Natural background levels (NBLs) and threshold values (TVs) are crucial parameters for identification and the quantification of groundwater pollution, and the evaluation of pollution control measures. The cumulative probability distribution technique was used for the evaluation of NBLs for 36 samples collected during two climate conditions in the part of the desert area from Rajasthan, India. The NBLs for Na⁺, Cl⁻, SO₄²⁻, HCO₃⁻, NO₃⁻ and F⁻ ions were assessed and compared with the natural and anthropogenic processes. The TVs were also calculated for Na⁺, Cl⁻, SO₄²⁻, HCO₃⁻, NO₃⁻ and F⁻ ions, and compared with the drinking limits of the Bureau of Indian Standards. Additionally, the pollution percentage (%) at the individual well was estimated and identified the polluted zones. Results indicate that most of the polluted areas were situated in the southern part, which was influenced by the natural and anthropogenic factors. The sodium concentrations above the TVs, in indicating the saline nature of water. Chloride threshold value above the drinking water limit was mainly observed in the dry season, related to intensive evaporation and industrial waste, which leads to groundwater quality degradation. The NO₃⁻ concentration (∼56% samples) above the TVs indicates extensive use of nitrate fertilizers and sewage effluent. The values of total dissolved solids (TDS) shows the suspicious scenario as about 84% of the samples in the dry period and about 89% in the wet season exceeding the drinking limit. Assessment of background concentrations and threshold values on regional and local scale assigns the basis for the identification of groundwater pollution, and helpful for better water quality guidelines to protecting of water resources.

Iron nanoparticles (Fe NPs) have often been used for in situ remediation of both groundwater and soil. However, the impact of Fe NPs on the distribution and transformation of As species in contaminated soil is still largely unknown. In this study, green iron oxide nanoparticles synthesized using a euphorbia cochinchinensis leaf extract (GION) were used to stabilize As in a contaminated soil. GION exhibited excellent As stabilization effects, where As in non-specifically-bound and specifically-bound fractions decreased by 27.1% and 67.3% after 120 days incubation. While both arsenate (As (V)) and arsenite (As (III)) decreased after GION application, As (V) remained the dominant species in soil. X-ray photoelectron spectroscopy (XPS) confirmed that As (V) was the dominant species in specifically-bound fractions, while As (III) was the dominant species in amorphous and poorly-crystalline hydrous oxides of Fe and Al. Correlation analysis showed that while highly available As fractions were negatively correlated to oxalate and DCB extractable Fe, they were positively correlated to Fe²⁺ content, which indicated that Fe cycling was the main process influencing changes in As availability. X-ray fluorescence (XRF) spectroscopy also showed that the Fe₂O₃ content increased by 47.9% following GION soil treatments. Overall, this work indicated that As would be transformed to more stable fractions during the cycling of Fe following GION application and that the application of GION, even in small doses, provides a low-cost and ecofriendly method for the stabilization of As in soil.

Contaminated groundwater is considered as one of the most important pathways of human exposure to the geogenic contaminants. Present study has been conducted in a part of Indus basin to investigate the presence and spatial distribution of arsenic (As) and other trace metals in groundwater. The As concentration varies from bdl-255.6 μg/L and 24.6% of the 73 collected groundwater samples have As above world health organization (WHO) guideline of 10 μg/L. High concentration of As is found along the newer alluvium of Ravi River. As is found with high bicarbonate (HCO3−) and Iron (Fe) and low nitrate (NO3−) indicating reductive dissolution of Fe bearing minerals. However, silicate weathering along with high sulphate (SO42) and positive oxidation-reduction potential (ORP) indicates mixed redox conditions. Weathering of minerals along with other major hydrogeochemical process are responsible for composition of groundwater. With 31.5% of the samples, sodium bicarbonate (Na–HCO3) is the major water facies followed by magnesium bicarbonate (Mg–HCO3) in 30% of samples. As, Fe and other trace metals including copper (Cu), cadmium (Cd), chromium (Cr), zinc (Zn) were used to calculate the health risk for children and adults in the region. Out of 73 samples, 58% has high Fe, 32.8% has high Zn, and 4.1% has high Cd which are above the prescribed limits of WHO guidelines. Health risk of the population has been assessed using chronic dose index (CDI), hazardous quotients (HQ) and hazardous index (HI) for children and adults. The mean CDI values follows the order as Fe > Zn > Cu > As > Cr > Cd, while the HQ values indicates high As hazards for both children and adults. 43.8% of the groundwater samples have high HI for adults, however, 49.3% has high HI for children indicating higher risk for children compared to adults. A large-scale testing should be prioritized to test the wells for As and other trace metals in the study region to reduce health risks.

The aquifer in Tondiarpet, Chennai, had been severely contaminated with petroleum fuels due to an underground pipeline leakage. Groundwater samples were analyzed quarterly for priority pollutants such as benzene, toluene, ethylbenzene, xylenes, and naphthalene (BTEXN) using purge and trap gas chromatography and mass spectrometer from 2016 to 2018. The maximum concentrations of BTEXN in groundwater at the site were found to be greater than the permissible limits significantly. Among the five sampling locations (MW1, MW2, MW3, MW4, and MW5), mean BTEXN levels were found to be higher near MW2, confirming the source location of petroleum leakage. Human health risk assessment was carried out using deterministic and probabilistic methods for exposure to BTEXN by oral and dermal exposure pathways. Risk analysis indicated that mean cancer and non-cancer risks were many times higher than the allowable limits of 1E-06 and 1 respectively in all age groups (children, teens, and adults), implying the adverse health effects. Oral exposure is predominately contributing (60–80%) to the total health risk in comparison to the dermal exposure route. Variability and uncertainty were addressed using the Monte Carlo simulations and the resultant minimum, maximum, 5th, 95th, and mean percentile risks were predicted. Under the random exposure conditions to BTEXN, it was estimated that the risk would become unacceptable for >98.7% of the exposed population. Based on the sensitivity analysis, exposure duration, and ingestion rate are the crucial variables contributing significantly to the health risk. As part of the risk management, preliminary remediation goals for the study site were estimated, which require >99% removal of the BTEXN contamination for risk-free exposures. It is suggested that the residents of Tondiarpet shouldn’t utilize the contaminated groundwater mainly for oral ingestion to lower the cancer incidence related to exposure to BTEXN.

Owing to the substantial consumption of caffeinated food, beverages, and medicines worldwide, caffeine is considered the most representative pharmaceutically active compound (PhAC) pollutant based on its high abundance in the environment and its suitability as an indicator of the anthropogenic inputs of PhACs in water bodies. This review presents a worldwide analysis of 132 reports of caffeine residues in freshwater environments. The results indicated that more than 70% of the studies reported were from Asia and Europe, which have densely populated and industrially developed areas. However, caffeine pollution was also found to affect areas isolated from human influence, such as Antarctica. In addition, the maximum concentrations of caffeine in raw wastewater, treated wastewater, river, drinking water, groundwater, lake, catchment, reservoir, and rainwater samples were reported to be 3.60 mg/L, 55.5, 19.3, 3.39, 0.683, 174, 44.6, 4.87, and 5.40 μg/L, respectively. The seasonal variation in caffeine residues in the freshwater environment has been demonstrated. In addition, despite the fact that there was a small proportion of wastewater treatment plants in which the elimination rates of caffeine were below 60%, wastewater treatment is generally believed to have a high caffeine removal efficiency. From a pharmacy perspective, we proposed to adopt effective measures to minimize the environmental risks posed by PhACs, represented by caffeine, through a new concept known as ecopharmacovigilance (EPV). Some measures of EPV aimed at caffeine pollution have been advised, as follows: improving knowledge and perceptions about caffeine pollution among the public; listing caffeine as a high-priority PhAC pollutant, which should be targeted in EPV practices; promoting green design and production, rational consumption, and environmentally preferred disposal of caffeinated medicines, foods, and beverages; implementing intensive EPV measures in high-risk areas and during high-risk seasons; and integrating EPV into wastewater treatment programs.

The ammonium sulphate ((NH₄)₂SO₄) in-situ leaching process is the most widely used extraction technology for weathered crust elution-deposited rare earth ores (WCED-REOs). Highly concentrated (NH₄)₂SO₄, a representative leaching agent, is often used in the leaching process of WCED-REOs. However, this in-situ leaching process causes nitrogen pollution in the soil, surrounding surface and ground water due to the high concentrations of (NH₄)₂SO₄ solutions used as a long term leaching agent. To date, the mechanism behind the variations in ammonia nitrogen (AN) in deep soil profiles is unclear. We conducted vertical and lateral soil sampling and analyzed the collected samples for soil moisture, pH, ammonia forms, and AN contents in soil profiles deeper than 500 cm in an in-situ leaching mining area of Ganzhou, Jiangxi Province, southern China. The results show that primary chemical pollutants in the soil are derived from residual leaching agents with high acidities and concentrations of AN. Twelve years after the mining process was completed, the mean pH values of the tailings in the mining area were 3.90 and 4.87 in its lower reaches. Due to the presence of chemical residues, the AN concentration was 12–40 times higher than that of the raw ore soil before it was mined. The percentages of different ammonium forms in the rare earth tailing soil were 65%, 30%, and 5% for the water-soluble, exchangeable, and fixed ammonium forms, respectively. The results of this study support effective prevention and remediation treatment of environmental problems caused by AN pollution of the soil in WCED-REOs.

Antibiotics, such as sulfonamides (SAs), have recently raised concern as wastewater treatment plants (WWTPs) partly remove them, and thus, SAs continuously enter the aquifers. In this context, the aims of this work are to (1) investigate the temporal evolution of SAs and metabolites in an urban aquifer recharged by a polluted river; (2) identify the potential geochemical processes that might affect SAs in the river-groundwater interface and (3) evaluate the ecological and human health risk assessment of SAs. To this end, 14 SAs and 4 metabolites were analyzed in river and urban groundwater from the metropolitan area of Barcelona (NE, Spain) in three different sampling campaigns. These substances had a distinct behavior when river water, which is the main recharge source, infiltrates the aquifer. Mixing of the river water recharge into the aquifer drives several redox reactions such as aerobic respiration and denitrification. This reducing character of the aquifer seemed to favor the natural attenuation of some SAs as sulfamethoxazole, sulfapyridine, and sulfamethizole. However, most of the SAs detected were not likely to undergo degradation and adsorption because their concentrations were constant along groundwater flow path. In fact, the intensity of SAs adsorption is low as the retardation factors are close to 1 at average groundwater pH of 7.2 for most SAs.Finally, risk quotients (RQs) are used to evaluate the ecological and human health risks posed by single and mixture of SAs in river water and groundwater, respectively. Life-stage RQs of the SAs detected in groundwater for the 8 age intervals were low, indicating that SAs and their mixture do not pose any risk to human beings. Concerning the environmental risk assessment, SAs do not pose any risk for algae, fish and crustaceans as the RQs evaluated are further lower than 0.1.

Hexavalent chromium and nitrate co-contaminated groundwater remediation are attracting extensive attention worldwide. However, the transformation pathways of chromium and nitrate and the interplay mechanism between them remain unclear. In this work, zeolite-supported nanoscale zero-valent iron/palladium (Z-Fe/Pd) was synthesized and used for the first time to simultaneously remediate Cr(VI) and nitrate. Transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that nanoscale zero-valent iron/palladium was successfully loaded onto zeolite and it exhibited good dispersibility and oxidation resistance. Results of batch experiments showed that the Cr(VI) and nitrate removal efficiencies decreased from 95.5% to 91.5% to 45% and 73%, respectively, with the initial solution pH increasing from 3.0 to 8.0. The removal rates and efficiencies of Cr(VI) and nitrate under anoxic conditions were higher than those under open atmosphere because the dissolved oxygen diminished the electron selectivity toward the target pollutants. Moreover, the presence of Cr(VI) inhibited nitrate reduction by forming Fe(III)-Cr(III) hydroxide to impede electron transfer. Cr(VI) removal was promoted by nitrate, within limits, by balancing the consumption and generation rate of Fe₃O₄, which enhanced electron migration from the Fe(0) core to the external surface. The removal capacities of Cr(VI) and nitrate reached 121 and 95.5 mg g⁻¹, respectively, which were superior to the removal capacities of similar materials. Results of product identification, XRD, and XPS analyses of spent Z-Fe/Pd indicated that the reduction of Cr(VI) was accompanied by adsorption and co-precipitation, whereas the reduction of nitrate was catalyzed by the synergism of Fe(0) and Pd(0). An alternative to the simultaneous remediation of Cr(VI) and nitrate from groundwater under anoxic conditions is provided.

Sulfate (SO₄²⁻) contamination in groundwater and surface water is an environmental problem of widespread concern. In this study, we combined stable isotope analyses of SO₄²⁻ (δ³⁴S and δ¹⁸O) and water (δ²H and δ¹⁸O) with a Bayesian mixing model (SIAR), for the first time, to identify sources and transformation of SO₄²⁻ in an area of northern China with multiple potential sources of pollution. The overall values of δ³⁴S and δ¹⁸O-SO₄²⁻ ranged from 1.3‰ to 16.3‰ and −3.8‰–8.8‰ in groundwater, and from −1.1‰ to 9.3‰ and 2.7‰–9.2‰ in surface waters, respectively. Analyses of SO₄²⁻ isotopes and water chemistry indicated that SO₄²⁻ in groundwater and surface water mainly originated from mixing of oxidation of sulfate, sewage, chemical fertilizers, dissolution of evaporite and precipitation. There was no significant correlation between δ³⁴S and δ¹⁸O and SO₄²⁻ concentration in groundwater, indicating that bacterial sulfate reduction did not affect the SO₄²⁻ isotopic composition. SIAR model showed the main sources of SO₄²⁻ in groundwater and surface water comprised oxidation of sulfide minerals and sewage. In groundwater, oxidation of sulfide minerals and sewage accounted for 37.5–44.5% and 35.5–42.7% of SO₄²⁻, respectively. In regard to surface waters, the contribution of oxidation of sulfide minerals to SO₄²⁻ was higher in the wet season (31.8 ± 9.9%) than in the intermediate (22.4 ± 7.8%) and dry (20.9 ± 8.2%) seasons, but the contribution proportion of sewage was slightly lower in the wet season (19.9 ± 8.5%) than in the intermediate (23.8 ± 8.7%) and dry (24.2 ± 8.5%) seasons. This study indicates that it is necessary for local government to improve the treatment infrastructure for domestic sewage and optimize methods of agricultural fertilization and irrigation to prevent SO₄²⁻ contamination of groundwater and surface water.

High concentration of fluoride (up to 20.9 mg/L) in groundwater with significant variation (p = 5.9E-128) among samples was reported from Birbhum district, an acknowledged fluoride endemic region in India. The groundwater samples (N = 368) were grouped based on their hydrochemical properties and aquifer geology for hydro-geochemical characterization. Friedman’s test showed p < 0.0001 confidence level which indicates that fluoride concentration among geological groups and water groups are independent. Bland-Altman plot was used to study the inter-relationships among the groups through bias value (∂) and limit of agreement (LoA). Among the geological groups, laterites and granite-gneiss groups exhibited statistically significantly difference in fluoride geochemistry; whereas the younger and older alluvium groups displayed similar characteristics. The fluoride concentration was found to be in the order Lateritic > Granite-gneiss > Older alluvium ≥ Younger alluvium. Dissolution of minerals (such as fluorite, biotite) in laterite sheeted basalt, and granite-gneiss is the main source of groundwater fluoride in the region. Fluoride concentration is also influenced by depth of water table. Hydrochemical study indicated that fluoride concentration was higher in Na–HCO₃ than in Ca–SO₄ and Ca–HCO₃ type of groundwater. The fluoride concentration were positively correlated with Na⁺ and pH and negatively correlated with the Ca²⁺ and Mg²⁺ signifying linkage with halite dissolution and calcite, dolomite precipitation. Geostatistical mapping of WQI through empirical bayesian kriging (EBK) with respect to regional optimal guideline value (0.73 mg/L) classified that groundwater in some parts of the district are unfit for drinking purpose. Health survey (N = 1767) based on Dean’s criteria for dental fluorosis indicated presence of slight to moderate dental hazard. Besides, providing baseline data for management of groundwater quality in the study area, the study demonstrated the applicability of Bland-Altman analysis and empirical bayesian kriging (EBK) in delineation and interpolation of fluoride contaminated region.