Groundwater contamination originating from anthropogenic industrial activities is a global concern, adversely impacting health of living organisms and affecting natural ecosystems. Monitoring contamination in a complex groundwater system is often limited by sparse data and poor hydrogeological delineation, so that numerous indicators (organic, inorganic, isotopic) are frequently used simultaneously to reduce uncertainty. We suggest that selected Technology-Critical Elements (TCEs), which are usually found in very low concentrations in the groundwater environment, might serve as contamination indicators that can be monitored through aquifer systems. Here, we demonstrate the use of selected TCEs (in particular, Y, Rh, Tl, Ga, and Ge) as indicators for monitoring anthropogenic groundwater contamination in two different groundwater systems, near the Dead Sea, Israel. Using these TCEs, we show that the sources of local groundwater contamination are phosphogypsum ponds located adjacent to fertilizer plants in two industrial areas. In addition, we monitored the spatial distribution of the contaminant plume to determine the extent of well and spring contamination in the region. Results show significant contamination of the groundwater beneath both fertilizer plants, leading to contamination of a series of wells and two natural springs. The water in these springs contains elevated concentrations of toxic metals; U and Tl levels, among others, are above the maximum concentration limits for drinking water.

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.

Platinum-Group Elements (PGEs, i.e. platinum; Pt, palladium; Pd and rhodium; Rh) are extensively employed in the production of automotive catalytic converters to catalyze and control harmful emissions from exhaust fumes. But catalytic converters wear out over time and the emission of PGEs along with the exhaust fumes are nowadays known to be the main reason of the presence of PGEs in urban environments. PGEs contents were studied on three gasoline 3-way catalytic convertors with low, medium and high kilometers. PGEs emission factors via exhaust gases from Euro 3, 4, 5 and 6 gasoline and diesel vehicles, were monitored using catalytic converters. Results show variable content for PGEs for the three converters, in the ranges of 6–511, 0.5–2507 and 0.1–312 mg kg⁻¹ for Pt, Pd and Rh respectively. PGEs contents in different catalyst supports show the replacement of Pt by Pd in more recent converters. Analysis of the exhaust gas shows that catalytic converters expel up to 36.5 ± 3.8 ng km⁻¹ of Pt, 8.9 ± 1.1 ng km⁻¹ of Pd and 14.1 ± 1.5 ng km⁻¹ of Rh. Higher emissions of PGEs have been observed by gasoline Euro 3 vehicle, possibly due to the older technology of motorization and of the catalytic converter in this vehicle. Euro 3 and 4 diesel vehicles seem to emit more PGEs during urban cycles. Emission of PGEs has been also observed during the cold start of the majority of vehicles which seems to be the result of incomplete combustion during the rise of temperature in the engine. Higher PGEs emissions were also observed during motorway cycles in newer (Euro 4 and 5) petrol and diesel vehicles, conceivably due to the greater combustion as the engine speeds up during this cycle.

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.

Rh/(Ce,Zr,La)O₂ (CZL) catalysts with different Ce/Zr molar ratios of 1:0, 8:1, 4:1, 2:1, 1:1, 1:2, 1:4, 1:8 and 0:1 were prepared. The relationship of microstructure, dynamic oxygen mobility and the redox properties with catalytic activity for HC, CO and NOₓ eliminations were investigated. The results demonstrate that CZL mixed oxide with Ce/Zr ratio of 1:1 exhibits the largest OSC values as 904.3 umol·g⁻¹ and structural defects. The increase of oxygen vacancies and structural defects would promote the interaction between Rh species and CZL mixed oxides, which further promotes the stabilization of RhOₓ particles and enhances the oxygen storage/release ability. Rh/CZLx catalysts with Ce/Zr molar ratio of 1:1–1:4 exhibit better catalytic activity and wider dynamic operation window due to their higher DOSC.

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.

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 concentrations of Platinum (Pt), Rhodium (Rh) and Palladium (Pd) were evaluated from a highly impacted estuary in Brazil influenced by industrial pole, highway traffic and sewage outfall. The Santos-São Vicente region presents important economic activities derived from a largest harbor of Latin America and an industrial pole surrounded by intensive highway traffic. Values of Rh varied from 0.08 to 1.7 ng g⁻¹ with highest values at stations impacted by domestic waste. Pt ranged from 0.15 to 40.3 ng g⁻¹ with highest concentrations located close to the ferryboat traffic. Pd levels varied from 1.05 to 22.0 ng g⁻¹ with values >5 ng g⁻¹ in 50% of the stations. The spatial distribution of PGEs was not always directly associated with muddy sediments, because high PGE levels found even in sandy sediments. Pollution indexes, including anthropogenic factor (AF), geoaccumulation index (Igₑₒ), Enrichment factor (EF), and Pollution Load Index (PLI) were used for evaluating contaminant potential. Based on EF, Igeo, and PLI, 50% of samples of the sediments from Santos-São Vicente Estuarine System (SSV) were classified with significant to strong PGE contamination. All stations on the Santos Channel (SC), São Vicente Channel (SVC) and Bertioga Channel (BC) had AF higher than 80% in at least one of PGE elements, as showed in station 2A, which presented AF <50% for Rh and Pd and 86% for Pt. Despite high anthropogenic enrichment, no correlations among PGE elements were observed in surface sediments. Only two stations presented Pd/Pt, Pt/Rh, and Pd/Rh typical ratios of auto catalyst (st. 14 and Piaçaguera) both located in the vicinity of highways. This could be due to the PGE deposition process in road dust, soil, and water as well as the biogeochemical cycling of PGEs involving organic metallic and inorganic complexes formed in the estuarine and seawaters.

Atmospheric pollution is one of the main concerns in modern society and it poses a direct impact on the environment and public health. Therefore, an enormous number of environmental samples are collected and analyzed around the world on a daily basis. In order to obtain reliable and comparable results, it is paramount to establish a well-defined protocol for environmental sampling and analysis considering the more relevant variations associated with these activities and the processes that affect the distribution of the analytes in the environment. The present case study proposes a protocol to determine the amounts of the platinum group elements (PGEs: palladium, platinum, rhodium) due to atmospheric deposition in Tibouchina granulosa leaves that takes into account the estimation of measurement uncertainties including the sampling component. The samples were collected at a standardized height, in the second node of the branches, with approximately 2 months of environmental exposure. The particulate matter was extracted from the leaf surface by acid leaching using an ultrasonic bath followed by aqua regia digestion. Platinum (Pt), palladium (Pd), and rhodium (Rh) were separated from impurities by cation chromatography and analyzed by ICP-MS. The measurement uncertainties found were in the range of 24 to 33% while the analytical uncertainty lied between 4.5 and 7.3%. The results were expressed regarding metrological aspects, with the expanded uncertainty, within a 95% confidence level, to allow for a more robust interpretation of their relevance in the environmental and regulatory context.