重工业区高脆弱岩溶含水层中多环芳烃污染的初步研究

以西南岩溶地区某市重工业区为研究对象,采集水文地质单元内地下水和土壤样品,利用气相色谱-质谱法（GC-MS)测试美国环保署16 种多环芳烃（PAHs）优控物。初步研究表明,研究区地下水16种PAHs均被检出,浓度为1 135.79～1 361.26 ng/L,以菲、蒽、萘、屈、芘为主;地下水处于中等污染程度,其中苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽4种浓度超过美国EPA2009《国家推荐的优先有毒污染物水质标准》标准;PAHs特征比值显示含水层中的PAHs来源于燃煤和炼焦污染源,与钢铁厂和化肥厂排放的特征有机污染物一致。研究区污染源下游大面积区域地下水已经受到PAHs污染,且出现排泄区PAHs浓度高于径流区的现象,岩溶含水层PAHs的污染主要受两方面影响:一是洼地、裂隙发育,断层破碎带和强风化白云岩等为PAHs在含水层中的运移提供了有利条件,同时污染源区内地下水大量开采加速了污染物向地下水的入渗;二是水电站建坝蓄水发电,江水水位抬高,河岸地下水排泄速度减慢,可能致使岩溶含水层中PAHs的自净能力减弱。生态风险评价显示地下水中菲、蒽、芘、苯并[a]蒽、苯并[b]荧蒽处于重污染风险,应采取措施降低污染风险。      

和田河流域绿洲区地下水有机污染特征与健康风险评估

为掌握和田河流域绿洲区地下水有机污染状况及对人体健康的影响,采样并检测了地下水中37项有机物,运用美国联邦环保署推荐的U.S.EPA模型对地下水有机污染的健康风险进行评估。结果表明,和田河流域绿洲区地下水中只有苯并[a]芘一种有机物被检出,含量0.037 8～0.869 1μg/L,检出率和超标率均为13.3%。该区地下水有机污染程度总体较低,仅局部区域存在地下水苯并[a]芘污染问题。健康风险评估显示,饮用地下水暴露途径下苯并[a]芘对人体健康产生的致癌风险值为3.77E-6～8.66E-5,超出了风险可接受水平。地下水中苯并[a]芘含量控制在3.76E～5μg/L以下可确保绿洲区地下水的饮用安全。     

高效液相色谱法测定地下水中苯并(a)芘的不确定度评定

通过对高效液相色谱法测定地下水中苯并(a)芘含量的全过程分析,确定了测定结果不确定度的来源。采用不确定度连续传递模型,对引入的不确定度分量进行评定,并采用最小二乘法对标准曲线进行拟合,确定了地下水中苯并(a)芘含量标准不确定度由样品取样量、样品定容体积及测定体积、样品重复性测定、标准溶液浓度和标准曲线拟合误差6部分不确定度合成。通过对2个不同含量样品测定结果不确定度评定,证明苯并(a)芘含量越低,测定结果的相对标准不确定度越大;且样品重复性测定和标准曲线拟合误差是测定结果不确定度的重要来源。     

典型有机物在饱气带土和地下水中迁移的影响因素研究

研究区位于河北省保定市东部排污渠旁,是一处有近40年污水灌溉历史的农田,灌溉用污水主要为保定天鹅化纤有限公司和保定钞票纸厂排放的污水,主要种植农作物为小麦、玉米。饱气带厚度2.4~2.7 m,饱气带土以粉质粘土为主。通过分析距排污渠不同距离、不同深度的土样有机物的测试分析结果,选择苯、甲苯、二氯甲烷、三氯甲烷、苯并[a]芘为典型污染物,从饱气带土的物理与化学特征、5种有机物的物理化学特征、地下水的动力条件角度,分析了典型有机物在饱气带土与地下水中迁移的影响因素。     

高砷含水层沉积物矿物学特征及砷的活化

利用X射线衍射和X射线荧光分析、沉积物序列提取试验及矿物饱和度的计算,对采自江汉平原中部沙湖地区典型高砷含水层钻孔沉积物样品矿物学进行了分析,并讨论了控制含水层中砷释放和迁移的地球化学机制.对矿物在沉积物与土壤中的分布及组成的对比分析,在一定程度上指示了矿物赋存环境和/或高砷水形成的环境背景:土壤与沉积物中高岭石以低于其他3种粘土矿物的含量普遍存在,指示了含水层沉积物形成过程江汉平原存在一定的湿热古气候环境;沉积物绿泥石含量低于土壤中绿泥石,恰恰反映了土壤比沉积物略强的碱性环境;沉积物中黄铁矿的存在,显示了含水层局部的强还原性环境,指示地下水中广泛存在的Fe2+容易与二价硫发生沉淀并结合砷.砷主要以无定形铁锰氧化物结合态(平均在31％以上)形式存在,其次以碳酸盐和有机质结合态存在.无定形铁锰氧化物的还原溶解可能是控制砷迁移到地下水中主要的地球化学机制.相对高含量的绿泥石容易在含水层中发生风化,其溶解过程可以将铁释放到地下水中,从而成为影响地下水中砷活化的潜在因素.     

废旧金属拆解场地浅层地下水芘污染特征与分析

在分析废旧金属拆解场地浅层地下水中芘的检出和分布特征的基础上,对地下水中芘的污染来源、污染途径和污染控制因素进行了探讨.研究结果表明,场地中心和地下水下游2km范围内芘污染明显,垂直于地下水流向芘迁移距离较小,一般小于0.5km.芘在地下水中的迁移转化受地下水中pH、Eh及DO等因素的控制,弱酸性或中性环境以及厌氧强还原条件下,芘易于检出和迁移,一般难以生物降解.     

华北平原某油田采油井密集区水土污染特征分析

为查明华北平原某油田采油井密集区的采油场地、输油管线对地下水、土壤污染程度、分布特征,依据《地下水污染调查评价规范》(DD2008-01)要求,在9个场地采集采集9个水样、31组土样,进行有机组分指标测试。结果表明,地下水样品中,有4个检出石油烃,检出率为50%,检出含量120~1 661μg/L,有2个样品含量大于300μg/L(《生活饮用水卫生标准》GB 5749—2006石油烃标准);有5个样品检出其他有机污染组分,为苯、甲苯和苯并[a]芘,均为芳烃类,检出的含量较低,多为目标检出限的1~5倍。采油井周围土壤中石油烃检出含量较高,检出含量多高于万分之一以上,采用重量法百分比表达;在同一场地内不同地点、不同深度土壤石油烃含量极不均匀,具有很大的不确定性;输油管道穿孔对土壤污染严重,输油管(1 m以下)附近土壤颜色变黑,石油烃检出含量高达4.19%;石油开采已经对采油场地附近农田造成污染,某处农田地表(0~0.2 m)处检出石油烃含量为266 mg/kg。初步认为,评价区内地下水石油烃污染主要是采油场地原生态的破坏和事故性污染造成。     

水体悬浮颗粒物的扫描电镜与X射线能谱显微分析

通过对湖州地区74个土壤样品多环芳烃含量的测定,分析了湖州市不同土地利用类型土壤中多环芳烃(PAHs)的含量特征及污染水平。结果表明,湖州地区PAHs各组分的含量均有检出,各种土地利用类型表层土壤均受到一定程度的PAHs污染,但均小于荷兰土壤修复标准;湖州市区耕地中PAHs的含量最高;从PAHs低环/高环比值小于1以及芘/苯并(a)芘比值小于2,反映了湖州地区土壤中PAHs主要是由燃煤和生活污染产生的。     

松辽盆地上白垩统嫩江组三四段沉积有机质及多环芳烃化合物组成分布与古气候意义

对松辽盆地上白垩统嫩江组嫩三段(K_2n~3)和嫩四段(K_2n~4)岩芯样品有机质组成丰度、多环芳烃化合物组成分布等进行了分析。结果显示,嫩三段和嫩四段沉积岩有机碳含量(TOC)分别在1.37%~2.52%和0.12%~0.82%之间,可溶有机质族组成含量为沥青质非烃饱和烃芳烃,沥青质、非烃、饱和烃和芳烃占可溶有机质的比例分别为21.1%~54.9%,15.4%~27.8%,12.7%~19.2%和1.7%~11.0%。在嫩三段和嫩四段沉积有机质中检出了多种高丰度的多环芳烃化合物,主要为萤蒽(Fla)、芘(Py)、苯并萤蒽(Bflas)、苯并a蒽(Ba An)、苯并e芘(Be Py)、晕苯(Cor)、茚并芘(Inpy)、菲(P)、苯并[g,h,i]苝(Bghi P)、■(Chry)、甲基菲(MP)、惹烯(Ret)和苝(Pery)等;其中,菲、甲基菲、惹烯和?等化合物主要是来自原始有机质输入和成熟转化的产物。多环芳烃化合物的相关比值及其在垂向上的变化表明,嫩三段中的萤蒽、芘、苯并萤蒽、苯并a蒽、苯并e芘等多环芳烃化合物主要是生物质燃烧的产物;茚并芘和苯并[g,h,i]苝等则主要形成于原始有机质的成熟转化。嫩四段中的萤蒽、芘、苯并萤蒽、苯并a蒽和苯并e芘等多环芳烃化合物主要是生物质燃烧的产物,茚并芘和苯并[g,h,i]苝为生物质燃烧成因和成岩演化混合来源,而嫩四段底部检测到的较高丰度的苝可能主要与陆源有机质的输入及转化有关。最后,嫩江组中的多环芳烃化合物,特别是生物质燃烧来源的多环芳烃环合物的相对丰度在垂向上的变化可能表明嫩三段和嫩四段沉积时期古气候发生了由温湿气候向干旱气候的转变。     

大气干湿沉降: 地下河多环芳烃的重要来源——以广西清水泉地下河为例

为证实大气干湿沉降物是岩溶地下河中多环芳烃(PAHs)的来源,研究选择了某城市典型的岩溶地下河水源地作为研究地点,采用大气干湿采样器、聚氨酯泡沫(PUF)大气被动采样器分别采集大气及其干湿沉降物样品,同时采集地下河水样和分层采集流域土壤,利用气相色谱-质谱联用仪(GC-MS)测定了16种PAHs优先控制污染物。结果表明,地下河流域大气干湿沉降中PAHs的干湿沉降通量为147.26 ng·(m2·d)-1,流域PAHs沉降量为1943.8 g;大气中的PAHs浓度为45.33 ng·m-3;地下河水中PAHs浓度平均值为220.98 ng·L-1;土壤中PAHs浓度为38.72 ng·g-1;大气、降雨和土壤中PAHs组成以2~3环的萘、芴、菲、荧蒽、芘5种为主,地下河水中以芴、菲、荧蒽、芘、苯并[a]蒽、苯并[a]芘6种为主。利用地下河多介质中的16种PAHs成分谱、特征比值结合它们的物理化学性质进行PAHs的源解析,研究显示大气干湿沉降是岩溶地下河水中多环芳烃的主要污染源之一,这归因于岩溶地区防污性能的脆弱性。     

Arsenic associations in sediments from shallow aquifers of northwestern Hetao Basin,Inner Mongolia

Understanding the mechanism of arsenic mobilization from sediments to groundwater is important for water quality management in areas of endemic arsenic poisoning, such as the Hetao Basin in Inner Mongolia, northern China. Aquifer geochemistry was characterized at three field sites (SH, HF, TYS) in Hangjinhouqi County of northwestern Hetao Basin. The results of bulk geochemistry analysis of sediment samples indicated that total As concentrations have a range of 6.8–58.5 mg/kg, with a median of 14.4 mg/kg. The highest As concentrations were found at 15–25 m depth. In the meanwhile, the range of As concentration in the sediments from background borehole is 3–21.8 mg/kg, with a median value of 9 mg/kg. The As sediments concentrations with depth from the SH borehole were correlated with the contents of Fe, Sb, B, V, total C and total S. Generally, the abundance of elements varied with grain size, with higher concentrations in finer fractions of the sediments. Distinct lithology profile and different geochemical characteristics of aquifer sediments indicate the sediments are associated with different sources and diverse sedimentary environments. Up to one third of arsenic in the sediments could be extracted by ammonium oxalate, suggesting that Fe oxyhydroxides may be the major sink of As in the aquifer. Sequential extraction results indicate that arsenic occurs as strongly adsorbed on and/or co-precipitated with amorphous Fe oxyhydroxides in sediments accounting for 35 and 20%, respectively, of the total contents of arsenic. The release of As into groundwater may occur by desorption from the mineral surface driven by reductive dissolution of the Fe oxide minerals. Furthermore, small proportions of As associated with iron sulfides occur in the reductive sediments.     

Vertical distribution and mobilization of arsenic in shallow alluvial aquifers of Chapai-Nawabganj district, Northwestern Bangladesh

Core sediments from two boreholes and groundwater from fifty four As-contaminated well waters were collected in the Chapai-Nawabganj area of northwestern Bangladesh for geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10 to 40 m of depth) range from 2.76?C315.15 mg/l (average 48.81 mg/l). Arsenic concentration in sediments ranges from 3.26?C10 mg/kg. Vertical distribution of arsenic in both groundwater and sediments shows that maximum As concentration (462 mg/l in groundwater and 10 mg/kg in sediments) occurs at a depth of 24 m. In January 2008, 2009 and 2010, maximum As concentration occurs at the same depth. Environmental scanning electron microscope (ESEM) with EDAX was used to investigate the presence of major and trace elements in the sediments. The dominant groundwater type is Ca-HCO₃ with high concentrations of As and Fe, but with low levels of NO₃ ^? and SO₃ ^?2. Statistical analysis clearly shows that As is closely associated with Fe (R² = 0.64) and Mn (R² = 0.91) in sediments while As is not correlated with Fe and Mn in groundwater samples. Comparatively low Fe and Mn concentrations in some groundwater, suggest that probably siderite and/or rhodochrosite precipitated as secondary mineral on the surface of the sediment particles. The correlations along with results of sequential leaching experiments suggest that reductive dissolution of FeOOH and MnOOH mediated by anaerobic bacteria represents mechanism for releasing arsenic into the groundwater.     

北京市城近郊区地下水的环境同位素研究

应用环境同位素方法,研究北京城近郊区地下水演化规律。沿北京市永定河冲洪积扇地下水流动方向取样15组(D、18O、T、14C及全分析),对所取水样进行D、18O、T、14C分析,并确定地下水同位素年龄。运用地下水14C和T含量在垂向和水平方向变化的结果,验证了地下水的流向并计算了地下水的流速变化范围为5·02~62·63m/a,从山前至平原浅层地下水径流速度逐渐变小,反映了地下水水平径流强度逐渐减弱,地下水交替逐渐变差;浅层孔隙水以垂向交替为主,深层孔隙水以水平径流为主。对地下水D、18O之间的关系进行分析,从而判断地下水的补给来源等。     

Accidents due to oxygen deficiency and methane gas blow-off in Tokyo area,Japan

The groundwater leve in the Tokyo area had declined to about 60 m below the surface because of excess withdrawal of groundwater from various aquifers. Many construction workers died due to oxygen deficiency at construction sites from 1960 to 1980, the period of decreasing groundwater level. The compressed air in pneumatic foundation construction sites passed easily through the aquifer, and the oxygen in it was consumed by ferrous ions oxidizing to ferric ions. During periods of high barometric pressure, atmospheric air penetrates into the strata and it is deoxygenated there. Suffocation occurred not only at construction sites in underground excavations, but also in residences in Tokyo. Such acidents have become less frequent with recovery of the pore-water pressure in aquifers, which has accompanied the recovery of the groundwater level since 1972.With the recovery of the pore-water pressure and the groundwater level in the aquifer, fires and explosions resulting from gushes of methane have occurred in Tokyo lowlands since 1973. These blow-off gases are classified into two types: Kameido and Asakusa.The gas of the Kameido type originates from the Kazusa Group and migrates into upper alluvial deposits or Pleistocene sediments because of the recovery of pore-water pressure in the Kazusa Group. The gas of the Asakusa type formed from the air that penetrated the aquifers during the period of low groundwater level. Methane was produced by the depletion of oxygen accumulated in alluvial deposits and Pleistocene sediments. This gas blows off through wells in alluvial deposits and Pleistocene sediments at times of low barometric pressure. Accidents of the Asakusa type will not happen when the groundwater level and pore-water pressure in alluvial and Pleistocene sediments is restored to previous levels.     

Isotopic and hydrochemical studies of groundwater flow and salinity in the Southern Upper Rhine Graben

In order to determine the origin and the propagation mechanisms of highly concentrated chloride brines within the Quaternary aquifer system in the southern part of the Upper Rhine Graben, a combined isotope (H, O, C) and hydrochemical analysis was carried out. Groundwater recharge in this area is a complex system, consisting of local precipitation, river bank filtration, lateral flow from the Graben borders and, to a minor extent, an old Pleistocene component. In some areas, groundwater consists of up to 90% of recent bank filtrate, reaching depths down to at least 100 m. The isotopic and hydrochemical results show, that the elevated chloride concentrations in the Quaternary aquifer mainly result from leaky settling basins charged by the French potash mines until the mid 1970s. Input of natural brines coming from tertiary salt diapirs is of only minor importance. While infiltrating, the anthropogenic brines were strongly diluted by local river bank filtrate of the Rhine. Nevertheless, maximum chloride concentrations nowadays still reach some 10,000 mg/l at the base of the aquifer at a depth of more than 100 m below surface. The main volume of the brines is stored in the less permeable lower part of the quaternary sediments (Breisgau-Formation) whereas only a minor part is transported northwards with the rapid convective groundwater flow. Brines undergoing only dilution preserve their hydrochemical characteristics (NaCl-type). In contrast, brines recirculated from the Breisgau-Formation show a northwards increasing alteration through ion exchange processes. Potassium and sodium may be fixed in the fine grained aquifer material while calcium is set free into the groundwater. After a flow distance of about 12 km, complex hydraulic interactions between groundwater and surface waters lead to the rise of strongly diluted and hydrochemically altered brines with chloride contents up to maximum 700 mg/l. The presented case study is an example for a detailed analysis of a multi-component groundwater mixing system using combined isotope and hydrochemical methods. Furthermore, cation exchange is shown as a major process affecting the hydrochemical evolution of the young groundwater in the southern Upper Rhine Graben which is locally strongly polluted by chloride as a consequence of former potash mining.     

复合含水层地区深基坑降水三维渗流场数值模拟以上海环球金融中心基坑降水为例

长江三角洲分布有巨厚、松散的第四纪沉积层,地下含水系统为一复合含水层系统,深基坑降水一般采用非完整井,且由于深基坑周围连续挡水墙难以深入含水层底板,所以其地下水渗流场变化极其复杂,具有明显的三维流特征。本文以上海环球金融中心深基坑降水为例,采用数值模拟方法,模拟了在多层含水层复合存在、含水层最深底板埋深达149m、基坑周围挡水连续墙埋深达34m、基坑内地下水位降深达26m的情况下的地下水三维渗流场特征,并以此为据确定出了该基坑降水的最优化方案。     

Arsenic-enriched aquifers: Occurrences and mobilization of arsenic in groundwater of Ganges Delta Plain, Barasat, West Bengal, India

Hydrogeochemical characteristics and elemental features of groundwater and core sediments have been studied to better understand the sources and mobilization process responsible for As-enrichment in part of the Gangetic plain (Barasat, West Bengal, India). Analysis of water samples from shallow tubewells (depth 24.3–48.5 m) and piezometer wells (depth 12.2–79.2 m) demonstrate that the groundwater is mostly the Ca-HCO₃ type and anoxic in nature (mean Eh_SHE = 34 mV). Arsenic concentrations ranged from <10–538 μg/L, with high concentrations only present in the shallow to medium depth (30–50 m) of the aquifer along with high Fe (0.07–9.8 mg/L) and relatively low Mn (0.15–3.38 mg/L) as also evidenced in core sediments. Most groundwater samples contained both As(III) and As(V) species in which the concentration of As(III) was generally higher than that of As(V), exhibiting the reducing condition. Results show lower concentrations of NO₃, SO₄ and NO₂ along with higher values of DOC and HCO₃, indicating the reducing nature of the aquifer with abundant organic matter that can promote the release of As from sediments into groundwater. Positive correlations of As with Fe and DOC were also observed. The presence of DOC may actively drive the redox processes. This study revealed that reduction processes of FeOOH was the dominant mechanism for the release of As into the groundwater in this part of the Ganges Delta plain.     

滹滏平原地下水系统脆弱性最佳地下水水位埋深探讨

笔者以滹滏平原为研究区, 采用统计分析的方法, 分析了地下水防污性与地下水资源脆弱性随地下水位埋深之间的变化关系。结果表明, 当地下水位埋深增大时, 地下水防污性增强的地区, 地下水资源脆弱性也增高;通过二者之间变化关系, 认为受地下水位埋深制约及地下水位埋深对二者的不同影响, 存在使地下水系统脆弱性最佳的地下水位埋深区间;通过地下水位埋深对地下水防污性与地下水资源脆弱性影响及其制约关系, 确定滹滏平原淡水区和咸水区地下水系统脆弱性最佳地下水位埋深分别为27~30 m和15~19 m。     

Factors controlling the heterogeneous distribution of Cr(VI) in soil, plants and groundwater: Evidence from the Assopos basin, Greece

The effective influence of industry or ultramafic rocks by natural processes to soil, plants and groundwater contamination by chromium, which is often a subject of debate, was investigated for the case of the Assopos basin, Greece. The Neogene Assopos basin, is mainly composed by Tertiary and Quaternary sediments of more than 400 m thick and is characterized by brittle type deformation (fault zones, faults). Chromium in soil, ranging from 67 to 204 ppm, is mostly hosted in chromite, Fe-chromite, Cr-bearing goethite and silicates.Special attention was given to the plants, which are a major source of organic matter that serves as the driving force for Cr(VI) reduction. The increase of the Fe, Mn and Ni contents, with the increasing Cr content in the plant-roots, in particular at the external parts of roots and those of bulb-type plants, suggest reduction and immobilization of Cr(VI) and that redox reactions play a significant role to the translocation processes from root to shoot.Groundwater samples from the Assopos aquifer showed a wide spatial variability, ranging from <2 to 180 ppb Cr_total content [almost same to the Cr(VI)-values] despite their spatial association. The presence of Cr(VI)-contaminated groundwater at depths >200 m is attributed to a direct injection of Cr(VI)-rich industrial wastes at depth rather than that Cr(VI) is derived from the Assopos river or by the interaction between water and Cr-bearing rocks. The heterogeneous distribution of Cr in groundwater may be related with the intense neotectonic deformation, as is exemplified by several sharp tectonic contacts between sediment types, while the Cr content in soil is mostly depend on the transported chromite grains.     

Assessment of the Hydrogeochemical Characteristics of Groundwater Resources at some Wadis in the East of El Minia Governorate, Eastern Desert, Egypt

The El Minia governorate lies within the Nile Valley, surrounded by calcareous plateaus to the east and west. The present study focuses on the hydrogeochemistry of the Eocene limestone aquifer at some wadis in the east El Minia governorate, Eastern Desert, Egypt. Hydrogeologically, two main aquifers are encountered in the study area, namely the Maghagha marly limestone and the Samalut chalky limestone aquifers. The Maghagha aquifer is composed of alternating layers of marly limestone and shale with thicknesses ranging from 3.49 m to 177.05 m and a groundwater depth ranging from 8.5 m to 59.27 m which reflects low groundwater potentiality. The groundwater salinity representing this aquifer ranges from 603.5 mg/L to 978.5 mg/L, reflecting fresh water type. Samalut aquifer is made up of chalky, cavernous and fractured limestone with thickness ranging from 30 m to 205 m and groundwater depth ranging from 9 m to 86.77 m, which indicates good groundwater potential. The groundwater salinity of the concerned aquifer ranges from 349.7 mg/L to 2043.9 mg/L, reflecting fresh to possibly brackish water types. Groundwater in the study area is of meteoric water origin; recent recharge is mainly controlled through the presence of fractures and their densities. The majority of groundwater samples in the study area are suitable for drinking and irrigation purposes.