Metal enrichment of road dust is well characterized but available data on the bioaccessibility of metals in particle size fractions relevant to human respiratory health remain limited. The study goal was to investigate the bioaccessibility of platinum group elements (PGE), which are used as catalysts in automotive exhaust converters, in the inhalable fraction of road dust. Street sweepings were provided by the City of Toronto, Canada, collected as part of its Clean Roads to Clean Air program.The particle size relevance of road dust for inhalation exposures was confirmed using a laser diffraction particle size analyzer (mean Dx(50): 9.42 μm). Total PGE were determined in both bulk and inhalable fractions using nickel sulfide (NiS) fire-assay and instrumental neutron-activation analysis (INAA). PGE lung solubility was examined for the inhalable fraction using Gamble’s extraction. Sample digests were co-precipitated with Te-Sn, to pre-concentrate and isolate PGE, prior to their measurement using inductively coupled plasma mass spectrometry (ICP-MS).Total PGE concentrations were enriched in the inhalable fraction of road sweepings. Geomean concentrations in the inhalable fraction were: palladium (Pd) (152 μg/kg), platinum (Pt) (55 μg/kg), rhodium (Rh) (21 μg/kg) and iridium (Ir) (0.23 μg/kg). Osmium (Os) concentrations were below the limit of detection (LOD). Bioaccessible PGEs (n = 16) using Gamble’s solution were below LOD for Ir and ruthenium (Ru). For the remainder, the geomean % bioaccessibility was highest for platinum (16%), followed by rhodium (14%) and palladium (3.4%). This study provides evidence that PGE in road dust are bioaccessible in the human lung.

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.

We studied arid desert soils from Namibia (Rosh Pinah) that were contaminated with up to 7 mg kg⁻¹ of thallium (Tl) via dust emitted from a local flotation tailing dam. Chemical extractions of waste and soil materials indicated that most of the Tl is strongly bound, in accordance with X-ray diffraction and X-ray absorption spectroscopy data that point to the predominant association of Tl with metal sulfides and phyllosilicates. The isotope fractionation factor ε²⁰⁵Tl of the soil samples (from −0.4 to +3.8) shows a positive linear relationship (R² = 0.62) with 1/Tl, indicative for the mixing of two major Tl pools, presumably anthropogenic Tl and geogenic Tl. The ε²⁰⁵Tl value for the topmost soil samples (∼+3) closely matches the ε²⁰⁵Tl value for post-flotation waste particles with a diameter of <0.05 mm, whereas the bulk flotation waste exhibits a significantly larger ε²⁰⁵Tl value (∼+6). These variations are in accordance with predominant atmospheric transfer of Tl from the tailings to the adjacent soils via fine (dust) particles. The identified minimal Tl alteration in soils indicates that only a small part of the Tl could be potentially released and passively enter the vegetation, local population and/or food chain in the long term. From this viewpoint, Tl does not represent such an important environmental concern as other (abundant) contaminants at the locality. Furthermore, there could be a relevance for other alkaline desert soils, including those where Tl pollution plays a major role.

Silver nanomaterials (AgNMs) are released into sewers and consequently find their way to sewage treatment plants (STPs). The AgNMs are transformed en route, mainly into silver sulfide (Ag₂S), which is only sparingly soluble in water and therefore potentially less harmful than the original AgNMs. Here we investigated the toxicity and fate of different sulfidized AgNMs using an exposure scenario involving the application of five different test materials (NM-300K, AgNO₃, Ag₂S NM-300K, Ag₂S NM and bulk Ag₂S) into a simulated STP for 10 days. The sewage sludge from each treatment was either dewatered or anaerobically digested for 35 days and then mixed into soil. We then assessed the effect on soil microorganisms over the next 180 days. After 60 days, a subsample of each test soil was used to assess chronic toxicity in oat plants (Avena sativa L) and a potential uptake into the plants. The effect of each AgNM on the most sensitive test organism was also tested without the application of sewage sludge. Although Ag sulfidized species are considered poorly soluble and barely bioavailable, we observed toxic effects on soil microorganisms. Furthermore, whether or not the AgNM was sulfidized before or during the passage through the STP, comparable effects were observed on ammonium oxidizing bacteria after sewage sludge application and incubation for 180 days. We observed the uptake of Ag into oat roots following the application of all test substances, confirming their bioavailability. The oat shoots generally containing less Ag than the roots.

Sediments nearby harbors are dredged regularly, and the sediments require the stringent treatment to meet the regulations on reuse and mitigate the environmental burdens from toxic pollutants. In this study, FeCl₃ was chosen as an extraction agent to treat marine sediment co-contaminated with Cu, Zn, and total petroleum hydrocarbons (TPH). In chemical extraction process, the extraction efficiency of Cu and Zn by FeCl₃ was compared with the conventional one using inorganic acids (H₂SO₄ and HCl). Despite the satisfactory level for extraction of Cu (78.8%) and Zn (73.3%) by HCl (0.5 M) through proton-enhanced dissolution, one critical demerit, particularly acidified sediment, led to the unwanted loss of Al, Fe, and Mg by dissolution. Moreover, the vast amount of HCl required the huge amounts of neutralizing agents for the post-treatment of the sediment sample via the washing process. Despite a low concentration, extraction of Cu (70.1%) and Zn (69.4%) was done by using FeCl₃ (0.05 M) through proton-enhanced dissolution, ferric-organic matter complexation, and oxidative dissolution of sulfide minerals. Ferric iron (Fe³⁺) was reduced to ferrous iron (Fe²⁺) with sulfide (S²⁻) oxidation during FeCl₃ extraction. In consecutive chemical oxidations using hydrogen peroxide (H₂O₂) and persulfate (S₂O₈²⁻), the resultant ferrous iron was used to activate the oxidants to effectively degrade TPH. S₂O₈²⁻ using FeCl₃ solution (molar ratio of ferrous to S₂O₈²⁻ is 19.8–198.3) removed 42.6% of TPH, which was higher than that by H₂O₂ (molar ratio of ferrous to H₂O₂ is 1.2–6.1). All experimental findings suggest that ferric is effectively accommodated to an acid washing step for co-contaminated marine sediments, which leads to enhanced extraction, cost-effectiveness, and less environmental burden.

Metal release from the deposition of sulfide-containing tailings in seawater was investigated using a batch reaction experiment inside a temperature and dissolved oxygen-controlled chamber. Two hundred grams of tailings from a porphyry Cu-Au and a sediment-hosted Cu deposit were submerged in 1.8 L synthetic seawater. The sulfides present in the porphyry Cu-Au tailings are pyrite (FeS2), chalcopyrite (CuFeS2) and bornite (Cu5FeS4) while in the sediment-hosted Cu tailings are bornite, chalcocite (Cu2S) and covellite (CuS). Galena occurs as a minor sulfide in both tailings. Pore water and overlying seawater samples were collected and analyzed for pH, redox potential and trace metals (Cu, Pb and Fe) concentration. Results show that there is very low Cu (10–40 μg/L), Pb (1–10 μg/L) and Fe (5–50 μg/L) released into solution throughout the course of 87 days. Long-term trace metal release from tailings in seawater is therefore theorized to be low and is a slow process.

The present study has evaluated temporal and spatial mercury trends based on surficial sediment samples and 210Pb-dated sediment profiles. The obtained results show that there are areas close to the main bay's tributary rivers where the Hg content has doubled during the last 15 years and regions where it has decreased by a factor of 2, mainly the area close to the navigation channel, which is submitted to periodic dredging. In the inner part of the bay, the most contaminated region, mercury shows a strong association with sulfide. In the same region, based on the 210Pb results, it was possible to calculate the yearly increment on the Hg concentration in the surface sediment, 0.62 μg kg−1 y−1 to 0.29 μg kg−1 y−1, according to the distance to the bay's main tributary rivers.

Seafloor massive sulphide samples from the Trans-Atlantic Geotraverse active mound on the Mid-Atlantic Ridge were characterised and subjected to leaching experiments to emulate proposed mining processes. Over time, leached Fe is removed from solution by the precipitation of Fe oxy-hydroxides, whereas Cu and Pb leached remained in solution at ppb levels. Results suggest that bulk chemistry is not the main control on leachate concentrations; instead mineralogy and/or galvanic couples between minerals are the driving forces behind the type and concentration of metals that remain in solution. Dissolved concentrations exceed ANZECC toxicity guidelines by 620 times, implying the formation of localised toxicity in a stagnant water column. Moreover, concentrations will be higher when scaled to higher rock-fluid ratios and finer grain sizes proposed for mining scenarios. The distance at which dilution is achieved to meet guidelines is unlikely to be sufficient, indicating a need for the refinement of the mining process.

Chemical analyses and toxicity testing using six marine species were used to characterize the hazard of produced waters (PW) to marine life from twelve Australian offshore platforms. Hazard data were used in conjunction with platform-specific plume discharge dilution and species sensitivity distribution modeling to estimate cumulative risks by calculating the multiple substance potentially affected fraction of species in the local marine environment. Results provided two independent lines of evidence demonstrating that cumulative risks to marine life from these discharges meet intended 95% species protection goals at the edge of the mixing zone. A limited number of PW constituents (hydrocarbons, sulphide and ammonia) appeared to dictate risk thereby informing management and providing a rationale for more targeted analyses in future monitoring studies. Based on these findings a tiered framework is proposed to foster consistent screening and potential refinement of cumulative risk evaluations for PW discharges.

Adsorption has been researched attempting to minimize the pollution caused by dyes, which represents a serious environmental problem as contamination of surface and ground water. Therefore, cellulose and its modified forms with amine and thiols groups constitute a class of versatile adsorbents for the removal of anionic dyes in aqueous solution. In this context, this work reports the preparation of cellulose modified by ethylene sulfide and ethylenediamine (Cel-ESEN), through the reaction of the cellulose modified by ethylene sulfide (CEL-ES) and ethylenediamine (EN). Materials were characterized by elemental analysis, which showed in the Cel-ESEN matrix 10.12 ± 0.10%, 5.52 ± 0.06% of sulfur and nitrogen, respectively. Nuclear magnetic resonance in the solid state of ¹³C (¹³C NMR) showed, for the Cel-ESEN matrix, a peak related to CH₂ groups from the molecules incorporated in the cellulose biopolymer. Crystalline Index obtained by X-ray diffraction (XRD) was in the order pure Cellulose > Cel-Cl > Cel-ES > Cel-ESEN. The adsorbent matrix (Cel-ESEN) was used in the removal of the remazol yellow GR (RY) dye in aqueous medium. Data obtained experimentally from kinetic study had the best adjustment to the proposed pseudo-second-order model. The adsorption process occurs in monolayer, is endothermic and thermodynamically favorable. Adsorption capacity of the modified material became 118 times higher than the starting material. These results suggest that the obtained biopolymer can be used as an alternative material to remove RY in aqueous solution.