Characterization and health risk assessment of arsenic in natural waters of the Indus River Basin, Pakistan.

The elevated concentrations of arsenic in natural water are one of the major environmental threats to human health. However, the existing characteristics, controlling mechanisms, and associated risks of arsenic in natural waters in the Indus River Basin (IRB), Pakistan, are yet to be unequivocally understood. In this study, a total of 203 samples of surface water (SW), shallow groundwater (SGW), and deep groundwater (DGW) were collected from the IRB to assess the geochemical characteristics of arsenic and its associated health risks, as all three kinds of waters are the main sources of drinking and domestic usage. The results revealed that the arsenic concentrations in the SW, SGW, and DGW were in the ranges of 1.1-26.45, 1.05-44.44, and 0.67-41.09 µg L-1, respectively. Furthermore, the predominance of As (V) (97 %) over As(III) (3 %) confirmed that the desorption of As in oxidizing environments with elevated pH and Eh is the controlling mechanism. The hazard quotient of 11-45 % and 20-60 % samples and cancer risk of 26-64 % and 26-68 % samples indicated high health risks for the adults and children, respectively, suggesting an immense need for appropriate measures of reducing natural water arsenic concentrations in IRB from the human health perspectives.

Hydrochemical characterization and irrigation suitability of the Ganges Brahmaputra River System: review and assessment.

The hydrochemical characterization and irrigation suitability assessment of the Ganges-Brahmaputra River System (GBRS) has immense importance for the livelihoods of people and ecosystem sustainability in the region. This study aims to assess the hydrochemical characteristics and evaluate the irrigation suitability of water in the GBRS by reviewing published literature of the major tributaries. The studied rivers were categorized into two groups namely Group-1 and Group-2 considering the similarities of climatic patterns, hydrochemical attributes, and drainage characteristics. The hydrochemistry of the river water was characterized by the Piper diagram, Gibbs plot, mixing plots, and ionic ratios. Furthermore, irrigation water qualities were evaluated by electrical conductivity (EC), sodium percentage (Na%), sodium adsorption ratio (SAR), magnesium hazard (MH), and Wilcox diagram. The results indicated that the hydrochemistry of the GBRS was slightly alkaline to alkaline (7.42-8.78) in nature. The average concentrations of most of the chemical attributes showed higher in Group-1, whereas the average concentrations of K+ and NO3 - were found higher in Group-2. The average concentration of the major ions followed the dominancy order Ca2+ > Mg2+ > Na+ > K+ for cations and HCO3 - >SO4 2- > Cl- > NO3 - for anions in both groups. Gibbs plot and mixing plot indicated that carbonate rock weathering dominates the hydrochemical process, which was further confirmed by the Piper diagram and the ionic ratios. From the analyses of irrigational water quality, almost all the rivers (except Gomti River in terms of MH and Rangit River in terms of Na%) in the GBRS were found to be suitable based on EC, SAR, Na%, MH, and Wilcox diagram. Finally, the majority of river systems in the GBRS were characterized by carbonate dominated lithology and irrigational water quality is mostly suitable for utilization. This study could be useful for water quality management in the glacial-fed Himalayan river under the context of global climate change.

Hydrochemical appraisal and solute acquisitions in Seti River Basin, Central Himalaya, Nepal.

The chemical characterization and assessment of the water quality in the headwater areas of the Himalaya are necessary for securing the water in the future. This study aims to assess the hydrochemistry and water quality concerning drinking and irrigational uses in the Seti River Basin (SRB), Nepal. A total of 45 water samples were collected in 2016 from the SRB during pre-monsoon, monsoon, and post-monsoon seasons, and pH, EC, TDS, and DO were measured on-site, whereas Ca2+, Mg2+, K+, Na+, Cl-, SO42-, NO3-, and dissolved Si were analyzed in the laboratory. The results revealed mildly alkaline pH (8.40 ± 0.43) with the pattern of average ionic dominancy: Ca2+ > Mg2+ > Na+ > K+ and HCO3- > SO42- > Cl- > NO3- for cations and anions, respectively. Gibbs diagram implied that the lithogenic weathering mainly controlled the solute acquisition process, which was further confirmed by the Piper diagram, exhibiting Ca-HCO3 as the governing hydrochemical facies (91%). The average molar ratios were 0.88, 8.33, and 6.86 of (Ca2+ + Mg2+)/TZ+, (Ca2+ + Mg2+)/(Na+ + K+), and HCO3-/(Na+ + K+), respectively, which specified that the carbonate weathering largely controlled the solute acquisition processes with a minor contribution of silicates. The mass budget calculation also confirmed the dominance of carbonate weathering (72.0%, 78.9%, and 62.0% in Pre-Monsoon, Monsoon, and Post-Monsoon, respectively) and the high monsoon rainfall's dilution effect to anthropogenic input of cations. Principal component analysis and correlation matrix exhibited that the major sources of ions in the basin were geogenic with minor anthropic signatures. Furthermore, water quality in connection to drinking and irrigation uses revealed that the basin has mostly retained its natural water quality. This investigation suggests that regular monitoring and assessment are essential for maintaining the water quality and ecological integrity in the Himalayan river basins.

Seasonal Variations and Health Risk Assessment of Trace Elements in Seti River Basin, Gandaki Province, Nepal.

To explore the seasonal variability and associated health risks of dissolved trace elements (TEs), a total of 45 water samples (15 samples in each season) were collected from the Seti River Basin during pre-monsoon, monsoon, and post-monsoon seasons. A total of 15 TEs were analysed and the results revealed that Arsenic (As), Chromium (Cr), and Nickel (Ni) were primarily controlled by lithogenic sources, whereas, Cadmium (Cd), Cobalt (Co), Cesium (Cs), Cupper (Cu), Manganese (Mn), Lead (Pb), and Zinc (Zn) were derived from both anthropic and geogenic sources. Additionally, the concentration of Zn was markedly high, especially during the post-monsoon season nearby the landfill site, indicating the anthropic signatures. The hazard index and cancer index were found to be < 1.00 and 10-6-10-4, respectively indicating minimum health impacts. The water quality index was < 50 throughout the sampling periods, with better water quality during the monsoon. This study could help to formulate the necessary policies for the sustainability of the Himalayan River Basins.

Recent stepwise sediment flux increase with climate change in the Tuotuo River in the central Tibetan Plateau.

The riverine sediment flux (SF) is an essential pathway for nutrients and pollutants delivery and considered as an important indicator of land degradation and environment changes. With growing interest in environmental changes over the Tibetan Plateau (TP), this work investigated the variation of the SF in response to climate change in the headwater of the Yangtze River over the past 30 years. Annual time series of hydro-meteorological variables during 1986-2014 indicate significantly increasing trends of air temperature, precipitation, ground temperature, river discharge, suspended sediment concentration and SF. Stepwise changes were identified with significantly higher values of the above variables in 1998-2014 compared with 1986-1997, which could potentially be attributed to the strong 1997 El Niño event. Double-mass plots indicated that both meltwater and rainfall contributed to the increased river discharge while the increased SF mostly resulted from enhanced erosive power and transport capacities of the increased discharge. However, it was buffered by a decrease in sediment source due to the shift of maximum monthly rainfall from June/July to July/August during which period a denser vegetation cover prevents soil erosion. Partial least squares structural equation modeling analysis confirmed the dominance of warming on the increase of discharge amplified by increased precipitation. It also confirmed that the increased precipitation drives the increase in suspended sediment concentration. Both processes conspire and equally contribute to the stepwise increase of SF. This study provides important insights into the controlling processes for recent SF changes and gives guidance for water and soil conservation on the TP.

Meltwater hydrochemistry at four glacial catchments in the headwater of Indus River.

Glacier runoff shows significant change under global warming in the headwater region of the Indus River with great impact on its highly populated downstream area, but the hydrochemistry characteristics of meltwater and the changing mechanism remain unclear in this region. In this study, runoff water samples were collected during May and June, 2015, from four glacial catchments in the Upper Indus Basin to investigate general characteristics and daytime dynamics of meltwater runoff together with sediment and chemical contents. Results showed that glacier runoff in the studied area had an alkaline pH and much higher sediment yields than the local average of the non-glacier areas. The carbonate-dominated geological feature in the four catchments resulted in single chemical facies of Ca-HCO3. The dominant process determining the glacier runoff chemistry was rock-water interaction, with less soluble minerals and less intensive evaporate weathering in the Passu and Gulmit catchments than the B&B and Hinarchi catchments. Comparing the investigated catchments, the larger glacier with longer flow path exhibited higher runoff but lower melting rate, higher SSC resulting from higher erosive power of flow, and higher solute concentrations as a consequence of more intensive contact of meltwater with rock minerals along the longer flow path. For individual catchments, a negative correlation between TDS and flow rate (R2 = 0.26~0.53) and changing trends of ion ratios with flow rate demonstrated that under intensive melting conditions, rock-water interactions were reduced, resulting in dilution of solutes. Overall, the general chemical characteristics of the investigated glacier runoff indicated geological control, whereas individual glacier illustrated hydrological control on the daytime dynamics of glacier runoff chemistry. The presence of glacier terminal lake and agriculture land can significantly alter the hydrochemistry of downstream runoff.

Spatial variation, source identification, and quality assessment of surface water geochemical composition in the Indus River Basin, Pakistan.

The Indus River Basin (IRB) with an area of 139,202 km2 is the lifeline river basin of Pakistan. An intensive study was conducted in six subcatchments of the IRB with five in the Upper Indus Basin (UIB) and one of the Lower Indus Basin (LIB; between Tarbela Dam and Panjand), i.e., the Gilgit River Basin (UIB-I), Hunza River Basin (UIB-II), UIB-III, UIB-IV and UIB-V, and LIB. A total of 84 surface water samples were collected from main stream and tributaries from June to August, 2016. The pH, electric conductivity (EC), and total dissolved solids (TDS) were measured in situ, whereas major ions (Ca2+, Mg2+, K+, Na+, Cl-, SO42-, and NO3-) and Si were analyzed in the laboratory. The results exhibited alkaline pH (8.55 ± 0.20) with diverse TDS (114.69 ± 77.65 mg L-1) and ion concentrations that were characterized primarily by the Ca-Mg-HCO3 type in the whole basin. The average TDS in the UIB and LIB were 93.99 ± 39.73 and 181.67 ± 167.82 mg L-1, respectively, under the influence of the arid to semi-arid climatic conditions and relatively higher anthropogenic interference in LIB compared to the UIB. The order of dominant major cations was different in the UIB and LIB, reflecting the diverse nature of geological formation. Gibbs plot, mixing diagrams, and ionic ratios were used to identify the controlling mechanism of river geochemistry in the IRB as carbonate weathering in general with different degrees of silicate weathering and minor contribution by evaporite dissolution. In addition, principal component/factor analysis also indicated that the major sources of dissolved loads in the basin are carbonates followed by silicates. Significant influences of silicate minerals were observed in the LIB, and there was a large contribution of evaporites in the UIB-II, UIB-III, and LIB. The suitability assessment showed that the river water fits the WHO permissible limits for drinking purposes from the perspective of major ions, whereas for irrigation purposes, most of the samples exhibited excellent and good levels except for a couple of permissible and doubtful levels from the Sawan and Deratang tributaries in the LIB, which may deteriorate the quality of soil and degrade the water quality downstream.

Spatiotemporal variations of hydrogeochemistry and its controlling factors in the Gandaki River Basin, Central Himalaya Nepal.

The characterization and assessment of water quality in the head water region of Himalaya is necessary, given the immense importance of this region in sustaining livelihoods of people and maintaining ecological balance. A total of 165 water samples were collected from 55 sites during pre-monsoon, monsoon and post-monsoon seasons in 2016 from the Gandaki River Basin of the Central Himalaya, Nepal. The pH, EC values and TDS concentrations were measured in-situ and the concentrations of major ions (Ca2+, Mg2+, K+, Na+, Cl-, SO42-, NO3-) and Si were analyzed in laboratory. Correlation matrices, paired t-test, cluster analysis, principal component analysis (PCA), the Piper, Gibbs, and Mixing plots, and saturation index were applied to the measurements for evaluating spatiotemporal variation of the major ions. The results reveal mildly alkaline pH values and the following pattern of average ionic dominance: Ca2+>Mg2+>Na+>K+ for cations and HCO3->SO42->Cl->NO3- for anions. The results of PCA, Gibbs plot and the ionic relationships displayed the predominance of geogenic weathering processes in areas with carbonate dominant lithology. This conclusion is supported by geochemically different water facies identified in the Piper plot as Ca-HCO3 (83.03%), mixed Ca-Mg-Cl (12.73.0%) and Ca-Cl (4.24%). Pronounced spatiotemporal heterogeneity demonstrates the influence of climatic, geogenic and anthropogenic conditions. For instance, the Ca2+-SO42-, Mg2+-SO42- and Na+-Cl- pairs exhibit strong positive correlation with each other in the upstream region, whereas relatively weak correlation in the downstream region, likely indicating the influence of evapo-crystallization processes in the upstream region. Analyses of the suitability of the water supply for drinking and irrigation reveal that the river has mostly retained its natural water quality but poses safety concern at a few locations. Knowledge obtained through this study can contribute to the sustainable management of water quality in the climatically and lithologically distinct segments of the Himalayan river basins.

Traffic-related trace elements in soils along six highway segments on the Tibetan Plateau: Influence factors and spatial variation.

The accumulation of traffic-related trace elements in soil as the result of anthropogenic activities raises serious concerns about environmental pollution and public health. Traffic is the main source of trace elements in roadside soil on the Tibetan Plateau, an area otherwise devoid of industrial emissions. Indeed, the rapid development of tourism and transportation in this region means it is becoming increasingly important to identify the accumulation levels, influence distance, spatial distribution, and other relevant factors influencing trace elements. In this study, 229 soil samples along six segments of the major transportation routes on the Tibetan Plateau (highways G214, S308, and G109), were collected for analysis of eight trace elements (Cr, Co, Ni, As, Cu, Zn, Cd, and Pb). The results of statistical analyses showed that of the eight trace elements in soils, Cu, Zn, Cd, and Pb were primarily derived from traffic. The relationship between the trace element accumulation levels and the distance from the roadside followed an exponential decline, with the exception of Segment 3, the only unpaved gravel road studied. In addition, the distance of influence from the roadside varied by trace element and segment, ranging from 16m to 144m. Background values for each segment were different because of soil heterogeneity, while a number of other potential influencing factors (including traffic volume, road surface material, roadside distance, land cover, terrain, and altitude) all had significant effects on trace-element concentrations. Overall, however, concentrations along most of the road segments investigated were at, or below, levels defined as low on the Nemero Synthesis index.

Traffic-related trace element accumulation in roadside soils and wild grasses in the Qinghai-Tibet Plateau, China.

This research examines traffic-source trace elements accumulations and distributions in roadside soils and wild grasses in the Qinghai-Tibet Plateau. A total of 100 soil samples and 100 grass samples including Achnatherum splendens, Anaphalis nepalensis, Artemisia sphaerocephala, Carex moorcroftii, Iris lacteal, Kobresia myosuroides, Oreosolen wattii, Oxytropis ochrocephala and Stellera chamaejasme were collected at 100 sites from different road segments. The contents of metals and metalloids, including Cu, Zn, Cd, Pb, Cr, Co, Ni and As, in the soil and grass samples were analyzed using ICP-MS. The total mean concentrations of the eight trace elements in soils are Cu (22.84 mg/kg), Zn (100.56 mg/kg), Cd (0.28 mg/kg), Pb (28.75 mg/kg), Cr (36.82 mg/kg), Co (10.24 mg/kg), Ni (32.44 mg/kg) and As (21.43 mg/kg), while in grasses are Cu (9.85 mg/kg), Zn (31.47 mg/kg), Cd (0.05 mg/kg), Pb (2.06 mg/kg), Cr (14.16 mg/kg), Co (0.55 mg/kg), Ni (4.03 mg/kg) and As (1.33 mg/kg). The metal and metalloid concentrations in the nine grass species were all below the critical values of hyperaccumulators. The mean values and Multivariate Analysis of Variance (MANOVA) results indicate that: (1) the concentrations of the trace elements in the soils are higher than those in the grasses, (2) the concentrations of Cu, Zn, Cd, Pb in the soils decrease as the roadside distance increases, (3) the concentrations of trace elements in the grasses are the highest at 10 m from the road edge, (4) the higher the traffic volume, the higher the concentrations of the trace elements in the roadside soils and grasses, and (5) when the land cover is meadow, the lower the sand content in the soil, the lower the trace element concentrations. With a trace element's bioavailability represented by its transfer factor (TF) from the soil to the grass, the TFs of the eight trace elements are not in the same orders for different grass species.

Parallel solution-phase synthesis of 4H-benzo[1,4]thiazin-3-one and 1,1-dioxo-1,4-dihydro-2H-1lambda6-benzo[1,4]thiazin-3-one derivatives from 1,5-difluoro-2,4-dinitrobenzene.

This paper discusses the synthesis of privileged structures 4H-benzo[1,4]thiazin-3-one and 1,1-dioxo-1,4-dihydro-2H-1lambda6-benzo[1,4]thiazin-3-one derivatives in a parallel solution-phase manner using 1,5-difluoro-2,4-dinitrobenzene. Each scaffold possesses four diversity points. A cheap and efficient oxidant, urea-hydrogen peroxide (UHP), was applied for the introduction of the sulfone group. The intramolecular cyclization to 1,1-dioxo-1,4-dihydro-2H-1lambda6-benzo[1,4]thiazin-3-one was achieved by microwave assistance or the use of an inorganic base.