Hydrogeochemical evaluation with emphasis on nitrate and fluoride in urban and rural drinking water resources in western Isfahan province, central Iran.

Nitrate (NO3-) and fluoride (F-) are two major potential contaminants found in the groundwater of Iran. These contaminants are highly dangerous to humans if consumed more than the safe limit prescribed by the WHO. Therefore, in this study, the urban and rural drinking water resources of Isfahan province (central Iran) were investigated to evaluate the quality of groundwater from the perspective of NO3- and F-. The calculated saturation index (SI) shows that the majority of samples are mainly undersaturated or in equilibrium with respect to potential minerals. The most likely interpretation for undersaturation with respect to most minerals is either that the minerals are not present if they are reactive or if they are present, then they are not reactive. This study reveals that the majority of the groundwater samples belong to the Ca-Mg-HCO3 water type. Further, in this study, potential physicochemical variables have been used to calculate entropy weighted water quality index (EWQI). The EWQI reveals that the majority of the groundwater in the area is of good quality. Results show that the water chemistry in the area is largely governed by the water-rock interaction. This study based on large data sets reveals that the majority of drinking water resources are uncontaminated by F-. However, the groundwater is found to be largely contaminated by NO3-. The bivariate plot suggests that the unscientific farming practices and overuse of manures and fertilizers are largely responsible for high content of NO3-. Therefore, emphasis should be given on the cost-effective environmentally friendly fertilizers. The findings from this study will aid the governing authorities and concerned stakeholders to understand the hydrogeochemical evolution of groundwater in this region. The results will help formulate policies in the area for sustainable water supply.

Mercury pollution in the coastal Urmia aquifer in northwestern Iran: potential sources, mobility, and toxicity.

The concentration of total dissolved mercury (HgT) in surface and groundwater resources in the coastal parts of Urmia aquifer (NW of Iran) was investigated to identify the possible sources and sinks of mercury and the geochemical mechanisms controlling its mobilization. The distribution of water samples on the Piper diagram demonstrates that most samples have the Ca-Mg-HCO3 facies. From 62 water samples collected in this area, one sample contained HgT concentrations exceeding the maximum contaminant level recommended by the WHO (6 µg/L). The principal component analysis (PCA) produced five principal components. The positive moderate correlation of HgT with EC, Cl, K, Mg, and Na indicated that the weathering of geological formations was one of the main sources of mercury in groundwater samples. Position of water samples in Eh-pH regions where microorganisms involved in mercury methylation and mineralization were potentially active demonstrated that the aquifer had undergone sulfate reduction and had reached the final stage of the terminal electron accepting process (TEAP) sequence in the methane production processes which are limited to only 37% of the water samples that have anaerobic conditions. Some Hg-bearing species are in nonequilibrium geochemical conditions. The supersaturation of water samples with magnetite and goethite indicated that these Fe-bearing minerals could act as the strong reducing agents for the reduction of Hg(II) to Hg(0).

Groundwater quality evaluation using Shannon information theory and human health risk assessment in Yazd province, central plateau of Iran.

This study aims to evaluate the quality of groundwater in the most arid province of Iran, Yazd. It is highly dependent on groundwater resources to meet the domestic, industrial, and agricultural water demand. Position of water samples on the modified Gibbs diagram demonstrates that the interaction with silicates and the increase in direct cation exchange are responsible for the increased salinity of groundwater. Based on entropy theory, the decreasing order of importance of variables in controlling groundwater chemistry is Fe > As > Ba > Hg > NO2 > Pb > K > Cl > Na > Mg > SO4 > NO3 > HCO3 > Ca. The results of entropy weighted water quality index (EWWQI) calculation show that about 34 and 32% of 206 samples in the wet and dry seasons, respectively, are classified as extremely poor quality (ranks 4 and 5). Approximately 60 and 55% of 206 samples in wet and dry seasons, respectively, have excellent, good, and medium quality (ranks 1, 2, and 3). The non-carcinogenic human health risk (NHHR) from intake and dermal contact pathways using deterministic approach show that 36 and 17 samples in both seasons are not suitable for drinking by children. Furthermore, 9 and 2 samples are not suitable for drinking by adults. The results show that children are more vulnerable than adults to these health risks. The non-carcinogenic risks through dermal contact were negligible.

Transport of N-CD and Pre-Sorbed Pb in Saturated Porous Media.

Carbon dots (CDs) are a new type of nanomaterials of the carbon family with unique characteristics, such as their small size (e.g., <10 nm), high water solubility, low toxicity, and high metal affinity. Modification of CDs by Nitrogen functional groups (N-CDs) enhances their metal adsorption capacity. This study investigated the influences of pH (4, 6, and 9), ionic strength (1, 50, and 100 mM), and cation valency (Na+ and Ca2+) on the competitive adsorption of Pb to quartz and N-CD surfaces, the transport and retention of N-CDs in saturated porous media, and the capacity of N-CDs to mobilize pre-adsorbed Pb in quartz columns. Pb adsorption was higher on N-CDs than on quartz surfaces and decreased with increases in ionic strength (IS) and divalent cations (Ca2+) concentration. N-CD mobility in quartz columns was highest at pH of 9- and 1-mM monovalent cations (Na+) and decreased with decreases in pH and increases in ionic strength and ion valency. N-CDs mobilized pre-adsorbed Pb from quartz due to the higher adsorption affinity of Pb to N-CD than to quartz surfaces. These findings provide valuable insights into the transport, retention, and risk assessment of lead in the presence of carbon-based engineered nanoparticles.

Assessing the chemical behavior and spatial distribution of yttrium and rare earth elements (YREEs) in a coastal aquifer adjacent to the Urmia Hypersaline Lake, NW Iran.

This study aims to shed light on the seasonal behavior of yttrium and rare earth elements (YREEs) in the Urmia Aquifer (UA), in the immediate vicinity of Urmia Lake (UL) in Iran. Samples of groundwater, collected under dry and wet conditions in coastal wells of UA, suggest a large degree of variability in both YREE abundance and normalized patterns. Although weathering or water-rock interactions (between the surface/groundwater and rock samples) were predicted to be the most probable source in explaining YREEs in groundwater samples, results to the contrary indicate that the groundwater do not inherit aquifer rock-like YREE signatures in the study area; this might be due to the relative stability of YREEs during the process of water-rock interactions, which suggest that methods based on YREEs can be beneficial in discrimination of water sources. Furthermore, findings demonstrated no significant relationship between Ce/Ce* and salinity (0.08 and 0.05 in wet and dry seasons, respectively), and between Eu/Eu* and salinity (0.1 and -0.04 in wet and dry seasons, respectively). Dissimilarity of patterns of YREEs in rock and water samples reveals YREEs as no conservative tracers in determining the UL saltwater intrusion into coastal groundwater. Therefore, the groundwater YREE concentrations and fractionation patterns in UA warrant controlling by coastal aquifer need to be controlled by other chemical weathering, adsorption, desorption, and solution complexation reactions. Finally, comparison of REE concentration values in groundwater samples with corresponding indicative admissible drinking water concentrations (IAC) demonstrated their suitability for drinking purposes.

Geophysical, isotopic, and hydrogeochemical tools to identify potential impacts on coastal groundwater resources from Urmia hypersaline Lake, NW Iran.

Measurements of major ions, trace elements, water-stable isotopes, and geophysical soundings were made to examine the interaction between Urmia Aquifer (UA) and Urmia Lake (UL), northwest Iran. The poor correlation between sampling depth and Cl(-) concentrations indicated that the position of freshwater-saltwater interface is not uniformly distributed in the study area, and this was attributed to aquifer heterogeneities. The targeted coastal wells showed B/Cl and Br/Cl molar ratios in the range of 0.0022-2.43 and 0.00032-0.28, respectively. The base-exchange index (BEI) and saturation index (SI) calculations showed that the salinization process followed by cation-exchange reactions mainly controls changes in the chemical composition of groundwater. All groundwater samples are depleted with respect to δ(18)O (-11.71 to -9.4 ‰) and δD (-66.26 to -48.41 ‰). The δ(18)O and δD isotope ratios for surface and groundwater had a similar range and showed high deuterium excess (d-excess) (21.11 to 31.16 ‰). The high d-excess in water samples is because of incoming vapors from the UL mixed with an evaporated moisture flux from the Urmia mainland and incoming vapors from the west (i.e., Mediterranean Sea). Some saline samples with low B/Cl and Br/Cl ratios had depleted δ(18)O and δD. In this case, due to freshwater flushing, the drilled wells in the coastal playas and salty sediments could have more depleted isotopes, more Cl(-), and consequently smaller B/Cl and Br/Cl ratios. Moreover, the results of hydrochemical facies evolution (HFE) diagram showed that because of the existence fine-grained sediments saturated with high density saltwater in the coastal areas that act as a natural barrier, increasing the groundwater exploitation leads to movement of freshwaters from recharge zones in the western mountains not saltwater from UL. The highly permeable sediments at the junction of the rivers to the lake are characterized by low hydraulic gradient and high hydraulic conductivity. These properties enhance the salinization of groundwater observed in the study area. The main factors influencing the salinity are base-exchange reactions, invasion of highly diluted saltwater, dissolution of salty pans, and water chemistry evolution along flow paths.

Investigating the salinization and freshening processes of coastal groundwater resources in Urmia aquifer, NW Iran.

This paper presents the results of an assessment about interaction between Urmia Lake (UL) and coastal groundwater in the Urmia aquifer (UA). This aquifer is the most significant contributor to the freshwater supply of the coastal areas. The use of hydrochemical facies can be very useful to identify the saltwater encroachment or freshening phases in the coastal aquifers. In this study, the analysis of salinization/freshening processes was carried out through the saturation index (SI), ionic deltas (Δ), binary diagrams, and hydrochemical facies evolution (HFE) diagram. Based on the Gibbs plot, the behavior of the major ions showed that the changes in the chemical composition of the groundwater are mainly controlled by the water-soil/rock interaction zone and few samples are relatively controlled by evaporation. A possible explanation for this phenomenon is that the deposited chloride and sulfate particles can form the minor salinity source in some coastal areas when washed down by precipitation. The SI calculations showed that all groundwater samples, collected in these periods, show negative saturation indices, which indicate undersaturation with respect to anhydrite, gypsum, and halite. In addition, except in a few cases, all other samples showed the undersaturation with respect to the carbonate minerals such as aragonite, calcite, and dolomite. Therefore, these minerals are susceptible to dissolution. In the dry season, the SI calculations showed more positive values with respect to dolomite, especially in the northern part of UA, which indicated a higher potential for precipitation and deposition of dolomite. The percentage of saltwater in the groundwater samples of Urmia plain was very low, ranging between 0.001 and 0.79 % in the wet season and 0.0004 and 0.81 % in the dry season. The results of HFE diagram, which was taken to find whether the aquifer was in the saltwater encroachment phase or in the freshening phase, indicated that except for a few wells near the coast, there is very little hydraulic interaction between UA and UL. In this coastal area, most of the samples that were collected repeatedly in both wet and dry seasons showed the same hydrochemical facies, which suggested that the seasonal groundwater fluctuations cannot significantly change the chemical composition of groundwater.

Evaluation of groundwater quality and assessment of scaling potential and corrosiveness of water samples in Kadkan aquifer, Khorasan-e-Razavi Province, Iran.

The chemical analysis of 129 groundwater samples in the Kadkan area, Khorasan-e-Razavi Province, NE of Iran was evaluated to determine the hydrochemical processes, assessment of groundwater quality for irrigation purposes, corrosiveness, and scaling potential of the groundwater. Accordingly, the suitability of groundwater for irrigation was evaluated based on the sodium adsorption ratio, residual sodium carbonate, sodium percent, salinity hazard, and US Salinity Laboratory hazard diagram. Based on the electrical conductivity and sodium adsorption ratio, the dominant classes are C3-S1, C3-S2, C2-S1, and C4-S2. According to the Wilcox plot, about 50 % of the samples fall in the "Excellent to Good" and "Good to Permissible" classes. Besides, the Langelier saturation index, Ryznar stability index (RSI), Larson-Skold index, and Puckorius scaling index were evaluated for assessing the corrosiveness and scaling potential of the groundwater. Corrosiveness and scaling indices stated that the majority of samples are classified into "Aggressive" and "Very Aggressive" category. In addition, chloride and sulfate interfere in 90 % of the samples. Assessment of hydrochemical characteristics indicates Na-Mg-Cl as the predominant hydrochemical type. Spatial distribution of hydrochemical parameters indicates that hydrochemical processes are influenced by geology and hydrogeology of Kadkan aquifer. The Gibbs plots gave an indication that groundwater chemistry in this area may have acquired the chemistry mainly from evaporation and mineral precipitation. Grouping the samples based on Q-mode hierarchical cluster analysis helped to more separation of similar samples. The R-mode HCA grouped analyzed parameters into two groups based on similarity of hydrochemical characteristics. As a result, the samples collected in northern and southern parts of the study area show the best quality (i.e., lowest salinity) for some purposes such as irrigation and drinking.