Mobility of arsenic in West Bengal aquifers conducting low and high groundwater arsenic. Part II: Comparative geochemical profile and leaching study

Aquifer sediments from areas of low- and high-As groundwater were characterized mineralogically and geochemically at a field site in the Nadia district of West Bengal, India. Leaching experiments and selective extraction of the sediments were also carried out to understand the release mechanism of As in the sub-surface. The correlation between measured elements (major, minor and trace) from low- and high-As groundwater areas are only significant for As, Fe and Mn. The borehole lithology and percentage of silt and clay fraction demonstrates the dominance of finer sediments in the high-As aquifer. Multivariate analysis of the geochemical parameters showed the presence of four different mineral phases (heavy-mineral fraction, phyllosilicates/biotite/Fe-oxyhydroxides, carbonates and sulphides) in the sediments. Selective extraction of sediment reveals that amorphous Fe-oxyhydroxide acts as a potential sink for As in the sub-surface. The result is consistent with microbially mediated redox reactions, which are controlled in part by the presence of natural organic matter within the aquifer sediments. The occurrences of As-bearing redox traps, primarily formed of Fe- and Mn-oxides/hydroxides, are also important factors that control the release of As into groundwater at the study site.     

Electrical resistivity investigation of the arsenic affected alluvial aquifers in West Bengal,India: usefulness in identifying the areas of low and high groundwater arsenic

This study aims at finding out possible relation between lithology and spatial pattern of dissolved arsenic (As) in groundwater around Chakdaha municipality, West Bengal, India. Satellite image, coupled with electrical resistivity survey and borehole drilling helps to delineate surface and sub-surface lithological framework of the As affected alluvial aquifers. The satellite imagery demonstrate that the high As area are presumably under active flood plain environment (low-lying areas), that constantly receive organics due to periodic flooding. Thick low resistive (fine-grained) layer was observed at the top around the high As areas, which, however, not found in low As areas. The result suggests that hydraulic properties of the surface/sub-surface soil/sediment have an important control on the fate and transport of As in the aquifer. This study demonstrates that electrical resistivity tools can be effectively used for the reconnaissance survey in characterizing the plausible lithological framework of an alluvial aquifer containing As.     

Mobilization of natural arsenic in groundwater: targeting low arsenic aquifers in high arsenic occurrence areas

研究表明饮用水中微小数量的砷会对人类健康产生不利影响.世界上居住在贫穷地区的人数超过了100万,目前他们正直接饮用来自含水层中砷离子含量(>10μg/L)非安全标准的地下水.砷有时称为毒中之王,在水环境中常常以五价氧化物形式出现.自2000年以来,许多国家开始执行更为严格的10μg/L(WHO认可的居民安全饮水标准)饮用水标准,可以确定地说,在世界范围内的饮用水中检测到砷的情况越来越多.亚洲地区砷中毒的人数比世界其他地区总和还多.最受影响的地区位于南亚和东南亚富砷带,环绕恒河一雅鲁藏布江-梅克纳河三角洲及恒河平原上游的冲洪积扇含水层、红河三角洲、湄公河和伊洛瓦底江;在中国境内包括内蒙黄河冲积盆地,山西大同盆地、新疆准噶尔盆地,其中的地下水富含砷和氟化物而引发砷中毒和氟中毒.尽管还未完全掌握其中的水文地质及生物地球化学作用的详细过程,但对大多数沉积介质含水层,在还原条件下砷离子容易从沉积介质转移到地下水中.孟加拉研究实例表明地质时期尺度的冲刷降低了沉积介质中的As和有机物含量从而形成低砷地下水.这一认识为孟加拉国的降砷策略提供了科学指导,是未来水文学,矿物学,地质学和生物地球化学方面很有意义的研究方向,并有利于地砷病区低砷地下水的可持续利用.     

Scinario of arsenic pollution in groundwater: West Bengal

目前,西孟加拉地区地下水砷污染问题日益严重并且已经波及到食物链中.由于吸收了砷污染地下水,谷物和蔬菜中砷含量日渐累积,超出了健康规定范围.尽管提出了若干补救方案,但是考虑到农业人口的社会经济状况,建议使用地表水灌溉方案.然而,实际中该方案仍然较难施行,且并无其他更经济有效的措施.若干年后,含水层可以减缓严酷的健康环境现状并为人们提供安全的饮用水.     

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.     

Mechanism of arsenic release to groundwater,Bangladesh and West Bengal

In some areas of Bangladesh and West Bengal, concentrations of As in groundwater exceed guide concentrations, set internationally and nationally at 10 to 50 μg l⁻¹ and may reach levels in the mg l⁻¹ range. The As derives from reductive dissolution of Fe oxyhydroxide and release of its sorbed As. The Fe oxyhydroxide exists in the aquifer as dispersed phases, such as coatings on sedimentary grains. Recalculated to pure FeOOH, As concentrations in this phase reach 517 ppm. Reduction of the Fe is driven by microbial metabolism of sedimentary organic matter, which is present in concentrations as high as 6% C. Arsenic released by oxidation of pyrite, as water levels are drawn down and air enters the aquifer, contributes negligibly to the problem of As pollution. Identification of the mechanism of As release to groundwater helps to provide a framework to guide the placement of new water wells so that they will have acceptable concentrations of As.     

Deeper groundwater chemistry and geochemical modeling of the arsenic affected western Bengal basin,West Bengal,India

A regional scale hydrogeochemical study of a ∼21,000-km² area in the western Bengal basin shows the presence of hydrochemically distinct water bodies in the main semiconfined aquifer and deeper isolated aquifers. Spatial trends of solutes and geochemical modeling indicate that carbonate dissolution, silicate weathering, and cation exchange control the major-ion chemistry of groundwater and river water. The main aquifer water has also evolved by mixing with seawater from the Bay of Bengal and connate water. The isolated aquifers contain diagenetically altered water of probable marine origin. The postoxic main aquifer water exhibits overlapping redox zones (metal-reducing, sulfidic and methanogenic), indicative of partial redox equilibrium, with the possibility of oxidation in micro-scale environments. The redox processes are depth-dependent and hydrostratigraphically variable. Elevated dissolved As in the groundwater is possibly related to Fe(III) reduction, but is strongly influenced by coupled Fe–S–C redox cycles. Arsenic does not show good correlations with most solutes, suggesting involvement of multiple processes in As mobilization. The main river in the area, the Bhagirathi–Hoogly, is chemically distinctive from other streams in the vicinity and probably has little or no influence on deep groundwater chemistry. Arsenic in water of smaller streams (Jalangi and Ichamati) is probably introduced by groundwater discharge during the dry season.     

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.     

Geostatistical analysis of arsenic concentration in the groundwater of Malda district of West Bengal, India

The problem of arsenic (As) poisoning in the upper deltaic plain of the Ganga-Bhagirathi river system in the Bengal Basin of West Bengal, India is an alarming issue. Four blocks (Kaliachak-1, 2, 3 and English Bazar) of Malda district, West Bengal were critically studied. Geomorphologically, the area exhibits three terraces: the present Youngest terrace (T₀-terrace), the Older Shaugaon Surface (T₁-terrace) and the Oldest Baikunthapur Surface (T₂-terrace). On the basis of numerous measurements, including As-content, pH, DO, specific conductivity and salinity, it was observed that maximum As-content beyond the permissible limit (0.05 mg/L, Indian standard) occurs within a depth range of 10–30 m with a non-linear distribution pattern. Variance test also found that a block effect was highly significant in an As-distribution pattern. Mean arsenic level of Kaliachak block-1 is 0.2253 mg/L, followed by Kaliachak-2 with arsenic level 0.1923, Kaliachak-3 with arsenic level 0.1755 and English Bazar with arsenic level 0.1324. The arsenious belt lies mainly within the Older terrace (T₁). The very recent flood plain deposits of silvery white, fine sands lying very close to the Ganga River margin do not contain significant amounts of As. Elevated As-concentration in the ground water was observed in alluvial sands, grayish white to brownish in color and occurring away from the Ganga margin. The Oldest terrace (T2) further away from the Ganga margin (e.g. English Bazar) and Barind surface contains less arsenic. Barind surface acts as a hard capping with ferruginous sands and lateritic concretions-chocolate, mottled and purple brown in color-occurring northeast of the studied area. Arsenic content of ground water in the same locality within a radius of ∼ 20 m varies within wide limits. Thus, it poses problem to delineate its distribution pattern. Such a patchy occurrence possibly could not be explained satisfactorily solely by geomorphology. Chemical analysis of aquifer clay samples of the cores shows a maximum Ascontent of up to 3 mg/kg, whereas the bulk samples (sandclay mixture) of the cores contain a maximum of 17 mg/kg As-value. Therefore, it is not always true that clay contains elevated As-value.     

Electrical geophysical and hydrogeological investigations of groundwater aquifers in Ruseifa municipal landfill, Jordan

The effect of the Ruseifa municipal landfill on the shallow groundwater aquifers in the area was investigated in two separate sites. The first one was not used since 1994, whereas the other is still being used for dumping. Fourteen electrical resistivity soundings were performed to detect the leachate and its effect on the quality of the groundwater. Results indicated that the solid waste thickness of the landfill was ranged from 3 to 20 m with resistivity value less than 10 Ω m. Based on the resistivity decreases of values less than 5 Ω m, the leachate was detected in the landfill sites at depths ranged from 10 to 50 m. However, the flow direction of the leachate at depth ranging 10–20 m in the terminated site was toward north, whereas the flow direction of the leachate in the site still used for dumping was toward east–northeast which causes the major source of groundwater pollution.     

Modeling freshening time and hydrochemical evolution of groundwater in coastal aquifers of Shenzhen,China

This work investigated the freshening time and hydrochemical evolution of coastal groundwater in two brackish aquifers in Shenzhen, China. One was the brackish aquifer that resulted from heavy pumping, and the other was the aquifer reclaimed from the coastal sea. Freshening time and hydrochemical evolution of brackish aquifers were quantitatively evaluated using PHREEQC 2.0, a one-dimensional reactive-transport model. Freshening time was shown to mainly depend on pore water velocity, while the chemical composition of groundwater was determined by the cation exchange capacity of the aquifer. It was shown that after heavy pumping ceased, the freshening time for the original coastal aquifer ranged from 20 to over 80 years. While for the coastal reclaimed aquifer, the freshening time was from 85 to 140 years, which depended on the hydraulic conductivity of the fill materials in the reclaimed site. During aquifer freshening, groundwater evolved from Na–Cl type to Ca–Mg–HCO₃ or Na–HCO₃ type. A sensitivity analysis showed that the freshening time was most sensitive to the pore water velocity in the aquifer, while the groundwater chemical composition was most sensitive to the values of cation exchange capacity of the aquifer. As for the dispersivity, it had almost no effect on the freshening time and the chemical composition of groundwater.     

原生高砷地下水的类型、化学特征及成因

由于分布广、危害大,原生高砷地下水严重威胁全球内数亿居民的身体健康。研究原生高砷地下水的分布、化学特征及成因有助于进一步理解地下水中砷的迁移转化规律,并确保高砷区地下水的可持续利用。在查阅大量文献资料的基础上,结合近10年的高砷地下水研究经验,把原生高砷地下水分为还原性中性高砷地下水（Ⅰ 1型）和还原性弱碱性高砷地下水（Ⅰ 2型）、氧化性弱碱性高砷地下水（Ⅱ型）和氧化性弱酸性高砷地下水（Ⅲ型）。Ⅰ 1型高砷地下水主要分布于河流三角洲地区,Ⅰ 2型分布于干旱半干旱封闭内陆盆地,Ⅱ型主要分布于干旱半干旱平原盆地,Ⅲ型主要分布于富含黄铁矿或硫化物矿物的基岩地区。Ⅰ 1型高砷地下水处于还原环境,pH呈中性,Fe/Mn氧化物矿物的还原性溶解是造成As富集的主要原因。Ⅰ 2型高砷地下水处于还原环境,pH呈弱碱性,除了Fe/Mn氧化物矿物的还原性溶解外,As的解吸附是含水层中砷释放的重要原因。Ⅱ型高砷地下水处于氧化弱氧化环境,pH呈弱碱性,As的解吸附是含水层中砷释放的主要原因。Ⅲ型高砷地下水处于氧化环境,pH呈弱酸性,黄铁矿及其他硫化物矿物的氧化溶解导致了含水层中砷的释放。对于Ⅰ 2型高砷地下水,需要深入研究Fe/Mn氧化物矿物的还原性溶解以及As的解吸附对地下水砷富集的相对贡献量。     

Urban impacts analysis on hydrochemical and hydrogeological evolution of groundwater in shallow aquifer Linares,Mexico

In northeast Mexico is Linares City, which has an extensive agricultural area and many industrial activities. Near this city is the Cerro-Prieto Dam (~12 km NE direction); this drinking water reservoir captures the water of the Pablillo River catchment area and constitutes an important source of potable water for the metropolitan area of Monterrey, the largest urban center of this region. Groundwater sources in this area provide drinking water to Linares inhabitants. A hydrogeological and hydrochemical study was conducted on the shallow aquifers surrounding the urban centers (Linares and Hualahuises) to determine the evolution of the water quality between 1981 and 2009. The hydrochemistry was assessed upgradient and downgradient from the potential contamination sources in Linares city. Groundwater showed a chemical evolution from calcium-bicarbonate type to calcium–sodium-sulfate type. The water qualities in the downstream area after Linares are inferior compared to the upstream area before the city. Nitrate concentrations in groundwater increased significantly after 28 years indicating an important pollutant process in this period of time over the study area. The possible pollution sources could be the agricultural and farm activities, industrial development, landfills leachate, septic tanks and wastewater of municipal and domestic consumption. If the present scenario continues, an aquifer vulnerability assessment would be important for the sustainable water management.     

江汉平原东北部浅层高铁锰地下水环境特征

铁、锰元素是影响江汉平原东北部浅层地下水质量的主要因素.为了查明该地区地下水中铁锰的分布特征及地下水环境特征,选择典型研究区,采集了13件地下水样品,测试了地下水中铁锰的含量以及酸碱度、矿化度和氧化还原条件,分析了上述条件对铁锰含量的影响,并与江汉平原腹地高铁锰地下水环境进行对比.结果表明,本研究区地下水以HCO3-Ca、HCO3-Ca·Mg型为主,高铁锰水主要分布于研究区东部和南部沿江地带,与江汉平原腹地地下水化学类型一致,铁锰的含量相对偏低.研究区上部土层中铁锰的氧化物为地下水中的铁锰提供了丰富的来源,地下水的酸碱度、矿化度和氧化还原环境是影响铁锰迁移的主要因素.研究区高铁锰地下水多呈弱酸性,矿化度较高,地下水中铁锰的含量与溶解氧具弱负相关,与氨氮具强烈正相关,表明相对还原的环境有利于铁锰释放到地下水中,江汉平原腹地处于更加还原的环境,是地下水中铁锰高于本研究区的主要原因.     

Arsenic in groundwater of the Bengal Basin, Bangladesh: Distribution, field relations, and hydrogeological setting

Arsenic contaminates groundwater across much of southern, central and eastern Bangladesh. Groundwater from the Holocene alluvium of the Ganges, Brahmaputra and Meghna Rivers locally exceeds 200 times the World Health Organisation (WHO) guideline value for drinking water of 10 µg/l of arsenic. Approximately 25% of wells in Bangladesh exceed the national standard of 50 µg/l, affecting at least 25 million people. Arsenic has entered the groundwater by reductive dissolution of ferric oxyhydroxides, to which arsenic was adsorbed during fluvial transport. Depth profiles of arsenic in pumped groundwater, porewater, and aquifer sediments show consistent trends. Elevated concentrations are associated with fine-sands and organic-rich sediments. Concentrations are low near the water table, rise to a maximum typically 20–40 m below ground, and fall to very low levels between about 100 and 200 m. Arsenic occurs mainly in groundwater of the valley-fill sequence deposited during the Holocene marine transgression. Groundwater from Pleistocene and older aquifers is largely free of arsenic. Arsenic concentrations in many shallow hand-tube wells are likely to increase over a period of years, and regular monitoring will be essential. Aquifers at more than 200 m below the floodplains offer good prospects for long-term arsenic-free water supplies, but may be limited by the threats of saline intrusion and downward leakage of arsenic.

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Resumen El arsénico ha contaminado gran parte de las aguas subterráneas en el Sur, centro y Este de Bangla Desh. Su concentración en las aguas subterráneas del aluvial Holoceno de los ríos Ganges, Brahmaputra y Meghna supera localmente en un factor 200 el valor guía del arsénico en el agua potable, establecido por la Organización Mundial de la Salud (OMS) en 10 µg/L. Aproximadamente, el 25% de los pozos de Bangla Desh superan el estándar nacional de 50 µg/L, afectando al menos a 25 millones de personas. El arsénico ha llegado a las aguas subterráneas por la disolución reductora de hidróxidos férricos a los que se adsorbe durante el transporte fluvial. Los perfiles del arsénico en las aguas subterráneas bombeadas, agua de poro y sedimentos del acuífero muestran tendencias coherentes. Las concentraciones elevadas están asociadas a arenas finas y sedimentos ricos en materia orgánica. Las concentraciones de arsénico son bajas cerca del nivel freático, se incrementan hasta un máximo que se localiza generalmente a entre 20 y 40 m bajo la cota del terreno, y disminuyen a valores muy pequeños entre alrededor de 100 y 200 m. El arsénico se encuentra sobretodo en las aguas subterráneas existentes en la secuencia de sedimentación que tuvo lugar en el valle durante la transgresión marina del Holoceno. Las aguas subterráneas del Pleistoceno y acuíferos más antiguos están mayoritariamente libres de arsénico. Es probable que las concentraciones de arsénico aumenten en los próximos años en muchos pozos de tipo tubo perforados manualmente, por lo que será esencial efectuar un muestreo regular. Los acuíferos ubicados a más de 200 m bajo las llanuras de inundación ofrecen buenas perspectivas de abastecimiento a largo plazo sin problemas de arsénico, pero pueden estar limitados por las amenazas de la intrusión salina y de la precolación de arsénico desde niveles superiores.

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Résumé Larsenic contamine les eaux souterraines dans la plus grande partie du sud, du centre et de lest du Bangladesh. Les eaux des nappes alluviales holocènes du Gange, du Brahmapoutre et de la Meghna dépassent localement 200 fois la valeur guide donnée par lOMS pour leau de boisson, fixée à 10 µg/l darsenic. Environ 25% des puits du Bangladesh dépassent la valeur standard nationale de 50 µg/l, affectant au moins 25 millions de personnes. Larsenic a été introduit dans les nappes par la dissolution par réduction doxy-hydroxydes ferriques sur lesquels larsenic était adsorbé au cours du transport fluvial. Des profils verticaux darsenic dans leau souterraine pompée, dans leau porale et dans les sédiments des aquifères montrent des tendances convergentes. Les concentrations élevées sont associées à des sédiments à sable fin et riches en matières organiques. Les concentrations sont faibles au voisinage de la surface de la nappe, atteignent un maximum typiquement entre 20 et 40 m sous le sol, puis tombent à des niveaux très bas entre 100 et 200 m. Larsenic est surtout présent dans les eaux souterraines de la séquence de remplissage de vallée déposée au cours de la transgression marine holocène. Les eaux souterraines des aquifères pléistocènes et plus anciens sont très largement dépourvus darsenic. Les concentrations en arsenic dans de nombreux puits creusés à la main doivent probablement augmenter au cours des prochaines années ; aussi un suivi régulier est essentiel. Les aquifères à plus de 200 m sous les plaines alluviales offrent de bonnes perspectives pour des alimentations en eau sans arsenic à long terme, mais ils peuvent être limités par les risques dintrusion saline et la drainance descendante de larsenic.

     

Assessment of groundwater quality and hydrochemical characteristics in Farashband plain,Iran

Groundwater in Farashband plain, Southern Iran, is the main source of water for domestic and agricultural uses. This study was carried out to assess the overall water quality and identify major variables affecting the groundwater quality in Farashband plain. The hydrochemical study was undertaken by randomly collecting 84 groundwater samples from observation wells located in 13 different stations covering the entire plain in order to assess the quality of the groundwater through analysis of major ions. The water samples were analyzed for various physicochemical attributes. Groundwater is slightly alkaline and largely varies in chemical composition; e.g., electrical conductivity (EC) ranges from 2314 to 12,678 μS/cm. All the samples have total dissolved solid values above the desirable limit and belong to a very hard type. The abundance of the major ions is as follows: Na⁺ > Ca²⁺ > Ma²⁺ > K⁺ and Cl^? > SO₄ ^2– > HCO₃ ^?. Interpretation of analytical data shows three major hydrochemical facies (Ca–Cl, Na–Cl, and mixed Ca–Mg–Cl) in the study area. Salinity, total dissolved solids, total hardness, and sodium percentage (Na%) indicate that most of the groundwater samples are not suitable for irrigation as well as for domestic purposes and far from drinking water standard. A comparison of groundwater quality in relation to drinking water standards showed that most of the water samples are not suitable for drinking purposes. Based on the US salinity diagram, most of samples belong to high salinity and low to very high sodium type.     

Dissolved organic matter tracers reveal contrasting characteristics across high arsenic aquifers in Cambodia:A fluorescence spectroscopy study

Organic matter in the environment is involved in many biogeochemical processes,including the mobilization of geogenic trace elements,such as arsenic,into groundwater.In this paper we present the use of fluorescence spectroscopy to characterize the dissolved organic matter(DOM)pool in heavily arsenicaffected groundwaters in Kandal Province,Cambodia.The fluorescence DOM(fDOM)characteristics between contrasting field areas of differing dominant lithologies were compared and linked to other hydrogeochemical parameters,including arsenic and dissolved methane as well as selected sedimentary characteristics.Absorbance-corrected fluorescence indices were used to characterize depth profiles and compare field areas.Groundwater fDOM was generally dominated by terrestrial humic and fulvic-like components,with relatively small contributions from microbially-derived,tryptophan-like components.Groundwater fDOM from sand-dominated sequences typically contained lower tryptophan-like,lower fulvic-like and lower humic-like components,was less bioavailable,and had higher humification index than clay-dominated sequences.Methane concentrations were strongly correlated with fDOM bioavailability as well as with tryptophan-like components,suggesting that groundwater methane in these arsenic-prone aquifers is likely of biogenic origin.A comparison of fDOM tracers with sedimentary OM tracers is consistent with the hypothesis that external,surface-derived contributions to the aqueous DOM pool are an important control on groundwater hydrogeochemistry.