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.     

A geochemical study of redox behavior of As in a contaminated aquifer from Sonargaon, Central Bangladesh

The Bengal Basin has been exposed to the most serious As problem in the world. Although it has been agreed well among many researchers that the contamination has been induced by natural geochemical process, detailed mechanisms are still under debate. Arsenic is easily soluble into groundwater as pentavalent arsenate and trivalent arsenite. Their adsorption behavior for various solid phases, particularly for Fe oxyhydroxide （FeOOH）, is different. Thus speciation of As in solid phase is essential to examine the process of contamination. However, few studies have been done about As speciation in sediment due to its analytical difficulty. In this study, we applied XANES （X-ray adsorption near the edge structure） spectroscopy to determine oxidation states of As and Fe, and investigate As behavior along change in redox condition. We studied the Sonargaon area located 25 km southeast of Dhaka. Sediment core samples were collected from one site in the area up to the depth of 100 m using penetration-drilling method. The samples were packed into oxygen impermeable film with deoxidizer on site,     

Groundwater contamination with arsenic in Sherajdikhan,Bangladesh: geochemical and hydrological implications

An integrated study has been carried out to elucidate the distribution and occurrence of arsenic in selected groundwater samples in the area of Sherajdikhan, Bangladesh. Arsenic and other parameters (T, pH, EC, Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, NO₃ ⁻, SO₄ ²⁻, HCO₃ ⁻, PO₄ ³⁻, Fe, Mn and DOC) have been measured in groundwater samples collected from shallow/deep tube wells at different depths. Hydrogeochemical data suggest that the groundwaters are generally Ca–Mg–HCO₃ and Mg–Ca–HCO₃ types with bicarbonate (HCO₃ ⁻) as the dominant anion, though the other type of water has also been observed. Dissolved arsenic in groundwater ranged from 0.006 to 0.461 mg/l, with 69% groundwater samples exceeded the Bangladesh limit for safe drinking water (0.05 mg/l). Correlation and principal component analysis have been performed to find out possible relationships among the examined parameters in groundwater. Low concentrations of NO₃ ⁻ and SO₄ ²⁻, and high concentrations of DOC, HCO₃ ⁻ and PO₄ ³⁻ indicate the reducing condition of subsurface aquifer where sediments are deposited with abundant organic matter. Distinct relationship of As with Fe and Mn, and strong correlation with DOC suggests that the biodegradation of organic matter along with reductive dissolution of Fe–Mn oxyhydroxides has being considered the dominant process to release As in the aquifers studied herein.     

Remobilization of arsenic from buried wastes at an industrial site: mineralogical and geochemical control

An industrial area contaminated by As was studied to determine the source of this element and its speciation in As-bearing solids and in run-off waters. Mineral precipitates and water samples were collected and analyzed to assess processes controlling As mobility at this site. The integrated study of a contaminated industrial area allowed identification of the source of the As and of the nature of secondary As-bearing phases. The results obtained both on solid and water samples were used to model As behavior during waste leaching on carbonate rocks. At the upper end of a topographic transect across the site, run-off waters (pH=7.9) interact with surficial waste piles (containing arsenolite, arsenopyrite and pyrite), becoming acidic (pH=2.2) and concentrated in dissolved arsenate species (As⁵⁺) (ΣAs ranging from 0.961 to 3.149·10⁻³ mol/l). Those acidic waters interact with the limestone substratum, providing dissolved Ca which reacts with As to precipitate 1:1 Ca arsenates (weilite CaHAsO₄, haidingerite CaHAsO₄.H₂O and pharmacolite CaHAsO₄.2H₂O) and, in minor amounts, Ca–Mg arsenates (picropharmacolite (Ca,Mg)₃(AsO₄)₂ 6H₂O). The 1:1 Ca arsenates identified are known to precipitate at low pH (3–6) and seem to be stable in media with high dissolved CO₂, in comparison with other types of Ca arsenates. However, due to their high solubilities, they are not strictly relevant candidates to immobilize As in contaminated surficial environments. Although reported solubilities decrease to values close to the French and US drinking standards in Ca-rich solutions, a thorough examination of the precipitation/dissolution kinetics of Ca arsenates should be undertaken to assess their long-term stability and their efficiency in rapidly immobilizing As in contaminated surficial environments.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

Groundwater chemistry and occurrence of arsenic in the Meghna floodplain aquifer,southeastern Bangladesh

Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25–33 m) and deep (191–318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl⁻ and higher proportions of Na⁺ relative to Ca²⁺, Mg²⁺, and K⁺ in groundwater suggest the influence by a source of Na⁺ and Cl⁻. Use of chemical fertilizers may cause higher concentrations of NH₄⁺ and PO₄³⁻ in shallow well samples. In general, most ions are positively correlated with Cl⁻, with Na⁺ showing an especially strong correlation with Cl⁻, indicating that these ions are derived from the same source of saline waters. The relationship between Cl⁻/HCO₃⁻ ratios and Cl⁻ also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO₃⁻ reflect the degree of water–rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO₄²⁻ and NO₃⁻ and high concentrations of dissolved Fe and PO₄³⁻ and NH₄⁺ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO₄²⁻ and NO₃⁻ but correlate weakly with Mo, Fe concentrations and positively with those of P, PO₄³⁻ and NH₄⁺ ions.     

Hydrochemical evolution and arsenic release in shallow aquifer in the Titas Upazila,Eastern Bangladesh

Groundwater arsenic (As) concentrations above 10 μg/L (World Health Organization; WHO standard) are frequently found in the Titas Upazila in Bangladesh. This paper evaluates the groundwater chemistry and the mechanisms of As release acting in an underground aquifer in the middle-northeast part of the Titas Upazila in Bangladesh. Previous measurements and analyses of 43 groundwater samples from the region of interest (ROI) are used. Investigation is based on major ions and important trace elements, including total As and Fe in groundwater samples from shallow (8–36 m below ground level: mbgl) and deep (85–295 mbgl) tube wells in the aforementioned ROI. Principal hydrochemical facies are Ca–HCO₃, with circumneutral pH. The different redox-sensitive constituents (e.g., As, Fe, Mn, NH₄, and SO₄) indicate overlapping redox zones, leading to differences regarding the redox equilibrium. Multivariate statistical analysis (factor analysis) was applied to reduce 20 chemical variables to four factors but still explain 81% of the total variance. The component loadings give hints as to the natural processes in the shallow aquifers, in which organic matter is a key reactant. The observed chemistry of As, Fe, and Mn can be explained by simultaneous equilibrium between Fe-oxide and SO₄ reduction and an equilibrium of rhodochrosite precipitation/dissolution. A correlation test indicates the likeliness of As release by the reductive dissolution of Fe-oxides driven by the degradation of sediments organic matter. Other mechanisms could play a role in As release, albeit to a lesser extent. Reactive transport modeling using PHREEQC reproduced the observed chemistry evolution using simultaneous equilibrium between Fe-oxide and SO₄ reduction and the equilibrium of rhodochrosite dissolution/precipitation alongside organic matter oxidation.     

Risk assessment of bottom ash from fuel oil power plant of Italy: mineralogical,chemical and leaching characterization

The main aim of the present study is to contribute to the field of environmental research by providing new data on bottom ash samples derived from an oil power plant located in Southern Italy. To achieve this purpose, the mineralogical and chemical properties of representative bottom ash samples were investigated through the integrated employment of different analytical techniques, i.e., X-ray powder diffraction, scanning electron microscopy, X-ray fluorescence and atomic absorption spectrometry. The obtained experimental results show that quartz, alunogen, rhomboclase and potassium hydrogen silicate are the major crystalline phases of all the analyzed samples. Furthermore, the revealed main ash constituents are SiO₂ and SO₃, with low contents of Fe₂O₃ and Al₂O₃, and little amounts of CaO, Na₂O, K₂O, MgO, P₂O₅ and TiO₂. Among the trace elements, very high amounts of heavy metals, i.e., V, Cr, Ni, La, Pb and Mo, were detected. The comparison of the obtained heavy metal abundance data with those reported in the literature highlights significant differences. Leaching test evidenced V, Ni and Cr values that make these ashes a potential contamination source for groundwater quality and for soil, nearby the ash disposal landfills area. All the obtained findings show that these materials are highly harmful for the human health, with a greater extent for the heavy metal concentrations.     

Marbles and carbonate rocks from central Morocco: a petrographic,mineralogical and geochemical study

Petrographic, mineralogical, and stable isotopes (δ¹³C, δ¹⁸O values) compositions were used to characterise marbles and sedimentary carbonate rocks from central Morocco, which are considered to be a likely source of ornamental and building material from Roman time to the present day. This new data set was used in the frame of an archaeometric provenance study on Roman artefacts from the town of Thamusida (Kenitra, north Morocco), to assess the potential employment of these rocks for the manufacture of the archaeological materials. A representative set of samples from marbles and other carbonate rocks (limestone, dolostone) were collected in several quarries and outcrops in the Moroccan Meseta, in a region extending from the Meknes–Khenifra alignment to the Atlantic Ocean. All the samples were studied using a petrographic, mineralogical and geochemical methods. The petrographic and minerological investigations (optical microscopy, electron microscopy, X-ray diffraction) allowed to group the carbonate rocks in limestones, foliated limestone, diagenetic breccias and dolostone. The limestones could be further grouped as mudstones, wackestones–packstones, crinoid grainstones, oolitic grainstone and floatstones. Textural differences allowed to define marbles varieties. The stable carbon and oxygen isotope composition proved to be quite useful in the discrimination of marble sources, with apparently less discriminatory potential for carbonate rocks.     

Geochemical,mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology and redox processes that occur in these zones, several cores from a region of naturally occurring reducing conditions in a U-contaminated aquifer (Rifle, CO) were examined. Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for U and Fe content, oxidation state, and mineralogy; reduced S phases; and solid-phase organic C content using a suite of analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase U concentrations were higher in the naturally reduced zone, with a high proportion of the U present as U(IV). The sediments were also elevated in reduced S phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and SO₄ reduction has occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentrations of solid-phase organic C and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic C concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic C for maintaining reducing conditions and U immobilization.     

Effect of indigenous bacteria on geochemical behavior of arsenic in aquifer sediments from the Hetao Basin, Inner Mongolia: Evidence from sediment incubations

Incubation studies were carried out using 5 freshly collected sediments from shallow aquifers of the Hetao Basin, Inner Mongolia. The aquifer sediments covering a range of redox conditions, as indicated by their deep grey to yellow color were mixed with degassed artificial As solution or degassed deionized water at a ratio of solid to water of about 1:10 (wt./wt.). Suspensions which were either amended with glucose or autoclaved, were incubated in parallel with unamended suspensions. Five microcosm cultures of unamended sediments gradually release the equivalent of 0.03–0.30 μg/g As to the dissolved phase. The addition of glucose as a potential electron donor results in a marked stimulation in the mobilization of As (0.71–3.81 μg/g) in the amended incubations for all sediments. The quantity of As released accounts for 60–70% of As bound to Fe/Mn oxides in the original sediments. The microbially mediated mobilization of As with the organic nutrient as an electron donor is strongly associated with the As bound to Fe/Mn oxides, as well as the exchangeable As. During the incubations amended with glucose, 2–4% of the sediment Fe is released. The results suggest that the introduction of labile dissolved organic C into the yellowish sediment aquifers with As-free groundwater would reduce a significant proportion of the Fe(III) oxyhydroxides mediated by anaerobic bacteria respiration and increase groundwater As concentrations.     

Authigenic carbonate precipitates from the NE Black Sea: a mineralogical,geochemical, and lipid biomarker study

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low δ¹³C values measured on carbonates (−41 to −32‰ V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. δ¹⁸O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly ¹⁸O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.     

Mobilisation of Iron from rocks in a fractured aquifer: Lithological and geochemical controls

Iron mobilisation from aquifer rocks in an important fractured aquifer system in South Africa is resulting in clogging of boreholes by Fe oxide minerals. Leach experiments using natural waters were conducted to determine the effects of redox conditions, pH lithology and presence of organic acids on the rate and extent of Fe dissolution from aquifer rocks, with the aim of clarifying the association of Fe clogging with geological formations that show Fe staining on weathering. The results indicate that the greatest amount of Fe (>30 mmol/kg rock) is leached from arenaceous rocks with low total Fe contents (49.0–75.0 mmol/kg) under anoxic conditions. Rocks with the highest Fe contents (>800 mmol/kg) generated low concentrations of Fe (<10 mmol/kg) even under favourable conditions of 0 mg/L DO and pH 3. The extent of Fe dissolution from the rocks was found to be most strongly dependent on the redox conditions, and the form of Fe present in the rock, with ascorbate-extracted amorphous Fe being the most mobile. The rate of dissolution is affected by pH and the presence of natural organic acids in the leachate. However, the effect of organic acids was only noticeable on arenaceous rocks.     

Modeling the multi-level plumbing system of the Changbaishan caldera from geochemical,mineralogical, Sr-Nd isotopic and integrated geophysical data

Changbaishan, an intraplate volcano, is characterized by an approximately 6 km wide summit caldera and last erupted in 1903. Changbaishan experienced a period of unrest between 2002 and 2006. The activity developed in three main stages, including shield volcano(basalts), cone-construction(trachyandesites to trachytes with minor basalts), and caldera-forming stages(trachytes to comendites). This last stage is associated with one of the more energetic eruptions of the last millennium on Earth, the 946 CE, VEI 7 Millennium Eruption(ME),which emitted over 100 km3 of pyroclastics. Compared to other active calderas, the plumbing system of Changbaishan and its evolution mechanisms remain poorly constrained. Here, we merge new whole-rock,glass, mineral, isotopic, and geobarometry data with geophysical data and present a model of the plumbing system. The results show that the volcano is characterized by at least three main magma reservoirs at different depths: a basaltic reservoir at the Moho/lower crust depth, an intermediate reservoir at 10–15 km depth, and a shallower reservoir at 0.5–3 km depth. The shallower reservoir was involved in the ME eruption, which was triggered by a fresh trachytic melt entering a shallower reservoir where a comenditic magma was stored. The trachytes and comendites originate from fractional crystallization processes and minor assimilation of upper crust material, while the less evolved melts assimilate lower crust material. Syn-eruptive magma mingling occurred during the ME eruption phase. The magma reservoirs of the caldera-forming stage partly reactivate those of the cone-construction stage. The depth of the magma storage zones is controlled by the layering of the crust.The plumbing system of Changbaishan is vertically extensive, with crystal mush reservoirs renewed by the replenishment of new trachytic to trachyandesitic magma from depth. Unlike other volcanoes, evidence of a basaltic recharge is lacking. The interpretation of the signals preceding possible future eruptions should consider the multi-level nature of the Changbaishan plumbing system. A new arrival of magma may destabilize a part of or the entire system, thus triggering eruptions of different sizes and styles. The reference model proposed here for Changbaishan represents a prerequisite to properly understand periods of unrest to potentially anticipate future volcanic eruptions and to identify the mechanisms controlling the evolution of the crust below volcanoes.     

New carbonatite complexes in the Archaean In'Ouzzal nucleus (Ahaggar,Algeria): mineralogical and geochemical data

Several massifs of very old carbonatites have been discovered in the Archaean granulitic block of In'Ouzzal (Western Ahaggar, Algeria). These carbonatites are original since they are associated with Silica — saturated syenitic magmatism and present, in the late stages of evolution, a very uncommon mineralogy, with silicate minerals, especially wollastonite, allanite, and quartz. The mineralogy, C and O isotopes and R.E.E. distributions indicate that the late stages of crystallization occurred under high SiO₂ activities, and produced the uncommon mineralogy and extremely high R.E.E. concentrations in phosphate minerals apatite and britholite. Interaction with continental crust is a possible mechanism to explain the original features of these carbonatite complexes.     

The sources of geogenic arsenic in aquifers at Datong basin,northern China: Constraints from isotopic and geochemical data

Mineralogical, geochemical and zircon U–Pb dating studies were carried out to identify the sources of arsenic in the shallow aquifers of Datong Basin in northern China. A sediment sample from 18 m depth containing 10.3 mg/kg arsenic showed a Zircon U–Pb concordant age of 2528 ± 20 to 271 ± 4 Ma that can be divided into two groups (2528 ± 20 to 1628 ± 21 Ma and 327 ± 4 to 271 ± 4 Ma) and is comparable to that of the sedimentary rocks of Taiyuan (upper Carboniferous) and Shanxi Formation (lower Permian) outcropping to the west of Datong Basin. In contrast, a sediment sample from 22.5 m depth containing 5.7 mg/kg arsenic displayed a Zircon U–Pb concordant age ranging from 2561 ± 21 to 1824 ± 26 Ma that is comparable to that of the Hengshan Complex (Ne-Archaean Precambrian) outcropping to the east of .     

Arsenic release from biotite into a Holocene groundwater aquifer in Bangladesh

Continuous core sediments (to a depth of 90.1 m) taken at a transitional area of Holocene and Pleistocene deposits in Sonargaon, Bangladesh were characterized for their mineralogy and chemistry. Among the sediments of the lower part of the Holocene aquifer (depth: 18–29 m), where most domestic wells are installed, As is mostly fixed in biotite and organic phases. A positive correlation of As concentration with those of Al and Fe but not that of total organic C clearly suggests that biotite is a primary source of As. Although microbial reduction–dissolution of As-containing Fe oxyhydroxides is thought to cause As-enriched groundwater in the Ganges–Brahmaputra–Meghna delta plain, the authors conclude that chemical weathering of biotite is the primary formation mechanism and prevailing reducing conditions contribute to the expansion of As-enriched groundwater in the study area.