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.

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.

Many estuaries have undergone severe saltwater intrusion in addition to simultaneously experiencing serious heavy metal pollution. To explore the effect of water density stratification associated with saltwater intrusion on the behaviour of heavy metals (Cr, Co, Ni, Cu, Zn, As, Pb, and Cd) in water and sediments, a field survey was conducted in a typical estuary (Modaomen). The content, distribution, and mobility of heavy metals were investigated, as well as the influence of environmental factors on their future. The results showed that Modaomen estuary was characterised by a notable variation in salinity along the estuary, presenting total freshwater upstream, high salinity stratification water in the mouth, and saltwater offshore. Dissolved metals presented a prominent gradient vertically, with 1.2–2.1 times higher in bottom water than in surface water and the highest contents in the highly–stratified bottom water. Elevated salinity and restricted mixing induced by water stratification were likely the causes of this outcome. The distribution of heavy metals in sediments was greatly governed by grain size, Fe/Mn (hydr)oxides, total organic carbon, salinity, and dissolved oxygen. Comprehensive evaluation, combined with total contents and chemical fractions of heavy metals, indicated that internal release from sediments contributed a considerable part to the higher levels of heavy metals in bottom water, particularly for Zn and Pb, which was fully consistent with their status in water body, and elevated salinity and lack of oxygen were likely the primary driving factors. During the phase-partition processes between bottom water and sediments, partitioning coefficients were markedly lower in the highly stratified zone, implying that saltwater intrusion facilitated the mobility and repartitioning processes of metals. Because of increased levels and toxicity of heavy metals in water and extended residence time during saltwater intrusion, the potential damage to the estuarine ecosystem should receive more attention.

Ecological risk assessment associated with seawater intrusions has been supported on the determination of lethal/sublethal effects following standard protocols that force exposure neglecting the ability of mobile organisms to spatially avoid salinized environments. Thus, this work aimed at assessing active emigration from climate change-caused seawater intrusion into freshwater habitats. To specific objectives were delineated: first, to compute median 12-h avoidance conductivities (AC₅₀,₁₂ₕ) for freshwater species, and second, to compare it with literature data (LC₅₀,₄₈ ₒᵣ ₉₆ₕ, EC₅₀,₆ ₒᵣ ₂₁d) to assess the relevance of the inclusion of stressor-driven emigration into risk assessment frameworks. Four standard test species, representing a broad range of ecological niches – Daphnia magna, Heterocypris incongruens, Danio rerio and Xenopus laevis – were selected. The salt NaCl was used as a surrogate of natural seawater to create the saline gradient, which was established in a 7-compartment system.At each specific LC₅₀, ₄₈ ₒᵣ ₉₆ₕ, the proportion of avoiders were well above 50%, ranging from 71 to 94%. At each LC₅₀, considering also avoiders, populations would decline by 85–97%. Furthermore, for D. magna and X. laevis it was noticed that at the lowest conductivities eliciting mortality, the avoidance already exceeded 50%.The results showed that the emigration from salinity-disturbed habitats exists and that can even be more sensitive than standard endpoints. Looking solely to standard endpoints involving forced exposure may greatly underestimate the risk of local population extinction, because habitat function can be severely disrupted, with subsequent stressor-driven emigration, before any adverse physiological effects at the organism level. Thus, the present study highlights the need to include non-forced exposure testing into ecological risk assessment, namely of salinity-menaced costal freshwaters.

Elevated inorganic arsenic concentrations in groundwater has become a major public and environmental health concern in different parts of the world. Currently, As-contaminated groundwater issue in many countries and regions is a major topic for publications at global level. However, there are many regions worldwide where the problem has still not been resolved or fully understood due to inadequate hydrogeochemical investigations. Hence, this study evaluates for the first time the hydrogeochemical behavior of the arid and previously unexplored inland basin of Sirjan Plain, south east (SE) Iran, in order to assess the controlling factors which influence arsenic (As) mobility and its distribution through groundwater resources. Total inorganic arsenic concentration was measured using inductive-coupled plasma optical emission spectrometry (ICP-OES). Arsenic content in groundwater of this region ranged between 2.4 and 545.8 μg/L (mean value: 86.6 μg/L) and 50% of the samples exceeded the World Health Organization (WHO) guideline value of 10 μg/L in drinking water. Groundwater was mainly of Na-Cl type and alkaline due to silicate weathering, ion exchange and evaporation in arid conditions. Elevated As concentrations were generally observed under weakly alkaline to alkaline conditions (pH > 7.4). Multivariate statistical analysis including cluster analysis and bi-plot grouped As with pH and HCO3 and demonstrated that the secondary minerals including oxyhydroxides of Fe are the main source of As in groundwater in this region. The desorption of As from these mineral phases occurs under alkaline conditions in oxidizing arid environments thereby leading to high levels of As in groundwater. Moreover, evaporation, ion exchange and saltwater intrusion were the secondary processes accelerating As release and its mobility in groundwater. Based on the results of this study, desorption of As from metal oxy-hydroxides surfaces under alkaline conditions, evaporation and intrusion of As-rich saline water are considered to be the major factors causing As enrichment in arid inland basins such as those in southeast Iran. This study proposes the regular monitoring and proper groundwater management practices to mitigate high levels of arsenic in groundwater and related drinking water wells of Sirjan Plain.

The Bohai Sea is a shallow-water, semi-enclosed marginal sea of the Northwest Pacific. Since the late 1990s, it has suffered from nutrient over-enrichment. To better understand the eutrophication characteristics of this important coastal sea, we examined four survey datasets from summer (June 2011), late autumn (November 2011), winter (January 2016), and early spring (April 2018). Nutrient conditions in the Bohai Sea were subject to seasonal and regional variations. Survey-averaged N/P ratios in estuarine and nearshore areas were 20–133. In contrast, the central Bohai Sea had mean N/P ratios of 16.9 ± 3.4 in late autumn, 16.1 ± 3.0 in winter and 13.5 ± 5.8 in early spring, which are close to the traditional N:P Redfield ratio of 16. In summer, both dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphate (DIP) were used up in the surface waters of the central Bohai Sea, suggesting that the biological consumption of DIN and DIP may also follow the Redfield ratio. Wintertime nutrient budgets of the central Bohai Sea water were then established based on a mass balance study. Our results suggest that the adjacent North Yellow Sea supplied additional DIP to the central Bohai Sea via wintertime water intrusion, balancing terrigenous excess DIN that was introduced in summer. A water-mixing simulation combining these two nutrient sources with atmospheric nitrogen deposition suggests that eutrophication in the central Bohai Sea will likely be enhanced by the large-scale accumulation of anthropogenic nitrogen in adjacent open oceans. Such changes in nutrients may have fundamentally contributed to the recent development of algal blooms and seasonal hypoxia in the central Bohai Sea.

Fifty-six groundwater samples were taken from the island of Favignana to evaluate the interaction between the groundwater and seawater, as well as the deterioration factors for the aquifers, using the combined hydrogeochemical and multivariate statistical approaches. Results show that the order of the groundwater chemistry in the study area was Na+> Ca2+>Mg2+>K+ and Cl->HCO3−>SO42->NO3−. The groundwater samples were in the moderate saline zone to highly saline zone and indicate that the groundwater of the island of Favignana was recharged with seawater. The spatial distribution maps of Cl− and NO3− show that most of the groundwater samples had high concentrations of Cl− and NO3− in the study area. The ionic ratio diagrams, such as Na+/Cl− versus Cl−, Mg2+/Ca2+ versus Cl− and Ca2+/HCO3− versus Cl−, and other hydrogeochemical plots reveal that the groundwater chemistry of the study was primarily controlled by the seawater intrusion and reverse ion exchange process, with a small contribution from carbonate dissolution. Additionally, the NO3−/Cl− versus Cl− diagram and principal component analysis (PCA) show that the contamination of nitrate in the study area was due to human activities (i.e. agriculture and domestic sewage disposal). The outcome of the present research could be helpful for groundwater resource management in coastal environments.

The Red River Delta is a major agricultural production area of Vietnam with year-round use of pesticides for paddy rice cultivation and other production systems. The delta is protected from flooding, storm surges and saline water intrusion by a sophisticated river and sea-dyke system. Little is known about the effects of such a dyke system on pesticide pollution in the enclosed landscape. Our aim was to address this gap by i) determining pesticide prevalence in soils and sediments within a dyked agricultural area, and by ii) assessing whether and to which degree this dyke system might affect the spatial distribution of pesticides. After sampling paddy rice fields (topsoil) and irrigation ditches (sediment) perpendicular to the dyke in Giao Thuy district, we analysed 12 of the most commonly used pesticides in this area. In soils, we detected most frequently isoprothiolane (100% detection frequency), chlorpyrifos (85%) and propiconazole (41%) while in sediments isoprothiolane (71%) and propiconazole (71%) were most frequently found. Maximum concentrations reached 42.6 μg isoprotiolane kg⁻¹ in soil, and 35.1 μg azoxystrobin kg⁻¹ in sediment. Our results supported the assumption that the dyke system influenced residue distribution of selected pesticides. More polar substances increasingly accumulated in fields closer to the sea-dyke (R² = 0.92 for chlorpyrifos and 0.51 for isoprothiolane). We can thus support initiatives from local authorities to use the distance to dykes as a mean for deliniating zones of different environmental pollution; yet, the degree at which dykes influence pesticide accumulation appear to be compound specific.

Estimated natural background levels (NBLs) are needed to assess groundwater chemical status according to the EU Groundwater Directive. They are commonly derived for different substances by applying statistical methodologies. Due to the complexity of the sea water intrusion process, some of those methods do not always provide appropriate assessment of chloride NBLs. This paper analyzes the applicability of different NBL estimation methods in five EU coastal aquifers with significant differences in available datasets and hydrogeological settings. A sensitivity analysis of results to different constraints was performed to remove samples with anthropogenic impacts. A novel statistical approach combining different methods to identify the range of chloride NBLs is proposed. In all pilots the estimated NBLs were below 85 mg/L and fitted well with previous studies and expert judgment, except Campina del Faro aquifer (the maximum being 167.5 mg/L). Although this approach is more time consuming, it provides a more robust solution.