Hexavalent chromium and nitrate co-contaminated groundwater remediation are attracting extensive attention worldwide. However, the transformation pathways of chromium and nitrate and the interplay mechanism between them remain unclear. In this work, zeolite-supported nanoscale zero-valent iron/palladium (Z-Fe/Pd) was synthesized and used for the first time to simultaneously remediate Cr(VI) and nitrate. Transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that nanoscale zero-valent iron/palladium was successfully loaded onto zeolite and it exhibited good dispersibility and oxidation resistance. Results of batch experiments showed that the Cr(VI) and nitrate removal efficiencies decreased from 95.5% to 91.5% to 45% and 73%, respectively, with the initial solution pH increasing from 3.0 to 8.0. The removal rates and efficiencies of Cr(VI) and nitrate under anoxic conditions were higher than those under open atmosphere because the dissolved oxygen diminished the electron selectivity toward the target pollutants. Moreover, the presence of Cr(VI) inhibited nitrate reduction by forming Fe(III)-Cr(III) hydroxide to impede electron transfer. Cr(VI) removal was promoted by nitrate, within limits, by balancing the consumption and generation rate of Fe₃O₄, which enhanced electron migration from the Fe(0) core to the external surface. The removal capacities of Cr(VI) and nitrate reached 121 and 95.5 mg g⁻¹, respectively, which were superior to the removal capacities of similar materials. Results of product identification, XRD, and XPS analyses of spent Z-Fe/Pd indicated that the reduction of Cr(VI) was accompanied by adsorption and co-precipitation, whereas the reduction of nitrate was catalyzed by the synergism of Fe(0) and Pd(0). An alternative to the simultaneous remediation of Cr(VI) and nitrate from groundwater under anoxic conditions is provided.

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.

Current synthesis routes of bismuth oxide nanosheets (BiONS) are relatively complicated, requiring the use of halogens or metalloids. Herein, a facile method to synthesize BiONS without the addition of halogens or other metalloids was developed. The synthesized BiONS were identified to have flake-shaped structures (300–1000 nm in width) with the thickness of 6–10 nm, which were predominantly made of β-Bi₂O₃. Such BiONS were applied to modify the surface of screen-printed carbon electrodes (BiONS-SPCEs) for the development of a robust palladium (Pd²⁺) sensor. After optimizing the electrochemical parameters of the sensor, it was found that the linear sensor response range and limit of detection for Pd²⁺ were 40–400 and 1.4 ppb, respectively. The electrocatalytic activity of the Pd²⁺-sensor was validated in the competing environment of other metal and metalloid ions. Real samples collected during a Pd recovery process from pharmaceutical wastewater were used to verify the application of BiONS-SPCEs in control of palladium recovery process. The quantitative results of post recovery palladium concentrations obtained using BiONS-SPCEs in treated pharmaceutical wastewater samples were in good agreement with those obtained by inductively coupled plasma-optical emission spectrometry (ICP-OES). Thus, such Pd²⁺-sensor provided the possibility of on-site process control of complex industrial samples for obtaining near-instant information that would lead to better management of resources used in the process, and same time assure environmental standards for both recovered products and processed discharge.

Noble metal–based nanomaterials (NMNs), such as platinum nanoparticles (Pt@NPs) and palladium nanoparticles (Pd@NPs), are increasingly being used as antibacterial agents. However, little information is available on bacterial resistance to NMNs. In this study, owing to their oxidase-like and peroxidase-like properties, both Pt@NPs and Pd@NPs induce reactive oxygen species (ROS) and manifest antibacterial activities: 6.25 μg/mL of either Pt@NPs or Pd@NPs killed >50% of Staphylococcus aureus strain ATCC29213. However, Pseudomonas aeruginosa strain PAO1 completely resisted 12.5 μg/mL of Pt@NPs and 6.25 μg/mL of Pd@NPs. Compared to the non-NMN groups, these NMNs promoted 2–3-fold upregulation of the quorum sensing (QS) gene lasR in strain PAO1. In fact, the lasR gene upregulation induced a 1.5-fold reduction in ROS production and increased biofilm formation by 11% (Pt@NPs) and 27% (Pd@NPs) in strain PAO1. The ΔlasR mutants (lasR gene knock out in strain PAO1), became sensitive to NMNs. The survival rates of ΔlasR mutants at 12.5 μg/mL Pt@NPs and Pd@NPs treatments were only 77% and 58%, respectively. This is the first report indicating that bacteria can resist NMNs through QS. Based on these results, evaluation of the ecological risks of using NMNs as antibacterial agents is necessary.

Adsorption and fractionation of Pt, Pd and Rh (defined here as platinum group elements, PGEs) onto the representative inorganic microparticles, including Fe2O3, MnO2, CaCO3, SiO2, Al2O3 and kaolinite in seawater were investigated. The effects of macromolecular organic compounds (MOCs) as the representatives of organic matter, including humic acids (HA), bovine serum albumin (BSA) and carrageenan, on the adsorption were also studied considering that organic matter is ubiquitous in seawater and indispensable to marine biogeochemical cycles. In the absence of MOCs, the representative mineral particles Fe2O3 and MnO2 had the strongest interaction with PGEs. The adsorption of PGEs onto the representative biogenic particles SiO2 and CaCO3 and lithogenic particles Al2O3 and kaolinite was similar or weaker than onto the mineral particles. MOCs inhibited the interaction between PGEs and the particles except for Pt and Pd onto the biogenic particles in artificial seawater. This impediment may be closely related to the interaction between particles, MOCs and elements. The partition coefficient (log Kd) of Pt was similar (∼4.0) in the presence of MOCs, indicating that the complexation between Pt and MOCs was less important than hydrolysis or adsorption onto the acid oxide particle surface. Rh tended to fractionate onto the mineral and lithogenic particles in the presence of HA and carrageenan, while Pd was more likely to fractionate onto the biogenic particles. However, BSA enhanced the fractionation tendency of Pd onto the mineral particles. The results indicate that the adsorption behavior of Pd onto inorganic particles was significantly affected by the composition or the type of MOCs. Hence, the interaction between PGEs and inorganic particles may be greatly affected by the macromolecular organic matter in the ocean.

The aim of this study was to evaluate the mobility of platinum (Pt) and palladium (Pd) emissions from automotive catalysts in soils and to contribute to the risk assessment of platinum group metals (PGMs) discharged from catalysts in the environment. To address this question, for the first time risk assessment code (RAC) was applied to consider the results from sequential extraction of different Pd and Pt species from soils. For this purpose, model soil samples were prepared spiking defined Pd or Pt species, respectively, at known concentrations. In order to mimic emitted species as well as possible transformation products of traffic-related Pd and Pt emissions in soils, coated and uncoated elemental nanoparticles (cPd/cPt NPs, Pd/Pt NPs) and ionic divalent metal species (Pd(II)/Pt(II)) were applied. All model samples were characterized in detail and the developed sequential extraction scheme was validated. RAC values ranged between 24 and 8% revealing medium to low risk. The order of mobility for the studied species was found to be Pt(II) > cPd NPs » Pd(II) > Pd NPs > Pt NPs > cPt NPs. Furthermore, migration of Pd species in gravity columns was studied confirming highest transport of cPd NPs.

Biogenic palladium nanoparticles (bio-Pd NPs) represent a promising catalyst for organohalide remediation in water and sediments. However, the available information regarding their possible impact in case of release into the environment, particularly on the environmental microbiota, is limited. In this study the toxicity of bio-Pd NPs on the model marine bacterium V. fischeri was assessed. The impacts of different concentrations of bio-Pd NPs on the respiratory metabolisms (i.e. organohalide respiration, sulfate reduction and methanogenesis) and the structure of a PCB-dechlorinating microbial community enriched form a marine sediment were also investigated in microcosms mimicking the actual sampling site conditions. Bio-Pd NPs had no toxic effect on V. fischeri. In addition, they had no significant effects on PCB-dehalogenating activity, while showing a partial, dose-dependent inhibitory effect on sulfate reduction as well as on methanogenesis. No toxic effects by bio-Pd NPs could be also observed on the total bacterial community structure, as its biodiversity was increased compared to the not exposed community. In addition, resilience of the microbial community to bio-Pd NPs exposure was observed, being the final community organization (Gini coefficient) of samples exposed to bio-Pd NPs similar to that of the not exposed one. Considering all the factors evaluated, bio-Pd NPs could be deemed as non-toxic to the marine microbiota in the conditions tested. This is the first study in which the impact of bio-Pd NPs is extensively evaluated over a microbial community in relevant environmental conditions, providing important information for the assessment of their environmental safety.

Palladium (Pd) emitted from vehicles equipped with exhaust catalytic converters has been accumulating at a greater rate relative to other platinum group elements (PGE) in the last 10–20 years. Little is known, however, regarding the various environmental factors and conditions which are likely to modulate the chemical behavior and bioaccessibility of this element post-emission. To meet data needs, soils and a Pd model substance were treated with solutions containing common anions (Cl−, NO3−, SO42− und PO43−) to shed light on the geochemical behavior of emitted Pd under ambient conditions. As part of this, the particle surface chemistry of treated residues (insoluble phase) and solutions (soluble phase) was examined using XPS to assess the chemical transformation of Pd in the presence of inorganic anions. The results show that Pd is the most soluble in the presence of anionic species, followed by rhodium (Rh) and platinum (Pt). Pd in field-collected samples was found to be considerably more soluble than the metallic Pd in the model substance, Pd black, when treated with anionic species. The results also demonstrate that the solubility of Pd black is strongly dependent on solution pH, concentration and the duration of reaction. The outer 3–4 atomic layers of metallic Pd was determined via XPS to be partially oxidized when treated with anion solutions, with the degree being dependent on anion type. The concentration of dissolved O2 in solution was found to have little impact on the transformation of metallic Pd. Given the ubiquitous nature of the anions examined, we can expect that Pd will become more bioaccessible post-emission.

Chemical and toxicological characterization of the water-soluble fraction of size-segregated urban particulate matter (PM) (<0.49, 0.49–0.97, 0.97–1.5, 1.5–3.0, 3.0–7.2 and >7.2 μm) was carried out at two urban sites, traffic and urban background, during the cold and the warm period. Chemical analysis of the water-soluble PM fraction included ionic species (NO3−, SO42−, Cl⁻, Na⁺, NH4⁺, K⁺, Mg²⁺, Ca²⁺), water-soluble organic carbon (WSOC), and trace elements (Al, As, Ba, Cd, Cr, Cu, Fe, Pb, Mn, Ni, Zn, Pt, Pd, Rh, Ru, Ir, Ca, and Mg). The dithiothreitol (DTT) assay was employed for the abiotic assessment of the oxidative PM activity. Cytotoxic responses were investigated in vitro by applying the mitochondrial dehydrogenase (MTT) and the lactate dehydrogenase (LDH) bioassays on human lung cells (MRC-5), while DNA damage was estimated by the single cell gel electrophoresis assay, known as Comet assay. The correlations between the observed bioactivity responses and the concentrations of water-soluble chemical PM constituents in the various size ranges were investigated. The results of the current study corroborate that short-term bioassays using lung human cells and abiotic assays, such as the DTT assay, could be relevant to complete the routine chemical analysis and to obtain a preliminary screening of the potential effects of PM-associated airborne pollutants on human health.

The intensified use of palladium nanoparticles (PdNPs) in many chemical reactions, jewellery, electronic devices, in car catalytic converters and in biomedical applications lead to a significant increase in palladium exposure. Pd can cause allergic contact dermatitis when in contact with the skin. However, there is still a lack of toxicological data related to nano-structured palladium and information on human cutaneous absorption. In fact, PdNPs, can be absorbed through the skin in higher amounts than bulk Pd because NPs can release more ions. In our study, we evaluated the absorption of PdNPs, with a size of 10.7 ± 2.8 nm, using intact and damaged human skin in Franz cells. 0.60 mg cm−2 of PdNPs were applied on skin surface for 24 h. Pd concentrations in the receiving solutions at the end of experiments were 0.098 ± 0.067 μg cm−2 and 1.06 ± 0.44 μg cm−2 in intact skin and damaged skin, respectively. Pd flux permeation after 24 h was 0.005 ± 0.003 μg cm−2 h−1 and 0.057 ± 0.030 μg cm−2 h−1 and lag time 4.8 ± 1.7 and 4.2 ± 3.6 h, for intact and damaged skin respectively.This study indicates that Pd can penetrate human skin.