In this study, we examined the removal of arsenite (As(III)) and arsenate (As(V)) by perilla leaf-derived biochars produced at 300 and 700 °C (referred as BC300 and BC700) in aqueous environments. Results revealed that the Langmuir isotherm model provided the best fit for As(III) and As(V) sorption, with the sorption affinity following the order: BC700-As(III) > BC700-As(V) > BC300-As(III) > BC300-As(V) (QL = 3.85–11.01 mg g⁻¹). In general, As removal decreased (76–60%) with increasing pH from 7 to 10 except for the BC700-As(III) system, where notably higher As removal (88–90%) occurred at pH from 7 to 9. Surface functional moieties contributed to As sequestration by the biochars examined here. However, significantly higher surface area and aromaticity of BC700 favored a greater As removal compared to BC300, suggesting that surface complexation/precipitation dominated As removal by BC700. Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy demonstrated that up to 64% of the added As(V) was reduced to As(III) in BC700- and BC300-As(V) sorption experiments, and in As(III) sorption experiments, partial oxidation of As(III) to As(V) occurred (37–39%). However, XANES spectroscopy was limited to precisely quantify As binding with sulfur species as As2S3-like phase. Both biochars efficiently removed As from natural As-contaminated groundwater (As: 23–190 μg L⁻¹; n = 12) despite in the presence of co-occurring anions (e.g., CO3²⁻, PO4³⁻, SO4²⁻) with the highest levels of As removal observed for BC700 (97–100%). Overall, this study highlights that perilla leaf biochars, notably BC700, possessed the greatest ability to remove As from solution and groundwater (drinking water). Significantly, the integrated spectroscopic techniques advanced our understanding to examine complex redox transformation of As(III)/As(V) with biochar, which are crucial to determine fate of As on biochar in aquatic environments.

The negative effect of carbonate on the rate and extent of bioreduction of aqueous U(VI) has been commonly reported. The solution pH is a key chemical factor controlling U(VI)ₐq species and the Gibbs free energy of reaction. Therefore, it is interesting to study whether the negative effect can be diminished under specific pH conditions. Experiments were conducted using Shewanella putrefaciens under anaerobic conditions with varying pH values (4–9) and bicarbonate concentrations ([CO32−]T, 0–50 mmol/L). The results showed a clear correlation between the pH-bioreduction edges of U(VI)ₐq and the [CO32−]T. The specific pH at which the maximum bioreduction occurred (pHₘbᵣ) shifted from slightly basic to acidic pH (∼7.5–∼6.0) as the [CO32−]T increased (2–50 mmol/L). At [CO32−]T = 0, however, no pHₘbᵣ was observed in terms of increasing bioreduction with pH (∼100%, pH > 7). In the presence of [CO32−]T, significant bioreduction was observed at pHₘbᵣ (∼100% at 2–30 mmol/L [CO32−]T, 93.7% at 50 mmol/L [CO32−]T), which is in contrast to the previously reported infeasibility of bioreduction at high [CO32−]T. The pH-bioreduction edges were almost comparable to the pH-biosorption edges of U(VI)ₐq on heat-killed cells, revealing that biosorption is favorable for bioreduction. The end product of U(VI)ₐq bioreduction was characterized as insoluble nanobiogenic uraninite by HRTEM. The redox potentials of the master complex species of U(VI)ₐq, such as (UO2)4(OH)7+, (UO2)2CO3(OH)3−, and UO2(CO3)34−, were calculated to obtain insights into the thermodynamic reduction mechanism. The observed dynamic role of pH in bioreduction suggests the potential for bioremediation of uranium-contaminated groundwater containing high carbonate concentrations.

Mining and metallurgy generate residues that may contain thallium (Tl), a highly toxic metal, for which it is currently not feasible to determine its geochemical speciation through X-ray absorption spectroscopy due to a combination of very low contents and the interference of accompanying high arsenic contents. Therefore, fractionation studies in residues and soils are required to analyze the mobility and bioavailability of this metal, which in turn provide information to infer its speciation. For this purpose, in this work a modification of the BCR procedure was applied to residues and contaminated soils from three mining zones of Mexico and two mining zones of Spain, spanning samples with acidic to alkaline pH values.The Tl extraction procedure consisted of the following fractions: (1) water-extractable, (2) easily exchangeable and associated to carbonates, associated to (3) poorly-crystalline and (4) crystalline Fe and Mn oxyhydroxides, and (5) associated to organic matter and sulfides; and finally a residual fraction as associated to refractory primary and other secondary minerals. The extracted contents were analyzed by Inductively-Coupled Plasma with Mass Spectrometry.Surprisingly, water-soluble, in Tl(I) oxidation state, was detected in most areas, regardless of the pH, a fact that has not been reported before in these environments, and alerts to potential health risks not previously identified. Most of the samples from a metallurgy area showed high levels of Tl in non-residual fractions and a strong correlation was obtained between extracted Mn and Tl in the third fraction, suggesting its association to poorly crystalline manganese oxides. In the majority of samples from purely mining environments, most of the Tl was found in the residual fraction, most probably bound to alumino-silicate minerals. The remaining Tl fractions were extracted mainly associated to the reducible mineral fractions, and in one case also in the oxidizable fraction (presumably associated to sulfides).Capsule: Soluble Tl(I) was found in all soil samples contaminated with either mining or metallurgical wastes. Additionally, in those affected by metallurgical wastes a very strong Tl-Mn correlation was found.

The sorption and desorption behaviour of samarium (Sm), an emerging contaminant, was examined in soil samples at varying Sm concentrations. The obtained sorption and desorption parameters revealed that soil possessed a high Sm retention capacity (sorption was higher than 99% and desorption lower than 2%) at low Sm concentrations, whereas at high Sm concentrations, the sorption-desorption behaviour varied among the soil samples tested. The fractionation of the Sm sorbed in soils, obtained by sequential extractions, allowed to suggest the soil properties (pH and organic matter solubility) and phases (organic matter, carbonates and clay minerals) governing the Sm-soil interaction. The sorption models constructed in the present work along with the sorption behaviour of Sm explained in terms of soil main characteristics will allow properly assessing the Sm-soil interaction depending on the contamination scenario under study. Moreover, the sorption and desorption Kd values of radiosamarium in soils were strongly correlated with those of stable Sm at low concentrations (r = 0.98); indicating that the mobility of Sm radioisotopes and, thus, the risk of radioactive Sm contamination can be predicted using data from low concentrations of stable Sm.

The main objectives of this study were to evaluate global uncertainty in the prediction of Distribution coefficients (Kds) for several Trace Metals (TM) (Cd, Cu, Pb, Zn) through the probabilistic use of a geochemical speciation model, and to conduct sensitivity analysis in speciation modeling in order to identify the main sources of uncertainty in Kd prediction. As a case study, data from the Loire river (France) were considered. The geochemical speciation model takes into account complexation of TM with inorganic ligands, sorption of TM with hydrous ferric oxides, complexation of TM with dissolved and particulate organic matter (i.e. dissolved and particulate humic acids and fulvic acids) and sorption and/or co-precipitation of TM to carbonates. Probability Density Functions (PDFs) were derived for physico-chemical conditions of the Loire river from a comprehensive collection of monitoring data. PDFs for model parameters were derived from literature review. Once all the parameters were assigned PDFs that describe natural variability and/or knowledge uncertainty, a stepwise structured sensitivity analysis (SA) was performed, by starting from computationally ‘inexpensive’ Morris method to most costly variance-based EFAST method. The most sensitive parameters on Kd predictions were thus ranked and their contribution to Kd variance was quantified. Uncertainty analysis was finally performed, allowing quantifying Kd ranges that can be expected when considering all the sensitive parameters together.

Metal contamination is a serious environmental concern in the Middle East. Herein, geochemical fractionation distribution and potential sources of thirteen metals (Fe, Al, Mn, Zn, Cu, Co, Cr, Ni, V, As, Hg, Pb and Cd) were investigated in sediments from ten coral reef Islands in the Persian Gulf, Iran. To properly assess availability and mobility of elements, enrichment factor (EF), pollution load index (PLI), pollution index (PI), contamination index (CI), sediment pollution index (SPI) and ecological risk assessment were provided. Sediment grain size showed an outstanding role in controlling the levels of potentially toxic inorganic elements (PTIEs). The highest values of total organic matter (TOM) were detected in Kharg and Lavan Islands. Different metals fractionation distribution was found across sites. As was noticed in carbonate (F2), exchangeable (F1), Fe-Mn oxy-hydroxide (F3), organic (F4) and residual (F5) fractions, Hg primarily associated with F2 and F1, whereas Pb and Cd with F2, followed by F1, F3, F5 and F4. Conversely, Ni and V accumulated in F1, suggesting their high mobility and bioavailability, and thus environmental risk to aquatic biota. All metals (except Al, Fe and As) had geological and anthropogenic sources. Based on modified risk assessment analysis, the sediments from Kharg, Lavan, Siri and Lark Islands showed medium adverse effects. Overall, results from this study corroborate that petroleum industry is the main source of pollution of PTIEs in the Persian Gulf, and offer a scientific basis for monitoring and preventing metal pollution in the environment.

MgO-based absorbent has been recognized as a promising CO₂ absorbent at intermediate temperature, though the carbonation performance of pure MgO is poor. Researchers have been devoted to optimize the CO₂ absorption ability via introducing alkali metal carbonates or nitrates. In this paper, the absorption performance of MgO-based absorbents promoted by alkali metal carbonates or modified by alkali metal nitrates has been summarized, and the affecting mechanism has been concluded. Alkali metal nitrates are essential for high absorption ability, and alkali metal carbonates facilitate high-temperature carbonation. Effects of fuel gas conditions and absorbent pelletization are also mentioned for practical applications. H₂O can accelerate the carbonation rate effectively, but the influencing mechanism of H₂O and the CO₂ absorption stability in presence of H₂O was not clearly reported. Further investigations on pelletized MgO-based absorbents modified by alkali metal salts considering regeneration conditions of high CO₂ concentration are proposed based on the recent research findings.

The dynamics of the aragonite saturation state (Ωarag) were investigated in the eutrophic coastal waters of Guanabara Bay (RJ-Brazil). Large phytoplankton blooms stimulated by a high nutrient enrichment promoted the production of organic matter with strong uptake of dissolved inorganic carbon (DIC) in surface waters, lowering the concentrations of dissolved carbon dioxide (CO2aq), and increasing the pH, Ωarag and carbonate ion (CO32−), especially during summer. The increase of Ωarag related to biological activity was also evident comparing the negative relationship between the Ωarag and the apparent utilization of oxygen (AOU), with a very close behavior between the slopes of the linear regression and the Redfield ratio. The lowest values of Ωarag were found at low-buffered waters in regions that receive direct discharges from domestic effluents and polluted rivers, with episodic evidences of corrosive waters (Ωarag<1). This study showed that the eutrophication controlled the variations of Ωarag in Guanabara Bay.

Spatial dynamics of heavy metals (Cd, Cu, Fe, Pb, and Zn) and metalloid As were investigated along the sedimentary column, inside and outside mangrove stands, and within the upper, middle, and lower Mangawhai Estuary, New Zealand. Organic matter contents (1.89 to 17.15%) were 10 times higher inside versus outside mangroves, and decreased sharply with depth to 30 cm. Cu, Fe, and Zn were highest in the upper estuary and Pb was highest close to a road (lower estuary), reflecting road run-off. A mangrove island (lower estuary; high energy) had lowest heavy metal and highest As concentrations (resulting from high absorption of As by the carbonate rich sediments). Most of the analysed sediment parameters in our study were higher inside versus outside mangroves, suggesting the accumulation of organic matter and build up capacity to buffer pollutants. Our results show that mangrove stands tend to accumulate heavy metals and may act as natural filters of pollution of coastal waterways.

Organic and elemental carbon were measured both in daily PM10 and PM2.5 and in 6 h range time PM2.5 samples collected from September 2015 to October 2015 in a coastal rural site near Brindisi in the Apulia region (Italy), in order to determine factors affecting the carbonaceous aerosol variations. Carbon content (total carbon TC) represented a considerable fraction for both PM10 and PM2.5. In particular, in PM10 samples, organic carbon (OC) varied from 1.06 to 18.32 μg m⁻³ with a mean concentration of 5 ± 4 μg m⁻³ and EC varied from 0.11 to 0.88 μg m⁻³ with a mean value of 0.41 ± 0.19 μg m⁻³. In PM2.5 samples, OC varied from 0.54 to 12.91 μg m⁻³ with a mean concentration of 3.5 ± 2.8 μg m⁻³ and EC varied from 0.11 to 0.85 μg m⁻³ with a mean value of 0.35 ± 0.18 μg m⁻³. The highest values for both parameters were recorded when the air masses were coming from NE Europe and when Saharan Dust events were recognized. The results show that OC and EC exhibited higher concentrations during the night hours, suggesting that stable atmosphere and lower mixing conditions play important roles for the accumulation of air pollutants and promote condensation or adsorption of semivolatile organic compounds. In samples from a Saharan Dust event and in samples with the lowest and the highest OCₛₑc, ATR-FTIR analysis allowed us to identify organic functional groups including the non-acid organic hydroxyl C–OH group (e.g., sugars, anhydrosugars, and polyols), carbonyl C=O group, carboxylic acid COOH group, aromatic and aliphatic unsaturated C=C–H group, aliphatic saturated C–C–H group, and amine NH₂ group. Some inorganic ions were also identified: carbonates, sulfate, silicate, and ammonium. The dusty samples are mainly characterized by the presence of carbonate and hydrogen sulfate ions and by kaolinite (absorption at 914 and 1010 cm⁻¹), while in samples with air masses coming from the NE, OC is mainly characterized by aliphatic and aromatic C–H and O–H and N–H groups (absorptions in the range 3500–2700 cm⁻¹) and by the presence of organonitrate, aromatic amide and amine, and carboxylic acids (absorptions at 1630 and 1770–1700 cm⁻¹). Graphical abstract ᅟ