内蒙古河套平原典型高砷区地下水中砷的演化规律

通过对高砷地下水典型区完整地质单元不同深度含水层地下水进行监测,分析了与砷释放、迁移和富集有关的敏感因素（水位、Eh、总铁、亚铁等）的时间和空间变化规律,探讨了高砷地下水的形成机理。结果发现,地下水灌溉区和黄河水灌溉区,地下水水位均受人为灌溉活动的影响。地下水砷含量在空间和时间尺度上发生有规律的变化。在空间尺度上,地下水中砷含量随着深度的增加而升高,井深小于10 m的地下水砷含量在1.88～2.58 μg/L;井深在10~15 m之间的地下水中砷含量在18.2～217 μg/L;井深在15~25 m之间的地下水中砷含量在38.3～226 μg/L。受人为灌溉影响,地下水中砷的含量会随着地下水位的抬升而升高。地下水砷含量随时间变化的原因是水位抬升使水位变化造成氧化还原环境改变。地下水系统中含砷铁氧化物矿物的还原性溶解、脱硫酸作用等是控制地下水砷含量的主要水文地球化学过程。     

吉林省饮水型砷中毒区地下水砷的分布规律与成因研究

吉林省饮水型砷中毒区是继中国内蒙古和山西病区后发现的新病区。该病区主要分布在吉林省西部的通榆县和洮南市,其水文地质单元属于松嫩平原大型蓄水盆地的西部,是由第四系潜水、承压水和新近系承压水组成的多层结构的含水系统。采用瞬时采样法采集了区内潜水和承压水样品,共194份;通过GIS的空间叠加技术、化验与测试技术,进行了区域水化学环境特征与饮水型砷中毒的关系研究。结果表明：受区域地质构造控制,在低洼地带堆积了巨厚的粉砂淤泥质冲积物和富含有机质的湖积物,为地下水砷的赋存提供了空间。区域地下水砷含量的范围值为0.001~0.339 mg·L-1,水砷价态以As(V)为主,高砷水主要分布在由若干隆起形成的中间低洼地带中地下水埋深大于10 m的潜水、第四系和新近系承压水含水层中。高砷地下水的形成与特定的水文地质条件和水化学环境有关,氯化物重碳酸钠型水中的砷含量最高。臭葱石（FeAsO4·2H2O）等含铁、含锰矿物在进入地下水的溶解过程中,形成铁、锰的氧化物和砷的化合物,如砷酸盐和亚砷酸盐。伴随着水环境中Eh的降低,氧化物被还原形成更为活泼的离子组分,吸附在氧化物表面的含砷化合物进而解吸,使砷从含水层的沉积物中向水中溶解和迁移。     

天鹅洲长江故道湿地地下水砷的时空分布特征及控制机理

高砷地下水不仅直接危害供水安全,还可通过与湿地之间的交互作用,影响湿地水质进而威胁湿地生态安全.长江中游河湖平原已被报道广泛分布有高砷地下水,而位于长江中游故道区域的天鹅洲湿地地下水中砷的空间分布特征尚不明确,湿地与地下水的交互作用对地下水中砷季节性动态的控制机理尚不明确.本研究在天鹅洲湿地采集2个水文地质钻孔的35件沉积物样品、12个分层监测井不同季节的共72组地下水样和18组地表水样,通过水位-水化学监测、沉积物地球化学组成分析和砷、铁形态表征探究天鹅洲湿地地下水中砷的时空分布规律及控制机理.研究发现天鹅洲湿地地下水砷含量为1.08~147 μg/L,牛轭湖外侧浅井（10 m）地下水砷含量普遍高于深井（25 m）和牛轭湖内侧浅井（10 m）、深井（25 m）地下水,枯水期和平水期的砷含量高于丰水期.牛轭湖外侧浅层地下水系统具有更厚的粘土、亚粘土沉积,沉积物中总砷、强吸附态砷和易还原的铁氧化物的含量更多,吸附砷的水铁矿等无定形铁氧化物还原性溶解导致砷释放进入地下水中.枯水期天鹅洲湿地底部向牛轭湖外侧浅层含水层输送不稳定的有机质,使天鹅洲湿地地下水-地表水界面成为砷释放的热点区域.丰水期时牛轭湖外侧含水层受长江补给的影响,还原环境发生改变使地下水中的砷和铁被氧化固定从而不利于砷向地下水释放.      

贵德盆地三河流域高砷地下水中溶解性有机物三维荧光特性及其指示意义

溶解性有机物(dissolved organic matter, DOM)可以通过多种方式控制含水层中砷的迁移转化。贵德盆地承压含水层地下水砷含量显著高于潜水含水层。为查明承压水中溶解性有机物对砷浓度的影响,对研究区地表水、潜水以及承压水进行吸光度和三维荧光光谱的分析,利用平行因子分析法确定了水样中有机物成分及荧光特征。结果表明,贵德盆地水体中DOM包含陆源类腐殖质(C1)、受人为影响的腐殖质(C2)、类醌化合物(C3)和微生物来源的腐殖质(C4)4种组分。陆源类腐殖质C1可在地下水中富集,占总有机质的40%~55%。相比于地下水,C2和C3则在地表水中占据较高的比例。高砷承压水中C2、C3所占比例高于低砷潜水。其中,C1可以通过络合作用促进溶解性砷浓度的提高,C3作为电子穿梭体可以促进含砷铁氧化物或氢氧化物的还原性溶解从而释放砷。微生物降解有机质生成的HCO-3可以与砷竞争吸附,促进砷的解吸附。此外,还原性溶解产生的Fe(II)与HCO-3形成FeCO3固定一部分的砷。该研究表明,地下水中的天然有机物通过络合作用和作为电子穿梭体促进铁氧化物还原导致地下水砷的富集,为分析黄河上游地区高砷地下水的成因提供理论依据。     

下辽河平原地下水多年动态变化特征分析

地下水水位动态变化,实际上是含水层中地下水资源量变化的一种反映,地下水水位的升降,直接反映了地下水补给与消耗量的变化.依据多年地下水水位监测数据,总结分析了下辽河平原1996~2005年间孔隙潜水的变化特征及趋势.揭示了孔隙潜水或孔隙承压水在多年升降变化过程中水位动态主要随降水量的变化而变化.此外,地下水开采规模、局部开采布局的调整等措施,也是影响其变化特征的主要因素.     

塔里木盆地南缘浅层高碘地下水的分布及成因:以新疆民丰县平原区为例

塔里木盆地位于欧亚大陆腹地,远离海洋,地下水是塔里木盆地南缘重要的供水水源,查明该区浅层地下水中碘（I-）的分布及成因至关重要.基于新疆塔里木盆地南缘的民丰县平原区44组浅层地下水水样,综合运用水化学图解法、数理统计法和GIS技术,分析潜水和浅层承压水水化学特征、碘的空间分布及高碘地下水的成因.结果表明:民丰县平原区浅层地下水中碘的富集和贫乏共存;潜水和浅层承压水I-含量范围分别为≤730 μg/L和≤183μg/L,潜水水样中缺碘水、适碘水、高碘水和超高碘水占比分别为19.4%、69.4%、5.6%和5.6%,浅层承压水水样中缺碘水、适碘水和高碘水占比分别为12.5%、75.0%和12.5%,潜水中缺碘水和超高碘水均高于承压水.从山前倾斜平原到细土平原,地下水中I-含量呈明显上升趋势.高碘水和超高碘水水化学类型主要为Cl·SO₄-Na型和Cl-Na型.除水文地质条件和偏碱性的地下水环境外,研究区潜水碘主要受强烈的蒸发浓缩作用、第四系全新统沼泽堆积物和矿物溶解沉淀的影响,浅层承压水碘主要受矿物溶解沉淀及还原环境的影响.      

江汉平原典型地区季节性水文条件影响下氮的动态变化规律

江汉平原东部地区地下水硝态氮和氨氮污染严重,地表水-地下水相互作用强烈,季节性水文条件变化极其显著.选取典型试验场地,对试验场内沉积物(0~25 m)氮形态进行测定,并对地下水氮含量及其他水化学指标进行连续性监测.研究表明:沉积物NO₃--N含量较高(25.8~119.48 mg/kg),是可交换态氮的主要组成部分,NH₃-N含量与TOC和TN均呈一定的正相关性,表明NH₃-N含量主要受沉积物中埋藏有机质的控制.试验场深度较深(≥2 m)地下水氮的含量和形态对地下水位波动有明显响应:雨季开始,地下水位抬升,含水介质还原性增强,NO₃--N生成受抑制且通过反应消耗,矿化作用加强,导致NH₃-N成为氮的主要赋存形态;雨季结束,地下水水位下降,含水介质的氧化性增强,NO₃--N的生成受到促进,硝化作用增强而反硝化作用减弱,导致NO₃--N的浓度增加.近地表人类活动(外源输入)对试验场浅表地层(＜2 m)地下水氮形态有明显的影响.自然或者人为因素引起的水文条件变化导致地下水流场的变化,从而改变含水介质固有的氧化还原环境,是导致试验场氮季节性变化的主要原因.      

江汉平原东部地区浅层地下水水化学特征

浅层地下水是江汉平原东部地区重要的供水水源,但面临着污染及天然水质异常等问题.基于水化学与氢氧同位素结果,并运用数理统计和因子分析等方法,查明了研究区浅层地下水的化学特征、控制过程以及影响因素.结果显示,浅层地下水的化学类型主要为HCO₃-Ca型;其中潜水中Ca2+和Mg2+含量与承压水接近,Fe、As和NH₄+含量低于承压水,而Cl-、SO₄2-、Mn和NO₃-含量高于承压水.浅层地下水主要为大气降水补给,其中潜水经历了一定程度的蒸发以及与地表水的混合.在影响浅层地下水化学特征的因素中,地质成因在总体上可能起主导作用;人类活动的输入显著地改变着潜水的化学特征,而浅层承压水则主要受径流过程中水-岩相互作用的影响.      

湛江市深层承压水铁分布和地球化学模拟研究

在广东省湛江市深层承压水开采过程中,在开采区内形成了区域水位降落漏斗。降落漏斗的形成对深层承压水的化学特性产生了一些影响,具体表现为：西部和西北部铁含量低,北部铁含量高,降落漏斗附近铁含量中等。对降落漏斗内深层承压水铁分布进行演化模拟计算,结果表明,降落漏斗内深层承压水的补给可能来自北部高铁承压水、西部和西北部低铁承压水以及浅层承压水。深层承压水由这些地下水混合而成,高铁地下水是主要补给来源。降落漏斗中心区深层承压水的大量人工开采导致其铁含量升高。地下水在向降落漏斗中心区的径流过程中,不但发生了方解石、白云石和赤铁矿的溶解作用以及菱铁矿和水绿矾的沉淀作用,而且发生了Na⁺与Ca²⁺的交换、铁氧化-还原反应等一系列复杂的水-岩作用。     

灌溉活动对大同盆地表层土壤中砷迁移的影响

大同盆地是我国原生高砷地下水典型分布区。高砷地下水常被用作灌溉水源,灌溉回流对表层土壤中砷迁移和富集有着重要影响,但具体机制尚不清晰。通过场地灌溉模拟试验,并结合室内分析,探讨了灌溉活动对表层土壤中砷迁移转化的影响机制。结果表明,灌溉回流不仅导致地表土壤载砷量显著增加,而且引起潜水位快速上升。近地表还原性环境的强化使得含砷铁氧化物还原溶解增强,从而导致了砷的释放。此外,土壤孔隙水离子强度增加促进了离子交换态砷的迁移。灌溉停止后,伴随潜水位回落,氧化环境的增强有利于结晶态铁氧化物的形成,水砷通过吸附和共沉淀作用重新被铁氧化物固定。因此,高砷地下水灌溉通过改变近地表氧化还原环境可促进砷的迁移,砷和铁的输入最终导致表层土壤总砷和铁含量增加。     

Fluoride contamination of groundwater and its seasonal variability in parts of Purulia district,West Bengal,India

The contamination of aquifers by fluoride and arsenic is a major cause of concern in several parts of India. A study has thus been conducted to evaluate the extent and severity of fluoride contamination and also its seasonal variability. Two blocks (Purulia-1 and Purulia-2) were considered for this purpose. Twenty groundwater samples (in each season) were collected from tube wells during the pre-monsoon and post-monsoon seasons. In addition to fluoride, groundwater samples were also analyzed for major cations, anions, and other trace elements. The concentration of fluoride shows significant seasonal variation and ranges between 0.94–2.52 and 0.25–1.43 mg/l during the pre-monsoon and post-monsoon seasons, respectively. In pre-monsoon season, more than 40% of the water samples show fluoride concentrations higher than the WHO limit. However, during the post-monsoon season, none of the groundwater sample shows fluoride concentrations higher than the WHO limit. Lesser concentration during the post-monsoon season is attributed to the dilution effect by the percolating rainwater, which has also been reflected in the form of a decrease in concentrations of other elements. The petrographic studies of the rock samples collected from the study area show that the rocks are mainly composed of plagioclase, orthoclase, and quartz with abundant biotite. The weathering and dissolution of biotite plays an important role in controlling the fluoride concentrations in the groundwater of the study area.     

江汉平原高砷地下水原位微生物的铁还原及其对砷释放的影响

微生物参与铁氧化物矿物的还原性溶解是高砷地下水形成的关键过程,其中具有砷还原功能的微生物如何参与含水层砷释放的生物地球化学过程亟待研究.利用从江汉平原典型高砷含水层中厌氧条件下分离出的四株细菌(Citrobacter sp.JH-1、Clostridium sp.JH-6、Exiguobacterium sp.JH-13、Paenibacillus sp.JH-33),通过室内厌氧模拟培养实验,查明其砷、铁还原能力,并通过分别与铁氧化物矿物及原位沉积物共同培养,探究原位含水层微生物参与的砷释放机理.结果表明:四株细菌均具有厌氧条件下砷、铁还原功能,Citrobacter sp.JH-1砷还原能力最强,96 h内还原的As(Ⅴ)浓度为2.22 μmol/L.其中Citrobacter sp.JH-1不仅可在厌氧和有氧条件下还原溶液中的As(Ⅴ),还可在厌氧条件下还原溶液中的Fe(Ⅲ)和无定型的水铁矿,在与含水层沉积物共培养12 d后,沉积物中铁与砷的释放量分别为510 mg/kg及1 150 μg/kg.江汉平原含水层中的原位微生物兼具砷/铁还原功能,在厌氧条件下可还原沉积物中的铁氧化物矿物并促进砷的释放,为深入揭示高砷地下水成因机理与地下水砷污染的防控提供重要科学依据.      

Assessment of the factors controlling groundwater quality in a coastal aquifer adjacent to the Bay of Bengal,India

A study has been conducted in the heavily populated coastal areas of the Puri district (Odisha, India) with the aim to: (1) identify the factors that influence the major ion composition and concentrations of trace elements in groundwater; (2) determine the spatial distribution of the water-quality parameters and how they vary on a seasonal basis. To do this, groundwater samples were collected from 60 shallow tube wells located along the Puri coast during the pre-monsoon and post-monsoon seasons. Based on their TDS content, 52% of the collected groundwater samples were identified as being brackish-to-saline and unsuitable for drinking purposes in both the pre- and post-monsoon seasons. Significant concentrations of trace elements including Ba, Br, F, Fe, Mn, and Sr were detected in most of the samples. Iron concentrations were found to be higher than the WHO drinking water guideline value (0.3 mg/l) in 92% of the samples irrespective of seasons. Elevated Mn concentrations were observed in 37% and 40% of samples during the pre-monsoon and post-monsoon seasons, respectively. In addition, fluoride concentrations in excess of the WHO limit (1.5 mg/l) were found in 15% of samples during the pre-monsoon and 23% of samples during the post-monsoon season. The concentrations of major and trace elements show wide spatial and minor temporal variations. Large spatial and limited temporal variations in Cl and Na concentrations along with considerable Br and Sr concentrations in groundwater suggest that saltwater intrusion is the dominant process controlling groundwater quality in the study area, although other processes including ion exchange, the precipitation and dissolution of minerals, microbial activity, and the weathering of aquifer material also play roles to some extent in determining the spatial and seasonal distribution of the major and trace elements in coastal groundwater. Grouping of various water-quality parameters related to these processes by principal component analysis and their linking to one cluster in the hierarchical cluster analysis further supports the view that these processes control the groundwater chemistry in the coastal aquifer.     

Temporal variations in arsenic concentration in the groundwater of Murshidabad District,West Bengal,India

Systematic investigations on seasonal variations in arsenic (As) concentrations in groundwater in both space and time are scarce for most parts of West Bengal (India). Hence, this study has been undertaken to investigate the extent of As pollution and its temporal variability in parts of Murshidabad district (West Bengal, India). Water samples from 35 wells were collected during pre-monsoon, monsoon and post-monsoon seasons and analyzed for various elements. Based on the Indian permissible limit for As (50 μg/L) in the drinking water, water samples were classified into contaminated and uncontaminated category. 18 wells were reported as uncontaminated (on average 12 μg/L As) and 12 wells were found contaminated (129 μg/L As) throughout the year, while 5 wells could be classified as either contaminated or uncontaminated depending on when they were sampled. Although the number of wells that alternate between the contaminated and uncontaminated classification is relatively small (14%), distinct seasonal variation in As concentrations occur in all wells. This suggests that investigations conducted within the study area for the purpose of assessing the health risk posed by As in groundwater should not rely on a single round of water samples. In comparison to other areas, As is mainly released to the groundwater due to reductive dissolution of Fe-oxyhydroxides, a process, which is probably enhanced by anthropogenic input of organic carbon. The seasonal variation in As concentrations appear to be caused mainly by dilution effects during monsoon and post-monsoon. The relatively high concentrations of Mn (mean 0.9 mg/L), well above the WHO limit (0.4 mg/L), also cause great concern and necessitate further investigations.     

高砷含水层沉积物含铁矿物特性及其对砷的水文地球化学作用

含水层沉积物中含铁矿物的特征与活性会影响砷的迁移转化行为。通过内蒙古含水层沉积物含铁矿物的溶解、还原动力学实验,研究了沉积物含铁矿物特征和活性及其与砷运移的关系。结果表明,沉积物中具还原活性的铁氧化物总量(m0)与岩性有关,细砂为52 μmol/g,黏土为45 μmol/g。初始还原速率k′均在10-5 s-1的数量级。表征活性均匀度的参数γ值介于合成铁氧化物矿物和表层沉积物之间。沉积物中Fe(Ⅲ)氧化物的还原活性主要介于人造纤铁矿与针铁矿的活性水平范围内。沉积物中可能存在两类活性水平不同的Fe(Ⅲ)氧化物。As更倾向于吸附在活性较强的Fe(Ⅲ)氧化物上。还原环境中,活性较强的Fe(Ⅲ)氧化物的还原性溶解,促进了沉积物中砷的释放。     

蒲阳河流域地下水水化学及同位素特征

保定西部山前地区位于太行山及华北平原交界带,为缓解极端气候灾害对生产生活的影响,维持地下水资源的可持续开发利用,开展相关的地下水水化学及同位素特征研究。研究区地下水化学类型以HCO3—Ca·Mg、HCO3·SO4—Ca·Mg及SO4·HCO3—Ca·Mg为主,区内地下水主要来源于大气降水,流域内地表水补给地下水;地下水中化学成分为Ca2＋、Mg2＋、HCO-3、SO2-4,主要来源于岩石风化作用,同时受到人类活动的影响,地下水中硝酸盐含量明显升高;由于受到褶皱构造的控制,流域的上游及平原区均出现年龄大于60年的地下水,多数岩溶水年龄较复杂,从现代水到大于60年的水均有分布。研究成果为流域内水资源的合理开发利用提供建议,区内岩溶地下水的开发将在一定程度上缓解极端天气的影响。     

Environmental geochemistry of high arsenic groundwater at western Hetao plain, Inner Mongolia

Environmental geochemistry of high arsenic groundwater at Hetao plain was studied on the basis of geochemical survey of the groundwater and a core sediment. Arsenic concentration in groundwater samples varies from 76 to 1093 μg/L. The high arsenic groundwater mostly appears to be weakly alkaline. The concentrations of NO₃⁻ and SO₄²⁻ are relatively low, while the concentrations of DOC, NH₄⁺, dissolved Fe and sulfide are relatively great. Analysis of arsenic speciation in 21 samples shows that arsenic is present in the solution predominantly as As(III), while particulate arsenic constitutes about 10% of the total arsenic. Methane is detected in five samples with the greatest content being 5107 μg/L. The shallow aquifer in Hangjinhouqi of western Hetao plain is of strongly reducing condition. The arsenic content in 23 core sediment samples varies from 7.7 to 34.6 mg/kg, with great value in clay and mild clay layer. The obvious positive relationship in content between Fe₂O₃, Mn, Sb, B, V and As indicates that the distribution of arsenic in the sediments may be related to Fe and Mn oxides, and the mobilization of Sb, B and V may be affected by similar geochemical processes as that of As.     

Seasonal disparity in the co-occurrence of arsenic and fluoride in the aquifers of the Brahmaputra flood plains,Northeast India

Arsenic (As) and fluoride (F^?) in groundwater are increasing global water quality and public health concerns. The present study provides a deeper understanding of the impact of seasonal change on the co-occurrence of As and F^?, as both contaminants vary with climatic patterns. Groundwater samples were collected in pre- and post-monsoon seasons (n = 40 in each season) from the Brahmaputra flood plains (BFP) in northeast India to study the effect of season on As and F^? levels. Weathering is a key hydrogeochemical process in the BFP and both silicate and carbonate weathering are enhanced in the post-monsoon season. The increase in carbonate weathering is linked to an elevation in pH during the post-monsoon season. A Piper diagram revealed that bicarbonate-type water, with Na⁺, K⁺, Ca²⁺, and Mg²⁺ cations, is common in both seasons. Correlation between Cl^? and NO₃ ^? (r = 0.74, p = 0.01) in the post-monsoon indicates mobilization of anthropogenic deposits during the rainy season. As was within the 10 µg L^?1 WHO limit for drinking water and F^? was under the 1.5 mg L^?1 limit. A negative correlation between oxidation reduction potential and groundwater As in both seasons (r = ?0.26 and ?0.49, respectively, for pre-monsoon and post-monsoon, p = 0.05) indicates enhanced As levels due to prevailing reducing conditions. Reductive hydrolysis of Fe (hydr)oxides appears to be the predominant process of As release, consistent with a positive correlation between As and Fe in both seasons (r = 0.75 and 0.73 for pre- and post-monsoon seasons, respectively, at p = 0.01). Principal component analysis and hierarchical cluster analysis revealed grouping of Fe and As in both seasons. F^? and sulfate were also clustered during the pre-monsoon season, which could be due to their similar interactions with Fe (hydr)oxides. Higher As levels in the post-monsoon appears driven by the influx of water into the aquifer, which drives out oxygen and creates a more reducing condition suitable for reductive dissolution of Fe (hydr)oxides. An increase in pH promotes desorption of As oxyanions AsO₄ ^3? (arsenate) and AsO₃ ^3? (arsenite) from Fe (hydr)oxide surfaces. Fluoride appears mainly released from F^?-bearing minerals, but Fe (hydr)oxides can be a secondary source of F^?, as suggested by the positive correlation between As and F^? in the pre-monsoon season.