Microplastics (MPs) are becoming an environmental growing concern, being the sewage sludge applied to agriculture fields one of the most important inputs to the environment. To date, there is no standardized protocol for their extraction and changes in vegetative growth and fruit maturation on cultivated plants induced by sludge containing MPs have not been studied yet. Sewage sludge from three different wastewater treatment plants located in Murcia, Spain, were studied. First, the microplastic concentration was estimated and, then, the effects of the sewage sludge in the development of tomato plants and fruit production was analyzed. The measured parameters in tomato plants were both, biomass and length, for shoot and root part, as well as, stem diameter and tomato production. The present work has developed and validated a protocol for the extraction and quantification of MPs comprising several shapes, materials and sizes from samples of sewage sludges, which offers a good compromise for the extraction of different types of microplastic. The protocol used for MPs extraction had a recovery efficiency of 80 ± 3% (mean ± SE) and used bicarbonate, to maximize MPs extraction. The mean abundance of MPs in the studied sewage sludge samples was 30,940 ± 8589 particles kg⁻¹ dry weight. Soils with sludge containing MPs fostered the growth of tomato plants, while delaying and diminished fruit production. However, other factors or their interactions with MPs could have influenced the outcomes. Further studies are necessary to corroborate these findings and explain the mechanisms of possible effects of MPs on plants.

Hydrogeochemistry and isotope hydrology were carried out to investigate the spatial distribution of fluoride (F−) and the mechanisms responsible for its enrichment in the western region of the Ordos basin, northwestern China. Sixty-two groundwater samples from the unconfined aquifer and fifty-six from confined aquifer were collected during the pre-monsoon (June 2016). Over 77% of groundwater samples from the unconfined aquifer (F− concentration up to 13.30 mg/L) and approximately 66% from confined aquifer (with a maximum F− concentration of 3.90 mg/L) exhibit F− concentrations higher than the Chinese safe drinking limit (1.0 mg/L). High-F− groundwater presents a distinctive hydrochemical characteristic: a high pH value and HCO3− concentration with Ca-poor and Na-rich. Mineral dissolution (e.g., feldspar, calcite, dolomite, fluorite), cation exchange and evaporation in the aquifers predominate the formation of groundwater chemistry, which are also important for F− enrichment in groundwater. Mixing with unconfined groundwater is a significant mechanism resulting in the occurrence of high-F− groundwater in confined aquifer. These findings indicate that physicochemical processes play crucial roles in driving F− enrichment and that may be useful for studying F− occurrence in groundwater in arid and semi-arid areas.

To investigate the removal characteristics of ammonium-nitrogen (NH₄⁺-N), nitrite-nitrogen (NO₂⁻-N), nitrate-nitrogen (NO₃⁻-N), and total nitrogen from groundwater by a degradable composite active medium, kinetics, thermodynamics, and equilibrium adsorption, experiments were performed using scoria and degrading bacteria immobilized on scoria. Removal of NH₄⁺-N, NO₂⁻-N, and NO₃⁻-N was conducted in adsorption experiments using different times, initial concentrations, pH values, and groundwater chemical compositions (Ca²⁺, Mg²⁺, HCO₃⁻, CO₃²⁻, Fe²⁺, Mn²⁺, and SO₄²⁻). The results showed that the removal of nitrogen by the composite active medium was obviously better than that of scoria alone. The removal rates of NH₄⁺-N (C₀ = 5 mg/L), NO₂⁻-N (C₀ = 5 mg/L), and NO₃⁻-N (C₀ = 100 mg/L) by the composite active medium within 1 h were 96.05%, 82.40%, and 83.16%, respectively. The adsorption kinetics were well fitted to a pseudo-second order model, whereas the equilibrium adsorption agreed with the Freundlich model. With changes in the pH, variation in the removal could be attributed to the combined effect of hydrolysis and competitive ion adsorption, and the optimum pH was 7. Different concentration conditions, hardness, alkalinity, anions, and cations showed different promoting and inhibiting effects on the removal of nitrogen. A careful examination of ionic concentrations in adsorption batch experiments suggested that the sorption behavior of nitrogen onto the immobilized medium was mainly controlled by ion exchange. The degrading bacteria on the scoria surface were eluted and analyzed by metagenomic sequencing. There were significant differences in the number of operational taxons, relative abundances, and community diversity among degrading bacteria after adsorption of the three forms of nitrogen. The relative abundance of degrading bacteria was highest after NO₃⁻-N removal, and the diversity was highest after NO₂⁻-N removal. Pseudomonas and Serratia were the dominant genera that could efficiently remove NH₄⁺-N and NO₂⁻-N.

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.

To explore the effect of elevated CO₂ concentrations ([CO₂]) on phosphine formation in paddy fields, the matrix-bound phosphine (MBP) content, different phosphorus fractions and various carbon forms in soil samples from rice cultivation under varying CO₂ concentrations of 400 ppm, 550 ppm and 700 ppm by indoor simulation experiment were determined. This study showed that MBP concentration did not increase significantly with elevated [CO₂] over four-week cultivation periods of rice seedlings, regardless of soil layers. MBP had a significant positive correlation with total phosphorus (TP) and inorganic phosphorus (IP), and multiple stepwise linear regression analysis further indicated that MBP preservation in neutral paddy soils with depths of 0–20 cm may have been due to conversion from FeP and CaP. Based on redundancy analysis and forward selection analysis, speculated that the formation of MBP in the neutral paddy soils as the response to atmospheric elevated [CO₂] was due to two processes: (i) FeP transformation affected by the changes of soil respiration (SCO₂) and TOC was the main precursor for the production of MBP; and (ii) CaP transformation resulting from variation in HCO₃⁻ was the secondary MBP source. The complex combination of these two processes is simultaneously controlled by SCO₂. In a word, the soil environment in the condition of elevated [CO₂] was in favor of MBP storage in neutral paddy soils. The results of our study imply that atmospheric CO₂ participates in and has a certain impact on the global biogeochemical cycle of phosphorus.

We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L−1) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L−1) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L−1) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

Appalachian surface coal mine overburden affects water quality as drainage percolates through spoil disposal fills. This study evaluated leaching potentials of 15 spoils from south-central Appalachia. Most bulk samples were non acid-forming, all were low in total-S, (≤0.34%), and initial saturated paste specific conductance (SC) ranged from 264 to 3560 μS cm−1. Samples were leached unsaturated (40 cycles) and leachates analyzed for pH, SC, and ion composition. Overall, leachates from unweathered spoils were higher in pH and SC than leachates from weathered spoils. Fine-textured spoils generally produced higher SCs than more coarsely textured spoils. Mean SC for all spoils decreased rapidly from an initial peak of 1468 μS cm−1 (±150) to 247 μS cm−1 (±23). Release patterns for most major ions reflected declining SC. Bicarbonate typically increased with successive leaches, replacing sulfate as the dominant anion. Column SC values were comparable to relevant published field data.

Synergistic effects of ozone (O₃) and peroxymonosulfate (PMS, HSO₅⁻) for isothiazolinone biocides degradation was studied. The synergistic ozonation process (O₃/PMS) increased the efficiency of methyl-isothiazolinone (MIT) and chloro-methyl-isothiazolinone (CMIT) degradation to 91.0% and 81.8%, respectively, within 90 s at pH 7.0. This is 30.6% and 62.5% higher than the corresponding ozonation efficiency, respectively. Total radical formation value (Rcₜ,R) for the O₃/PMS process was 24.6 times that of ozonation alone. Calculated second-order rate constants for the reactions between isothiazolinone biocides and ▪ (kSO₄₋,MIT and kSO₄₋,CMIT) were 8.15 × 10⁹ and 4.49 × 10⁹ M⁻¹ s⁻¹, respectively. Relative contributions of O₃, hydroxyl radical (OH) and ▪ oxidation to MIT and CMIT removal were estimated, which were 15%, 45%, and 40% for O₃, OH and ▪ oxidation to MIT, and 1%, 67%, and 32% for O₃, OH and ▪ oxidation to CMIT at pH 7.0, respectively. Factors influencing the O₃/PMS process, namely the solution pH, chloride ions (Cl⁻), and bicarbonate (HCO₃⁻), were evaluated. Increasing the solution pH markedly accelerated O₃ decay and OH and ▪ formation, thus weakening the relative contribution of O₃ oxidation while enhancing that of OH and ▪. Cl⁻ had a negligible effect on MIT and CMIT degradation. Under the dual effect of bicarbonate (HCO₃⁻) as inhibitor and promoter, low concentrations (1–2 mM) of bicarbonate weakly promoted MIT and CMIT degradation, while high concentrations (10–20 mM) induced strong inhibition. Lastly, oxidation performance of O₃ and O₃/PMS processes for MIT and CMIT degradation in different water matrices was compared.

Copper ferrite (denoted as CuFe₂O₄MOF), prepared via a complexation reaction to obtain bimetal–organic frameworks (Cu/Fe bi-MOFs), followed by a combustion process to remove the MOF template, is employed as a heterogeneous activator to promote sulfite autoxidation for the removal of organic contaminants. At pH 8.0, more than 80% of the recalcitrant organic contaminant iohexol (10 μM) can be removed within 2 min by the activation of sulfite (500 μM) with CuFe₂O₄MOF (0.1 g L⁻¹). CuFe₂O₄MOF exhibits more pronounced catalytic activity in accelerating sulfite autoxidation for iohexol abatement compared to that fabricated by hydrothermal and sol–gel combustion methods. Radical quenching studies suggest that the sulfate radical (SO₄•⁻) is the main reactive species responsible for iohexol abatement. The performance of CuFe₂O₄MOF/sulfite for iohexol abatement can be affected by several critical influencing factors, including the solution pH and the presence of humic acid, Cl⁻, and HCO₃⁻. The effect of the ionic strength and the results of the attenuated total reflectance–Fourier transform infrared (ATR–FTIR) analysis indicate that sulfite autoxidation in the presence of CuFe₂O₄MOF involves an inner-sphere interaction with the surface Cu(II) sites of CuFe₂O₄MOF. X-ray photoelectron spectroscopy (XPS) characterization suggests that the surface Cu(II)–Cu(I)–Cu(II) redox cycle is responsible for efficient SO₄•⁻ production from sulfite. Overall, CuFe₂O₄MOF can be considered an alternative activator for sulfite autoxidation for potential application in the treatment of organic-contaminated water.

The extent of per- and polyfluoroalkyl substances (PFAS) in groundwater surrounding legacy landfills is currently poorly constrained. Seventeen PFAS were analysed in groundwater surrounding legacy landfills in a major Australian urban re-development precinct. Sampling locations (n = 13) included sites installed directly in waste material and down-gradient from landfills, some of which exhibited evidence of leachate contamination including elevated concentrations of ammonia-N (≤106 mg/L), bicarbonate (≤1,740 mg/L) and dissolved methane (≤10.4 mg/L). Between one and fourteen PFAS were detected at all sites and PFOS, PFHxS, PFOA and PFBS were detected in all samples. The sum of detected PFAS (∑₁₄PFAS) varied from 26 ng/L at an ambient background site to 5,200 ng/L near a potential industrial point-source. PFHxS had the highest median concentration (34 ng/L; range: 2.6–280 ng/L) followed by PFOS (26 ng/L; range: 1.3–4,800 ng/L), PFHxA (19 ng/L; range: <LOQ – 46 ng/L) and PFOA (12 ng/L; range: 1.7–74 ng/L). Positive correlations between ∑₁₄PFAS, PFOA and other perfluoroalkyl carboxylic acids (PFCAs) (e.g. PFHxA) with typical leachate indicators including ammonia-N and bicarbonate were observed. In contrast, no such correlations were found with perfluoroalkyl sulfonic acids (PFSAs) (e.g., PFOS and PFHxS). In addition, a strong positive linear correlation (R² = 0.69) was found between the proportion of PFOA in the sum of detected perfluorinated alkylated acids (PFOA/∑PFAA) and ammonia-N concentrations in groundwater. This is consistent with previous research showing relatively high PFOA/∑PFAA in municipal landfill leachates, and more conservative behaviour (e.g. less sorption and reactivity) of PFCAs during subsurface transport compared to PFSAs. PFOA/∑PFAA in groundwater may therefore be a useful indicator of municipal landfill-derived PFAA. One site with significantly elevated PFOS and PFHxS concentrations (4,800 and 280 ng/L, respectively) appears to be affected by point-source industrial contamination, as landfill leachate indicators were absent.