This work investigates the absorption properties of soluble brown carbon (BrC), extracted in methanol and water, from ambient aerosol (PM₁₀) samples, collected over an urban background site in Mumbai, India. The diurnal variability was investigated in samples collected in the morning (7–11 a.m.) and afternoon (12–4 p.m.) periods. Absorption properties of BrC (in the 300–600-nm wavelength range) were measured in filter extracts of water-soluble organic carbon (WSOC) and methanol-soluble organic carbon (MSOC). WSOC and MSOC accounted for on average 52% and 77%, respectively, of the measured OC, potentially indicating unextracted BrC and rendering these values the lower bound. Compared with afternoon samples, the morning samples of MSOC and WSOC had increased BrC concentrations and absorption coefficients (bₐbₛ365; 40%–65%). The correlation between bₐbₛ365 and EC, ns-K⁺, and NO₃⁻ in the morning samples indicated contributions from primary sources, including both biomass and vehicular sources. The decreased bₐbₛ365 in the afternoon samples was partly explained by mixing layer dilution, accompanied by a reduction in the concentrations of primary aerosol constituents. Furthermore, in the afternoon samples, ¹HNMR spectroscopy revealed the presence of more oxidized functional groups and significantly higher OC/EC and WSOC/OC ratios, indicating the greater aging of afternoon aerosol. The MAC₃₆₅ (m²gC⁻¹) for both WSOC and MSOC extracts decreased significantly by 20%–34% in the afternoon samples compared with the morning samples, indicating degradation in the absorption properties of the particles and potentially a change in the constituent BrC chromophores.

The binding of metal ions with humic acid (HA) plays an important role in the aggregation of HA and the migration of metal ions in the environments. The effects of common cations (Na⁺, Mg²⁺, Ca²⁺ and Al³⁺) and heavy metal ions (Ag⁺, Cd²⁺, Cu²⁺, Cr³⁺ and Eu³⁺) on the aggregation of HA were investigated systematically by aggregation kinetics, spectroscopic techniques and molecular dynamic (MD) simulations. The critical coagulation concentration (CCC) of mono-, di- and trivalent cations could be predicted by the Schulze-Hardy rule. The aggregation of HA in the presence of Na⁺ and Ag⁺ was mainly due to the reduction of repulsive force and the hydrogen bonds between HA molecules. While the complexation of di- and trivalent cations with carboxylic/phenolic groups, or the cation-π interactions enhanced the intra- or inter-molecular bridges in HA and then contributed greatly to the aggregation of HA. Heavy metal ions could easily pass through the electric double-layer of HA compared with common cations. MD simulations further signified the strong aggregation ability of HA molecules in solutions containing high valence metal ions. These findings are important for understanding not only how the influence of metal ions on the aggregation of HA, but also the conditions which ions more efficient for aggregation.

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.

Dissolved organic carbon (DOC) has a major influence upon sorption/desorption and transport of hydrophobic organic contaminants (HOCs) in soil environments. However, the molecular mechanisms of DOC sorption and its effects on aged HOC desorption in contaminated soils still remain largely unclear. Here, effects of three different DOC (one from commercial peat and two from biochars produced at 300 °C and 500 °C pyrolysis temperatures, respectively) and oxalate (as a reference) on abiotic desorption behavior of aged phenanthrene from three agricultural soils were investigated. Results showed that desorption of aged phenanthrene from soils was predominantly dependent on soil organic carbon content. The presence of DOC and oxalate resulted in higher desorption of phenanthrene compared to water alone, and the effects were positively related to soil organic carbon content and DOC/oxalate concentration. The facilitating effects of DOC were further increased during the second consecutive desorption, whereas oxalate had no such effect. Ultra-high-resolution Fourier transform-ion cyclotron resonance-mass spectrometry confirmed the molecular fractionation of DOC at the soil-water interface during DOC sorption. Specifically, the DOC molecules with O-rich moieties were preferentially adsorbed, whereas the molecules with phenolic and aromatic structures were selectively retained in the soil solutions through competitive displacement and co-sorption reactions during sorption. The enriched phenyl structures in the retained DOC facilitated its association with phenanthrene in the solutions and thus the release of phenanthrene from the soils. In contrast, oxalate replaced some organic carbon from the soils and thus released the associated phenanthrene into the solutions. Our findings highlight the importance of the molecular composition and structure of DOC for the desorption of phenanthrene in soil-water environments, which may help improve our understanding of the release and transport of organic compounds in the environments.

Removal of toxic formaldehyde from environmental waters is crucial to maintain ecosystem sustainability and human health. In this work, MIL-100(Fe) as a heterogeneous Fenton-like photocatalyst was used for the treatment of formaldehyde-contaminated water. The MIL-100(Fe) was synthesized via a facile solvothermal method and fully characterized using different spectroscopic and microscopic techniques. Based on the results, the formation of highly porous, crystalline, and stable visible light-responsive MIL-100(Fe) was confirmed. The Fenton-like photocatalytic efficiency of the MIL-100(Fe) toward the degradation of formaldehyde was then studied under visible light irradiation. For this purpose, the effect of initial concentration of formaldehyde, photocatalyst dose, H₂O₂ concentration, solution pH, and contact time on the removal efficiency of the MIL-100(Fe) was investigated using central composite design. The obtained results showed that the removal efficiency of the MIL-100(Fe) is significantly affected by the initial concentration of formaldehyde. A second-order model with R² = 0.93 was developed for the system that was able to adequately predict the percentage removal of formaldehyde by the MIL-100(Fe) under different experimental conditions. According to the numerical optimization results, by using 1.13 g L⁻¹ photocatalyst and 0.055 mol L⁻¹ H₂O₂, 93% of formaldehyde can be removed after 119 min from an aqueous solution containing 700 mg L⁻¹ of formaldehyde at pH 6.54.

Microplastic (MP) has become ubiquitous in the marine environment. Its threat to marine organisms has been demonstrated under laboratory conditions, yet studies on wild populations still face methodological difficulties. We reviewed the methods used to separate MP from soft animal tissues and highlighted a lack of standardised methodologies, particularly critical for synthetic microfibres. We further compared enzymatic and a potassium hydroxide (KOH)-based alkaline digestion protocols on wild crabs (Carcinus aestuarii) collected from three coastal lagoons in the north Adriatic Sea and on laboratory-prepared synthetic polyester (PES) of different colour and polypropylene (PP). We compared the cost-effectiveness of the two methods, together with the potential for adverse quantitative or qualitative effects on MP that could alter the capability of the polymers to be recognised via microscopic or spectroscopic techniques. Only 5.5% of the 180 examined crabs contained MP in their gastrointestinal tracts, with a notably high quantitative variability between individuals (from 1 to 117 particles per individual). All MP found was exclusively microfibres, mainly PES, with a mean length (±SE) of 0.5 ± 0.03 mm. The two digestion methods provided comparable estimates on wild crabs and did not cause any visible physical or chemical alterations on laboratory-prepared microfibres treated for up to 4 days. KOH solution was faster and cheaper compared to the enzymatic extraction, involving fewer procedural steps and therefore reducing the risk of airborne contamination. With digestion times longer than 4 days, KOH caused morphological alterations of some of the PES microfibres, which did not occur with the enzymatic digestion. This suggests that KOH is effective for the digestion of small marine invertebrates or biological samples for which shorter digestion time is required, while enzymatic extraction should be considered as alternative for larger organisms or sample sizes requiring longer digestion times.

Birnessites are abundant naturally occurring minerals with high sorption and oxidation capacity that could therefore play an important role in antimony (Sb) migration and transformation. There are various types of birnessites in the environment. However, little is known about the similarities and differences in Sb oxidation and sorption on birnessites with different properties. In this study, the behavior of Sb oxidation and sorption on two contrasting birnessites (δ-MnO₂ and triclinic birnessite (TrBir)) were investigated via batch and kinetic experiments and various spectroscopic techniques. Our results showed that the reaction mechanisms between Sb and the two birnessites were similar. The edge sites of birnessites were responsible for Sb(III) oxidation. Mn(IV) was reduced to Mn(III) and Mn(II), bound with birnessites and released to the solution, respectively. Because of the rapid rate of electron transfer of adsorbed Sb(III) to birnessites, the only Sb species on δ-MnO₂ after the oxidation reaction was Sb(V). Sb(V) was adsorbed at the edge sites of birnessites by replacing the OH group of birnessites, forming corner-sharing complexes with birnessites. However, the Sb sorption and oxidation capacities of the two birnessites were significantly different. Poorly-crystallized δ-MnO₂ exhibited a much higher oxidation and sorption capacity than well-crystallized TrBir because the former had many more edge sites than the latter. This study reveals the general mechanism of the reaction between Sb and birnessite and indicates that birnessite with a high number of edge sites would exhibit a huge capacity in Sb oxidation and sorption.

Constructed wetlands are an environmentally friendly and economically efficient sewage treatment technology, with fillers playing an important role in treatment processes. However, traditional wetland fillers (e.g. zeolite) are known to be imperfect because of their low adsorption capacity. In this paper, the adsorbent sodium titanate nano fillers (T3-F) was synthesized as an alternative to traditional filler with sodium titanate nanofibers (T3) as the raw material, epoxy adhesive as the adhesive agent and NH₄HCO₃ as the pore-making agent. The properties of T3-F were characterized by powder X-ray diffraction (XRD), scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX), porosity. The effect of different parameters such as pH, co-existing ions, contact time, initial metal ion concentrations and temperature was investigated for heavy metal adsorption. The results showed that the adsorption of heavy metal by T3-F followed the pseudo-second-order kinetic and Langmuir isotherm models. The maximum adsorption capacities for Cu²⁺, Pb²⁺, Zn²⁺, Cd²⁺ were about 1.5–1.98 mmol/g, which were 4–5 times that of zeolite, the traditional commonly used filler. Moreover, T3-F could entrap toxic ions irreversibly and maintain structural stability in the adsorption process, which solved the issue of secondary pollution. In the presence of competing ions, the adsorption efficiency for Pb²⁺ was not reduced significantly. Adsorption was strongest at high pH. From the results and characterization, an adsorption mechanism was suggested. This study lays a foundation for the practical application of T3-F as a constructed wetland filler in the future.

Pollution by microplastics (MPs) is currently a global problem in the coastal and marine environment. Transfer of MPs from land to sea and their inclusion in the food web has a significant adverse effect on the marine life and human health. The present study was carried out at the fishing harbour of Chennai, southeast coast of India. The possible MPs were isolated from the soft tissues of the commercially important bivalve Perna viridis and examined by microscopic and DXR Raman spectroscopic methods. The MPs were identified as to be polystyrene polymers in the soft tissues. This investigation revealed that size and color are the major factors affecting the bioavailability of MPs to bivalves in the study area. The presence of colorants in organisms revealed an anthropogenic origin through the use of a wide array of applications. Hence, coastal zones are a hotspot for pollution by MPs, and filter feeding bivalves are at the highest risk. Therefore, further studies are required to understand the accumulation rates and residence time of MPs across the food webs.

Naturally occurring radioactive material was characterized in selected seafood samples from three areas in the Gulf of Mexico. Relatively desirable and abundant fish such as Red Snapper, Red Drum, Northern Whiting, and Spotted Trout as well as oysters were collected and analyzed using gamma spectroscopy to determine the concentration of ²²⁸Ra, ²²⁶Ra, and ⁴⁰ K. Average total activity concentration from these radionuclides were 0.9 ± 0.6, 1.6 ± 1.2, and 132 ± 57 Bq kg⁻¹ respectively, in the edible portion of wet weight samples. The results were consistent with previous studies for other bodies of water. A small but statistically significant increase in ²²⁶Ra was found in comparison to similar research performed 20 years prior. These measurements provide a reasonable baseline for the examined species from the Gulf of Mexico.