Effect of humic acid on the pH-dependent adsorption of terbium (III) onto geological materials

Mobilization of actinides by interaction with humic colloids in aquifers is essentially determined by the geochemical conditions. In this study, the pH dependence of the influence of humic acid on metal adsorption on a variety of geological solids (kaolinite, phyllite, diabase, granite, sand) was investigated for Tb(III) as an analogue of trivalent actinides, using ¹⁶⁰Tb as a radiotracer. Humic material was radiolabelled with ¹³¹I to allow experiments at low DOC concentrations, as encountered in subsurface systems in the far-field of a nuclear waste repository. For all solids, a changeover from mobilization to demobilization is observed on acidification. Except for phyllite, the reversal occurs at slightly acidic pH values, and is thus relevant in respect of risk assessments. A composite distribution model was employed to reproduce the changeover on the basis of the underlying constituent processes. For this purpose, humate complexation of Tb(III) and adsorption of humic acid as a function of pH were investigated as well. Although the ternary systems cannot be constructed quantitatively by combining the binary subsystems, the relevant interdependences are adequately described by the composite approach. For a more general discussion in view of the diversity of natural organic colloids, adsorption isotherms of various humic and fulvic acids on sand were compared.     

The removal kinetics of dissolved organic matter and the optical clarity of groundwater

Concentrations of dissolved organic matter (DOM) and ultraviolet/visible light absorbance decrease systematically as groundwater moves through the unsaturated zones overlying aquifers and along flowpaths within aquifers. These changes occur over distances of tens of meters (m) implying rapid removal kinetics of the chromophoric DOM that imparts color to groundwater. A one-compartment input-output model was used to derive a differential equation describing the removal of DOM from the dissolved phase due to the combined effects of biodegradation and sorption. The general solution to the equation was parameterized using a 2-year record of dissolved organic carbon (DOC) concentration changes in groundwater at a long-term observation well. Estimated rates of DOC loss were rapid and ranged from 0.093 to 0.21 micromoles per liter per day (μM d^?1), and rate constants for DOC removal ranged from 0.0021 to 0.011 per day (d^?1). Applying these removal rate constants to an advective-dispersion model illustrates substantial depletion of DOC over flow-path distances of 200 m or less and in timeframes of 2 years or less. These results explain the low to moderate DOC concentrations (20–75 μM; 0.26–1 mg L^?1) and ultraviolet absorption coefficient values (a ₂₅₄?<?5 m^?1) observed in groundwater produced from 59 wells tapping eight different aquifer systems of the United States. The nearly uniform optical clarity of groundwater, therefore, results from similarly rapid DOM-removal kinetics exhibited by geologically and hydrologically dissimilar aquifers.     

骆驼山煤矿不同含水层水中荧光性DOM分布特征

结合骆驼山煤矿不同含水层水文地质条件,通过检测分析各含水层水中天然有机质三维荧光光谱、总有机碳TOC和无机阴离子,研究了荧光性溶解有机物(Dissolved Organic Matter,DOM)的分布特征,结果表明:TOC和有机物在254 mm波长紫外光下的吸光度UV₂₅₄整体上随着含水层层位加深而减少,奥灰水中TOC和UV₂₅₄比其他水体分别低2~3.3倍和2.4~4.7倍;有机物芳香度也逐渐降低,紫外吸光度SUVA值在地表水、第四系水、砂岩水和奥灰水中分别为3.28、2.27、2.24和1.96。地表水和第四系水的三维荧光光谱(3DEEM)图存在5个指纹区域,随着地层层位的加深,水中有机物总体上呈递减趋势,最深层的奥灰水中没有酪氨酸、疏水性有机酸和海洋性腐植酸,而色氨酸的荧光强度比其他水体都高,表明地下水中有机物会反应生成色氨酸类有机物。奥灰水中TOC随着地下水流向逐渐减少(从0.27 mg/L减少至0.22 mg/L);有机物反应生成色氨酸,导致色氨酸FI随着水流而逐渐增加;根据3DEEM光谱图,骆驼山煤矿区奥灰水中有机物比较稳定,能够明显区分出其作为突水水源的特征离子。      

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin,Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l⁻¹ and 1480 μg l⁻¹. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH₄, dissolved organic C (DOC), HCO₃ and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l⁻¹) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO₄ concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO₄ reduction has been an active process. High concentrations of Fe, Mn, NH₄, HCO₃ and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg⁻¹ (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO₃, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l⁻¹) and F⁻ (up to 6.8 mg l⁻¹). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO₃ as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.     

Dissolved organic carbon and methane in a regional confined aquifer,southern Ontario,Canada: Carbon isotope evidence for associated subsurface sources

Information regarding the origin, composition and transport of natural dissolved organic carbon (DOC) in groundwater is necessary to understand the transport of metals and organic pollutants, as well as for the use of¹⁴C in DOC as an isotopic groundwater dating method. Previous research in several groundwater systems has suggested soil organic C is the predominant source of high molecular weight DOC to the subsurface. Through the use of stable isotopes,¹⁴C and geochemical analyses, this study shows that significant concentrations of DOC and CH₄ in a regional confined aquifer can be generated in situ from subsurface sedimentary organic sources. The DOC and CH₄ produced is a combined result of degradation of buried peats and bacterial action, resulting in high DOC concentrations and strongly methanogenic conditions in the aquifer. The DOC and CH₄ comprise, on average, nearly 50% of the total dissolved C pool in the central part of the aquifer. Methanogenic conditions complicate isotopic groundwater dating by the conventional dissolved inorganic carbon (DIC) method. Estimates of isotopic groundwater residence time using DOC¹⁴C data are proposed by the application of¹⁴C isotope and mass balance corrections.     

Chemistry and transport of soluble humic substances in forested watersheds of the Adirondack Park,New York

Studies were conducted in conjunction with the Integrated Lake-Watershed Acidification Study (ILWAS) to examine the chemistry and leaching patterns of soluble humic substances in forested watersheds of the Adirondack region. During the summer growing season, mean dissolved organic carbon (DOC) concentrations in the ILWAS watersheds ranged from 21–32 mg C l^?1 in O/A horizon leachates, from 5–7 mg C l^?1 in B horizon leachates, from 2–4 mg C l^?1 in groundwater solutions, from 6–8 mg C l^?1 in first order streams, from 3–8 mg C l^?1 in lake inlets, and from 2–7 mg C l^?1 in lake outlets. During the winter, mean DOC concentrations dropped significantly in the upper soil profile. Soil solutions from mixed and coniferous stands contained as much as twice the DOC concentration of lysimeter samples from hardwood stands. Results of DOC fractionation analysis showed that hydrophobia and hydrophilic acids dominate the organic solute composition of natural waters in these watersheds. Charge balance and titration results indicated that the general acid-base characteristics of the dissolved humic mixture in these natural waters can be accounted for by a model organic acid having an average_pK_a of 3.85, an average charge density of 4–5 μeq mg^?1 C at ambient pH, and a total of 6–7 meq COOH per gram carbon.     

北方典型内陆盆地高砷地下水的水化学特征及处理技术

我国高砷地下水分布广泛,是受砷污染最严重的地区之一,严重危害居民身体健康,开发经济、高效、环境友好的高砷地下水修复治理技术极具必要性。以大同盆地、呼包平原、河套平原和银川平原为代表性研究区域,归纳总结了北方干旱、半干旱地区典型高砷地下水区水化学特征。通常情况下,高砷地下水的pH值较高,共存阴离子(HCO^-3、SO^2-₄和Cl^-)浓度较大,溶解性有机碳含量较高,并且As(Ⅲ)为主要砷形态。开展了针对北方典型高砷地下水特定水化学环境特点(如pH值、共存阴阳离子以及溶解性有机物等)的改性天然菱铁矿除砷性能研究。结果表明,改性天然菱铁矿对溶液pH值具有良好的缓冲能力,其除砷性能基本不受pH值、共存阴离子、Ca/Mg阳离子及以腐殖酸为代表的溶解性有机物等典型高砷地下水水化学特征因素的影响,表明吸附剂对砷具有良好的吸附选择性。另外,改性天然菱铁矿对As(Ⅲ)的去除效果优于对As(V)的去除效果,因此,利用改性天然菱铁矿作为反应介质材料,将其应用于处理主要以As(Ⅲ)形式存在的高砷地下水具备良好的发展前景。     

Organic carbon mobilization in a Bangladesh aquifer explained by seasonal monsoon-driven storativity changes

Currently, the most widely accepted hypothesis to explain high As concentrations in Bangladesh groundwaters is that dissolved organic C (DOC) reduces solid Fe (hydr)oxides and mobilizes sorbed arsenate. The nature of the DOC and its release mechanism are still controversial. Based on weekly to biweekly sampling over the course of one monsoon cycle at six monitoring wells of different depths, it is proposed that storativity changes drive natural DOC release from clay–peat layers to the adjacent aquifers. With a decrease in hydraulic heads during the dry season, total mineralization and DOC concentrations increased. With the onset of the rainy season and an increase in hydraulic heads, release of clay–peat derived components stopped and vertical water displacement due to groundwater recharge from rainwater occurred, causing aquifer flushing and a decrease in total mineralization and DOC concentrations. Total As and DOC concentrations correlated over depth. However, at the depth of maximum concentrations, the As peak was observed during the rainy season. At present, the reason for this inverse seasonal trend between As and DOC is unclear. Higher mineralization or DOC concentrations could lead to increased As sorption or the increased arsenite release is a time-lag abiotic or microbial response to the DOC peak. The vulnerability of the Pleistocene aquifer towards increased As concentrations was found to be much higher than previously assumed. Though sorption capacities were determined to be higher than in the Holocene aquifer, probably due to intact Fe (hydr)oxides, long-term continuous As input from overlying clay and peat layers by the proposed seasonal storativity changes has led to increased aqueous As concentrations of 85 μg/L, considerably higher than drinking water standards. Until now, aquifer and especially aquitard and aquiclude hydraulics have not been considered sufficiently when attempting to explain As mobilization in Bangladesh.     

Characterization of groundwater humic substances: influence of sedimentary organic carbon

A total of 35 groundwaters from 4 different aquifer systems in Germany are investigated for their physico-chemical properties, dissolved organic C (DOC) and humic and fulvic acids. Humic substances are isolated and characterized for their elemental composition, UV/Vis and fluorescence spectroscopic properties, size distribution by gel permeation chromatography (GPC) and ¹⁴C content. For isolation of sufficient quantities of humic substances a mobile sampling system is developed based on a combination of reverse osmosis (RO) and XAD–8 adsorption chromatography. One of the aquifer systems (Gorleben) covers a wide range of hydrogeochemical conditions, whereas the other 3 aquifer systems (Munich, Franconian Albvorland and Fuhrberg) have less diverse properties. One specific feature of the Gorleben aquifer system is the presence of a very high DOC, which, in contrast to other aquifer systems, contains considerable amounts of aquatic humic acid. This is attributed to the release of aquatic humic substances originating from sedimentary organic C (SOC) that is abundant in Gorleben sediments. The results show that aquatic humic substances from different aquifer systems have dissimilar properties which differ from one another. Systematic differences are found among humic substances from different regions of the Gorleben aquifer system. Such differences are considered to be caused by the mixing of humic substances from the SOC. However, exact quantification of such mixing appears difficult because overlapping effects of different geochemical processes feigning a dissolution of SOC cannot be excluded.     

Bromine and water quality – Selected aspects and future perspectives

Bromine is a microelement present in waters, both in inorganic and in a wide range of organic compounds, though at lower concentrations. Typically, concentrations of organobromine compounds in waters are several orders of magnitude lower than of bromides. Two issues are addressed in the paper: the influence of bromides on the quality of treated waters and organobromines as contaminants of natural waters. Bromide presence in treated water gives rise to formation of potentially mutagenic disinfection by-products (DBPs). Registered amounts of DBPs in potable waters, exceeding the admissible levels, and the published data on DBPs in waters used for leisure and recreation activities, clearly indicate the health risk. Major sources are identified and registered concentrations of EDB, DBCB, methyl bromide, bromacil and PBDEs in the aquatic environment are summarized. The effects of bromide on DBPs formation and numerous examples of organobromine contamination of the aquatic environment indicate that the presence of bromides and organobromine compounds in the aquatic environment will have to be given more consideration, for several reasons. Firstly, larger amounts of bromide are present in saline and contaminated waters and the proportion of such waters being handled is increasing. Similarly, the processes of water purification, treatment and disinfection are now playing a major role. Secondly, emissions from manufacturing of bromine-containing materials growing, due to, inter alia, intensive development of the electronic industry and the plastic manufacturing sector. Thirdly, bromine compounds are also used as medicine ingredients. There is now a growing awareness of the presence of pharmaceuticals in the aquatic environment. Fourth, low bromide concentrations in hypergene zones may be modified in the future, partly because of the climate changes, which may give rise to difficulties with water treatment systems.Water quality standards having relevance to water used for consumption are based only on the best-known (most widespread) DBPs. However new more restrictive legal regulations relating to the use of bromine compounds have been put in place prohibiting the use of certain bromine-based substances or restricting their amount in finished products. In the light of current legislation, the monitoring of water contamination with potentially toxic, mutagenic and endocrine-disrupting organobromine compounds is still unsatisfactory because newly discovered compounds are not included and certain factors governing the exposure to those substances are still left out.The effects of bromine (bromide and organobromine compounds) on water quality have been investigated by researchers from several fields of expertise. The water management authorities ought to make use of the available research data and identify the problems which need to be addressed directly and those which may emerge in the future.     

Groundwater chemistry of Al under Dutch sandy soils: Effects of land use and depth

Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)₃ and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from <0.4 μmol L⁻¹ at pH > 7 to 1941 μmol L⁻¹ at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al³⁺ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)₃ minerals (e.g. gibbsite or amorphous Al(OH)₃), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater.     

Biogeochemistry of landfill leachate plumes

The literature has been critically reviewed in order to assess the attenuation processes governing contaminants in leachate affected aquifers. Attenuation here refers to dilution, sorption, ion exchange, precipitation, redox reactions and degradation processes. With respect to contaminants, focus is on dissolved organic matter, xenobiotic organic compounds, inorganic macrocomponents as anions and cations, and heavy metals. Laboratory as well as field investigations are included. This review is an up-date of an earlier comprehensive review. The review shows that most leachate contamination plumes are relatively narrow and do not in terms of width exceed the width of the landfill. The concept of redox zones being present in the plume has been confirmed by the reported composition of the leachate contaminated groundwater at several landfills and constitutes an important framework for understanding the behavior of the contaminants in the plume as the leachate migrates away from the landfill. Diverse microbial communities have been identified in leachate plumes and are believed to be responsible for the redox processes. Dissolved organic C in the leachate, although it appears to be only slowly degradable when the volatile organic acids are gone, apparently acts as substrate for the microbial redox processes. Several xenobiotic organic compounds have been found to be degradable in leachate contaminated groundwater, but degradation rates under anaerobic redox conditions have only been determined in a few cases. Apparently, observations in actual plumes indicate more extensive degradation than has been documented in the laboratory. The behavior of cations in leachate plumes is strongly influenced by exchange with the sediment, although the sediment often is very coarse and sandy. Ammonium seems to be subject to anaerobic oxidation, but the mechanisms are not yet understood. Heavy metals do not seem to constitute a significant pollution problem at landfills, partly because the heavy metal concentrations in the leachate often are low, and partly because of strong attenuation by sorption and precipitation. Although complexation of heavy metals with dissolved organic matter is significant, the heavy metals are in most cases still strongly attenuated in leachate-polluted aquifers. The information available on attenuation processes has increased dramatically during the last 15 a, but the number of well-documented full scale leachate plumes are still few and primarily from sandy aquifers. Thus, the diversity of attenuation processes in leachate plumes is probably not yet fully understood. Apparently, the attenuation processes in leachate plumes may for many contaminants provide significant natural remediation, limiting the effects of the leachate on the groundwater to an area usually not exceeding 1000 m from the landfill.     

Potential of groundwater contamination by polybrominated diphenyl ethers (PBDEs) in a sensitive bedrock aquifer (Canada)

It is necessary to understand the presence, movement, and persistence of contaminants in aquifers to develop adequate groundwater protection plans. Fractured bedrock aquifers with thin overburden cover are very sensitive to contamination, and little is known about transport processes from the ground surface to depth in this setting. This study was undertaken to investigate the potential of groundwater contamination by polybrominated diphenyl ethers (PBDEs), which are flame retardants, in a natural fractured bedrock aquifer in Canada proven to be sensitive to contamination. PBDEs, which had not been previously measured in groundwater in detail, were detected in the study aquifer at concentrations greater than those observed in surface-water bodies. Potential sources include manure, septic tanks, and the atmosphere. From this scoping study, it is evident that additional surveys of PBDE concentrations in groundwater are warranted, especially in settings with high potential source concentrations coupled with sensitive aquifers.     

Holocene estuarine sediments as a source of arsenic in Pleistocene groundwater in suburbs of Hanoi,Vietnam

Groundwater pollution by arsenic is a major health threat in suburban areas of Hanoi, Vietnam. The present study evaluates the effect of the sedimentary environments of the Pleistocene and Holocene deposits, and the recharge systems, on the groundwater arsenic pollution in Hanoi suburbs distant from the Red River. At two study sites (Linh Dam and Tai Mo communes), undisturbed soil cores identified a Pleistocene confined aquifer (PCA) and Holocene unconfined aquifer (HUA) as major aquifers, and Holocene estuarine and deltaic sediments as an aquitard layer between the two aquifers. The Holocene estuarine sediments (approximately 25–40 m depth, 9.6–4.8 cal ka BP) contained notably high concentrations of arsenic and organic matter, both likely to have been accumulated by mangroves during the Holocene sea-level highstand. The pore waters in these particular sediments exhibited elevated levels of arsenic and dissolved organic carbon. Arsenic in groundwater was higher in the PCA (25–94 μg/L) than in the HUA (5.2–42 μg/L), in both the monitoring wells and neighboring household tubewells. Elevated arsenic concentration in the PCA groundwater was likely due to vertical infiltration through the arsenic-rich and organic-matter-rich overlying Holocene estuarine sediments, caused by massive groundwater abstraction from the PCA. Countermeasures to prevent arsenic pollution of the PCA groundwater may include seeking alternative water resources, reducing water consumption, and/or appropriate choice of aquifers for groundwater supply.     

Groundwater in-situ generation of aquatic humic and fulvic acids and the mineralization of sedimentary organic carbon

In this paper the groundwater in-situ generation of dissolved organic carbon (DOC) is discussed based on the origin of groundwaters, their physico-chemical and isotopic properties, chemical composition and the dissolved inorganic carbon (DIC) concentration and its ¹³C content. Three aquifer systems are investigated. Two of these have relatively well defined hydrological and geochemical conditions (Fuhrberg and Munich) and are used as reference systems. The third aquifer (Gorleben) is a complex system containing DOC concentrations up to 200 mg C/L in deep groundwaters. From this aquifer system 19 groundwaters from different hydrogeochemical conditions are analyzed. The in-situ generation of DOC is found to occur in conjunction with the microbiologically mediated mineralization of sedimentary organic carbon (SOC). Thereby, SO₄ is reduced and phosphate is released into the groundwater. Where SO₄ is depleted, the mineralization of SOC occurs via fermentation, resulting in CH₄ generation.     

高砷地下水中溶解性有机碳和无机碳稳定同位素特征

随着稳定同位素分析技术的逐步完善,碳稳定同位素被广泛应用于地球化学领域。高砷地下水砷的生物地球化学循环是目前环境化学研究热点之一。分析概括了碳稳定同位素应用于地下水领域的研究现状,介绍了地下水中有机碳和无机碳稳定同位素的前处理方法以及测试技术。在此基础上,选取了内蒙古河套平原具有代表性的高砷地下水进行氧化还原敏感组分、碳稳定同位素的测定与分析。结果表明,As分布极不均匀,其含量为1.24~387 μg/L。地下水溶解性有机碳(DOC)含量相对较高,与溶解性无机碳(DIC)浓度基本呈正相关。δ¹³C_DIC相对δ¹³C_DOC较富集¹³C;δ¹³C_DIC-δ¹³C_DOC与δ¹³C_DIC之间具有显著的正相关关系;表明δ¹³C_DIC值越贫化,δ¹³C_DIC-δ¹³C_DOC越小,地下水中来源于有机物氧化分解的无机碳越多,进一步说明有机碳的氧化分解在无机碳稳定同位素贫化过程中起主要作用。此外,δ¹³C_DIC-δ¹³C_DOC与As浓度呈一定的负相关关系;表明有机物的微生物降解对砷的富集具有明显的促进作用。微生物可利用的碳源增加,促进异养微生物的代谢,并消耗氧气,最终形成有利于地下水As富集的还原环境。     

Contrasting sorption behaviours affecting groundwater arsenic concentration in Kandal Province,Cambodia

Natural arsenic(As)contamination of groundwater which provides drinking water and/or irrigation supplies remains a major public health issue,particularly in South and Southeast Asia.A number of studies have evaluated various aspects of the biogeochemical controls on As mobilization in aquifers typical to this region,however many are predicated on the assumption that key biogeochemical processes may be deduced by sampled water chemistry.The validity of this assumption has not been clearly established even though the role of sorption/desorption of As and other heavy metals onto Fe/Mn(hydr)oxides is an important control in As mobilization.Here,selective chemical extractions of sand-rich and clay-rich sediments from an As-affected aquifer in Kandal Province,Cambodia,were undertaken to explore the potential role of partial re-equilibrium through sorption/desorption reactions of As and related solutes(Fe,Mn and P)between groundwater and the associated solid aquifer matrix.In general,groundwater As is strongly affected by both pH and Eh throughout the study area.However,contrasting sorption behaviour is observed in two distinct sand-dominated(T-Sand)and clay dominated(T-Clay)transects,and plausibly attributed to differing dominant lithologies,biogeochemical and/or hydrogeological conditions.Sorption/desorption processes appear to be re-setting groundwater As concentrations in both transects,but to varying extents and in different ways.In T-Sand,which is typically highly reducing,correlations suggest that dissolved As may be sequestered by sorption/re-adsorption to Fe-bearing mineral phases and/or sedimentary organic matter;in T-Clay Eh is a major control on As mobilization although binding/occlusion of Fe-bearing minerals to sedimentary organic matter may also occur.Multiple linear regression analysis was conducted with groups categorised by transect and by Eh,and the output correlations support the contrasting sorption behaviours encountered in this study area.Irrespective of transect,however,the key biogeochemical processes which initially control As mobilization in such aquifers,may be "masked" by the re-setting of As concentrations through in-aquifer sorption/desorption processes.     

高砷地下水研究的热点及发展趋势

全球范围内广泛分布的高砷地下水给人们的健康造成了极大的威胁.高砷地下水的形成机理是一项世界性的科学问题.介绍了高砷地下水的分布特点、富集机理,阐明了溶解性有机物、地下水流动特征对高砷地下水形成的影响机制.现今的研究揭示了有机物和微生物协同作用下高砷地下水的形成过程,并且在高砷地下水的空间分布、时间变化特征以及人类活动对高砷地下水形成的影响等方面取得了一些创新性成果.这3方面的研究也逐渐成为近些年高砷地下水研究的热点.这些研究不仅丰富了砷迁移转化的理论成果,而且有助于开辟低砷水源,保障水资源的可持续利用,具有重要的理论和现实意义.     

The recharge process in alluvial strip aquifers in arid Namibia and implication for artificial recharge

Alluvial strip aquifers associated with ephemeral rivers are important groundwater supply sources that sustain numerous settlements and ecological systems in arid Namibia. More than 70 % of the population in the nation’s western and southern regions depend on alluvial aquifers associated with ephemeral rivers. Under natural conditions, recharge occurs through infiltration during flood events. Due to the characteristic spatial and temporal variability of rainfall in arid regions, recharge is irregular making the aquifers challenging to manage sustainably and they are often overexploited. This condition is likely to become more acute with increasing water demand and climate change, and artificial recharge has been projected as the apparent means of increasing reliability of supply. The article explores, through a case study and numerical simulation, the processes controlling infiltration, significance of surface water and groundwater losses, and possible artificial recharge options. It is concluded that recharge processes in arid alluvial aquifers differ significantly from those processes in subhumid systems and viability of artificial recharge requires assessment through an understanding of the natural recharge process and losses from the aquifer. It is also established that in arid-region catchments, infiltration through the streambed occurs at rates dependent on factors such as antecedent conditions, flow rate, flow duration, channel morphology, and sediment texture and composition. The study provides an important reference for sustainable management of alluvial aquifer systems in similar regions.     

Hydrochemical evidence for mixing of river water and groundwater during high-flow conditions, lower Suwannee River basin, Florida, USA

 Karstic aquifers are highly susceptible to rapid infiltration of river water, particularly during periods of high flow. Following a period of sustained rainfall in the Suwannee River basin, Florida, USA, the stage of the Suwannee River rose from 3.0 to 5.88 m above mean sea level in April 1996 and discharge peaked at 360 m³/s. During these high-flow conditions, water from the Suwannee River migrated directly into the karstic Upper Floridan aquifer, the main source of water supply for the area. Changes in the chemical composition of groundwater were quantified using naturally occurring geochemical tracers and mass-balance modeling techniques. Mixing of river water with groundwater was indicated by a decrease in the concentrations of calcium, silica, and ²²²Rn; and by an increase in dissolved organic carbon (DOC), tannic acid, and chloride, compared to low-flow conditions in water from a nearby monitoring well, Wingate Sink, and Little River Springs. The proportion (fraction) of river water in groundwater ranged from 0.13 to 0.65 at Wingate Sink and from 0.5 to 0.99 at well W-17258, based on binary mixing models using various tracers. The effectiveness of a natural tracer in quantifying mixing of river water and groundwater was related to differences in tracer concentration of the two end members and how conservatively the tracer reacted in the mixed water. Solutes with similar concentrations in the two end-member waters (Na, Mg, K, Cl, SO₄, SiO₂) were not as effective tracers for quantifying mixing of river water and groundwater as those with larger differences in end-member concentrations (Ca, tannic acid, DOC, ²²²Rn, HCO₃). Received, March 1999 / Revised, July 1999 / Accepted, July 1999