Mobilization of arsenic and iron from Red River floodplain sediments, Vietnam

Sediments from the Red River and from an adjacent floodplain aquifer were investigated with respect to the speciation of Fe and As in the solid phase, to trace the diagenetic changes in the river sediment upon burial into young aquifers, and the related mechanisms of arsenic release to the groundwater. Goethite with subordinate amounts of hematite were, using Mössbauer spectroscopy, identified as the iron oxide minerals present in both types of sediment. The release kinetics of Fe, As, Mn and PO₄ from the sediment were investigated in leaching experiments with HCl and 10 mM ascorbic acid, both at pH 3. From the river sediments, most of the Fe and As was mobilized by reductive dissolution with ascorbic acid while HCl released very little Fe and As. This suggests As to be associated with an Fe-oxide phase. For oxidized aquifer sediment most Fe was mobilized by ascorbic acid but here not much As was released. However, the reduced aquifer sediments contained a large pool of Fe(II) and As that is readily leached by HCl, probably derived from an unidentified authigenic Fe(II)-containing mineral which incorporates As as well. Extraction with ascorbic acid indicates that the river sediments contain both As(V) and As(III), while the reduced aquifer sediment almost exclusively releases As(III). The difference in the amount of Fe(II) leached from river and oxidized aquifer sediments by ascorbic acid and HCl, was attributed to reductive dissolution of Fe(III). The reactivity of this pool of Fe(III) was quantified by a rate law and compared to that of synthetic iron oxides. In the river mud, Fe(III) had a reactivity close to that of ferrihydrite, while the river sand and oxidized aquifer sediment exhibited a reactivity ranging from lepidocrocite or poorly crystalline goethite to hematite. Mineralogy by itself appears to be a poor predictor of the iron oxide reactivity in natural samples using the reactivity of synthetic Fe-oxides as a reference. Sediments were incubated, both unamended and with acetate added, and monitored for up to 2 months. The river mud showed the fastest release of both Fe and As, while the effect of acetate addition was minor. This suggests that the presence of reactive organic carbon is not rate limiting. In the case of the river and aquifer sediments, the release of Fe and As was always stimulated by acetate addition and here reactive organic carbon was clearly the rate limiting factor. The reduced aquifer sediment apparently can sustain slower but prolonged microbially-driven release of As. The highly reactive pools of Fe(III) and As in the river mud could be due to reoxidation of As and Fe contained in the reducing groundwater from the floodplain aquifers that are discharging into the river. Deposition of the suspended mud on the floodplain during high river stages is proposed to be a major flux of As onto the floodplain and into the underlying aquifers.     

Palaeo-hydrogeological control on groundwater As levels in Red River delta,Vietnam

To study the geological control on groundwater As concentrations in Red River delta, depth-specific groundwater sampling and geophysical logging in 11 monitoring wells was conducted along a 45 km transect across the southern and central part of the delta, and the literature on the Red River delta’s Quaternary geological development was reviewed. The water samples (n = 30) were analyzed for As, major ions, Fe²⁺, H₂S, NH₄, CH₄, δ¹⁸O and δD, and the geophysical log suite included natural gamma-ray, formation and fluid electrical conductivity. The SW part of the transect intersects deposits of grey estuarine clays and deltaic sands in a 15–20 km wide and 50–60 m deep Holocene incised valley. The NE part of the transect consists of 60–120 m of Pleistocene yellowish alluvial deposits underneath 10–30 m of estuarine clay overlain by a 10–20 m veneer of Holocene sediments. The distribution of δ¹⁸O-values (range −12.2‰ to −6.3‰) and hydraulic head in the sample wells indicate that the estuarine clay units divide the flow system into an upper Holocene aquifer and a lower Pleistocene aquifer. The groundwater samples were all anoxic, and contained Fe²⁺ (0.03–2.0 mM), Mn (0.7–320 μM), SO₄ (<2.1 μM–0.75 mM), H₂S (<0.1–7.0 μM), NH₄ (0.03–4.4 mM), and CH₄ (0.08–14.5 mM). Generally, higher concentrations of NH₄ and CH₄ and low concentrations of SO₄ were found in the SW part of the transect, dominated by Holocene deposits, while the opposite was the case for the NE part of the transect. The distribution of the groundwater As concentration (<0.013–11.7 μM; median 0.12 μM (9 μg/L)) is related to the distribution of NH₄, CH₄ and SO₄. Low concentrations of As (?0.32 μM) were found in the Pleistocene aquifer, while the highest As concentrations were found in the Holocene aquifer. PHREEQC-2 speciation calculations indicated that Fe²⁺ and H₂S concentrations are controlled by equilibrium for disordered mackinawite and precipitation of siderite. An elevated groundwater salinity (Cl range 0.19–65.1 mM) was observed in both aquifers, and dominated in the deep aquifer. A negative correlation between aqueous As and an estimate of reduced SO₄ was observed, indicating that Fe sulphide precipitation poses a secondary control on the groundwater As concentration.     

Arsenic mobilization in an oxidizing alkaline groundwater: Experimental studies,comparison and optimization of geochemical modeling parameters

Arsenic (As) mobilization and contamination of groundwater affects millions of people worldwide. Progress in developing effective in-situ remediation schemes requires the incorporation of data from laboratory experiments and field samples into calibrated geochemical models.In an oxidizing aquifer where leaching of high pH industrial waste from unlined surface impoundments led to mobilization of naturally occurring As up to 2 mg L⁻¹, sequential extractions of solid phase As as well as, batch sediment microcosm experiments were conducted to understand As partitioning and solid-phase sorptive and buffering capacity. These data were combined with field data to create a series of geochemical models of the system with modeling programs PHREEQC and FITEQL. Different surface complexation modeling approaches, including component additivity (CA), generalized composite (GC), and a hybrid method were developed, compared and fitted to data from batch acidification experiments to simulate potential remediation scenarios. Several parameters strongly influence the concentration of dissolved As including pH, presence of competing ions (particularly phosphate) and the number of available sorption sites on the aquifer solids. Lowering the pH of groundwater to 7 was found to have a variable, but limited impact (<63%) on decreasing the concentration of dissolved As. The models indicate that in addition to lowering pH, decreasing the concentration of dissolved phosphate and/or increasing the number of available sorption sites could significantly decrease the As solubility to levels below 10 μg L⁻¹. The hybrid and GC modeling results fit the experimental data well (NRMSE<10%) with reasonable effort and can be implemented in further studies for validation.     

PHREEQC在地下水溶质反应-运移模拟中的应用

由于地下水污染的加剧,对地下水中污染物运移规律的研究日益受到重视。地下水中的溶质在运移过程中伴随着溶质组分间的化学反应,因此需要建立地下水溶质运移与化学反应的耦合模型。PHREEQC是近年来发展起来的描述局部平衡反应、动态生物化学反应的水文地球化学模拟软件。本文利用该模拟软件对一维地下水流动过程中溶质离子交换反应和动态氧化还原反应进行了模拟。结果表明,PHREEQC能够成功地进行溶质运移情况下复杂水化学反应模拟,但对于复杂地下水流和溶质运动的情况,有必要耦合其它的地下水流动和溶质运移软件来共同完成。     

Hydrogeochemical characteristics of groundwater from the two main aquifers in the Red River Delta,Vietnam

In the Red River Delta, situated in the northern part of Vietnam, nearly its entire population depends solely on groundwater for daily water consumptions. For this reason, groundwater quality assessments must be carefully carried out using hydrogeochemical properties, to ensure effective groundwater resource planning for the Delta’s present and future groundwater use. In this study, the spatial and seasonal changes in the hydrogeochemical characteristics of groundwater in the two main aquifers of the RRD were investigated by analyzing the physicochemical data obtained in 2011 from 31 conjunctive wells in the Delta’s Holocene unconfined aquifer (HUA) and Pleistocene confined aquifer (PCA) using the Piper diagram and the Gibbs diagram. Results of the data analysis show that the groundwater in both aquifers in the upstream area of the delta is dominated by the [Ca²⁺–HCO₃⁻] water-type, while the [Na⁺–Cl⁻] dominates along the middle-stream and downstream areas. Seasonal changes in the hydrogeochemical facies in both aquifers, comparing the results for the dry and the rainy seasons, were detected in about one third of the sampling wells, which were mainly located at the upstream portion of the Delta. The hydrogeochemical facies of HUA were different from that of PCA by about 45% of the sampling wells in both the dry and the rainy seasons, which were found mostly in the upstream and middle-stream areas.     

2010—2020年黄河下游河南典型灌区浅层地下水中砷和氟的演化特征及变化机制

豫北平原地处黄河中下游,同时存在着高砷和高氟地下水,但目前这种零星分布区砷和氟的共存机制尚不明确。本文采集了豫北平原332组浅层地下水样品,采用原子荧光光谱法测定砷含量,离子色谱和电感耦合等离子体发射光谱等方法测定氟及其他阴阳离子含量,探讨地下水中砷和氟的空间分布规律,并结合水化学图解和因子分析法提取出影响该区地下水演化的主要因子,以此为思路对该区高砷和高氟地下水的成因机制进行探讨。结果表明：该平原地下水中砷和氟的浓度范围分别为0.0001~0.1900mg/L和0.13~4.94mg/L。高砷地下水主要分布在太行山前冲洪积洼地和黄河决口扇垂向15~80m;高氟地下水分布于黄河沿岸的黄河现代河道影响带垂向7~100m。蒸发浓缩作用、矿物的溶解/解吸附作用和氧化还原环境是控制该区地下水演化的主要因子。氟在因子F1(蒸发浓缩作用)和F2(矿物的溶解/解吸附作用)中分别占有0.214和0.743的载荷,氟浓度与ρ(Na⁺)/[ρ(Na⁺)+ρ(Ca²⁺)]呈正相关,高浓度氟出现在Ca²⁺浓度较低的地下水中。黄河现代河道影响带强烈的蒸发浓缩作用有助于含氟矿物的溶解,黄河水的灌溉增加了地下水中Na⁺浓度,进一步增强了其溶解作用,在这种环境下氟会浓缩并富集在地下水中。砷在因子F3(氧化还原环境)中占有0.728的载荷,与Fe²⁺、NH₄⁺呈正相关,与NO₃^-、SO₄^2-呈负相关,Eh越低,砷浓度越高。太行山前冲洪积洼地和黄河决口扇的还原环境有利于含砷的铁氧化物/氢氧化物发生还原性溶解,从而形成高砷地下水。pH值升高引起的以阴离子形式存在的砷酸根/亚砷酸根/氟化物在矿物表面的解吸附作用有利于该区砷和氟在地下水中共存。然而,该区地下水中砷和氟的相关性并不十分显著,这是由于高砷区高浓度的钙离子不利于氟的富集,而高氟区的弱还原条件不利于含砷铁氧化物/氢氧化物的溶解。本文研究结果探讨了豫北平原地下水中砷和氟的共存机制,进一步丰富了高砷高氟地下水共污染的理论体系。

     

Inverse geochemical modeling of groundwater salinization in Azraq Basin,Jordan

The aim is to define the mechanism of chemical reactions that are responsible for the salinization of the Azraq basin along groundwater flow path, using inverse modeling technique by PHREEQC Interactive 2.8 for Windows. The chemical analysis of representative groundwater samples was used to predict the causes of salinization of groundwater. In addition, the saturation indices analysis was used to characterize the geochemical processes that led to the dissolution of mineral constituents within the groundwater aquifer system. According to the modeling results, it was noted that the groundwater at the recharge area was undersaturated with respect to calcite, dolomite, gypsum, anhydrite, and halite. Thus, the water dissolved these minerals during water rock interaction, and therefore, the concentration of Ca, Mg, Na, and SO₄ increased along the groundwater flow path. Furthermore, the groundwater at the discharge area was oversaturated with respect to calcite and dolomite. This meant that the water would precipitate these minerals along the flow path, while the water was undersaturated with respect to gypsum and halite throughout the simulated path; this showed the dissolution processes that take place during water-rock interaction. Therefore, the salinity of the groundwater increased significantly along the groundwater flow paths.     

Origin and extent of fresh groundwater, salty paleowaters and recent saltwater intrusions in Red River flood plain aquifers, Vietnam

A model has been established on the origin and extent of fresh groundwater, salty paleowaters and saltwater from recent seawater intrusions in the Red River flood plain in Vietnam. This was done with geological observations, geophysical borehole logging and transient electromagnetic methods. Salt paleowater is present up to 50–75?km from the coastline, with occurrence controlled by the Holocene transgression. A density-driven leaching of salty porewater has occurred from high-permeability Holocene sediments into underlying Pleistocene deposits, whereas diffusion has dominated in low-permeability layers. In the Pleistocene aquifer, the highest content of dissolved solids is found below two intrinsic valleys with Holocene marine sediments and along the coastline. Recent intrusion of saltwater from the South China Sea is observed in shallow groundwater 35?km inland, probably a result of transport of salty water inland in rivers or leaching of paleowaters from very young near-coast marine sediments. The observed inverted salinity profile, with high saline water overlying fresher groundwater, has been formed due to the global eustatic sea-level changes during the last 8,000–9,000?years. The proposed model may therefore be applicable to other coastal aquifers, with a proper incorporation of the local geological environments.     

Evidence for the occurrence of hydrogeochemical processes in the groundwater of Khoy plain,northwestern Iran,using ionic ratios and geochemical modeling

Rapid population growth, industrialization, and agricultural expansion in the Khoy area (northwestern Iran) have led to its dependence on groundwater and degradation of groundwater quality. This study attempts to decipher the major processes and factors that degrade the groundwater quality of the Khoy plain. For this purpose, 54 groundwater samples from unconfined and confined aquifers of the plain were collected in July 2017 and analyzed for major cations and anions (Na, K, Ca, Mg, HCO₃, SO_4, and Cl), minor ions (NO₃ and F), and Al. Magnesium and bicarbonate were identified as the dominant cation and anion, respectively. Several ionic ratios and geochemical modeling using PHREEQC indicated that the most important hydrogeochemical processes to affect groundwater quality in the plain were weathering and dissolution of evaporitic and silicate minerals, mixing, and ion exchange. There were smaller effects from evaporation and anthropogenic factors (e.g., industries). Results showed that the high salinity of the groundwater in the northeast area of the plain was due to the high solubility of the evaporitic minerals, e.g., halite and gypsum. Reverse ion exchange and the contribution of mineral dissolution were more significant than ion exchange in the northeastern part of the plain. Elevated salinity of the groundwater in the southeast was attributed mostly to reverse ion exchange and somewhat to evaporation.     

Regional groundwater flow and geochemical evolution in the Amacuzac River Basin,Mexico

An approach is presented to investigate the regional evolution of groundwater in the basin of the Amacuzac River in Central Mexico. The approach is based on groundwater flow cross-sectional modeling in combination with major ion chemistry and geochemical modeling, complemented with principal component and cluster analyses. The hydrogeologic units composing the basin, which combine aquifers and aquitards both in granular, fractured and karstic rocks, were represented in sections parallel to the regional groundwater flow. Steady-state cross-section numerical simulations aided in the conceptualization of the groundwater flow system through the basin and permitted estimation of bulk hydraulic conductivity values, recharge rates and residence times. Forty-five water locations (springs, groundwater wells and rivers) were sampled throughout the basin for chemical analysis of major ions. The modeled gravity-driven groundwater flow system satisfactorily reproduced field observations, whereas the main geochemical processes of groundwater in the basin are associated to the order and reactions in which the igneous and sedimentary rocks are encountered along the groundwater flow. Recharge water in the volcanic and volcano-sedimentary aquifers increases the concentration of HCO₃ ^–, Mg²⁺ and Ca²⁺ from dissolution of plagioclase and olivine. Deeper groundwater flow encounters carbonate rocks, under closed CO₂ conditions, and dissolves calcite and dolomite. When groundwater encounters gypsum lenses in the shallow Balsas Group or the deeper Huitzuco anhydrite, gypsum dissolution produces proportional increased concentration of Ca²⁺ and SO₄ ^2–; two samples reflected the influence of hydrothermal fluids and probably halite dissolution. These geochemical trends are consistent with the principal component and cluster analyses.     

Spatio-temporal analysis of recent groundwater-level trends in the Red River Delta, Vietnam

A groundwater-monitoring network has been in operation in the Red River Delta, Vietnam, since 1995. Trends in groundwater level (1995?C2009) in 57 wells in the Holocene unconfined aquifer and 63 wells in the Pleistocene confined aquifer were determined by applying the non-parametric Mann-Kendall trend test and Sen??s slope estimator. At each well, 17 time series (e.g. annual, seasonal, monthly), computed from the original data, were analyzed. Analysis of the annual groundwater-level means revealed that 35?% of the wells in the unconfined aquifer showed downward trends, while about 21?% showed upward trends. On the other hand, confined-aquifer groundwater levels experienced downward trends in almost all locations. Spatial distributions of trends indicated that the strongly declining trends (>0.3?m/year) were mainly found in urban areas around Hanoi where there is intensive abstraction of groundwater. Although the trend results for most of the 17 time series at a given well were quite similar, different trend patterns were detected in several. The findings reflect unsustainable groundwater development and the importance of maintaining groundwater monitoring and a database in the Delta, particularly in urban areas.     

Ore transport and deposition in the Red Sea geothermal system: a geochemical model

Thermodynamic calculation of distribution of dissolved aqueous species in the Red Sea geothermal brine provides a model of ore transport and deposition in good agreement with observed accumulations of base metal sulfides, anhydrite, and barite.The Red Sea brine is recirculated seawater that acquires high salinity by low-temperature interaction with Miocene evaporites and is subsequently heated to temperatures in excess of 200°C by interaction with recent rift zone intrusive rocks. At temperatures up to 250°C, NaSO^?₄ and MgSO⁰₄ are the dominant sulfur-bearing species. H₂S forms by inorganic sulfate reduction at the higher temperatures but is maintained at a uniform concentration of about 2 ppm by the strength of the sulfate complexes.Chloride complexes solubilize metals at the higher temperatures, and thus sulfide and metals are carried together into the Atlantis II Deep. Below 150°C, the brine becomes supersaturated with respect to chalcopyrite, sphalerite, galena, and iron monosulfide due to chloride-complex dissociation. Sulfide precipitation rates, based on the rate of brine influx, are in good agreement with measured sedimentation rates. Anhydrite precipitates as crystalline fissure infillings from high-temperature inflowing brine. Barite forms from partial oxidation of sulfides at the interface between the lower hot brine and the transitional brine layer.     

Arsenic enrichment in groundwater of West Bengal,India: geochemical evidence for mobilization of As under reducing conditions

The mechanism of As release and source(s) of As has been investigated in a small part of a watershed in the Murshidabad district of West Bengal. Analyses include major ion and trace element concentrations, as well as O, H and S isotope ratios of groundwater, surface water and a thermal spring. The results indicate that all water samples belong to the Ca–HCO₃ type, except for the thermal spring which is of the Na–HCO₃ type. Shallow and deeper groundwaters have distinct hydrochemical features. High As contents were registered only in the deeper groundwater horizon. Factor analysis and the distribution pattern of major and trace elements indicate that As is present in the aquifer as a scavenged phase by Fe(III) and to a lesser extent by Mn(IV) phases. The release of As into the groundwater occurs gradually in successive stages, corresponding to the actual redox state in the aquifer. The main stage of As release is related to the bacterial reduction of Fe(III) to Fe(II) (i.e. to the simultaneous dissolution of Fe oxyhydroxides). Low redox conditions in highly polluted areas are indicated by low SO₄ concentration and high δ³⁴S values. During bacterial SO₄ reduction, residual SO₄ in groundwater is depleted in the lighter S isotope (³²S). However, the cause of the gradual decrease of the redox state in the groundwater is still not well understood.     

Evaluation of food risk parameters in the Day River Flood Diversion Area,Red River Delta,Vietnam

An interdisciplinary approach is necessary for flood risk assessment. Questions are often raised about which factors should be considered important in assessing the flood risk in an area and how to quantify these factors. This article defines and quantitatively evaluates the flood risk factors that would affect the Day River Flood Diversion Area in the context of integrated flood management in the Red River Delta, Vietnam. Expert analysis, in conjunction with field survey and Analytical Hierarchy Process (AHP), is applied to define and quantify parameters (indicators, subcomponents, and components) that contribute to flood risk. Flood duration is found to be the most prominent indicator in determining flood hazard. Residential buildings, population, and pollution are other fairly significant indicators contributing to flood vulnerability from the economic, social, and environmental perspectives, respectively. The study results will be useful in developing comprehensive flood risk maps for policy-makers and responsible authorities. Besides, local residents will also be able to implement suitable measures for reducing flood risk in the study area.     

Arsenic distribution and source in groundwater of Yangtze River Delta economic region,China

This thesis focuses Arsenic(As) distribution and occurrence in groundwater of Yangtze River Delta economic region, East China. 2019 groundwater samples were collected to analyze 26 chemical compositions, including As. The Principal Component Analysis(PCA) was used to find out As source in groundwater. The results show that average As concentration in groundwater of this study is 9.33 μg/l, and maximum As concentration is up to 510 μg/l. The variation coefficient is 314.34%. High arsenic phreatic water(10 μg/l) distributes along the Yangtze River and its estuary. Weak hydrodynamic conditions, wide p H value variation range and deteriorating environment are dominating factors, especially in Yangtze River Delta. The PCA suggests that arsenic in phreatic water is mainly of natural origin. Part of arsenic may directly originate from sediment organics and be related to organics decomposition.