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.

Large quantities of lead/zinc (Pb/Zn) mine tailings were deposited at tailings impoundments without proper management, which have posed considerable risks to the local ecosystem and residents in mining areas worldwide. Therefore, the geochemical behaviors of potentially toxic elements (PTEs) in tailings were in–depth investigated in this study by a coupled use of batch kinetic tests, statistical analysis and mineralogical characterization. The results indicated that among these studied PTEs, Cd concentration fluctuated within a wide range of 0.83–6.91 mg/kg, and showed the highest spatial heterogeneity. The mean Cd concentrations generally increased with depth. Cd were mainly partitioned in the exchangeable and carbonate fractions. The release potential of PTEs from tailings was ranged as: Cd > Mn > Zn > Pb > As, Cd > Pb > Zn > Mn > As and Cd > Pb > Mn > Zn > As, respectively, under the assumed environmental scenarios, i.e. acid rain, vegetation restoration, human gastrointestinal digestion. The results from mineralogical characterization indicated that quartz, sericite, calcite and pyrite were typical minerals, cumulatively accounting for over 80% of the tailings. Sulfides (arsenopyrite, galena, and sphalerite), carbonates (calcite, dolomite, cerussite and kutnahorite), oxides (limonite) were identified as the most relevant PTEs–bearing phases, which significantly contributed to PTEs release from tailings. A combined result of statistical, geochemical and mineralogical approaches would be provided valuable information for the alteration characteristics and contaminant release of Pb/Zn mine tailings.

The sulfate pollution in water environment gains more and more concerns in recent years. The discharge of domestic, municipal, and industrial wastewaters increases the riverine sulfate concentrations, which may cause local health and ecological problems. To better understand the sources of sulfate, this study collected water samples in a typical agricultural watershed in East Thailand. The source apportionment of sulfide was conducted by using stable isotopes and receptor models. The δ³⁴SSO₄ value of river water varied from 1.2‰ to 16.4‰, with a median value of 8.9‰. The hydrochemical data indicated that the chemical compositions of Mun river water were affected by the anthropogenic inputs and natural processes such as halite dissolution, carbonate, and silicate weathering. The positive matrix factorization (PMF) model was not suitable to trace source of riverine sulfate, because the meaning of the extracted factors seems to be vague. Based on the elemental ratio and isotopic composition, the inverse model yielded the relative contribution of sulfide oxidation (approximately 46.5%), anthropogenic input (approximately 41.5%), and gypsum dissolution (approximately 12%) to sulfate in Mun river water. This study indicates that the selection of models for source apportionment should be careful. The large contribution of anthropogenic inputs calls an urgent concern of the Thai government to establish effective management strategies in the Mun River basin.

Selenium (Se) radioactive wastes can be disposed through stabilization/solidification (S/S) based on the cementitious matrix on hydration products, where hydrocalumite (Ca₂Al-LDH) is expected to play an important role in the retention of SeO₄²⁻. Natural organic matters (NOMs) are known to be a risk to affect the transportation and mobility of undesirable chemical species in the pedosphere which receives the low level radioactive wastes (LLW). In the present work, five amino acids were selected as the simplified models of NOMs in the pedosphere to explore their effects on the stability of Ca₂Al-LDH after immobilized SeO₄²⁻ under alkaline conditions. As the loading amount of amino acids on Ca₂Al-LDH increasing, release of SeO₄²⁻ was enhanced in HGly, H₂Asp, and H₂Cys series, while no enhancement was observed in HPhe and HTrp series. Density functional theory (DFT) calculation predicted ion-exchange of amino acids and CO₃²⁻ with SeO₄²⁻ in a unit cell of LDH model. The intercalation of Asp²⁻ and CO₃²⁻ caused 003 peaks in XRD sharper and d₀₀₃ decreased from 8.15 Å to 7.70 Å which is assigned to Ca₂Al-LDH(Asp, CO₃). In H₂Cys series, the 003 peaks were kept broad and SeO₄²⁻ was still relatively maintained in LDH which was caused by the lower amounts of intercalated CO₃²⁻ in the presence of H₂Cys. Amino acids in the interlayer of Ca₂Al-LDH have several possible configurations, where the most stable one is prone to be in a horizontal direction through hydrogen bonds and Ca–O chemical bonds. This provides an insight on the stability of selenate immobilized in hydrocalumite, which can be produced in cement disposing in the pedosphere for a long term of burying. Not only carbonate but also small molecular organic matters like amino acids possibly give environmental impact on the mobility of low level anionic radionuclides in LDH.

The Lijiang River is of great ecological and environmental importance for Guilin City, which is located in the karst area of southeast China. Given its importance, a detailed evaluation of the heavy metals (HMs) in the river sediment is required. For the first time, 61 sediment samples were collected along the entire Lijiang River to determine pollution level and ecological risk posed by 10 HMs (Co, Cr, Cu, Mn, Ni, Pb, Zn, As, Hg, and Cd). These were assessed using the geo-accumulation index, potential ecological risk index, and modified degree of contamination. The results showed that the mean concentrations of the majority of HMs exceeded their corresponding background values and followed the trend: midstream > downstream > upstream. Based on the spatial distributions and pollution indices of the 10 HMs, the Lijiang River was found to have a high accumulation of Cd, Hg, Zn, and Pb in the sediments. The midstream area was the most polluted with respect to Cd and Hg, and also posed a relatively higher potential ecological risk than the downstream and upstream areas. The sources of the assessed HMs were inferred based on a correlation analysis and principal component analysis, which identified both natural and anthropogenic sources. A higher pollution potential was associated with Cd, Hg, Pb, and Zn in the midstream and downstream areas due to higher organic and carbonate content, urbanization, agricultural activities, and leisure activities (e.g., boating and cruises). In contrast, natural erosion and weathering processes were responsible for the HM concentrations in the upstream area. The findings of this study will help the local authorities to protect the important water resource of the Lijiang River.

Uranyl carbonate (UC(VI)) is a stable form of uranyl (U(VI)) that widely coexists with amorphous colloidal silica (ACSi) and humic acid (HA) in carbonate-rich U-contaminated areas. In this context, the cotransport behavior and mechanism of UC(VI) with ACSi (100 mg L⁻¹) and HA colloids in saturated porous media were systematically investigated. It was found that the ACSi and strip-shaped HA have a strong adsorption capacity for UC(VI), and their adsorption distribution coefficient (Kd) is 4–5 orders of magnitude higher than that of quartz sand (QS). In the ternary system, UC(VI) was mainly existing in the colloid-associated form at low UC(VI) concentration (4.2 × 10⁻⁶ M). Compared with the individual transport of UC(VI), the presence of ACSi and strip-shaped HA in the binary system promotes the transport of low-concentration UC(VI) (4.2 × 10⁻⁶ M) but shows a hindering effect when UC(VI) = 2.1 × 10⁻⁵ M. When ionic strength (IS) increased from 0 to 100 mM, the individual transport of UC(VI) and ACSi was weakened owing to the masking effect and the compression of the electrical double layer, respectively; this weakening effect is more pronounced in the binary (UC(VI)–ACSi) system. Notably, the transport of UC(VI) and ACSi in the ternary system is independent of the changes in IS due to the surface charge homogeneity strengthening the electrostatic repulsion between HA and QS. The Derjaguin–Landau–Verwey–Overbeek theory and retention profiles reveal the co-deposition mechanism of ACSi and UC(VI) in the column under different hydrochemical conditions. The nonequilibrium two-site model and the mathematical colloidal model successfully described the breakthrough data of UC(VI) and ACSi, respectively. These results are helpful for evaluating the pollution caused by UC(VI) migration in an environment rich in HA and formulating corresponding effective control strategies.

Periphyton plays a significant role in heavy metal transfer in wetlands, but its contribution to cadmium (Cd) bioavailability in paddy fields remains largely unexplored. The main aim of this study was to investigate the effect of periphyton on Cd behavior in paddy fields. Periphyton significantly decreased Cd concentrations in paddy waters. Non-invasive micro-test technology analyses indicated that periphyton can absorb Cd from water with a maximum Cd²⁺ influx rate of 394 pmol cm⁻² s⁻¹ and periphyton intrusion significantly increased soil Cd concentrations. However, soil Cd bioavailability declined significantly due to soil pH increase and soil redox potential (Eh) decrease induced by periphyton. With periphyton, more Cd was adsorbed and immobilized on organic matter, carbonates, and iron and manganese oxides in soil. Consequently, Cd content in rice decreased significantly. These findings give insights into Cd biogeochemistry in paddy fields with periphyton, and may provide a novel strategy for reducing Cd accumulation in rice.

This study describes the development of a sequential extraction procedure for the evaluation of metal nanoparticle mobility and bioaccessibility in soils. The procedure, that was developed using gold nanoparticles (AuNPs) as model species, relies on the fractionation of nanoparticles by sequentially dissolving soil matrix components (carbonates, metal oxides, organic matter and mineral phases) in order to release the entrapped nanoparticle species in the extract solution. By summing up the concentration of AuNPs recovered in each fraction it was found that 93.5% of the spiked AuNP concentration could be recovered which satisfactorily represents the nominal AuNP concentration in the soil. The efficiency of the procedure was found to depend on several procedural artifacts related to the separation of AuNPs from soil colloids and the reactivity of the extraction reagents with AuNPs and their precursor metal ions. Based on the results obtained a protocol for the speciation of the AuNPs and Au ions in the soil sample was also developed. The results of the study show that both AuNPs and Au ions are mainly associated with soil organic matter, which significantly reduces their mobility, while a small amount (<10%) is associated with metal oxides which are more mobile and potentially bioaccessible. The developed procedure provides a springboard for further development of sequential extraction procedures of metal nanoparticles in soils that could be used to assess both the exposure and release of metal nanoparticles and their precursor metal ions in the environment (as total extractable concentration) as well as provide evidence regarding their bioaccessibility and potential bioavailability by determining the concentration of nanoparticles in each specific soil fraction.

This study was initiated after the appearance of chlorotic and necrotic lesions on vegetation in the vicinity of a glassworks. The aim was to establish whether the cause was an uncontrolled release of gaseous fluorides. Five different plant species (Norway spruce, peach, common hornbeam, common bean, common grape vine) were collected in the influenced area, and the fluorine (F) content was determined by a fluoride ion selective electrode after prior total sample decomposition by alkaline carbonate fusion. The measurement results were reported together with their measurement uncertainties (MUs), which were evaluated according to the Guide to the Expression of Uncertainty in Measurement. The F contents at comparable distances from the emitter and in a clean area, free from natural or anthropogenic fluoride emissions, were 87–676 and 10 μg g⁻¹, respectively, thereby confirming the release of gaseous fluorides from the glassworks. The F contents in samples of Norway spruce taken at various radial distances from the emitter suggest that the emitted gaseous fluorides were spread about evenly in all directions from the source following an inverse-power function. Estimated distances at which the F content would decrease to 50 μg g⁻¹ (allowed maximum content of F in feeding stuffs) and 21 μg g⁻¹ (maximum fluoride content in vegetables and fruits in relation to the upper limit of fluoride intake for humans) were 378 m and 571 m, respectively, from the emitter. Evaluation of our results for compliance with specification revealed a lack of regulation on fluoride content in the diet of humans and animals as well as a lack of guidelines on how to take into account MU.

Abiotic reduction represents an attractive technology to control U(VI) contamination. In this work, an abiotic route of U(VI) reduction with humic acid at mineral surfaces is proposed and reaction mechanisms are addressed by periodic density functional theory calculations. Different influencing factors such as ligand effect, content of CO₃²⁻ ligands and substituent effect are inspected. The coordination chemistry of uranyl(VI) surface complexes relies strongly on substrates and ligands, and the calculated results are in good agreements with experimental observations available. For the OH⁻ ligand, two competitive mechanisms co-exist that respectively produce the U(IV) and U(V) species, and the former is significantly preferred because of lower energy barriers. Instead, the NO₃⁻ ligand leads to the formation of U(V) while for the Cl⁻ ligand, the U(VI) surface complex remains very stable and is not likely to be reduced because of very high energy barriers. The U(V) and U(IV) complexes are the predominant products for low and high CO₃²⁻ contents, respectively. Accordingly, the abiotic reduction processes with humic acid are efficient to manage U(VI) contamination and become preferred under basic conditions or at higher CO₃²⁻ contents. The U(VI) reduction is further promoted by introduction of electron-donating rather than electron-withdrawing substituents to humic acid. Electronic structure analyses and vibrational frequency assignments are calculated for the various uranium surface complexes of the reduction processes, serving as a guide for future experimental and engineered studies. The molecular-level understanding given in this work offers an abiotic route for efficient reduction of U(VI) and remediation of U(VI)-contaminated sites at ambient conditions.