Sulfate-reducing bacteria (SRB) mediated carbonate dissolution and arsenic release: Behavior and mechanisms.

Carbonate bound arsenic act as an important reservoir for arsenic (As) in nature aquifers. Sulfate-reducing bacteria (SRB), one of the dominant bacterial species in reductive groundwater, profoundly affects the biogeochemical cycling of As. However, whether and how SRB act on the migration and transformation of carbonate bound arsenic remains to be elucidated. Batch culture experiment was employed using filed collected arsenic bearing calcite to investigate the release and species transformation of As by SRB. We found that arsenic in the carbonate samples mostly exist as inorganic As(V) (93.92 %) and As(III). The present of SRB significantly facilitated arsenic release from carbonates with a maximum of 22.3 µg/L. The main release mechanisms of As by SRB include 1) calcite dissolution and the liberate of arsenic in calcite lattices, and 2) the break of H-bonds frees arsenic absorbed on carbonate surface. A redistribution of arsenic during culture incubation took place which may due to the precipitation of As2Sx or secondary FeAl minerals. To our best knowledge, it is the first experimental study focusing on the release of carbonate bound arsenic by SRB. This study provides new insights into the fate and transport of arsenic mediated by microorganism within high arsenic groundwater-sediment system.

Hydrogeochemical characteristics, stable isotopes, positive matrix factorization, source apportionment, and health risk of high fluoride groundwater in semiarid region.

Chronic exposure to high fluoride (F-) levels in groundwater causes community fluorosis and non-carcinogenic health concerns in local people. This study described occurrence, dental fluorosis, and origin of high F-groundwater using δ2H and δ18O isotopes at semiarid Gilgit, Pakistan. Therefore, groundwater (n = 85) was collected and analyzed for F- concentrations using ion-chromatography. The lowest F- concentration was 0.4 mg/L and the highest 6.8 mg/L. F- enrichment is linked with higher pH, NaHCO3, NaCl, δ18O, Na+, HCO3-, and depleted Ca+2 aquifers. The depleted δ2H and δ18O values indicated precipitation and higher values represented the evaporation effect. Thermodynamic considerations of fluorite minerals showed undersaturation, revealing that other F-bearing minerals viz. biotite and muscovite were essential in F- enrichment in groundwater. Positive matrix factorization (PMF) and principal component analysis multilinear regression (PCAMLR) models were used to determine four-factor solutions for groundwater contamination. The PMF model results were accurate and reliable compared with those of the PCAMLR model, which compiled the overlapping results. Therefore, 28.3% exceeded the WHO permissible limit of 1.5 mg/L F-. Photomicrographs of granite rocks showed enriched F-bearing minerals that trigger F- in groundwater. The community fluorosis index values were recorded at > 0.6, revealing community fluorosis and unsuitability of groundwater for drinking.

Mechanisms and health implications of toxicity increment from arsenate-containing iron minerals through in vitro gastrointestinal digestion.

Inadvertent oral ingestion is an important exposure pathway of arsenic (As) containing soil and dust. Previous researches evidenced health risk of bioaccessible As from soil and dust, but it is unclear about As mobilization mechanisms in health implications from As exposure. In this study, we investigated As release behaviors and the solid-liquid interface reactions toward As(V)-containing iron minerals in simulated gastrointestinal bio-fluids. The maximum As release amount was 0.57 mg/L from As-containing goethite and 0.82 mg/L from As-containing hematite at 9 h, and the As bioaccessibility was 10.8% and 21.6%, respectively. The higher exposure risk from hematite-sorbed As in gastrointestinal fluid was found even though goethite initially contained more arsenate than hematite. Mechanism analysis revealed that As release was mainly coupled with acid dissolution and reductive dissolution of iron minerals. Proteases enhanced As mobilization and thus increased As bioaccessibility. The As(V) released and simultaneously transformed to high toxic As(III) by gastric pepsin, while As(V) reduction in intestine was triggered by pancreatin and freshly formed Fe(II) in gastric digests. CaCl2 reduced As bioaccessibility, indicating that calcium-rich food or drugs may be effective dietary strategies to reduce As toxicity. The results deepened our understanding of the As release mechanisms associated with iron minerals in the simulated gastrointestinal tract and supplied a dietary strategy to alleviate the health risk of incidental As intake.

Geochemical control, water quality indexing, source distribution, and potential health risk of fluoride and arsenic in groundwater: Occurrence, sources apportionment, and positive matrix factorization model.

Fluoride (F-), and arsenic (As) in the groundwater cause health problems in developing countries, including Pakistan. We evaluated the occurrence, distribution, sources apportionment, and health hazards of F-, and As in the groundwater of Mardan, Pakistan. Therefore, groundwater samples (n = 130) were collected and then analyzed for F-, and As by ion-chromatography (IC) and Inductively-coupled plasma mass-spectrometry (ICP-MS). The F-, and As concentrations in groundwater were 0.7-14.4 mg/L and 0.5-11.2 µg/L. Relatively elevated F-, and As coexists with higher pH, Na+, HCO3-, SO4-2, and depleted Ca+2 due to fluoride, sulfide-bearing minerals, and anthropogenic inputs. Both F-, and/or As are transported in subsurface water through adsorption and desorption processes. Groundwater samples 45%, and 14.2% exceeded the WHO guidelines of 1.5 mg/L and 10 µg/L. Water quality indexing (WQI-model) declared that 35.7% samples are unfit for household purposes. Saturation and undersaturation of minerals showed precipitation and mineral dissolution. Groundwater contamination by PCA-MLR and PMF-model interpreted five factors. The fitting results and R2 values of PMF (0.52-0.99)>PCA-MLR (0.50-0.95) showed high accuracy of PMF-model. Human health risk assessment (HHRA-model) revealed high non-carcinogenic and carcinogenic risk for children than adults. The percentile recovery of F- and As was recorded 98%, and 95% with reproducibility ± 5% error.

Groundwater Quality, Health Risk Assessment, and Source Distribution of Heavy Metals Contamination around Chromite Mines: Application of GIS, Sustainable Groundwater Management, Geostatistics, PCAMLR, and PMF Receptor Model.

Groundwater contamination by heavy metals (HMs) released by weathering and mineral dissolution of granite, gneisses, ultramafic, and basaltic rock composition causes human health concerns worldwide. This paper evaluated the heavy metals (HMs) concentrations and physicochemical variables of groundwater around enriched chromite mines of Malakand, Pakistan, with particular emphasis on water quality, hydro-geochemistry, spatial distribution, geochemical speciation, and human health impacts. To better understand the groundwater hydrogeochemical profile and HMs enrichment, groundwater samples were collected from the mining region (n = 35), non-mining region (n = 20), and chromite mines water (n = 5) and then analyzed using ICPMS (Agilent 7500 ICPMS). The ranges of concentrations in the mining, non-mining, and chromite mines water were 0.02-4.5, 0.02-2.3, and 5.8-6.0 mg/L for CR, 0.4-3.8, 0.05-3.6, and 3.2-5.8 mg/L for Ni, and 0.05-0.8, 0.05-0.8, and 0.6-1.2 mg/L for Mn. Geochemical speciation of groundwater variables such as OH-, H+, Cr+2, Cr+3, Cr+6, Ni+2, Mn+2, and Mn+3 was assessed by atomic fluorescence spectrometry (AFS). Geochemical speciation determined the mobilization, reactivity, and toxicity of HMs in complex groundwater systems. Groundwater facies showed 45% CaHCO3, 30% NaHCO3, 23.4% NaCl, and 1.6% Ca-Mg-Cl water types. The noncarcinogenic and carcinogenic risk of HMs outlined via hazard quotient (HQ) and total hazard indices (THI) showed the following order: Ni > Cr > Mn. Thus, the HHRA model suggested that children are more vulnerable to HMs toxicity than adults. Hierarchical agglomerative cluster analysis (HACA) showed three distinct clusters, namely the least, moderately, and severely polluted clusters, which determined the severity of HMs contamination to be 66.67% overall. The PCAMLR and PMF receptor model suggested geogenic (minerals prospects), anthropogenic (industrial waste and chromite mining practices), and mixed (geogenic and anthropogenic) sources for groundwater contamination. The mineral phases of groundwater suggested saturation and undersaturation. Nemerow's pollution index (NPI) values determined the unsuitability of groundwater for domestic purposes. The EC, turbidity, PO4-3, Na+, Mg+2, Ca+2, Cr, Ni, and Mn exceeded the guidelines suggested by the World Health Organization (WHO). The HMs contamination and carcinogenic and non-carcinogenic health impacts of HMs showed that the groundwater is extremely unfit for drinking, agriculture, and domestic demands. Therefore, groundwater wells around the mining region need remedial measures. Thus, to overcome the enrichment of HMs in groundwater sources, sustainable management plans are needed to reduce health risks and ensure health safety.

Comparative study on effects of pH, electrolytes, and humic acid on the stability of acetic and polyacrylic acid coated magnetite nanoparticles.

The poor colloidal stability of magnetite nanoparticles (MNPs) limits their mobility and application, so various organic coatings (OCs) were applied to MNPs. Here, a comparative study on the colloidal stability of MNPs coated with acetic (HAc) and polyacrylic acids (PAA) was conducted under varied pH (5.0-9.0) in the presence of different concentrations of cations and anions, as well as humic acid (HA). Comparing the effects of various cations and anions, the stability of both HAc/PAA-MNPs followed the order: Na+ > Ca2+and PO43- > SO42- > Cl-, which could be explained by their adsorption behaviors onto HAc/PAA-MNPs and the resulting surface charge changes. Under all conditions even with more anion adsorption onto HAc-MNPs (0.14-22.56 mg/g) than onto PAA-MNPs (0.04-18.34 mg/g), PAA-MNPs were more negatively charged than HAc-MNPs, as PAA has a lower pHIEP (2.6 ± 0.1) than that of HAc (3.7 ± 0.1). Neither the HAc nor PAA coatings were displaced by phosphate even at considerably high phosphate concentration. Compared with HAc-MNPs, the stability of PAA-MNPs was greatly improved under all studied conditions, which could be due to both stronger electrostatic and additional steric repulsion forces among PAA-MNPs. Besides, under all conditions, Derjaguin-Landau-Verwey-Overbeek (DLVO) explained well the aggregation kinetic of HAc-MNPs; while extended DLVO (EDLVO) successfully predict that of PAA-MNPs, indicating steric forces among PAA-MNPs. The aggregation of HAc/PAA-MNPs was all inhibited in varied electrolyte solutions by HA (2 mg C/L) addition. This study suggested that carboxyl coatings with higher molecular weights and pKa values could stabilize MNPs better due to stronger electrostatic and additional steric repulsion. However, in the presence of HA, these two forces were mainly controlled by adsorbed HA instead of the organic pre-coatings on MNPs.

Mobilization of arsenic from As-containing iron minerals under irrigation: Effects of exogenous substances, redox condition, and intermittent flow.

Irrigation activities can cause strong geochemical and hydrological fluctuations in the unsaturated zone, and affect arsenic (As) migration and transformation. The As geochemical cycle in the unsaturated zone is coupled with that of iron minerals through sorption-desorption, coprecipitation and redox processes. Dynamic batch experiments and wetting-drying cycling column experiments were conducted to evaluate As mobilization behaviors under the effects of exogenous substances, redox condition and intermittent flow. Our results show that As release under exogenous substances carried by irrigation (e.g., phosphate, carbonate, fulvic acid, humic acid, etc.) followed three trends with the types of exogenous inputs. Inorganic anions and organic matter resulted in opposite trends of arsenate release in different redox conditions. In anoxic environments, As(V) release was favored by the addition of phosphate and carbonate, while in oxic environments, the mobilization of As(V) was promoted by the addition of fulvic acid (FA). Further, intermittent irrigation promoted the reductive dissolution of Fe oxides and the mobilization of As. The addition of humic acid (HA) resulted in the mobilization of arsenate as As-Fe-HA ternary complexes. The mechanism of arsenic mobilization under irrigation has importance for prevention of arsenic exposure through soil to food chain transfer in typical high arsenic farmland.

Geochemical Modeling Source Provenance, Public Health Exposure, and Evaluating Potentially Harmful Elements in Groundwater: Statistical and Human Health Risk Assessment (HHRA).

Groundwater contamination by potentially harmful elements (PHEs) originating from the weathering of granitic and gneissic rock dissolution poses a public health concern worldwide. This study investigated physicochemical variables and PHEs in the groundwater system and mine water of the Adenzai flood plain region, in Pakistan, emphasizing the fate distribution, source provenance, chemical speciation, and health hazard using the human health risk assessment HHRA-model. The average concentrations of the PHEs, viz., Ni, Mn, Cr, Cu, Cd, Pb, Co, Fe, and Zn 0.23, were 0.27, 0.07, 0.30, 0.07, 0.06, 0.08, 0.68, and 0.23 mg/L, respectively. The average values of chemical species in the groundwater system, viz., H+, OH−, Ni2+, Mn2+, Mn3+, Cr3+, Cr6+, Cu+, Cu2+, Cd2+, Pb2+, Pb4+, Co2+, Co3+, Fe2+, Fe3+, and Zn2+, were 1.0 × 10−4 ± 1.0 × 10−6, 1.0 × 10−4 ± 9.0 × 10−7, 2.0 × 10−1 ± 1.0 × 10−3, 3.0 × 10−1 ± 1.0 × 10−3, 1.0 × 10−22 ± 1.0 × 10−23, 4.0 × 10−6 ± 2.0 × 10−6, 4.0 × 10−11 ± 2.0 × 10−11, 9.0 × 10−3 ± 1.0 × 10−2, 2.0 × 10−1 ± 2.0 × 10−3, 7.0 × 10−2 ± 6.0 × 10−2, 5.0 × 10−2 ± 5.0 × 10−2, 2.0 × 10−2 ± 1.5 × 10−2, 6.0 × 10−2 ± 4.0 × 10−2, 8.0 × 10−31 ± 6.0 × 10−31, 3.0 × 10−1 ± 2.0 × 10−4, 4.0 × 10−10 ± 3.0 × 10−10, and 2.0 × 10−1 ± 1.0 × 10−1. The mineral compositions of PHEs, viz. Ni, were bunsenite, Ni(OH)2, and trevorite; Mn viz., birnessite, bixbyite, hausmannite, manganite, manganosite, pyrolusite, and todorokite; Cr viz., chromite and eskolaite; Cu viz., CuCr2O4, cuprite, delafossite, ferrite-Cu, and tenorite; Cd viz., monteponite; Pb viz, crocoite, litharge, massicot, minium, plattnerite, Co viz., spinel-Co; Fe viz., goethite, hematite, magnetite, wustite, and ferrite-Zn; and Zn viz., zincite, and ZnCr2O4 demarcated undersaturation and supersaturation. However, EC, Ca2+, K+, Na+, HCO3−, Cr, Cd, Pb, Co, and Fe had exceeded the WHO guideline. The Nemerow's pollution index (NPI) showed that EC, Ca2+, K+, Na+, HCO3−, Mn, Cd, Pb, Co, and Fe had worse water quality. Principal component analysis multilinear regression (PCAMLR) and cluster analysis (CA) revealed that 75% of the groundwater contamination originated from geogenic inputs and 18% mixed geogenic-anthropogenic and 7% anthropogenic sources. The HHRA-model suggested potential non-carcinogenic risks, except for Fe, and substantial carcinogenic risks for evaluated PHEs. The women and infants are extremely exposed to PHEs hazards. The non-carcinogenic and carcinogenic risks in children, males, and females had exceeded their desired level. The HHRA values of PHEs exhibited the following increasing pattern: Co > Cu > Mn > Zn > Fe, and Cd > Pb > Ni > Cr. The higher THI values of PHEs in children and adults suggested that the groundwater consumption in the entire region is unfit for drinking, domestic, and agricultural purposes. Thus, all groundwater sources need immediate remedial measures to secure health safety and public health concerns.

Hydrogeochemical assessment of carcinogenic and non-carcinogenic health risks of potentially toxic elements in aquifers of the Hindukush ranges, Pakistan: insights from groundwater pollution indexing, GIS-based, and multivariate statistical approaches.

Globally, potentially toxic elements (PTEs) and bacterial contamination pose health hazards, persistency, and genotoxicity in the groundwater aquifer. This study evaluates PTE concentration, carcinogenic and noncarcinogenic health hazards, groundwater quality indexing (GWQI-model), source provenance, and fate distribution in the groundwater of Hindukush ranges, Pakistan. The new estimates of USEPA equations record new research dimensions for carcinogenic and noncarcinogenic hazards. The principal component analysis (PCA), mineral phases, and spatial distribution determine groundwater contamination and its impacts. The average concentrations of PTEs, viz., Cd, Cu, Co, Fe, Pb, and Zn, were 0.06, 0.27, 0.07, 0.55, 0.05, and 0.19 mg/L, and E. coli, F. coli, and P. coli were 27.5, 24.0, and 19.0 CFU/100 ml. Moreover, the average values of basic minerals, viz., anhydrite, aragonite, calcite, dolomite, gypsum, halite, and hydroxyl apatite, were 0.4, 2.4, 2.6, 5.1, 0.6, and - 4.0, 11.2, and PTE minerals like monteponite, tenorite, cuprite, cuprous ferrite, cupric ferrite, ferrihydrite, goethite, hematite, lepidocrocite, maghemite, magnetite, massicot, minium, litharge, plattnerite, and zincite were - 5.5, 2.23, 4.65, 18.56, 20.0, 4.84, 7.54, 17.46, 6.66, 9.67, 22.72, - 3.36, 22.9, 3.16, - 18.0, and 1.46. The groundwater showed carcinogenic and non-carcinogenic health hazards for children and adults. The GWQI-model showed that 58.3% of samples revealed worse water quality. PCA revealed rock weathering, mineral dissolution, water-rock interaction, and industrial effluents as the dominant factors influencing groundwater chemistry. Carbonate weathering and ion exchange play vital roles in altering CaHCO3 type to NaHCO3 water. In this study, E. coli, F. coli, P. coli, EC, turbidity, TSS, PO43─, Na+, Mg+2, Ca+2, Cd, Co, Fe, and Pb have exceeded the World Health Organization (WHO) guidelines. The carcinogenic and non-carcinogenic impacts of PTEs and bacterial contamination declared that the groundwater is unfit for drinking and domestic purposes.

Occurrence and behavior of arsenic in groundwater-aquifer system of irrigated areas.

Groundwater arsenic pollution has received much attention worldwide for decades as a serious threat to public health, but the mechanisms responsible for arsenic mobilization are not fully understood. Groundwater and bore drilling sediment samples from Qiji county, a small geographical agricultural area with endemic arsenicosis, are collected for demonstrating the occurrence and speciation of arsenic in groundwater and sediments, and arsenic release between solid-liquid phase influenced by human activities. Results show that arsenic concentrations in groundwater vary from 5 µg/L to 19.6 µg/L, with 80% exceeding the maximum permissible limits required by WHO (10 µg/L) for drinking water and therefore constituting a health risk for humans. In a weak oxidizing environment (oxidation-reduction potential (ORP): 12.9 mV-151 mV), inorganic As(V) accounts for 85% of total dissolved As, which to some extent alleviates the harm of As pollution on humans. Total As content in the sediments is in the range of 6.98 mg/kg and 14.34 mg/kg (median of 10.71 mg/kg), three times higher than the average value of many countries. Sequential chemical leaching indicates that 11% of arsenic in sediments is labile bound and may be closely related to the arsenic in groundwater. Additionally, irrigation intensity contributes to arsenic release with diverse As3+/As5+ by dissolving weakly bound arsenic rapidly. Subsequently part of As(III) is oxidized to As(V). Competitive and/or alkaline desorption of As(V), which had been adsorbed by FeMn (hydrous)-oxides and carbonates in the unsaturated zone and the aquifer, exerts a significant role in releasing arsenic into the groundwater. Our study indicates that systematic management and regulation of irrigation intensity are required to prevent further deterioration of groundwater resources.

Aggregation of varied organic coated magnetite nanoparticles: Adsorbed mass and thickness of coatings and interactions with natural organic matter.

Magnetite nanoparticles (MNPs) with varied organic coatings (OCs) which improved their stability have broad environmental applications. However, the adsorbed amounts and layer thickness of varied OCs onto MNPs during the synthesis were generally not or poorly characterized, and their interactions with natural organic matter (NOM) were still in progress. In this study, acetic (HAc), citric (CA), and polyacrylic acid (PAA) were selected as model OCs, the adsorption behaviors of OCs on MNPs were characterized under varied aqueous C/Fe ratios, and the aggregation behaviors of MNPs with varied OCs (OC-MNPs) at neutral pH (7.0 ± 0.2) with NaCl (5-800 mM) in the presence/absence of NOM were systematically investigated. Under low aqueous C/Fe ratio, the adsorbed amounts of model OCs as -COOH/Fe ratio followed the order: CA ≈ PAA > > HAc. With high aqueous C/Fe ratio, the maximum adsorbed masses of OC-MNPs were similar. The adsorbed layer thicknesses of OC-MNPs were thoroughly characterized using three different methods, all showing that the adsorbed layer of PAA was thicker than that of CA and HAc. Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended DLVO (EDLVO) calculations showed that electrostatic and van der Waals forces were dominant for CA-MNPs and HAc-MNPs stabilization; while steric repulsion played major roles in stabilizing PAA-MNPs, probably due to a thicker PAA layer. In the presence of NOM, stability behaviors of all OC-MNPs were similar, ascribing to the much greater amounts of NOM adsorbed than the OCs, causing greater steric repulsion. This study provides new mechanistic insights which could help better understand the effects of varied OCs on MNPs' colloidal stability.

Assessment of shallow aquifer vulnerability to fluoride contamination using modified AHP-DRASTICH model as a tool for effective groundwater management, a case study in Yuncheng Basin, China.

Vulnerability assessment is an effective tool for the precaution of groundwater quality to specific pollutants. Groundwater fluoride pollution is severe and universal in the world, however, the method of groundwater risk assessment to fluorine is never built. The objective of this study was to establish an effective method to assess the potential level of groundwater vulnerability to fluoride by a modification of the typical DRASTIC model. The hydrogeochemical (H) factor (pH and TDS) was designed as a complementary parameter in the DRASTICH model. The weights of the parameters were revised by Analytical Hierarchy Process (AHP) method. The built AHP-DRASTICH model was applied to evaluate the groundwater vulnerability to fluoride contamination in Yuncheng basin, northern China, where groundwater with high fluoride concentration occurred extensively. The assessment result indicates that about 40 percent of the area belonged to relatively high and high vulnerability zones, which mainly distributed at the central part of the basin with strong evaporation and longer water-rock interaction time. The AHP-DRASTICH model shows a stronger positive correlation between risk scores and F concentration, giving better vulnerability assessment to F pollution compared with DARSTIC and DRASTICH models. The AHP-DRASTICH model is reliable and useful for guiding government and policy maker to take effective actions protecting groundwater from specific pollution.

The occurrence of geogenic fluoride in shallow aquifers of Kenya Rift Valley and its implications in groundwater management.

Widespread concerns about high-fluoride groundwater and their health risks have been raised worldwide. Weathering of volcanic minerals is regarded as a principal source of groundwater fluoride in regions with volcanic bedrocks. However, how does the volcanic minerals control fluoride occurrence, if it induces other hydrogeochemical processes participating in and how this relates to human health still remain unclear. This study takes Kenya Rift Valley, which has volcanic geological formations, as an example to delineate the occurrence and origins of high-fluoride shallow groundwater with analysis of hydrochemistry, graphical and multivariate statistical methods. Over 40% of shallow groundwater (F-: up to 23.5 mg/L) show elevated fluoride values over the WHO standards of 1.5 mg/L. High fluoride groundwater are generally Na-rich and Ca-poor with high pH and HCO3¯ concentrations. Hydrogeochemical and principal component analysis indicate that weathering of hyper-alkaline volcanic rocks could release accumulated fluoride in melts and volatile fractions, as well as in clay minerals. Alkaline condition and high HCO3- contents lead to the competitive desorption of F- from clay minerals and Fe-hydroxides into groundwater. Clay minerals also provide abundant exchange sites where cation exchange happens and promotes the release of F- from the sediments by controlling the dissolution/precipitation of calcite and fluorite. Health risk assessment results show that chronic health risks by groundwater geogenic fluoride ingestion are identified to various individuals, with highest threats in children. Finally, a conceptual model has been developed to demonstrate the formations of high geogenic fluoride groundwater in regions with volcanic bedrocks and its relation with human health.

Sources and pollution path identification of PAHs in karst aquifers: an example from Liulin karst water system, northern China.

Karst water, with constituting major sources for water supply worldwide, is vulnerable and prone to be polluted. In this study, it is reported that karst water polycylic aromatic hydrocarbons (PAHs) pollution is caused by the infiltration of surface runoff in the bared carbonate areas, which is of universal significance for the protection of groundwater resources in karst region. Hydro-geochemistry, stable isotopes (δD, δ18O and 87Sr/86Sr) and characteristic ratio method were conducted together to illustrate the concentration, distribution, sources and pollution path of polycyclic aromatic hydrocarbons in groundwater in the Liulin karst water system of northern China. The results showed that total concentration of polycyclic aromatic hydrocarbons ranged from 39.25 to 16,830 ng/L in groundwater, with Naphthalene being the dominant component, and the median value increased gradually along the flow path. The highest polycyclic aromatic hydrocarbons concentrations in karst water were mainly observed in the coal mining and the discharge areas. Based on the characteristic ratios, the polycyclic aromatic hydrocarbons in the study area mainly come from local incomplete combustion of woods, fossil fuels, coal and liquid fuels. The slight shift of δD and δ18O and moderate 87Sr/86Sr ratios suggest that the polycyclic aromatic hydrocarbons in karst water is mainly polluted by surface runoff during rain events in the bared karst region. The leakage of river water may partly contribute to the polycyclic aromatic hydrocarbons in some karst water, which normally located close to the karst water - river water mixing line. This study provides a new technical method for tracing the sources and identifying the pollution paths of organic pollution in a karst water system.

A review of the distribution, sources, genesis, and environmental concerns of salinity in groundwater.

Awareness concerning the degradation of groundwater quality and their exacerbating adverse effects due to salinization processes is gaining traction, raising for adequate understanding of the distribution, sources, genesis, and environmental concerns of salinity in groundwater. Saline groundwater is widely distributed all over the world, with an area of 24 million km2 (16% of the total land area on earth) and 1.1 billion people living in the affected areas, especially the arid/semi-arid areas in developing countries. These large-scale groundwater salinization problems are sourced from two major ways: natural and anthropogenic. The natural sources are diversified from connate saline groundwater, seawater intrusion, evaporation, dissolution of soluble salts, membrane filtration process to geothermal origin. The anthropogenic sources include irrigation return flow, road deicing salts, industrial and agricultural wastewater, and gas and oil production activities. The integrated approach of geochemical tracers and multiple isotopes (δ18OH2O, δ2HH2O, δ11B, δ36Cl, δ34Ssulfate, 87Sr/86Sr, and δ7Li) is proved to be useful in the constraints of the origin and transport of solutes in groundwater. Groundwater salinization is often associated with high levels of some toxic elements like arsenic, fluoride, selenium, and boron. Four "triggers" lead to this association: salt effect, competing adsorption, microbial processes, and cation exchange.

Human Activity and Hydrogeochemical Processes Relating to Groundwater Quality Degradation in the Yuncheng Basin, Northern China.

Groundwater quality degradation has raised widespread concerns about water supplies and ecological crises in China. In this study, hydrogeochemistry, environmental stable isotopes (δ18O, δD), and principal component analysis were conducted together to reveal the mechanism's response to the hydrogeochemical and quality degradation of groundwater in Yuncheng Basin, Northern China, so that reasonable water resource management strategies can be developed. The study reveals that groundwater faces a tremendous risk of quality decrease during the past decade: (1) the hydrochemical facies of groundwater shows that the bicarbonate and chloride type water was replaced with sulfate type water and the occupying area of SO4·Cl-Na, SO4·HCO3-Na type water expanded dramatically in shallow and intermediate-deep aquifers. (2) Major ion chemistry and hydrogen and oxygen isotope compositions indicate that the major hydrogeochemical processes responsible for groundwater quality deterioration include the dissolution of evaporates (i.e., halite, gypsum, and mirabilite), ion exchange, and evaporation process. Additionally, (3) anthropogenic activities (overutilization of fertilizer) have resulted in nitrate contamination, and have thereby led to groundwater quality degradation.

Temporal Network Pattern Identification by Community Modelling.

Temporal network mining tasks are usually hard problems. This is because we need to face not only a large amount of data but also its non-stationary nature. In this paper, we propose a method for temporal network pattern representation and pattern change detection following the reductionist approach. The main idea is to model each stable (durable) state of a given temporal network as a community in a sampled static network and the temporal state change is represented by the transition from one community to another. For this purpose, a reduced static single-layer network, called a target network, is constructed by sampling and rearranging the original temporal network. Our approach provides a general way not only for temporal networks but also for data stream mining in topological space. Simulation results on artificial and real temporal networks show that the proposed method can group different temporal states into different communities with a very reduced amount of sampled nodes.

Geochemical modeling, source apportionment, health risk exposure and control of higher fluoride in groundwater of sub-district Dargai, Pakistan.

The present study examined the hydrogeochemical profile of higher fluoride (F─) in groundwater of mixed industrial and mining areas of Dargai, northern Pakistan. Groundwater samples (n = 75) were collected from three hydrogeochemical environments. The mean concentrations of pH, EC, TDS, Depth and Temperature were (7.6, 1081 µS/cm, 590 mg/L, 75 m, 28.03 °C), for chemical ions viz. NO3, PO4, SO4, Cl, HCO3, Na, K, Ca and Mg were (18.5, 2.7, 161, 107, 330, 150, 9.76, 33, 52) mg/L respectively. Whereas, the mean concentration of F─ was 2.0 mg/L. Therefore, 51% groundwater samples exceeded the WHO guideline of F─ 1.5 mg/L. Additionally, we measured the mean F─ concentration in rocks, coal and wastewater, which were (670, 98) mg/Kg and 2.3 mg/L respectively. The principal component analysis multilinear regression (PCA─MLR) extracted five significant factors which shows natural, mixed and anthropogenic pollution. Thus, fluorite is the primary source of F─ contamination in groundwater. While apatite, biotite and muscovite minerals are the secondary sources which occurs in association with quartzite, granite rocks. Under alkaline conditions, F─ contamination is supported by higher Na+, HCO3─ and lower Ca++ concentrations. The accuracy and reproducibility of the measurement of fluoride was assessed by adopting a standard method of water. The percentage recovery of F─ was 97% and reproducibility was within ±5% error limit. Lastly, a health risk community fluorosis index (CFI) was calculated through Dean's formula which shows unsuitability of groundwater sources conceiving community fluorosis in the entire study area.

Fluoride contributes to the shaping of microbial community in high fluoride groundwater in Qiji County, Yuncheng City, China.

As a toxic element, excessive amounts of fluoride in environment can be harmful because of its antimicrobial activity, however little is known about the relationship between fluoride and the bacterial community in groundwater systems. Here, we use samples from a typical fluorosis area to test the hypothesis that fluoride concentration is a fundamental structuring factor for bacterial communities in groundwater. Thirteen groundwater samples were collected; high-throughput 16S rRNA gene sequencing and statistical analysis were conducted to compare the bacterial community composition in individual wells. The results showed that Proteobacteria, with most relative abundance in groundwater, decreased along the groundwater fluoride concentration. Additionally, relative abundances of 12 families were also statistically correlated with fluoride concentration. The bacterial community was significantly explained by TOC (P = 0.045) and fluoride concentration (P = 0.007) of groundwater. This suggests that fluoride and TOC likely plays an important role in shaping the microbial community structure in these groundwater systems. Our research suggest that fluoride concentration should be taken into consideration in future when evaluating microbial response to environmental conditions in groundwater system, especially for fluoride rich groundwater.

Indigenous microbes induced fluoride release from aquifer sediments.

Release of fluoride from Quaternary sediments produces F-contaminated groundwater which threatens the health of millions of people worldwide. Despite the mechanisms of fluoride release from sediments are documented by numerous studies, it remains poorly understood that whether indigenous microbes participate in or not for the formation of F-rich groundwater by releasing fluoride from aquifer sediments. A microcosm-based approach, geochemistry and techniques of microbiology and molecular ecology were conducted together to investigate these mechanisms. Results show that microbes are abundant in high [F] groundwater containing at least 1129 operational taxonomic units (OTUs), and indigenous microbes can have an essential role in the mobilization of fluoride in sediments collected from aquifers in a typical fluorosis area in China. It also shows that for the sediments in this study, fluoride release (ca. 2 mg/L) is coupled with elevated concentrations of Ca (△ = 75 mg/L), Mg (△ = 33 mg/L), Al (△ = 0.2 mg/L) and Mn (△ = 1.4 mg/L). This suggests that the fluoride may source from the dissolution of F-bearing carbonate minerals and/or Al-Mn hydroxides in a local acidic environment. The findings provide additional insights into the biogeochemical circulation of fluoride in natural environment, especially in groundwater system and the development of effective strategies for the management of F-contaminated groundwater worldwide.