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.

Degradation of 2,4,6-trichloropenol (TCP) with peroxymonosulfate (PMS) catalyzed by iron porphyrin tetrasulfonate ([FePTS)] was investigated in an 8-to-1 (v/v) CH3OH-H2O mixture. Typical reaction medium contained a 4.00 mL methanol solution of TCP (0.100 mmol), a 0.50 mL aqueous solution of catalyst (5.0 × 10⁻⁴ mmol), and 0.100 mmol PMS (as 0.031 g of Oxone). The reaction was performed at ambient temperature. The conversion of TCP was 74% in 30 min and 80% in 6 h when the catalyst was [FePTS]. Amberlite IRA-900 supported [FePTS] catalyst was also prepared. In the recycling experiments the homogeneous [FePTS] lost its activity after the first cycle, while [FePTS]-Amberlite IRA 900 maintained its activity for the first 2 cycles. After the second cycle, the conversion of TCP dropped to <10% for Amberlite IRA-900 supported [FePTS] catalyst. The degradation of TCP with PMS was also attempted using cobalt, copper, nickel and palladium porphyrin tetrasulfonate catalysts, however, no catalytic activity was observed with these structures.

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.

In the present study, endpoints including in vitro pollen performance (i.e., germination and tube growth) and lethality were used as assessments of nanotoxicity. Pollen was treated with 5–10 nm-sized Pd particles, similar to those released into the environment by catalytic car exhaust converters. Results showed Pd-nanoparticles altered kiwifruit pollen morphology and entered the grains more rapidly and to a greater extent than soluble Pd(II). At particulate Pd concentrations well below those of soluble Pd(II), pollen grains experienced rapid losses in endogenous calcium and pollen plasma membrane damage was induced. This resulted in severe inhibition and subsequent cessation of pollen tube emergence and elongation at particulate Pd concentrations as low as 0.4 mg L−1. Particulate Pd emissions related to automobile traffic have been increasing and are accumulating in the environment. This could seriously jeopardize in vivo pollen function, with impacts at an ecosystem level. Nanoparticulate Pd – which resembles emissions from automobile catalysts – affects pollen to a higher extent than soluble Pd.

The present work summarizes data about palladium contents of road tunnel dust from 1994 to 2007 and sewage sludge ash from 1972 to 2006. Since palladium is emitted from automotive catalytic converters as elemental particles, road dust is quiet useful to study traffic-related Pd emissions. Very high Pd values of up to 516 μg Pd kg−1 were found in the road dust samples collected in 2007. Heavy metals of all urban emissions, also dental practice effluent, are enriched in sewage sludge ash and thus this matrix is useful for the documentation of palladium emission caused by the use of Pd alloys in dental medicine. In sewage sludge ash highest Pd contents of maximum 460 μg Pd kg−1 were found in the years 1986–1997. In both matrices correlations of Pd content to Pd demand of industry are discussed. This work reveals the link between intensified industrial Pd use and Pd content in according environmental samples.

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.

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.

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.