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.

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.

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.

The increasing content of platinum group metal particles emitted into the environment by car traffic is gradually attracting the attention of the scientific community. However, the methods for the determination of platinum group metals in environmental matrices are either costly or suffer from low sensitivity. To facilitate the use of less sensitive, but significantly cheaper, devices, the preconcentration of platinum group metals is employed. For platinum, a multitude of preconcentration approaches have been published. On the contrary, the preconcentration approaches for palladium are still rare. In this work, the development, optimization, and testing of a new approach is described; it is based on a preconcentration of palladium on octadecyl modified silica gel together with the complexing agent dimethylglyoxime, and it is then analyzed with the high-resolution continuum-source atomic absorption spectrometry. For comparison, a newly developed sorbent, QuadraSil™ TA, with a high affinity for platinum group metals was also tested. The preconcentraiton approach was tested on the lichen Hypogymnia physodes, which served as a bioindicator of palladium emissions. The case study site was a mid-sized city in central Europe: Brno, Czech Republic. The dry “bag” monitoring technique was used to collect the palladium near roads with a large span of traffic density. The developed analytical approach confirmed an increasing concentration of palladium with increasing exposure time and intensity of the traffic. Consequently, a simple relationship between the amount of bioaccumulated palladium and traffic density was established.

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.

Mainly due to automobile traffic, but also due to other sources, the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) are introduced into aquatic biotopes where they accumulate in sediments of lakes and rivers. However, the toxicity of these noble metals to aquatic organisms is not well understood and especially toxicity studies under standardized condition are lacking. Thus, the toxicity of Pt, Pd and Rh to Daphnia magna was tested in single metal exposure experiments according to OECD guideline 202. Immobility and lethality was recorded after 24 h and 48 h of exposure and EC50 and LC50, respectively, were determined. As the nominal exposure concentration of Pd differed significantly from the quantified concentration, the control of the real exposure concentration by chemical analysis is mandatory, especially for Pd.The toxicity decreased in the order Pd > Pt ≫ Rh with e.g. LC50(48 h) values of 14 μg/L for Pd, 157 μg/L for Pt and 56,800 μg/L for Rh. The exposure period had a clear effect on the toxicity of Pt, Pd and Rh. For Pt and Rh the endpoint immobility was more sensitive than the endpoint lethality whereas Pd toxicity was similar for both endpoints. The Hill slopes, which are a measure for the steepness of the concentration-response curves, showed no significant discrepancies between the different metals.The binary metal exposure to Pt and Pd revealed a more-than-additive, i.e. a synergistic toxicity using the toxic unit approach. The present study is a start to understand the toxicity of interacting PGE. The modes of action behind the synergistic effect are unclear.

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.

Palladium/magnetite nanoparticulate catalysts were developed for efficient elimination of halogenated organic pollutants from contaminated wastewater. Particle recovery from treated water can be ensured via magnetic separation. However, in worst-case scenarios, this catalyst removal step might fail, leading to particle release into the environment. Therefore, a toxicological study was conducted to investigate the impact of both pure magnetite and palladium/magnetite nanoparticle exposure upon human skin (HaCaT) and human colon (CaCo-2) cell lines and a cell line from rainbow trout gills (RTgill-W1). To quantify cell viability after particle exposure, three endpoints were examined for all tested cell lines. Additionally, the formation of reactive oxygen species was studied for the human cells. The results showed only minor effects of the particles on the tested cell systems and support the assumption that palladium/magnetite nano-catalysts can be implemented for a new wastewater treatment technology in which advantageous catalyst properties outweigh the risks. Impact of nano-Pd/magnetite on cell viability was studied and appears to be low.