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Arsenic (As) contamination in groundwater is a worldwide concern for drinking water safety. Environmental changes and anthropogenic activities are making groundwater vulnerable in Pakistan, especially in Southern Punjab. This study explores the distribution, hydrogeochemical behavior, and pathways of As enrichment in groundwater and discusses the corresponding evolution mechanism, mobilization capability, and health risks. In total, 510 groundwater samples were collected from three tehsils in the Punjab province of Pakistan to analyze As and other physiochemical parameters. Arsenic concentration averaged 14.0 μg/L in Vehari, 11.0 μg/L in Burewala, and 13.0 μg/L in Mailsi. Piper-plots indicated the dominance of Na+, SO42−, Ca2+, and Mg2+ ions in the groundwater and the geochemical modeling showed negative saturation indices with calcium carbonate and salt minerals, including aragonite (CaCO3), calcite (CaCO3), dolomite (CaMg(CO3)2), and halite (NaCl). The dissolution process hinted at their potential roles in As mobilization in groundwater. These results were further validated with an inverse model of the dissolution of calcium-bearing mineral, and the exchange of cations between Ca2+ and Na+ in the studied area. Risk assessment suggested potential carcinogenic risks (CR > 10−4) for both children and adults, whereas children had a significant non-carcinogenic risk hazard quotient (HQ > 1). Accordingly, children had higher overall health risks than adults. Groundwater in Vehari and Mailsi was at higher risk than in Burewala. Our findings provide important and baseline information for groundwater As assessment at a provincial level, which is essential for initiating As health risk reduction. The current study also recommends efficient management strategies for As-contaminated groundwater.

To investigate co-transport behavior of ammonium and colloids in saturated porous media under different hydrochemical conditions, NH4+ was selected as the target contaminant, and silicon and humic acid (HA) were selected as typical organic and inorganic colloids in groundwater. Column experiments were then conducted to investigate the transport of NH4+ colloids under various hydrochemical conditions. The results showed that because of the different properties of colloidal silicon and HA after combining with NH4+, the co-transport mechanism became significantly different. During transport by the NH4+–colloid system, colloidal silicon occupied the adsorption sites on the medium surface to promote the transport of NH4+, while humic acid (HA) increased the number of adsorption sites of the medium to hinder the transport of NH4+. The co-transport of NH4+ and colloids is closely related to hydrochemical conditions. In the presence of HA, competitive adsorption and morphological changes of HA caused NH4+ to be more likely to be transported at a higher ionic strength (IS = 0.05 m, CaCl2) and alkalinity (pH = 9.3). In the presence of colloidal silicon, blocking action caused the facilitated transport to be dependent on higher ionic strength and acidity (pH = 4.5), causing the recovery of NH4+ to improve by 7.99%, 222.25% (stage 1), and 8.63%, respectively. Moreover, transport increases with the colloidal silicon concentrations of 20 mg/L then declines at 40 mg/L, demonstrating that increased concentrations will lead to blocking and particle aggregation, resulting in delayed release in the leaching stage.

For shallow groundwater, hydrogeochemical processes and quality assessment must be addressed because shallow groundwater is freely available in many parts of the globe. Due to recent anthropogenic activities and environmental changes in Sakrand, Sindh, Pakistan, the groundwater is extremely vulnerable. To provide safe drinking and agricultural water, hydrogeochemical analysis is required. Ninety-five groundwater samples were analyzed using agricultural and drinking indices to determine the hydrogeochemical parameters using multivariate analysis such as Pearson correlations, principal component cluster analysis, as well as Piper diagrams and Gibbs plot for drinking and agricultural indices. An abundance of ions was observed through the statistical summary; however, cations and anions were recorded in the orders Na+ > Ca2+ > Mg2+ > K+ and HCO3− > Cl− > SO42− > NO3− > F−. The hydrogeochemical process used to quantify the major reactions occurring in the groundwater system showed rock dominance; the Piper diagrams evaluated the water type. A mixed pattern of calcium, magnesium, and chloride ions (Ca2+−Mg2+−Cl− type) was observed. Additionally, the ion exchange method showed an excess of bicarbonate ions due to carbonic acid weathering. The water quality index (WQI) resulted 32.6% of groundwater being unsuitable for human consumption; however, the United States Salinity Laboratory (USSL) diagram showed 60% of samples were unsuitable for irrigation due to high salinity and the Wilcox diagram depicted 5% of samples lying in the unsuitable region. Most of the water samples were suitable for drinking; only a few samples were unsafe for drinking purposes for children due to the high hazard index.

To bolster freshwater supply, artificial groundwater recharge with recycled water has increasingly attracted research attentions and interests. However, artificial groundwater recharge has potential risks to groundwater quality, as recharge water disinfection is frequently used for pathogen inactivation and causes the concerns of disinfection by-products (DBPs). Colloid supplement is a good approach solving this problem, but its roles in mitigating DBPs remains unclear. In this study, we collected 20 groundwater and soil samples from a field-scale groundwater recharge project, and explored the impacts of silica colloids on chloroform migration and groundwater bacterial communities during the recharge process. Water physicochemical variables changed along the recharge time, and colloid supplement significantly reduced chloroform formation and slowed its migration in groundwater. Bacterial communities in groundwater, river water and recharge water were significantly different. Gammaproteobacteria in recharge water (71.7%) was more abundant than in river water (30.5%) and groundwater (33.5%), while Actinobacteria dominated groundwater (40.6%). After recharge, Gammaproteobacteria increased more with colloid supplement (75.7%) than without (52.6%), attributing to its dominance in soils (74.6%). Our results suggested more bacterial lineages released from soils into aquifer by silica colloid supplement, owing to the competitive adsorption encouraging microbial transfer, especially Gram-negative bacteria. Our findings unraveled the effects of colloid supplement on chloroform formation and migration during artificial groundwater recharge, which consequently altered groundwater bacterial communities, and offered valuable suggestions for the safety management of DBPs in aquifer recharge.

Graphical abstract, The global outbreak of coronavirus infectious disease-2019 (COVID-19) draws attentions in the transport and spread of Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) in aerosols, wastewater, surface water and solid wastes. As pathogens eventually enter the subsurface system, e.g., soils in the vadose zone and groundwater in the aquifers, they might survive for a prolonged period of time owing to the uniqueness of subsurface environment. In addition, pathogens can transport in groundwater and contaminate surrounding drinking water sources, possessing long-term and concealed risks to human society. This work critically reviews the influential factors of pathogen migration, unravelling the impacts of pathogenic characteristics, vadose zone physiochemical properties and hydrological variables on the migration of typical pathogens in subsurface system. An assessment algorithm and two rating/weighting schemes are proposed to evaluate the migration abilities and risks of pathogens in subsurface environment. As there is still no evidence about the presence and distribution of SARS-CoV-2 in the vadose zones and aquifers, this study also discusses the migration potential and behavior of SARS-CoV-2 viruses in subsurface environment, offering prospective clues and suggestions for its potential risks in drinking water and effective prevention and control from hydrogeological points of view.

Benzene is one of the most harmful compounds in groundwater. In the groundwater environment, adsorption plays a major role in benzene attenuation. In this study, laboratory experiments were conducted using jars to systematically investigate the effect of benzene adsorption under static conditions. Experiments were conducted using colloidal silica, which is representative of colloids in groundwater. In the single benzene system, more benzene was adsorbed at high than low pH because of the reduction in available H+ to compete with benzene for adsorption with increased pH. In addition, more benzene was adsorbed at high than low ionic strengths (ISs), because the presence of metal cations neutralized more negative charges and weakened the electrostatic interaction between benzene and the media. In the benzene-colloidal silica system, the presence of colloidal silica accelerated benzene adsorption, because colloidal silica can attach to the surface of the porous media and act as additional sites for adsorption while also enhancing the adsorption capacity of the C–H bonds. As the pH increased, the particle size of the colloidal silica also increased, which increased the colloidal silica adsorption capacity of benzene. As ISs increased, the colloidal silica became more unstable, and colloidal silica could easily attach to the surface of the porous media, enabling more benzene to be adsorbed. However, in the presence of colloidal silica, the effects of pH and ISs on benzene adsorption are not obvious and colloidal silica plays a leading role in benzene adsorption. Colloidal silica promotes benzene adsorption, primarily because it provides sites for adsorption and has a higher affinity for benzene than the surfaces of the porous media. This allows the porous media to rapidly adsorb benzene until reaching the saturation point, which has a much stronger effect on benzene adsorption than hydro-chemical conditions.

Because of the complexity of contaminants infiltrating groundwater, it is necessary to study the co-transport of contaminants in the vadose and saturated zones. To investigate the role of inorganic colloids in the transport of biocolloids through porous media, a series of experiments were performed using columns packed with sand. The Escherichia coli phage (E. coli phage) was used as the model virus and silica as the model colloid in this study. The model virus exhibited a higher degree of attachment when compared with silica under similar experimental conditions. Under unsaturated flow conditions, the degree of virus retention was higher than in the corresponding saturated flow case, regardless of the presence of silica. Mass recovery and breakthrough curve data showed that silica hindered virus transport in saturated porous media. The model virus exhibited a higher degree of retention in the presence of silica. This could be related to pore structure changes caused by aggregated virus-silica particles located within the pores of the sand. Conversely, the suspended virus retained at the air-water interface provided new retention sites for other colloids; the retention was observed to be higher in the presence of colloidal silica in the saturated columns. In the corresponding unsaturated experiments, silica was observed to play the opposite function with respect to virus transport, which demonstrated that silica facilitated virus transport in the presence of unsaturated porous media. Capillary forces were stronger than the virus-silica interactions, and inhibited the aggregation of particles. Suspended silica competes with the virus for sorption sites because of a high affinity for the air-water interface. This competition inhibits virus retention by electrostatic repulsion of like-charged particles, and concomitantly facilitates virus transport under unsaturated conditions.