成因模式为:地下水在东北部高山区接收大气降水入渗补给,沿岩溶裂隙管道径流,经深循环获得大地热流加热,受构造及岩层阻水影响沿断层上升,在上升过程中与份额达0.79~0.91的浅层地下水混合,于沟谷等地势切割处出露成泉。综合水文地质条件与隧道位置分析,隧道穿越的两处岩溶富水条带,东部岩溶富水区对隧道突涌水威胁较小;西部岩溶富水区对隧道存在构造岩溶水高压突涌水风险,后期应注意防范。     

塔里木盆地南缘绿洲带地下水砷氟碘分布及共富集成因

由于地表水资源稀缺,地下水是塔里木盆地南缘绿洲带重要用水水源,因此,系统查明该区地下水砷氟碘的分布及成因至关重要。基于塔里木盆地南缘绿洲带233组地下水水样检测结果,分析不同含水层中高砷、高氟和高碘地下水的空间分布及水化学特征,结合研究区地质、水文地质条件和地下水赋存环境进一步揭示影响地下水砷氟碘的来源、迁移与富集的水文地球化学过程。结果表明:地下水砷、氟、碘浓度变化范围分别为1.091.2 μg/L、0.0128.31 mg/L、10.02 637.0 μg/L。地下水高砷、高氟和高碘水样分别占总水样的7.3%、47.2%和11.6%,砷氟碘共富集占比为3.0%。砷氟碘共富集地下水主要分布于研究区中部的民丰县,水化学类型主要为Cl·SO₄-Na型。自补给区至过渡区再至蒸发区,地下水氟、碘浓度明显增大,砷浓度在过渡区和蒸发区均较大;砷氟碘共富集地下水取样点主要分布于36.060.0 m深度的浅层承压含水层中。浅层地下水受蒸发作用和矿物溶解沉淀作用的影响,随砷氟碘富集项的增多而增大。第四纪成因类型中风积物对氟浓度的影响较大,洪积-湖积物对砷和碘浓度的影响较大。细粒岩性、平缓的地形、地下水浅埋条件、偏碱性的地下水环境、微生物降解作用下有机质介导的矿物溶解是利于砷氟碘共富集的主要机制。     

Br/Cl ratio,Zn and radon constraints on the origin and fate of geothermal fluids in the coastal region of southeastern China

Low-to-medium temperature geothermal fluids in the granite regions of southeastern China are an important renewable energy resource, but they are also a source of contamination containing highly toxic elements such as fluoride and arsenic. This study analyzed the origin of the geothermal fluids in a regional-scale hydrogeological unit in the city of Xiamen, China, based on isotope and hydrochemical analyses. The Br/Cl ratios suggested that the inland geothermal fluid is merely recharged by rainwater from the mountain edge, while the coastal geothermal fluid is originally recharged by the seawater and later mixed with rain-derived groundwater. The geothermal water featured high SiO₂ and detectable Zn concentrations. The former reflects the significant water–granite interaction along the flow path, and the latter indicates the active hydraulic connection between surface waters, shallow aquifers and deep geothermal fluids. High radon content was detected near the deep conductive fault adjacent to a geothermal well, demonstrating that the fault damage zone acts as a major conduit for upward transport of the deep geothermal fluid. As a result, the fault damage zones developed in the granite are necessary for the formation of geothermal water, which leads to the uneven distribution of geothermal water in the subsurface. High-temperature geothermal water can be found in those regions with fairly sparse fault damage zones. In contrast, in the region with high-density fault activities, the active communication between shallow cool water and deep geothermal fluids can decrease the water temperature.

     

Isotope hydrochemical approach to understand fluoride release into groundwaters of Ilkal area,Bagalkot District,Karnataka, India

Isotope and hydrochemical investigations have been carried out in the Ilkal area of Karnataka, India, in order to determine the source and mechanism of fluoride release into groundwaters and to understand groundwater hydrochemistry. Agriculture, granite quarrying and rock-polishing industries are the main occupations in this area. Closepet granite, Peninsular gneiss and Dharwar schists are the major geological formations. Results show that the fluoride concentration in groundwater is 0.3–6.5 mg/L and it is found to increase from recharge area to discharge area. Fluoride variability is found to be influenced by the geology of the area and depth wise correlation was not observed. Water samples are unsaturated with respect to fluorite, indicating the possibility of further increase in fluoride in groundwater. Positive correlations between fluoride with sodium and bicarbonate in groundwater show that high fluoride content and alkaline sodic characteristics are the result of dissolution of fluoride bearing minerals, possibly derived from weathered granite and gneiss. A positive correlation between fluoride and δ¹⁸O, and the presence of high tritium in fluoride-contaminated groundwater, point to contribution from surface waters, contaminated by anthropogenic activities. Dumping of rock wastes that are rich in fluoride into the streams by the rock-polishing industries plays a significant role in contaminating groundwater.     

Early Triassic palynomorphs from Manuguru area of Godavari graben,Andhra Pradesh

High fluoride content in the groundwater is reported from parts of the Gad River Basin, Sindhudurg district, coastal Maharashtra, India. The fluoride content of up to 5 mg/l has been found in the groundwater in laterite, basalt and the Precambrian basement (gneiss) aquifers in the region. The presence of high fluoride in groundwater well above the permissible levels for consumption poses a serious health threat to the rural populace in the region. The presence of tourmaline bearing pegmatites in the Precambrian basement is considered as a potential fluorine source. Deep circulation of fluoride rich groundwater between the latetritised basalts and the underlying crystalline basement could be responsible for the occurrence of fluoride in both the shallow and deeper aquifers of the region.     

Hydrogeological conditions for the forming and quality of mineral waters in Serbia

In the past researches conducted on the territory of Serbia, 5 regional geotectonic units have been distinguished with registered occurrences of 230 mineral springs. Recent analyses of the bottled mineral waters quality have not included systematic examinations of micro-components present in these waters. Based on the analyses of the bottled mineral waters (EuroGeoSurveys Geochemistry Expert Group), it has been observed that the water quality is greatly influenced by the chemical composition of igneous intrusions, regardless of the fact that the analyzed waters have been taken from different aquifers (Neogene sediments, limestone, flysch, schist).     

The distribution and hydrogeological controls of fluoride in the groundwater of central Ethiopian rift and adjacent highlands

Occurrence of fluoride (F) in groundwater has drawn worldwide attention, since it has considerable impact on human health. In Ethiopia high concentrations of F in groundwaters used for community water supply have resulted in extensive dental and skeletal fluorosis. As a part of a broader study, the distribution of F in groundwater has been investigated, and compared with bedrock geology and pertinent hydrochemical variables. The result indicates extreme spatial variations. High F concentration is often associated with active and sub-active regional thermal fields and acidic volcanics within high temperature rift floor. Variations in F can also be related to changes in calcium concentration resulting from dissolution of calcium minerals and mixing with waters of different chemical composition originated from variable hydrogeological environment across the rift valley. The concentration of F dramatically declines from the rift towards the highlands with the exception of scattered points associated with thermal springs confined in local volcanic centers. There are also interactions of F-rich alkaline lakes and the surrounding groundwater. Meteoric waters recharging volcanic aquifers become enriched with respect to F along the groundwater flow path from highland recharge areas to rift discharge areas. Locally wells drilled along large rift faults acting as conduits of fresh highland waters show relatively lower F. These areas are likely to be possible sources of better quality waters within the rift. The result of this study has important implications on site selection for water well drilling.     

Strontium as a tracer of weathering processes in a silicate catchment polluted by acid atmospheric inputs, Strengbach, France

This paper determines the weathering and atmospheric contributions of Ca in surface water from a small spruce forested silicate catchment (N–E France) receiving acid atmospheric inputs. The bedrock is a granite with K-feldspar and albite as dominant phases. The calcium content in plagioclase is low and the Ca/Na ratio in surface water is high, reflecting other sources of calcium from those expected from the weathering of major mineral phases. The biotite content is low. Only traces of apatite were detected while no calcite was found in spite of a major hydrothermal event having affected the granite. The strontium isotopic ratio ⁸⁷Sr/⁸⁶Sr and Sr content was used as a tracer of weathering and was determined in minerals and bulk bedrock, open field precipitation, throughfall, soil solution, spring and stream water. The Sr isotopic ratio of the reacting weathering end-member was predicted by simulating the alteration of the granite minerals by incorporating strontium into the water–rock interaction kinetic code KINDIS. In the early stages of water–rock interaction, K-feldspar and biotite strongly influence the isotopic composition of the weathering solution whereas, the Na-rich plagioclase appears to be the main long-term reactive weathering end-member. Approximately 50% of dissolved Sr in streamwater are atmospherically derived. The ⁸⁷Sr/⁸⁶Sr ratios of exchangeable Sr in the fine fraction at 1-m depth from a soil profile indicate that the amount of exchangeable Sr seems essentially controlled by atmospheric inputs. The exception is the deep saprolite where weathering processes could supply the Sr (and Ca). Na-Plagioclase weathering obviously control the chemistry and the isotopic composition of surface waters. The weathering of trace mineral plays a secondary role, the exception is for apatite when plagioclase is absent. Our hydrochemical, mineralogical and isotopic investigations show that a major part of the strong Ca losses detected in catchment hydrochemical budgets that result from the neutralization of acid precipitation has an atmospheric origin. Consequently, in the long term, in such areas, the availability of such an exchangeable base cation might be strongly limited and surface waters consequently acidified.     

隘高岩体地下水的放射性特征及其找矿效果

本文通过对隘高岩体放射性水化学普查、详查、揭露资料的野外调查和综合分析研究,论述了岩体水化找矿效果好的放射性水文地质条件;研究了水异常的展布特征和控制因素;肯定了岩体的水化找矿效果;给出了水化找矿的标志;进而对放射性水化学普查、详查以及成矿远景预测、水异常点找矿意义的评价提出了看法和建议。     

Morphological Dynamics of the Rivers of Brahmaputra

The Singrauli region is known for fluoride contamination and its effect on human population. In this work the possible sources of fluoride contamination in Rihand reservoir water is constrained. They include slurry water, fly ash and coal samples of various thermal power plants, coal seams and granites of the region. Petrographic study depicted the presence of fluoride bearing minerals - flour apatite in pink granite. Preliminary scanning electron microscope studies revealed presence of fluorine peak in coal samples. The chemical analysis confirmed the presence of fluoride in fly ash (12.6 mg/kg), drain water (5.34 mg/l), soil (6.1 mg/kg), coal (3.1 mg/kg). They confirmed the source of fluoride from coal of thermal power plant which utilized coal from Singrauli coal seam (1.6 mg/kg). Further the Rihand reservoir water is also enriched by fluoride contaminant (upto 4.7 mg/l). This contaminates groundwater of the area as well. The contaminated water used for drinking and agriculture affects health of inhabitants in the area. It is concluded that the main source of fluoride contamination in the study area is due to coal burnt in thermal power plant and pink granite formation of the area, both anthropogenic and geogenic sources are implied.     

Experimental evidence on formation of imminent and short-term hydrochemical precursors for earthquakes

The formation of imminent hydrochemical precursors of earthquakes is investigated by the simulation for water–rock reaction in a brittle aquifer. Sixty-one soaking experiments were carried out with granodiorite and trachyandesite grains of different sizes and three chemically-distinct waters for 6 to 168 h. The experimental data demonstrate that water–rock reaction can result in both measurable increases and decreases of ion concentrations in short times and that the extents of hydrochemical variations are controlled by the grain size, dissolution and secondary mineral precipitation, as well as the chemistry of the rock and groundwater. The results indicate that water–rock reactions in brittle aquifers and aquitards may be an important genetic mechanism of hydrochemical seismic precursors when the aquifers and aquitards are fractured in response to tectonic stress.     

Hydrogeochemical study in the Main Ethiopian Rift: new insights to the source and enrichment mechanism of fluoride

The central Main Ethiopian Rift suffers a severe water quality problem, characterized by an anomalously high fluoride (F) content that causes an endemic fluorosis disease. The current study, conducted in the Ziway–Shala lakes basin, indicates that the F content exceeds the permissible limit for drinking prescribed by the World Health Organization (WHO; 1.5 mg/l) in many important wells (up to 20 mg/l), with even more extreme F concentration in hot springs and alkaline lakes (up to 97 and 384 mg/l respectively). The groundwater and surface water from the highlands, typically characterized by low total dissolved solids (TDS) and Ca (Mg)–HCO₃ hydrochemical facies, do not show high F content. The subsequent interaction of these waters with the various rocks of the rift valley induces a general increase of the TDS, and a variation of the chemical signature towards Na–HCO₃ compositions, with a parallel enrichment of F. The interacting matrixes are mainly rhyolites consisting of volcanic glass and only rare F-bearing accessory minerals (such as alkali amphibole). Comparing the abundance and the composition of the glassy groundmass with other mineral phases, it appears that the former stores most of the total F budget. This glassy material is extremely reactive, and its weathering products (i.e. fluvio/volcano-lacustrine sediments) further concentrate the fluoride. The interaction of these “weathered/reworked” volcanic products with water and carbon dioxide at high pH causes the release of fluoride into the interacting water. This mainly occurs by a process of base-exchange softening with the neo-formed clay minerals (i.e. Ca–Mg uptake by the aquifer matrix, with release of Na into the groundwater). This is plausibly the main enrichment mechanism that explains the high F content of the local groundwater, as evidenced by positive correlation between F, pH, and Na, and inverse correlation between F and Ca (Mg). Saturation indices (SI) have been calculated (using PHREEQC-2) for the different water groups, highlighting that the studied waters are undersaturated in fluorite. In these conditions, fluoride cannot precipitate as CaF₂, and so mobilizes freely without forming other complexes. These results have important implications for the development of new exploitation strategies and accurate planning of new drilling sites. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

冀东北地区中低温对流型地热系统的氟指示意义研究

为查明冀东北地区中低温对流型地热系统中氟的富集过程,通过对地热流体水化学特征和同位素数据的分析,研究地热流体中氟的分布特征、富集规律、水化学过程及影响因素。结果表明:研究区地热流体F^-含量为1.36~23.83 mg/L,呈现北高南低的趋势;在HCO3^-—Na^+和SO4^2-·HCO3^-—Na^+等Na型水中富集程度高于HCO3^-—Ca^2+和HCO3^-—Ca^2+·Mg^2+等Ca型水;碱性环境、温度和循环深度是影响氟离子富集的主要因素;水岩作用、含氟矿物溶解及阳离子交换作用,是控制高氟地热水水化学特征的主要地球化学过程。氟浓度异常可为寻找地热资源提供基础参考线索,为地热资源的科学合理利用提供科学依据。     

江苏丰,沛,铜地区高氟地下水不成因探讨

通过该区太古界一新生界氟的地层地球化学剖面及岩浆岩和土壤中氟的丰度的研究,论证了该区为一高氟的地球化学区。根据重矿物对比研究和地貌分析,阐明了泰沂隆起区太古界和元古界的高氟古老岩系为该区土壤沉积物源,黄河多次泛滥堆积（粘土矿物对氟的吸附）对土壤氟起了叠加富集的作用。研究揭示该区土壤水溶氟较高,经降水淋滤和浸取作用氟转入地下水,并在凹陷区或河间洼地中聚集,水体停泄、蒸发浓缩形成高氟地下水区。     

The chemistry of bottled mineral and spring waters from Norway,Sweden, Finland and Iceland

Twenty-two bottled mineral and spring waters from Norway, Sweden, Finland and Iceland have been analysed for 71 inorganic chemical parameters with low detection limits as a subset of a large European survey of bottled groundwater chemistry (N = 884). The Nordic bottled groundwaters comprise mainly Ca–Na–HCO₃–Cl water types, but more distinct Ca–HCO₃, Na HCO₃ and Na–Cl water types are also offered. The distributions for most elements fall between groundwater from Fennoscandian Quaternary unconsolidated aquifers and groundwater from Norwegian crystalline bedrock boreholes. Treated tap waters have slightly lower median values for many parameters, but elements associated with plumbing have significantly higher concentrations in tap waters than in bottled waters. The small dataset is able to show that excessive fluoride and uranium contents are potential drinking water problems in Fennoscandia. Nitrate and arsenic displayed low to moderate concentrations, but the number of samples from Finland and Northern Sweden was too low to detect that elevated concentrations of arsenic occur in bedrock boreholes in some regions. The data shows clearly that water sold in plastic bottles is contaminated with antimony. Antimony is toxic and suspected to be carcinogenic, but the levels are well below the EU drinking water limit. The study does not provide any health-based arguments for buying bottled mineral and spring waters for those who are served with drinking water from public waterworks. Drinking water from crystalline bedrock aquifers should be analysed. In case of elevated concentrations of fluoride, uranium or arsenic, most bottled waters, but not all, will be better alternatives when treatment of the well water is not practicable.     

SOME LAWS GOVERNING THE MIGRATION OF COPPER,LEAD, AND ZINC IN WATER,AND THEIR SIGNIFICANCE IN PROSPECTING

The author attempts to explain some of the problems of hydrochemical prospecting by study of the migration of certain metals in water. In general the metal content of natural waters is lower than might be expected from their solubilities in pure water. In deposits of Kazakhstan there is a strong influence on the concentration of these elements by the chemical composition and pH of the water. Lead and copper contents are strongly dependent on pH (decreasing with greater pH) and zinc less so. The pH limit of indistinct and discontinuous hydrochemical anomalies is about 7 for copper, 7.2 for lead, and 7.5 for zinc. The predominantly alkaline or neutral waters of raremetal deposits precludes usage of copper, lead, and zinc as indicators. Careful studies are therefore necessary to adequately evaluate anomalies. Data from diverse, unmineralized rocks indicates that limestones and carbon-enriched bottom deposits, and acid intrusives and their tuffs, are most active in lead sorption. The structure of rocks and microorganisms influence metal content in associated waters.—J. A. Redden.     

Fluorine distribution in waters of Nalgonda District, Andhra Pradesh, India

Geochemical and hydrochemical studies were conducted in Nalgonda District (A.P.), to explore the causes of high fluorine in waters, causing a widespread incidence of fluorosis in the local population. Samples of granitic rocks, soils, stream sediments, and waters were analyzed for F and other salient chemical parameters. Samples from the area of Hyderabad city were analyzed for comparison. The F content of waters in areas with endemic fluorosis ranges from 0.4 to 20 mg/l. The low calcium content of rocks and soils, and the presence of high levels of sodium bicarbonate in soils and waters are important factors favoring high levels of F in waters.     

Halogens in water from the crystalline basement of the Gotthard rail base tunnel (central Alps)

Drilling of the new Gotthard rail base tunnel (central Alps) opened a large number of water-conducting fractures in granite and gneiss of the crystalline basement. The overburden reaches locally more than 2000 m and water and rock temperature is up to 45 °C. The tunnel crosses a series of steeply dipping fractured rock units that also crop out at the surface above the tunnel. Recharge water enters the fractured rocks in the high mountainous area, migrates gravity driven to the sampling locality in the tunnel. Along its flow path it reacts with rocks exposed on the fractures where it dissolves the principal granite minerals, resulting in high-pH Na₂CO₃ waters.The tunnel waters contain unusually high concentrations of fluoride ranging from 5 to 29 mg/L. Alteration of F-bearing biotite to F-free chlorite is one of the sources of fluorine. The highest F-concentrations result from the equilibration of low-Ca waters with fluorite. Fluoride concentration is strongly lithology-dependent and sharp discontinuities in both, concentration and saturation state with respect to fluorite occur at the contacts of the different gneiss and granite slabs.Chloride concentrations vary between 1 and 1300 mg/L. In contrast, the Cl/Br mass ratio exhibits small variations and centers around 110 suggesting a common source for the Cl and Br, which is independent of the lithology. In the northern part of the tunnel, Cl and Br are chiefly derived from saline pore fluids of one lithology which is then mixed with low-salinity water along flow paths. Cl/Br ratios of the waters in the southern part of the tunnel section are similar to those measured in experimental leachates from different tunnel rocks, suggesting that leaching of metamorphic fluids in the pore space is the main source of both Cl and Br.