Co-occurrence of arsenic and fluoride in groundwater of Guide basin in China: Genesis, mobility and enrichment mechanism.

Endemic arsenic poisoning and fluorosis caused by primary high arsenic (As) and high fluoride (F-) groundwater have become one of the most serious environmental geological problems faced by the international society. High As and high F- groundwater exists in Neogene confined aquifers in Guide basin, with concentrations of 355 µg/L and 5.67 mg/L, respectively, and showing a co-occurrence phenomenon of As and F- in the groundwater. This poses a double threat to the health of tens of thousands of local residents. In this study, based on the systematic collection of groundwater and borehole sediment samples, analysis of hydrochemistry and isotope indexes, combined with laboratory tests, purpose of this study is to reveal the migration rule and co-enrichment mechanism of As and F- in aquifers, and finally establish a hydrogeochemical conceptual model of the enrichment process of As and F-. The main conclusions are as follows: hydrochemical type of unconfined and confined groundwater in Guide basin is Ca-Na-HCO3 and Na-Cl-HCO3 type, respectively. Main minerals in sediments are quartz and plagioclase. Concentrations of As and F- are lower in unconfined groundwater, but higher in confined groundwater, and which show a gradual increasing trend along the groundwater flow path. The mineralization of natural organic matter in confined aquifer causes iron and manganese oxide minerals containing As to dissolve gradually, which leads to the gradual release of As into groundwater. Large amount of HCO3- produced by mineralization of organic matter precipitate with Ca2+ in groundwater, resulting in reduction of Ca2+ content, promoting the dissolution of fluoride-containing minerals such as fluorite (CaF2), and continuously releasing F- into groundwater. Meanwhile, competitive adsorption reactions in confined aquifers causes more As and F- to be released from mineral surface into groundwater, which gradually migrate and accumulate along groundwater flow. Finally, it is established that a conceptual model for the formation of high As and F- groundwater in the confined aquifer of Guide basin. The research results not only help to improve our understanding of the formation and evolution of groundwater with high As and F- with similar geological background, but also provide scientific basis for rational development and utilization of groundwater, and prevention and control of chronic As and F- poisoning in local and similar areas.

Hydrogeochemical processes controlling surface water quality for irrigation in a Mediterranean wetland ecosystem, Northeast Algeria.

Fetzara Lake, considered one of the most important wetlands in northeastern Algeria, was designated a Ramsar site in 2002. The waters in its watershed are affected by salinity, which influences their suitability for irrigation. To identify the factors influencing the quality of these surface waters, geochemical and statistical analyses were carried out on the basis of the results of chemical analyses of 51 samples collected, during two monitoring campaigns, from all the tributaries in the watershed. The findings show the dominance of three hydrochemical facies over the two campaigns: Na-Cl facies (55.17% and 22.73%) characterizes the waters water from Fetzara Lake outlet (drainage channel and wadi Meboudja), in relation to the influx of saliferous elements due to water evaporation in the lake. Ca-Mg-Cl (27.59% and 40.91%) and Ca-Mg-HCO3 (13.79%. and 13.79%) facies characterize the waters of the remaining tributaries, reflecting the dissolution of carbonate formations and the alteration of the Edough metamorphic basement. Multivariate statistical analysis, using principal component analysis (PCA), shows three water types: highly mineralized (EC > 3000 µS/cm), moderately mineralized (1000 < EC < 3000 µS/cm), and weakly mineralized (EC < 1000 µS/cm). Evaporation and silicate weathering are the main mechanisms controlling water mineralization according to the different bivariate plots. Furthermore, cation exchange indices (CAI-I and CAI-II) reveal that these reactions involve the adsorption of Na+ and K+ onto clay minerals, as well as the simultaneous release of Ca2+ and Mg2+ ions. Finally, the various quality indices (SAR, %Na, RSC and KR) revealed that the water in 36% of tributaries is unsuitable for irrigation. These findings will provide important information on surface water quality in the study area, particularly for irrigation purposes, and will contribute to the thoughtful and sustainable management of this resource.

Mapping of lineaments for groundwater assessment in the Desert Fringes East El-Minia, Eastern Desert, Egypt.

The Eocene aquifer system in Egypt is an important source of water to meet the increasing necessities of the agricultural, drinking, and domestic purposes. This study aimed to assess the impact of the hydro-structural features identified as lineaments on the groundwater occurrence, assess the water quality status for various purposes, and provide useful information for future management. To achieve this, Landsat images have been used in conjunction with the chemical data (major, trace ions, and physicochemical parameters) and statistical analysis. The hydrochemical facies showed that the water samples belong to (1) Ca-HCO3; (2) mixed facies CaMgHCO3 and mixed CaNaHCO3, and (3) Na-Cl hydrochemical facies. The water chemistry is controlled by the carbonate weathering, ion exchange, and evaporite dissolution. The groundwater analysis has indicated that the water is suitable for drinking purposes when compared with the drinking water standards. Furthermore, salinity, electric conductivity, sodium adsorption ratio (SAR), and sodium percentage (%Na) assessment show that majority of the groundwater samples are appropriate for irrigation. The satellite imagery of the area has been analyzed to determine the orientation, density, and intersection. The orientation of the lineaments is well-confirmed with regional structural setting; in addition, density maps show that the density is high throughout the study area. The results reflect a correlation between the lineaments and the hydrologic phenomena. The statistical analysis with the one-way ANOVA confirmed the importance of lineaments as explanatory variable for the observed variation in water quality. This in turn supported that the fracture is structurally controlled and mostly influences both the occurrence and quality.

Identification of hydrogeochemical processes in groundwater of Dawa River basin, southern Ethiopia.

Dawa River basin in southern Ethiopia is covered by volcanic, basement, and sedimentary rocks. Locating good quality groundwater is a challenge in most parts of the basin. Statistical analysis and graphical plots of 94 hydrochemical data of groundwater were used as a main tool to acquire an insight into the major processes that control groundwater chemistry. In the volcanic terrain groundwater is dilute (mean total dissolved solids (TDS): 152 mg/l), while salinity is the highest in the sedimentary terrain (mean TDS: 1750 mg/l). NO3 (-) varies from below the detection limit to 433 mg/l NO3 (-). In 26 % of the water samples, nitrate concentration is above the human-affected value, 5 mg/l NO3 (-). In 6 % of the samples, NO3 (-) concentration is above the limit recommended in drinking water, 50 mg/l NO3 (-), by WHO. Concentration range of the other major ions is also high and hydrochemical water types are diverse, suggesting the effect of various hydrogeochemical processes on the water chemistry. Chemical data analysis revealed that in the volcanic and most parts of the basement terrains silicate hydrolysis is the dominant process. Gypsum dissolution is the main process in the sedimentary terrain. Dissolution of gypsum is also important at few locations along dry riverbeds in the semiarid area where the effect of evaporation on the water chemistry is considerable. Loading of factors with K(+) and SO4 (2-), K(+) and NO3 (-), and NO3 (-) and correlation of SO4 (2-) with Cl(-), along with the observed high nitrate concentration, indicate the effect of surface contamination sources on the water quality.

Sources and hydrogeochemical processes of groundwater under multiple water source recharge condition.

Ecological water replenishment (EWR) is an essential approach for improving the quantity and quality of regional water. The Chaobai River is a major river in Beijing that is replenished with water from multiple sources, including reclaimed water (RW), the South-North Water Transfer Project (SNTP), reservoir discharge (RD). The effects of multiple water source recharge (MWSR) on groundwater quality remain unclear. In this study, hydrochemical ions, isotopes (δ2H-H2O, δ18O-H2O, δ15N-NO3-, and δ18O-NO3-), mixing stable isotope analysis in R (MixSIAR), and hydrogeochemical modeling were used to quantify the contributions and impacts of different water sources on groundwater and to propose a conceptual model. The results showed that during the period before reservoir discharge, RW and SNTP accounted for 38 %-41 % and 54 % of the groundwater in their corresponding recharge areas, respectively. The groundwater in the RW recharge area contained high levels of Na+ and Cl- leading to the precipitation of halite, and was the main factor for the spatial variation in groundwater hydrochemical components. The surface water changed from Na·K - Cl·SO4 type to Ca·Mg - HCO3 type which was similar to groundwater after reservoir discharge. RD accounted for 30 % of the groundwater; however, it did not change the hydrochemical type of groundwater. Dual nitrate stable isotopes and MixSIAR demonstrated that RW was the primary source of NO3- in groundwater, contributing up to 76-89 %, and reservoir discharge effectively reduced the contribution of RW. δ15N-NO3- or δ18O-NO3- in relation to NO3-N suggests that denitrification is the main biogeochemical process of nitrogen in groundwater, whereas water recharge from the SNTP and RD reduces denitrification and dilutes NO3-. This study provides insights into the impact of anthropogenically controlled ecological water replenishment from different water sources on groundwater and guides the reasonable allocation of water resources.

Enrichment mechanisms for the co-occurrence of arsenic-fluoride-iodine in the groundwater in different sedimentary environments of the Hetao Basin, China.

Abnormal levels of co-occurring arsenic (As), fluoride (F-) and iodine (I) in groundwater at the Hetao Basin are geochemically unique. The abnormal distribution of As, F- and I is obviously related to the sedimentary environment. It is necessary to study the enrichment mechanisms for the co-occurrence of As, F- and I in groundwater under the influence of the sedimentary environment in Hetao Basin. In this study, 499 groundwater samples were collected. Sedimentary environments, hydrogeochemical process, isotopes were analyzed to elucidate their enrichment mechanisms. The environment of groundwater is weakly alkaline. The hydrochemical types of groundwater are mainly Na-Cl-HCO3. The distribution of isotope δ18O demonstrates that irrigation from the Yellow River is the main recharge source. The main drainage channel is the discharge area in the Hetao basin. Based on the clay-sand ratio (R), the number of clay layers (N) and terrain slope (S), Hetao Basin was divided into four sedimentary environmental zones. The distribution of As (0-916.70 µg/L), F- (0.05-8.60 mg/L) and I (0.01-3.00 mg/L) was featured by a clear zonation of the sedimentary environment. The high As and high I groundwater were mainly distributed in the paleochannel zone of the Yellow River, with exceedance rates of 80.28% and 52.58%, and the median values of 73.91 µg/L and 0.11 mg/L, respectively. In the reducing environment, the release of As initially adsorbed on iron hydrogen and iron oxide, the reductive of iron hydroxide itself, rock weathering and evaporation are the key factors affecting the enrichment of As in groundwater. In this area, large amounts of aquatic organisms and plankton deposited in the sediment and channel filling deposits abundant with organic matter is the premise of high-I groundwater. The reduction of iodate and nitrate directly leads to the high concentration of I in groundwater. The high F- groundwater was mainly distributed in the piedmont alluvial-pluvial fan and the north margin of Ordos Plateau, with exceedance rates of 58.62% and 43.30%, and the median values of 1.10 mg/L and 0.86 mg/L, respectively. High F- groundwater in the two zones is affected by the abundant biotite and hornblende in Langshan Mountain and Ordos Plateau. Under evaporation, the precipitation rate of CaF2 and pH plays key roles in the enrichment of F- in groundwater. In the Hetao Basin, sedimentary environment is the main controlling factor for the co-mobilization of As, F- and I in groundwater.

Enrichment of High Arsenic Groundwater Controlled by Hydrogeochemical and Physical Processes in the Hetao Basin, China.

Based on 447 samples collected from a shallow aquifer (depths from 0 to 150 m) in the Hetao Basin, Northern China, an integrated hydrogeochemical approach was used in this study to conceptualize the enrichment of high arsenic groundwater in the Hetao Basin. An unconventional method of distinguishing hydrogeochemical and physical processes from a dataset was tested by investigating the cumulative frequency distribution of ionic ratios expressed on a probability scale. By applying cumulative frequency distribution curves to characterize the distribution of ionic ratios throughout the Hetao Basin, hydrogeochemical indicators were obtained that distinguish the series of hydrogeochemical processes that govern groundwater composition. All hydrogeochemical processes can basically be classified as recharge intensity of groundwater, evaporation concentration intensity, and reductive degree controlling the spatial distribution of arsenic. By considering the three processes, we found that the concentration of arsenic was more than 10 µg/L when the (HCO3-+CO32-)/SO42- ratio was over 4.1 (strong reductive area). As the evaporation concentration intensity increased, the median value of arsenic increased from 10.74 to 382.7 µg/L in the median reductive area and rapidly increased from 89.11 to 461.45 µg/L in the strong reductive area. As the river recharge intensity increased (with the intensity index increasing from 0 to 5), the median value of arsenic dropped from 40.2 to 6.8 µg/L in the median reductive area and decreased more markedly from 219.85 to 23.73 µg/L in the strong reductive area. The results provide a new insight into the mechanism of As enrichment in groundwater.

Interpreting the salinization and hydrogeochemical characteristics of groundwater in Dongshan Island, China.

The groundwater salinization is a global problem that degrades water quality and endangers sustainable use of water resources, particularly in coastal areas. In this paper, 24 water samples were collected from 12 monitoring wells during the dry (January) and wet (June) seasons for analyzing the salinization and hydrogeochemical characteristics of groundwater in Dongshan Island of China through combined hydrogeochemical and multivariate statistical approaches. Results showed that groundwater in the study area is primarily Cl-Na and followed by Cl-Ca·Mg type in the dry season, Cl-Na and followed by Cl-Ca·Mg and HOC3·Cl-Na type in the wet season. The groundwater chemistry is predominantly controlled by carbonate, gypsum, and silicate dissolution. However, some areas are strongly influenced by seawater intrusion, sewage infiltration and reverse ion exchange process. Around 40% of water samples from the dry season and 50% from the wet season are at injuriously, highly and severely saline levels while other samples at slightly and moderately saline levels, suggesting that groundwater in the area is partially recharged by seawater. Furthermore, the NO3-/Cl- versus Cl- diagram and principal component analysis (PCA) indicated nitrate pollution in groundwater that is subjected to anthropogenic activities such as domestic sewage, agricultural and industrial practices, which lead to degradation of groundwater quality in the area. The findings of this study provide helpful insights for understanding the genesis and hydrogeochemical evolution of groundwater in those coastal areas.

[Hydrochemical Characteristics and Factors of Surface Water and Groundwater in the Upper Yongding River Basin].

The Yongding River basin is an important water conservation and ecological barrier area in the Northwest of Hebei Province. Reduced runoff and deterioration of the water environment in this area have become increasingly prominent under the effects of climate change and intensive human activities. Clarifying the chemical characteristics and factors of surface water and groundwater in the upper Yongding River basin can provide data and support for the sustainable use of water resources. Stable isotopes of hydrogen and oxygen (δ2H and δ18O) were used to study the sources of surface water and groundwater. Mathematical statistics and hydrogeochemical methods were then used to analyze the regional hydrogeochemical processes and factors of surface water and groundwater. The results showed that precipitation was the main source of surface water and groundwater. Under the effects of natural factors and human activities, the Yang River and Sanggan River basins exhibited significant differences in surface water chemistry. The sub-basins were ranked by ion concentration as follows: Sanggan River>Yang River. The main cation and anions of the Sanggan River basin were Na+, Cl-, and SO42-, while in the Yang River basin, Ca2+ and HCO3- were the most common. The water chemistry of the Sanggan River exhibited greater variation than that of the Yang River. Surface water chemistry were mainly controlled by mineral dissolution and evaporation, but human activities were reflected in different sub-basins. Surface water in the Sanggan River basin was affected by industrial wastewater discharge, while that of the Yang River basin was affected by agricultural production and cities. However, the continuous increase of Cl- and SO42- concentrations, caused by industrial wastewater discharge and acid rain, was the limiting factor for sustainable use of surface water resources. In future, surface water in Sanggan River basin should be used with consideration to the effects of both total salinity and chemical composition of the water, while in Yang River, a focus should be placed on total salinity. The use of surface water resources in accordance with local conditions is an effective measure for the sustainable use of water resources and the restoration of groundwater levels in this region.

Controls of paleochannels on groundwater arsenic distribution in shallow aquifers of alluvial plain in the Hetao Basin, China.

Less is known about controls of sedimentary structures in groundwater As distributions in sedimentary aquifers, and quantitative description of relationship between sedimentary environment and high As groundwater (according to WHO, As>10µg/L) is a challenging issue. Three hundred and eighty-two hydrogeological borehole loggings (well depths of 50-300m) were collected and four hundred and ninety nine groundwater samples were taken to investigate controls of paleochannels on groundwater arsenic distribution in shallow aquifers of alluvial plain in the Hetao Basin. Results showed that the swing zone, formed by bursting, diversion and swing of ancient Yellow River course since the Late Pleistocene, has an obviously corresponding relationship with spatial variability of groundwater As in the Hetao Basin. "Swing Intensity Index" (S), which is firstly defined as the sum of clay-sand ratio (R) and the number of clay layers (N), can be used as the sedimentary facies symbol to establish the new recognition method for hosting high As groundwater. There is a positive correlation between the swing intensity index (S) of paleochannels and groundwater As concentrations. The swing zones of paleochannels with high S values represent hydrogeochemical characteristics of the strong reducing environment, serious evaporation, strong cation exchange, and the low infiltration recharge of surface water, which lead to enrichment of groundwater As in the shallow aquifers.

Hydrogeochemical characterization and groundwater quality assessment in intruded coastal brine aquifers (Laizhou Bay, China).

The aquifer in the coastal area of the Laizhou Bay is affected by salinization processes related to intense groundwater exploitation for brine resource and for agriculture irrigation during the last three decades. As a result, the dynamic balances among freshwater, brine, and seawater have been disturbed and the quality of groundwater has deteriorated. To fully understand the groundwater chemical distribution and evolution in the regional aquifers, hydrogeochemical and isotopic studies have been conducted based on the water samples from 102 observation wells. Groundwater levels and salinities in four monitoring wells are as well measured to inspect the general groundwater flow and chemical patterns and seasonal variations. Chemical components such as Na+, K+, Ca2+, Mg2+, Sr2+, Cl-, SO42-, HCO3-, NO3-, F-, and TDS during the same period are analyzed to explore geochemical evolution, water-rock interactions, sources of salt, nitrate, and fluoride pollution in fresh, brackish, saline, and brine waters. The decreased water levels without typical seasonal variation in the southeast of the study area confirm an over-exploitation of groundwater. The hydrogeochemical characteristics indicate fresh-saline-brine-saline transition pattern from inland to coast where evaporation is a vital factor to control the chemical evolution. The cation exchange processes are occurred at fresh-saline interfaces of mixtures along the hydraulic gradient. Meanwhile, isotopic data indicate that the brine in aquifers was either originated from older meteoric water with mineral dissolution and evaporation or repeatedly evaporation of retained seawater with fresher water recharge and mixing in geological time. Groundwater suitability for drinking is further evaluated according to water quality standard of China. Results reveal high risks of nitrate and fluoride contamination. The elevated nitrate concentration of 560 mg/L, which as high as 28 times of the standard content in drinking water is identified in the south region. In addition, the nitrate and ammonia data of the Wei River suggests decreasing nitrification rate in the study area from inland to estuary. High fluoride concentration, larger than 1 mg/L, is also detected in an area of about 50% of the study region. The saltwater intrusion is analyzed to be responsible for part of dissolution of minerals containing fluoride. Therefore, water treatment before drinking is needed in urgent to reduce the health expose risk.