Use of per- and polyfluoroalkyl substance (PFAS)-containing aqueous film-forming foams (AFFF) at firefighting training sites (FFTS) has been linked to PFAS contamination of drinking water. This study investigated PFAS transport and distribution in an urban groundwater aquifer used for drinking water production that has been affected by PFAS-containing AFFF. Soil, sediment, surface water and drinking water were sampled. In soil (n = 12) at a FFTS with high perfluorooctane sulfonate (PFOS) content (87% of ∑PFAS), the ∑PFAS concentration (n = 26) ranged from below detection limit to 560 ng g⁻¹ dry weight. In groundwater (n = 28), the ∑PFAS concentration near a military airbase FFTS reached 1000 ng L⁻¹. Principal component analysis (PCA) identified the military FFTS as the main source of PFAS contamination in drinking water wellfields >10 km down-gradient. Groundwater samples taken close to the military FFTS site showed no ∑PFAS concentration change between 2013 and 2021, while a location further down-gradient showed a transitory 99.6% decrease. Correlation analysis on PFAS composition profile indicated that this decrease was likely caused by dilution from an adjacent conflating aquifer. ∑PFAS concentration reached 15 ng L⁻¹ (PFOS 47% and PFHxS 41% of ∑PFAS) in surface river water (n = 6) and ranged between 1 ng L⁻¹ and 8 ng L⁻¹ (PFHxS 73% and PFBS 17% of ∑PFAS) in drinking water (n = 4). Drinking water had lower PFAS concentrations than the wellfields due to PFAS removal at the water treatment plant. This demonstrates the importance of monitoring PFAS concentrations throughout a groundwater aquifer, to better understand variations in transport from contamination sources and resulting impacts on PFAS concentrations in drinking water extraction areas.

Contaminant vulnerability in the critical zones like groundwater (GW)-seawater (SW) continuum along the entire Gujarat coast was investigated for the first time through an extensive water monitoring survey. The prime focus of the study was to evaluate whether or not: i) seawater intrusion induced metal load translates to toxicity; ii) in the coastal groundwater, metal distribution follows the pattern of other geogenic and anthropogenic contaminants like NO₃- and F-; and iii) what future lies ahead pertaining to metal fate in association with saturation conditions of the coastal aquifers. The spatial distribution of contaminants depicts that the Gulf of Khambhat area is highly contaminated. Ecological risk assessment (ERA) indicates that the Gujarat coast is experiencing a high ecological risk compared to the southeast coast of India. Investigation results revealed that metals, pH, NO₃, and CO₃ are more vulnerable at the SW-GW mixing interface. An increase in pH is reflected in fewer ionic species of metals in the GW. Salinity ingress due to seawater intrusion (SWI) reduces the toxicities of all trace metals except Cu, attributed to the increase of Ca in GW, leading to dissociation of CuCO₃. Reactive species are dominant for Zn and Cd; and M-CO₃ ligands are dominant for Cu and Pb owing to the undersaturation of dolomite and calcite in the aquifer system. SWI tends to increase the metal load but the toxicity of metals varies with the density of industries, anthropogenic activities, changes in the mixing-induced saturation conditions, and intensive salt production across the coast. Multivariate analysis confirmed that the hydrogeochemical processes change due to GW-SW mixing and dictates over natural weathering. The ecological risk index (ERI) for the Arabian sea is experiencing moderate (300 ≥ ERI>150) to high ecological risk (ERI >600). Children population is likely to encounter a high health risk through ingestion and dermal exposure than adults. Overall, the study emphasizes the complexity of toxicity-related health impacts on coastal communities and suggests the dire need for frequent water monitoring along the coastal areas for quick realization of sustainable development goals.

Globally distributed karstic soils are characterized by the high accumulation of heavy metal(loid)s, such as Cd. Biogeochemistries and transferability of metal(loid)s in such soils are notably different from that in soils of anthropogenic pollution as evidenced by increasing studies about rice and maize. To solve the question about metal(loid) background and transferability in the system of karstic soils and crops with underground fruits, we designedly collected 246 paired soil–peanut seed samples in a world-famous karstic region in Southwestern China covering an area of 98,700 km². The concentrations of eight regulatory metal(loid)s (Cd, As, Cr, Cu, Hg, Ni, Pb, and Zn) in soil samples exceeded current standards to different degrees, demonstrating a typical high background. However, the transferability of metal(loid)s from soils to peanut seeds is quite low, resulting in a low exceedance rate of metal(loid)s (Cd, 12.2% and Pb, 1.2%) in seeds (“seed metal(loid)s”), in accordance with the results that metal(loid)s in soils mostly distributed in the inert/residual fractions. Based on the distinct response characteristics of peanut seed metal(loid)s to soil status from rice/maize grain metals, a model was further developed for effectively predicting the concentration of Cd in peanut seeds. Collectively, this study provides a basis for the assessment of soil environmental quality and safety zoning of upland field in karst areas.

To evaluate the chemical status of groundwater bodies (GWB) according to the European Groundwater Directive, EU Member States are required to take into account natural background levels (NBLs) where needed. Assessing the NBLs in coastal GWBs is complicated by seawater intrusion which can be amplified by groundwater withdrawals increasing the salinization of such groundwater systems. This paper proposes a new method for the NBLs assessment in coastal areas based on a double pre-selection (PS) with fixed/dynamic limits. A case study in the Apulia region, located in southeastern Italy, is proposed, where we investigated four adjacent GWBs which form the complex karst, fractured Murgia aquifer, hosted in the Jurassic-Cretaceous carbonate platform, bounded by two seas and sustained by saltwater of marine intrusion in the coastal areas. Data related to 139 monitoring stations (MSs) of the regional groundwater monitoring network were used. The first PS, “static”, based on a fixed limit of anthropogenic contamination markers (NO₃ and NH₄), allows for the elimination of MSs impacted by human activities. On these, the second PS, “dynamic”, based on the identification of Cl anomalous values, allows for the identification of additional MSs affected by saline contamination. The residual dataset of MSs was used for the definition of NBLs of Cl, SO₄, F and B. A statistical comparison with historical Cl observations finally allowed us to verify if the salinity of current groundwater is representative of pristine conditions. The calculated NBLs of salinity parameters are higher for the two coastal GWBs, with chloride values between 0.8 and 2 mg/L. Conversely, fluorides always show very low NBLs. The double PS approach seems more effective for NBLs calculation in coastal aquifers affected by saline contamination, where the use of a fixed Cl limit fails. It may respond to the international needs for a standardized procedure for NBL assessment.

During the last decades, the coastal areas of Morocco have witnessed an intense socioeconomic development associated with a continuous population growth and urban extension. This has led to an overexploitation of coastal aquifers leading to a degradation of their water quality. In order to obtain large scale overview on the quality status of Morocco's coastal aquifers (MCA) to assist national water managers to make informed decisions, a comprehensive scrutinization of the MCA against common indicators and using unified methods is essential. In this study, databases from thirteen MCA were analyzed, using multivariate statistical approaches and graphical methods in order to investigate the degree of mineralization in each aquifer and to identify the main salinization processes prevailing in groundwater. The results showed that the dominant groundwater types are Na–Cl, Ca–Mg–Cl, Ca–Mg–SO₄, Ca–Mg–HCO₃ and Ca–HCO₃–Cl. The Gibbs diagram and the seawater contribution (0–37%) indicate that the mineralization is mainly due to the seawater intrusion and water-rock interaction. The salinity degree diagram illustrates that almost all groundwater samples are located in the moderate to very saline zone, indicating that MCA are recharged by water from variable sources. The groundwater quality assessment shows a deterioration, particularly by seawater intrusion and significant nitrate pollution. The temporal evolution confirm that the MCA are influenced by seawater namely in the Atlantic part. The Wilcox and USSL diagram indicate that the majority of sampled water are unsuitable for irrigation uses. In addition, and by referring to the WHO and the Moroccan standards for water potability, large number of samples from the groundwaters of the MCA is not fully adequate for drinking purposes. A set of management actions (e,g., artificial recharge) are proposed in order to mitigate the effect of groundwater overexploitation and seawater intrusion to ensure the sustainability of MCA.

In many countries, including Morocco, groundwater contamination with pesticides such as globally banned organochlorides (e.g., dichlorodiphenyltrichloroethane (DDT)) and some accredited organophosphates and pyrethroids poses ecological and human health risks. To assess these risks, we herein monitored pesticides in Saïss plain groundwater (Morocco) during the summer of 2017 and the winter of 2018 using polar organic chemical integrative samplers. The two types of passive samplers were deployed in 22 traditional wells for 14–20 days and subjected to solid-phase extraction. The extracts were analyzed by gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry using a multiresidue method, and 27 pesticides were detected in total. In the summer campaign, 22 pesticides with individual concentrations ranging from <limit of quantitation (LOQ) to 243.1 ng L⁻¹ were identified, whereas 17 compounds with concentrations ranging from <LOQ to 53.8 ng L⁻¹ were detected in the winter campaign. In the summer period, the maximum individual concentrations of chlorothalonil, DDT, and α-hexachlorocyclohexane (α-HCH) equaled 111.7, 36.1, and 22.3 ng L⁻¹, respectively, with the respective values for the winter period equaling 18.14, 16.62, and 22.2 ng L⁻¹. Health risk assessment indicated that the carcinogenic α-HCH, β-HCH, DDT, and dichlorodiphenyldichloroethylene present in groundwater may also contaminate drinking water and thus pose a threat to human health, particularly to that of infants and children. Further analysis revealed that the Saïss aquifer presents a high ecological risk. Thus, the monitoring of pesticides in groundwater by passive sampling was effective and could be combined with human health and ecological risk assessment to develop ways of reducing human and environmental exposure to pesticides.

Groundwater contamination originating from anthropogenic industrial activities is a global concern, adversely impacting health of living organisms and affecting natural ecosystems. Monitoring contamination in a complex groundwater system is often limited by sparse data and poor hydrogeological delineation, so that numerous indicators (organic, inorganic, isotopic) are frequently used simultaneously to reduce uncertainty. We suggest that selected Technology-Critical Elements (TCEs), which are usually found in very low concentrations in the groundwater environment, might serve as contamination indicators that can be monitored through aquifer systems. Here, we demonstrate the use of selected TCEs (in particular, Y, Rh, Tl, Ga, and Ge) as indicators for monitoring anthropogenic groundwater contamination in two different groundwater systems, near the Dead Sea, Israel. Using these TCEs, we show that the sources of local groundwater contamination are phosphogypsum ponds located adjacent to fertilizer plants in two industrial areas. In addition, we monitored the spatial distribution of the contaminant plume to determine the extent of well and spring contamination in the region. Results show significant contamination of the groundwater beneath both fertilizer plants, leading to contamination of a series of wells and two natural springs. The water in these springs contains elevated concentrations of toxic metals; U and Tl levels, among others, are above the maximum concentration limits for drinking water.

Xanthan gels were assessed to control the reductive dechlorination of hexachlorocyclohexanes (HCHs) and trichlorobenzenes (TCBs) in a strong permeability contrast and high velocity sedimentary aquifer. An alkaline degradation was selected because of the low cost of NaOH and Ca(OH)₂. The rheology of alkaline xanthan gels and their ability to deliver alkalinity homogeneously, while maintaining the latter, were studied. Whereas the xanthan gels behaved like non-Newtonian shear-thinning fluids, alkalinity and Ca(OH)₂ microparticles had detrimental effects, yet, the latter decreased with the shear-rate. Breakthrough curves for the NaOH and Ca(OH)₂ in xanthan solutions, carried out in the lowest permeability soil (9.9 μm²), demonstrated the excellent transmission of alkalinity, while moderate pressure gradients were applied. Injection velocities ranging from 1.8 to 3.8 m h⁻¹ are anticipated in the field, given the permeability range from 9.9 to 848.7 μm². Despite a permeability contrast of 8.7 in an anisotropic aquifer model, the NaOH and the Ca(OH)₂ both in xanthan gels spread only 5- and 7-times faster in the higher permeability zone, demonstrating that the delivery was enhanced. Moreover, the alkaline gels which were injected into a high permeability layer under lateral water flow, showed a persistent blocking effect and longevity (timescale of weeks), in contrast to the alkaline solution in absence of xanthan. Kinetics of alkaline dechlorination carried out on the historically contaminated soil, using the Ca(OH)₂ suspension in xanthan solution, showed that HCHs were converted in TCBs by dehydrodechlorination, whereas the latter were then degraded by reductive hydrogenolysis. Degradation kinetics were achieved within 30 h for the major and most reactive fraction of HCHs.

Bacteria and archaea (prokaryotes) are vital components for maintaining healthy function of groundwater ecosystems. The prokaryotic community composition and associated putative functional processes were examined in a shallow sandy aquifer in a wet-dry tropical environment. The aquifer had a contaminated gradient of saline mine-water, which primarily consisted of elevated magnesium (Mg²⁺) and sulfate (SO₄²⁻), although other major ions and trace metals were also present. Groundwaters were sampled from piezometers, approximately 2 m in depth, located in the creek channel upstream and downstream of the mine-water influence. Sampling occurred during the dry-season when only subsurface water flow was present. Next generation sequencing was used to analyse the prokaryote assemblages using 16S rDNA and metabolic functions were predicted with FAPROTAX. Significant changes in community composition and functional processes were observed with exposure to mine-waters. Communities in the exposed sites had significantly lower relative abundance of methanotrophs such as Methylococcaceae and methanogens (Methanobacteriaceae), but higher abundance in Nitrososphaeraceae, associated with nitrification, indicating potentially important changes in the biogeochemistry of the exposed sites. The changes were most strongly correlated with concentrations of SO₄²⁻, Mg²⁺ and Na⁺. This knowledge allows an assessment of the risk of mine-water contamination to groundwater ecosystem function and aids mine-water management.

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.