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The development of an efficient palladium probe holds significant application value, considering the detrimental impact of palladium contaminants on human health. Thus, it is critical to create a sensitive detection method. To this end, a fluorescent probe TM-TPA-Pd based on benzothianone structure was designed, using allyl carbonate as the Pd 0 recognition unit. TM-TPA-Pd exhibited high sensitivity (1.4 eq), selectivity, near-infrared (NIR) fluorescence (798 nm), and low detection limit (0.46 μM) for Pd 0 with a rapid "turn-on" fluorescence signal (5 min). Furthermore, TM-TPA-Pd has extremely low cytotoxicity and has been successfully applied to detecting cells and zebrafish, which has great potential for palladium detection in biological systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Based on the automatic light wave ashing instrument, palladium nitrate was used as an ashing aid for the first time to collect selenium in the process of food ashing pre-treatment, and a method for the determination of selenium in food by ashing method was established with inductively coupled plasma mass spectrometry. At the same time, the effects of magnesium nitrate, rhodium nitrate, and nickel nitrate as ashing aids on selenium collection were investigated using certified plant standard materials. The capture of selenium by magnesium nitrate, rhodium nitrate, and nickel nitrate as ashing aids did not exceed 50%. Using palladium nitrate as an ashing aid, six food standard materials were measured, with selenium recovery rates ranging from 97 to 106%. A complete analysis cycle can be completed within an hour. The method detection limit of selenium was 0.021 μg g -1 , and the relative standard deviation of five measurements was less than 7%. The experimental results show that palladium nitrate is an excellent ashing aid for capturing selenium, and it is far superior to the other three aids. In addition, the mechanism of palladium nitrate as an ashing aid for capturing selenium was discussed., (© 2024. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

Access to better health care anticipates that more medical devices can be found alongside skeletal remains. Those employed in oral rehabilitation, with available brands or batch/series, can prove useful in the identification process. A previous study in the Colecção de Esqueletos Identificados Século XXI described macroscopically the dental prostheses. An unusual case of a dental device with chromatic alterations demonstrated to require a more detailed analysis. The individual, a 53-year-old male, exhibited, at both arches, a fixed tooth-supported rehabilitation, with gold colouring classified initially as a gold-palladium alloy. Simultaneously, a green pigmentation deposit was observable in bone and prosthesis. This investigation aimed to verify the elemental composition of the dental prosthesis alloy. Elemental analysis was performed by X-ray fluorescence in two regions (labial surface of the prosthetic crown and the root surface of the lower right lateral incisor). Both the spectra and the qualitative results found higher levels of copper and aluminium, followed by nickel, iron, zinc, and manganese. No gold or palladium was detected. The most probable assumption is that a copper-aluminium alloy was used, as its elemental concentration corresponds to those measured in similar devices. Dental prostheses of copper-aluminium alloys have been made popular since the 1980s, particularly in the USA, Japan, and Eastern Europe. Apart from the biographical information, it was also known that the individual's place of birth was an Eastern European country, which highlighted the usefulness of this type of information when dealing with missing people cases., (© 2023. The Author(s).)

Efficient recognition, separation and recovery of palladium from high-level liquid waste (HLLW) not only helps the safe, green and environmentally friendly disposal of nuclear waste, but also is an essential important supplement to overcome the growing shortage of natural palladium resources. Herein, a novel silica-based functional adsorbent named 2AT-SiAaC was prepared by a two-step method, i.e., grafting of 2-aminothiazole (2AT) via the amidated reaction after in-situ polymerization of acrylic monomers on porous silica. SEM, EDS, TG-DSC, BET and PXRD all proved the successful preparation of 2AT-SiAaC, and it exhibited ultrahigh adsorption selectivity for Pd(II) (K d (distribution coefficient) ≥ 10,344.2 mL/g, SF Pd/M (separation factor) ≥ 613.7), fast adsorption kinetics with short equilibrium time (t ≤ 1 h) and good adsorption capacity (Q ≥ 62.1 mg Pd/g). The dynamic column experiments shows that 2AT-SiAaC achieved efficiently separation of Pd(II) from simulated HLLW, and the enrichment coefficients (C/C 0 ) of Pd(II) was as high as about 14 with the recovery rate nearly 99.9% and basically kept the same performance in three adsorption-desorption column cycle experiments. The adsorption mechanism was analyzed by FT-IR, XPS and DFT calculations, and the ultrahigh selectivity of 2AT-SiAaC was attributed to the preferred affinity of the soft N-donor atoms in 2AT for Pd(II). NO 3 - ions participated in the adsorption reaction to keep charge balance, and the frontier orbital electron density distribution diagram shows the charge transfer in the process of material preparation and adsorption. To sum up, 2AT-SiAaC adsorbent provided a new insight for precise recognition and efficient separation of Pd(II) from HLLW., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Platinum group elements (PGEs) can be naturally found at very low concentrations in the Earth's crust. However, the increasing uses of PGEs in vehicle exhaust catalysts, in addition to some other applications (industry, jewelry, anticancer drugs) cause their anthropogenic emission and dispersion in the environment. The use of human hair samples analysis is considered a suitable biological indicator to assess human occupational and environmental exposure. It is an easily accessible material for individuals or population groups of non-invasive sampling. The aim of this study is a comparative analysis to investigate human hair content of Pd and Pt in adolescents, of both genders, residing near petrochemical plants of Augusta and Gela, in urban area of Palermo, and Lentini as control site (Sicily, Italy). A total of 108 samples were taken from school students (11-14 years old). Hair samples were cleaned, mineralized, and processed for analyses by inductively coupled plasma-mass spectrometry (ICP-MS). The samples from the industrial sites of Gela and Augusta do not have statistically significant differences between them for either Pd for Pt; however, they differ from the samples relating to the city of Palermo. Median Pd concentrations are higher than Pt in industrial sites and control site. In urban site the levels of both metals were comparable. The study does not reveal any statistically significant difference between Pd and Pt concentrations in female and male samples. The data confirm that the study areas are heavily affected by industrial and urban emissions of Pd and Pt, representing a potential hazard to the local population., Competing Interests: Declaration of competing interest The authors declare that they have no competing interests., (Copyright © 2023. Published by Elsevier B.V.)

The wide use of palladium (Pd) raises the concern about environmental pollution and human diseases, evoking the need for the development of detection methods for Pd species. However, the development of near-infrared (NIR) luminescence probes for subcellular Pd species remains challenging. In this work, we presented a NIR iridium(III) complex-based luminescence probe for the detection of Pd 0 species through incorporating an allyl group and amino group into the N^N ligand. We found that the probe was capable of detecting Pd 0 species with a limit of detection (LOD) of 0.5 μM. Importantly, cell imaging experiments showed that the probe is applicable for visualizing mitochondrial Pd 0 ions in living cells, which are also suitable for Pd(II) species. To the best of our knowledge, this is the first NIR luminescence imaging probe for the detection of mitochondria Pd species in living cells, paving the way for studying subcellular distributions and related toxicity analysis of exogenous Pd species in living cells., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Extensive use of palladium in many catalysts and catalytic converters causes a high degree of pollution of water and soil resources. Therefore, there is an urgent need to develop rapid and sensitive palladium probes. Herein, a novel "turn-on" near-infrared (NIR) fluorescence and colorimetric probe for Pd has been designed on the basis of the deallylation of the probe, followed by the release of NIR emissive fluorophore through the Tsuji-Trost reaction. The probe can selectively discriminate between the oxidation states of Pd 0 and Pd 2+ . Sensing results demonstrates that the probe has excellent selectivity, sensitivity, fast response time, NIR fluorescence, high biocompatibility, and low detection limit for the Pd detection over a series metal ion. The probe has been successfully applied in visualization of residual Pd content from water, soil, drug and living cell samples by fluorescence observation with the naked eye., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Ammunition wastewater contains toxic nitrated explosives like RDX and oxyanions like nitrate and perchlorate. Its treatment is challenged by low efficiency due to contaminant recalcitrance and high cost due to multiple processes needed for separately removing different contaminant types. This paper reports a H 2 -based low-energy strategy featuring the treatment of explosives via catalytic denitration followed by microbial mineralization coupled with oxyanion reduction. After a nitrate- and perchlorate-reducing biofilm incapable of RDX biodegradation was coated with palladium nanoparticles (Pd 0 NPs), RDX was rapidly denitrated with a specific catalytic activity of 8.7 g cat -1 min -1 , while biological reductions of nitrate and perchlorate remained efficient. In the subsequent 30-day continuous test, >99% of RDX, nitrate, and perchlorate were coremoved, and their effluent concentrations were below their respective regulation levels. Detected intermediates and shallow metagenome analysis suggest that the intermediates after Pd-catalytic denitration of RDX ultimately were enzymatically utilized by the nitrate- and perchlorate-reducing bacteria as additional electron donor sources.

Switchable-hydrophilicity solvent liquid-liquid microextraction was coupled with smartphone digital image colorimetry for the determination of palladium as its metal chelate with N,N-diethyl-N'-benzoylthiourea. Images of the colored extract were captured in a homemade colorimetric box, which were split into their red-green-blue channels. The blue channel was used to determine the concentration of palladium. Optimum extraction conditions were achieved using 600 μL of triethylamine as the extraction solvent and 4.0 mL of 10 M sodium hydroxide as the hydrophilicity-switching trigger within 1.0 min extraction time. Optimum complexation conditions were obtained at a sample pH of 4.50, and metal/ligand mole ratio of 1:2 within 3.0 min. Optimum detection conditions were achieved at a distance of 7.0 cm between the sample solution and the detection camera, a region of interest of 175.0 px 2 at a detection wavelength of 480.0 nm and 30.0% brightness of the monochromatic light source. Limits of detection and quantitation were found to be less than 0.7 and 1.8 µg g -1 , respectively. A good linearity with coefficients of determination above 0.9974 was obtained. Accuracy was checked via a single-factor analysis of variance (ANOVA) test by comparing the results with the ones obtained using flame-atomic absorption spectrometry and the results were statistically in a good agreement (P > 0.05). The proposed method was applied for the determination of palladium in catalytic converters with percentage relative recoveries ranging between 95.7 and 103.7% and percentage relative standard deviations below 4.0%., (© 2022. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

Platinum group metals (PGMs) present a variety of forms in the environment, and analysis of speciation is essential for identifying their ecological risk. Here, we reviewed the methods for the morphological analysis of three major PGMs (platinum, palladium and rhodium) in the environment, including chemical sequential extraction, hyphenated techniques for instruments, computer simulations. We outlined the types, characteristics and applications of these methods, elaborated the weaknesses, and provided prospects for future development. Among them, chemical sequential extraction is universally applied in the morphological analysis of solid-phase samples, with diverse extraction conditions and procedures proposed in the current study. However, it has not been well standardized. The hyphenated techniques for instruments have significant advantages for the determination of elemental forms in solution, of which capillary electrophoresis system can separate similar substances with the same electrophoresis ability. Liquid chromatography systems have better performance in terms of separation capacity and detection limit. The computer simulations further expand the access to morphological analysis, enabling complex morphological calculations. It was proposed to combine multiple methods in the future to continuously improve the accuracy of analytical techniques by complementing and optimizing each other.

Palladium nanoparticles (PdNPs) play an integral role in motor vehicles as the primary vehicle exhaust catalyst (VEC) for tackling environmental pollution. Automobiles equipped with Pd-based catalytic converters were introduced in the mid-1970s and ever since the demand for Pd has steadily increased due to stringent emission standards imposed in many developed and developing countries. However, at the same time, the increasing usage of Pd in VECs has led to the release of nano-sized Pd particles in the environment, thus, emerging as a new source of environmental pollution. The present reports in the literature have shown gradual increasing levels of Pd particles in different urban environmental compartments and internalization of Pd particles in living organisms such as plants, aquatic species and animals. Occupational workers and the general population living in urban areas and near major highways are the most vulnerable as they may be chronically exposed to PdNPs. Risk assessment studies have shown acute and chronic toxicity exerted by PdNPs in both in-vitro and in-vivo models but the underlying mechanism of PdNPs toxicity is still not fully understood. The review intends to provide readers with an in-depth account on the demand and supply of Pd, global distribution of PdNPs in various environmental matrices, their migration and uptake by living species and lastly, their health risks, so as to serve as a useful reference to facilitate further research and development for safe and sustainable technology., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in the paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

An efficient, sensitive, and easy deep eutectic solvent based (DESb) liquid phase microextraction (LPME) method was developed to preconcentrate palladium for quantification at trace level by a flame atomic absorption spectrometry (FAAS) system, equipped with a lab made slotted quartz tube (SQT). All parameters of the DESb-LPME-SQT-FAAS system were optimized to lower the detection limit of the system. Using the optimized conditions, quantification and detection limits were obtained as 24.7 and 7.4 μg L -1 , respectively, which are compatible with the literature findings. Detection power of the FAAS system was enhanced by almost 50-fold using the optimum method based on LOD comparison. Recovery experiments were also performed with spiked wastewater matrix to examine the applicability/validity of the proposed method. The % recovery results were calculated between 85 and 91%. This established that the applicability of the developed method is high, and determination of this element in complex matrix can be performed accurately using the developed method.

Platinum group elements (PGE: Ru, Rh, Pd, Os Ir, Pt) are rare metals with low abundance in the continental crust. The elements of the palladium subgroup of PGE (PPGE: Pt, Pd, Rh) have been exploited more and more over the last thirty years for their physicochemical properties such as high melting point, high resistance to corrosion, mechanical strength and ductility. This led to emerging environmental contamination in different media such as air, road dust, soil, sediment, vegetation, and snow. The aim of this review is to summarize the available data on soil contamination by PPGE and its potential environmental impact. In this paper, the environmental issue of PPGE is discussed with regard to their anthropogenic emission and fate, which includes speciation, possible transformations into bioavailable forms and toxicity. Soil contamination by PPGE is described taking into account urban and non-urban areas. The analytical determination process is also discussed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

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 (I geo ), 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., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Determination of Pd traces in environmental samples is still a challenging analytical task. The aim of this study was to propose an efficient system (i.e. ion-exchange resin and eluent) for Pd elution from SPE column after the analyte preconcentration. Moreover, the search was focused on solvents that would not interfere voltammetric determination of Pd, as well as ICP-MS analysis. Five ion-exchange sorbents were compared in terms of effective Pd separation from matrix components when using different eluents. The highest recovery (up to 91%) of palladium was obtained for Dowex 1 and ammonium buffer as the eluent. This solution not only provides relatively high palladium elution efficiency but also allows both voltammetric and ICP-MS determinations, without any additional sample preparation. It was proven that the proposed procedure including SPE separation and determination with AdSV and/or ICP-MS could be used for quantitative Pd measurement in environmental samples, such as quartz sand used for the monitoring of Pd emission in the areas of high traffic density., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The pressed powder sample is a common method for elemental analysis using X-ray fluorescence analysis whereas suitable light hydrocarbon materials should be added to the sample as a binder. The present study demonstrates the applicability of using different commercial binders for elemental analysis of urinary stone samples. In order to confirm the obtained results, a comparison with pure chemical grade binders was presented. Different commercial and pure binders were tested for quantitative elemental analysis of urinary stones, namely, cellulose, starch, wax, and urea. Energy dispersive X-ray fluorescence (EDXRF) was used for elemental analysis. Differential thermal analysis was used to estimate the loss on ignition (LOI) in the urinary stone samples. The signal to background ratios (I/I B ) of the different detected elements in the commercial and pure binders were calculated, compared, and studied at eight different photon energies starting from 2.5 up to 37 keV. Standard-less quantitative analysis method based on the fundamental parameter approach was applied for elemental analysis of selected urinary stones. The commercial and low-cost binders could be an excellent alternative binder for urinary stone analysis using energy dispersive X-ray fluorescence. The commercial binders could provide an advantage as pure chemical grade binders or even better especially at photon energy higher than 10 keV. The best commercial binder candidate was found to be the wax. The quantitative analysis results using commercial and pure chemical grade binders give good agreement results, which indicate the applicability of commercial binders for quantitative elemental analysis of urinary stones in the form of pressed powder samples.

Platinum group elements (PGE) including Ru, Rh, Pt and Pd have been quantified in air particulate matter with an aerodynamic diameter equal or less than 10 microns (PM 10 ) using inductively coupled plasma mass spectrometry (ICP-MS). PM 10 aerosols have been collected from three sites representing various activities in Jeddah city, Saudi Arabia. These locations are residential site with heavy traffic, industrial site and heavy traffic and a light traffic site outside the city. To obtain reasonable data of the PGE concentrations, a group from 10 to 15 PM 10 samples were collected every month. The annual and seasonal variation of the mass concentration of the PGE were demonstrated. In all locations, Pt and Pd were relatively higher than Ru and Rh possibly because their main use is in automobile catalytic converters. Concentrations of observed PGE in PM 10 could be arranged in ascending order as: Rh < Ru < Pd < Pt. In case of Ru and Pt, there are clear similarities in terms of the overall mean concentrations at the sampling locations. Due to the high concentration of Ru, Rh and Pd at low traffic site, there are certainly other sources of these elements rather than vehicle catalytic converters. However, at the industrial/heavy traffic location, high concentrations of Ru were detected during February 2015. In addition, high Pt concentrations were also detected at the light traffic site during May 2015. Results indicate that Pt source in PM 10 is mainly the automobile catalytic converters.

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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Palladium (Pd) has been acknowledged to be a rare inner transition metal, which plays a pivotal role in many fields. This article focuses on developing a safe and effective near-infrared fluorescent probe, MW-PD, which would make a great contribution to the detection of palladium residue in drugs, especially trace residues. The fluorescent probe was rationally designed by combining the dicyanoisophorone fluorophore with an allyloxycarbonyl group. Based on the Tsuji-Trost reaction, the probe exhibited high selectivity and sensitivity toward Pd (0) over other common metal ions with a low detection limit (8.0 nM). Moreover, MW-PD showed biocompatibility and was successfully applied to imaging Pd (0) in Hela cells.

Measurable quantities of platinum, palladium, and rhodium, even in remote areas of the planet, evidence the global nature of pollution with these metals, mostly from catalytic converters of modern vehicles (other sources are jewellery production, chemical industry, and anticancer drugs). The amount of the platinum group metals (PGMs) emitted from automobile catalysts varies with the type, age, and condition of the engine and the catalyst, as well as the style of driving. Current literature suggests that the concentrations of these metals have increased considerably over the last twenty years, palladium concentrations in particular, as it has been proved more effective catalyst than platinum. However, whether and to what extent the emitted PGMs are toxic for people is still a controversy. The potential health risk from exposure to these elements is most likely for those living in urban environments with busy roads or along major highways. Because of the importance of PGMs and their trace levels in particulate matter, sensitive methods are required for reliable determination. This review discusses particular steps of analytical procedures for PGM quantification in airborne particulate matter and addresses the common preparation, detection, and determination methods.

Adsorption and fractionation of Pt, Pd and Rh (defined here as platinum group elements, PGEs) onto the representative inorganic microparticles, including Fe 2 O 3 , MnO 2 , CaCO 3 , SiO 2 , Al 2 O 3 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 Fe 2 O 3 and MnO 2 had the strongest interaction with PGEs. The adsorption of PGEs onto the representative biogenic particles SiO 2 and CaCO 3 and lithogenic particles Al 2 O 3 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 K d ) 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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Silver nanoparticles (AgNPs) coated with whey peptides are shown to be a useful optical nanoprobe for the highly sensitive determination of Pd(II). The peptidic surface of the AgNPs works as a molecular receptor for the rapid detection of Pd(II) via a color change from dark yellow to orange/red along with a spectral red-shift with a gap about 120 nm. The effect is caused by the formation of a coordination complex between Pd(II) and the peptide ligands. This results in the aggregation of AgNPs and an absorbance spectral shift from 410 to 530 nm. The absorbance response is linear in the range 0.1 to 1.3 μM Pd(II) with a low detection limit of 115 nM. The nanoprobe responds within a few minutes and is not interfered by other metal ions except for Mg(II). The probe potentially can be applied to the determination of Pd(II) contamination in the products of Pd(II)-catalyzed organic reactions and in pharmaceutical settings. Graphical abstractSchematic representation of the nanoprobe for Pd(II). (a) Synthesis of whey peptide-coated silver nanoparticles (AgNPs), (b) the nanoprobe design for Pd(II) detection, (c) HR-TEM imaging and elemental mapping, (d) quantitative determination of Pd(II) (Inset shows colorimetric results).

In this study, a rapid and effective dispersive solid-phase microextraction (d-SPME) method was developed to preconcentrate Pd from aqueous extract of soil samples by slotted quartz tube-flame atomic absorption spectrometry (SQT-FAAS). The unique properties of magnetic nanoparticles (MNPs) were used to directly isolate Pd from the sample solutions without the need for complexation. Significant parameters of the extraction method such as magnetic nanoparticle type and amount, pH and amount of buffer solution, amount of eluent, and mixing type and period were optimized together with other instrumental parameters to boost the absorbance signal of Pd. An SQT was fitted onto the burner head to boost the interaction between Pd atoms and hollow cathode lamp radiation to enhance absorbance signals. The limit of detection (LOD) and limit of quantification (LOQ) values for Pd determined (d-SPME-MNP-SQT-FAAS) were 6.4 and 21.4 ng/mL, respectively. The percentage relative standard deviation of the developed method was calculated as 6.6%. The method was applied to soil samples taken from the campus area and spiked recovery experiments were performed to evaluate the method's accuracy/applicability. Satisfactory percent recovery results (90-101%) were obtained for different spiked concentrations and this proved the accuracy/applicability of the method.

Palladium (Pd) has drawn worldwide attentions because its connections to industry, chemistry, biological material and public health. Quantitative and selective detection tools for Pd and its ion forms are in urgent necessity. Here an umbelliferone derivative Umb-Pd2 was provided as a small, steady, safe and selective sensor for detecting Pd(II). It indicated advantages including sensitive (LOD 1.1 nM), wide pH tolerance (5.0-10.0), applicable linear range (0-1.8 equivalent) and low toxicity. The most attractive point was its explicit selectivity towards Pd(II) from Pd(0) in both independent and coexistence systems. This distinguishing ability was further utilized in imaging in living cells, raising this work as a rare and important example among all the published papers on palladium sensing. Thus, Umb-Pd2 supplied a potential approach for further improvement and applications in both daily chemistry and public health., (Copyright © 2019. Published by Elsevier B.V.)

The spatial distribution of Pt and Rh was assessed in Tagus estuary and their sources discussed. Both elements were analysed in superficial sediment samples (n = 72) by adsorptive cathodic stripping voltammetry. Concentrations varied within the following ranges: 0.18-5.1 ng Pt g -1 and 0.02-1.5 ng Rh g -1 . Four distinct areas were established: "reference"; waste- and pluvial water discharge; motorway bridges and industrialised areas. The calculated reference median concentrations were 0.55 ng Pt g -1 and 0.27 ng Rh g -1 . Linear relationships were found between Pt and Al, Fe and LOI, whereas Rh depicted scattered patterns. The highest concentrations were found nearby industrialised areas and a motorway bridge, corresponding to the enrichment of 10 and 6 times the background of Pt and Rh, respectively. The main sources of contamination to the Tagus estuary derived from historical and present industrial activities and from automotive catalytic converters. Large variations of Pt/Rh ratio (0.48-39) point to different sources, reactivity and dilution effects.

A novel magnetic ion-imprinted polymer with high accessibility to palladium ions was synthesized via co-precipitation polymerization. Accordingly, a ternary complex composed of PdCl 2 as an imprinting ion, 8-aminoquinoline (AQ) as a ligand, and 4-vinyl pyridine (4-VP) as a complexing monomer was applied to Fe 3 O 4 @SiO 2 as magnetic core, followed by precipitation polymerization using 2-hydroxyethyl methacrylate (2-HEMA) as a co-monomer, ethylene glycol dimethacrylate (EGDMA) as the crosslinker, and 2,2-azobisisobutyronitrile (AIBN) as an initiator in the presence of 2-methoxyethanol as a solvent. The palladium ions were leached out by a solution containing 50% (v/v) HCl. The synthesized polymer was characterized physically and morphologically using different techniques. In order to assess the conditions required for adsorption, as well as the selectivity and reusability, batch adsorption experiments were carried out. The experiments exhibited that the maximum adsorption capacity was about 65.75 mg g -1 at 25 °C, while the pH solution and the adsorbent dose were 4 and 1 g L -1 , respectively. Kinetic studies of experimental data demonstrated that they correspond very much to the pseudo-second-order kinetic model. The development of the Langmuir and Freundlich isothermal models on the equilibrium data proved to correspond well to the Langmuir isotherm model. Interferences studies of the magnetic polymer demonstrated higher affinity and discernment for palladium ions than other co-existing ions in the solutions. Spontaneous (ΔG < 0) and exothermic (ΔH < 0) behavior of the adsorption process is confirmed by thermodynamic studies. In addition, the affinity of the spent polymer has not been dramatically reduced over at least five regeneration cycles.

A convenient and sensitive spectrophotometric methods was proposed for determination of Malathion (Mala) using Erythrosin B (EryB) as a probe through the Resonance Rayleigh scattering (RRS) technique. The interaction between EryB, Pd 2+ and malathion in the system was investigated by fluorescence, RRS and UV-Vis spectroscopy. Under the optimum conditions, the RRS intensity of EryB, Pd 2+ and malathion was weak when exist in alone or any two kinds, however, the RRS intensity of the EryB-Pd 2+ -Mala system had an obvious enhancement due to Pd 2+ could interact with the hydrolysis products of Mala and EryB each other form a new complexes. At the same time, the fluorescence intensity of EryB was decreased significantly in the presence of Pd 2+ , and the fluorescence intensity of EryB-Pd 2+ system further decreased when Mala added, interestingly. So it was further proved that there was a forming complex in EryB-Pd 2+ -Mala system. Under the optimal conditions, the RRS enhanced intensity of the system was linearly proportional to the Mala's concentration in the range of 0.012-0.8 μg/mL, and the LOD was 1.7 ng/mL, with the correlation coefficient was R 2  = 0.9960. So, a new method for determination of Mala was established and this method has been demonstrated in real sample with satisfactory results., (Copyright © 2019 Elsevier B.V. All rights reserved.)

To develop a strategy for visualizing palladium species in the biological system, several turn-on bioluminescent probes were designed and synthesized by using a Pd-induced reductive reaction herein. Such probes exhibited high sensitivity (detection limit: 0.5 μM) and excellent selectivity toward Pd 2+ in vitro. In particular, probe 2 was identified as a viable molecule with the capability of visualizing the fluctuations of level and distribution of Pd 2+ in living cells and animals, which provides a valuable tool for tracing Pd 2+ in biological system., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study presents a green analytical method for palladium determination by slotted quartz tube flame atomic absorption spectrometry (SQT-FAAS) following switchable liquid-liquid microextraction (SLLME). Efficient extraction of palladium was facilitated by complexation with a Schiff base ligand, synthesized specifically for this study. A three-stage thorough optimization procedure was carried out to boost the absorbance output of palladium. Complex formation was the first stage, and parameters evaluated included buffer solution pH and amount, concentration of ligand, and mixing period. The amount of switchable solvent and concentration and amount of sodium hydroxide and acid amount were optimized in the second stage. Optimization of sample and fuel flow rates and SQT parameters completed the third stage of optimization, and all optimum parameters were used to determine analytical performance of the method. The method had a broad linear dynamic range, and the calibration plots showed good linearity with R 2 values greater than 0.9991. The limits of detection and quantification of the SLLME-SQT-FAAS method were 15 and 50 μg/L, respectively. The precision of the method, expressed as percent relative standard deviation, was below 9.0% for all measurements. Spiked recovery results performed for a palladium electroplating bath solution gave poor results when quantified against aqueous calibration standards. Matrix matching was therefore used to improve recovery results which ranged between 97 and 105% for four different spike concentrations.

The environmental levels of platinum group elements (PGEs) are steadily rising, primarily due to exhaust emissions of vehicle catalytic converter (VCC) materials containing solid PGEs. Once these VCC materials reach soil and water, the PGEs may be transported in the form of nanoparticles (dimensions 1-100 nm) or they may be mobilized by forming coordination complexes with ligands in the environment. Chloride (Cl-) and ammonia (NH3) are two ligands of particular concern due to their ubiquity as well as their potential to form the chemotherapy drug cisplatin (Pt(NH3)2Cl2) or other potentially bioactive complexes. This initial study examines the release of Pd and Pt into solutions exposed to VCC materials at pH 8 and 25 °C, using elemental analysis of metal content in post-exposure extracts. The solutions had total ammonia nitrogen concentrations (TAN, [NH4+] + [NH3]) of 0 μM, 5.56 μM, 55.6 μM and 1.13 × 105 μM (0 ppm, 0.1 ppm, 1 ppm, and 2147 ppm). The former three represent background environmental levels had a minimal effect on release. However, when combined with 1.13 × 105 μM Cl- (4000 ppm Cl-), 55.6 μM TAN induced a marked increase in metal release (∼41× for Pd). High TAN solutions induced more Pd and Pt release than equimolar NaCl solutions. Materials characterization revealed that ∼4 nm palladium-containing nanoparticles were present, spatially associated with nanoparticles of γ-Al2O3; ceria-zirconia nanoparticles were also present but did not have any metal associated with them. Platinum-containing nanoparticles were not observed.

A novel lysosome-targetable phthalimide fluorescent probe was designed for detecting palladium based on ESIPT for signal transduction. The fluorescent probe conjugating with allylcarbamate displayed weak fluorescent due to the ESIPT process hinder by allylcarbamate. But with the addition of palladium, the ESIPT emission was recovery though the palladium-catalyzed deallylation reaction and the fluorescence intensity exhibited 40-fold enhancement at 511 nm. In addition, the probe showed excellent selectivity, high sensitivity, fast responds and low limit detection for palladium with a larger Stoke-shift. Moreover, the targetable probe was also successfully applied for detecting palladium in lysosomes of living cells. Hence, the probe though ESIPT modulation is a promising for monitoring palladium in practical samples., (Copyright © 2018. Published by Elsevier B.V.)

A method was modified for the preconcentration of platinum (Pt), palladium (Pd) and rhodium (Rh) from seawater by a solid phase extraction using a commercially available resin Nobias-chelate PA1 ® . All the determination was conducted using inductively coupled plasma mass spectrometry (ICP-MS) which had a low detection limit for Pt, Pd and Rh, about 16.53, 16.41 and 26.88 pg L -1 , respectively. It was found that the adsorption performance of the resin was closely related to the matrix, ligands and pH of the samples. Significant difference in recovery was found in various samples: seawater ≈ artificial seawater > ultra-pure deionized water. This method had low method blank in the range of 5.51-8.89 pg L -1 and high enrichment factor of up to 180-200. The recoveries of Pt and Pd were 93 ± 4.2% in the spiked real seawater. However, the recovery of Rh on the resin was below 70% but stable in the range of 65-68%. It indicated that the Rh recovery seemed to be reproducible and higher volumes of seawater must be processed in order to obtain the lower limit of quantification and excellent recovery., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Platinum (Pt), palladium (Pd) and rhodium (Rh) are most widely used in the production of automotive catalytic converters that serve to reduce toxic emissions from motor vehicles. The aim of this study was to quantitatively determine the levels of platinum, palladium and rhodium in the PM 10 and PM 2.5 fraction of airborne particle matter and find their spatial and temporal distribution at different polluted areas of the city of Zagreb, Croatia. The method used in this paper included weekly sampling of airborne particle matter on quartz filters, microwave digestion in acid under high pressure and temperature, and analysis by inductively coupled plasma mass spectrometry (ICP MS). The results have shown that the highest mean values at all three sampling stations (North, Center, South) were obtained for palladium (3.856 pg m -3 , 5.396 pg m -3 , 5.600 pg m -3 ) and the lowest for rhodium (0.444 pg m -3 , 0.643 pg m -3 , 0.750 pg m -3 ). The average mass concentrations of platinum group elements (PGE) in PM 10 increased for all three elements in the direction North < Center < South which had to do with the traffic load nearby the monitoring stations. The ratio of measured mass concentrations to all measuring stations was similar to platinum, palladium and rhodium content in automotive catalytic converters. Factor analysis grouped platinum, palladium and rhodium at all of the monitoring stations, and their relation to other metals together with the aforementioned results indicate that their main source of pollution is traffic or precisely automotive catalytic converters. At all three of the monitoring sites, higher values were measured during the colder part of the year. The results of measuring platinum, palladium and rhodium levels in the city of Zagreb are the first results of their kind for this area and will provide insights into the contribution of catalytic converters to the presence of these elements in the environment., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The efficient fluorescent property of coumarin 460 (C460) is utilized to sense the Pd 2+ selectively and sensitively. Fabrication of a sensor strip using commercial adhesive tape is achieved and the detection of Pd 2+ is attempted using a handy UV torch. The naked eye detection in solution state using UV chamber is also attempted. The calculated high binding constant values support the strong stable complex formation of Pd 2+ with C460. The detection limit up to 2.5 × 10 -7  M is achieved using fluorescence spectrometer, which is considerably low from the WHO's recommendation. The response of coumarin 460 with various cations also studied. The quenching is further studied by the lifetime measurements. The binding mechanism is clearly explained by the 1 H NMR titration. The sensing mechanism is established as ICT. C460 strip's Pd 2+ quenching detection is further confirmed by solid-state PL study. The in-vitro response of Pd 2+ in a living cell is also studied using fluorescent imaging studies by means of HeLa cell lines and this probe is very compatible with biological environments. It could be applicable to sense trace amounts of a Pd 2+ ion from various industries. Compared with previous reports, this one is very cheap, sensitive, selective and suitable for biological systems., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Palladium (Pd) is widely used in chemistry, biology, environmental science etc., and Pd 2+ is the most plenitudinous oxidation state of the Pd that can exist under physiological conditions or in living cells, which could have adverse effects on both our health and environment. Thus, it is of great significance to monitor the changes of Pd 2+ . Hence, a novel near-infrared fluorescent probe M-PD has been developed for selective detection of Pd 2+ based on naphthofluorescein in this work. The result demonstrated that M-PD exhibited favorable properties for sensing Pd 2+ such as excellent water solubility, high selectivity and sensitivity. And the limit of detection was estimated as 10.8 nM, much lower than the threshold in drugs (5-10 ppm) specified by European Directorate for the Quality Control of Medicines. More importantly, detection and recovery experiments of Pd 2+ in aspirin aqoeous solution and soil are satisfactory. In addition, M-PD has also been successfully used for near-infrared fluorescence imaging of Pd 2+ in living cells, indicating that the probe has better feasibility and application potential in the determination of Pd 2+ ., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Herein, a novel ferrocene-rhodamine receptor conjugated with an allylimine bridge was facilely synthesized. This triple channel receptor can selectively and sensitively monitor Pd 2+ ions through chromogenic, fluorogenic and electrochemical assays in aqueous medium with a low detection limit (8.46 × 10 -9 M) and a fast response (<8 min). It can be applied as a fluorescent probe for effective survey of Pd 2+ ions in living cells. Moreover, a plausible recognition mode was proposed and rationalized by theoretical calculations.

Palladium is a highly valuable metal in automobile, chemical, and pharmaceutical industries. The metal is generally quantified by atomic absorption spectrometry or inductively coupled plasma mass spectrometry. These techniques are tedious and require expensive instruments that are operated mostly off site. As cost-effective and user-friendly alternatives to these techniques, we previously reported two practical fluorometric or colorimetric methods to quantify palladium. Both methods rely on the use of NaBH 4 , which cannot be stored in solution for more than 10 days. Commercially available solutions of NaBH 4 are partially or fully degraded to di- or triborohydride species and cannot be used for palladium(0)-catalyzed allylic C-O bond cleavage for quantification purposes. Here, we report a new method that replaces NaBH 4 with NH 2 NH 2 for the palladium-catalyzed deallylation of fluorogenic and colorimetric chemodosimeter resorufin allyl ether. This method is slower but as sensitive as the most recent method from our laboratory. The method is selective for palladium and depends on the presence of tri(2-furyl)phosphine as a palladium ligand and NH 2 NH 2 as a palladium-reducing reagent.

A novel ratiometric ESIPT fluorescent probe, which is specific for palladium species of all the typical oxidation states (0, +2, and +4), has been designed. Notably, based on the excited state intramolecular proton transfer (ESIPT) process, the probe exhibits a ratiometric fluorescent response to palladium species with a low detection limit (9.0 nM, 0.96 ppb) in about 1.5 min at room temperature. Moreover, it has been successfully used as a two-photon ratiometric fluorescent palladium probe for in vivo and three-dimensional imaging with low cytotoxicity and autofluorescence. Compared with other reported palladium probes, the probe displays a shorter ratiometric response time and lower detection limit in milder test conditions. All of the results indicate that the probe may be favorable for environmental and biological applications.

A new rhodamine based allyl-ether Schiff base (RD) was spectroscopically characterized and used as a colorimetric and fluorimetric sensor. RD acts as turn-on highly selective fluorescent chemosensor for Pd(ii) from only a mixture of Pd(0) and Pd(ii) in the presence of 25 other cations in aqueous-acetonitrile medium. The mechanism for Pd(ii) sensing with RD involves Pd(ii)-triggered terminal (C-O)-allyl bond cleavage followed by opening of the spirolactam ring. Pd(ii) is allylphilic and the (rhodamine)O-allyl moiety selects Pd(ii) from the mixture (Pd(0) + Pd(ii)), and a fluorescence enhancement is observed. The proposal has been supported by spectroscopic data (FTIR, 1 H NMR, 13 C NMR, and mass spectroscopy). It is again supported by examining the Pd(ii) selectivity of an non-allylated rhodamine appended iminephenol (RD'), which failed to selectively detect Pd(ii). Hence, the presence of the allylether is mandatory in the fluorogenic motif for Pd(ii) selectivity. The limit of detection (LOD) of Pd(ii) by RD is 50 nM at pH 7.4. Fluorescence microscopic studies help in imaging the cellular uptake of Pd 2+ at the nM level in the HCT116 (Human colorectal carcinoma) cell line.

This study examined a method for determination of rhodium (Rh), palladium (Pd) and platinum (Pt) in particulate matter using standard solutions, model samples and certified reference materials (NIST 1648a and ERM CZ120). The method was based on microwave digestion followed by inductively coupled plasma mass spectrometry (ICP-MS). The results showed that the stability of the standard solution mixture of Rh, Pd and Pt was better when chlorides were present in the solution. A membrane filter and one type of quartz filter were the most adequate for analyzing platinum group elements (PGE). Respective limits of detection for Rh, Pd and Pt were 0.028, 0.503 and 0.0265 pg/m 3 with a membrane filter and 0.478, 4.530 and 0.070 pg/m 3 for one type of quartz filters. The sample matrix had no significant effects on the determination of three PGEs.

Roadside dust and soil samples were collected at different sites in the area of Ulm and Munich in Germany. Road dust samples were collected in tunnels where the traffic-related dust is less influenced by atmospheric conditions. Soil samples were taken with a drill bar at varying distances to motorways, district and regional roads with different traffic densities. The soil cylinders of 30cm length were divided into four sections in order to obtain depth profiles for palladium (Pd) distribution. Determination of Pd in total digests of the samples was performed by ligand-assisted selective separation and preconcentration of Pd(II) using solid phase extraction followed by high-resolution continuum source graphite furnace spectrometry. The analytical procedure was successfully validated using the certified reference material BCR-723 Road Tunnel Dust and by recovery experiments in spiked soil samples. The average Pd concentration found in the road dusts was 311μgkg -1 , the maximum Pd concentration in the topsoil layer was 193μgkg -1 . Pd depth profiles reveal transportation of Pd into deeper soil layers, where even at a depth of 25 to 30cm a Pd concentration of 19μgkg -1 was found, proving the high mobility of Pd. Different factors like traffic density and age of the soils are discussed in the context of the found Pd depth profiles., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Ratiometric two-photon fluorescent probes can not only eliminate interferences from environmental factors but also achieve deep-tissue imaging with improved spatial localization. To quantitatively track Pd(2+) in biosystems, herein, we reported a ratiometric two-photon fluorescent probe, termed as Np-Pd, which based on a D-π-A-structure two-photon fluorophore of the naphthalimide derivative and deprotection of aryl propargyl ethers by palladium species. The probe Np-Pd displayed a more than 25-fold enhancement towards palladium species with high sensitivity and selectivity. Additionally, the probe Np-Pd was further used for fluorescence imaging of Pd(2+) ions in living cells and tissues under two-photon excitation (820nm), which showed large tissue-imaging depth (19.6-184.6μm), and a high resolution for ratiometric imaging., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A novel water-soluble colorimetric and fluorescent palladium probe with excellent selectivity and sensitivity has been designed. Notably, based on a palladium triggered terminal allyl ether cleavage reaction, the probe could detect and discriminate Pd(0) and Pd(2+)/Pd(4+) in about 2.5 min at room temperature with a low detection limit (0.29 ppb) and significant colour change (from light yellow to pink). The probe could serve as an excellent "naked-eye" colorimetric probe for selective and quantitative determination of palladium in aqueous solutions. Moreover, it could be used as a two-photon palladium probe for in vitro/vivo and three-dimensional imaging with low cytotoxicity and autofluorescence.

The use of transplanted moss (Pleurozium schreberi) in active biomonitoring of traffic-related emissions of Pd, Pt, and Rh was studied. Moss mats were transplanted to three locations along highway E75 (in Oulu, Finland) at three different distances from the highway. Five samples were collected from a background site after the same exposure period. Mass fractions of Pd, Pt, and Rh as well as mass fractions of 18 other elements were determined in these samples. The results indicated that P. schreberi is well suited for active biomonitoring of Pd, Pt, and Rh. Mass fractions above the background values were observed in the samples exposed to traffic-related emissions. When the results were compared with those of the other elements, high correlations of Pd, Pt, and Rh with commonly traffic-related elements (e.g., Cu, Ni, Sb, Zn, etc.) were found. It was also found that the amounts of Pd, Pt, and Rh in moss samples decreased when the distance to the highway increased. This trend gives evidence for the suitability of P. schreberi for active biomonitoring of Pd, Pt, and Rh. Furthermore, it can be concluded that the mass fractions determined in this study provide valuable evidence about the current state of Pd, Pt, and Rh emissions in Oulu, Finland.

The new monophosphine ligand HandaPhos has been identified such that when complexed in a 1:1 ratio with Pd(OAc)2, enables Pd-catalyzed cross-couplings to be run using ≤1000 ppm of this pre-catalyst. Applications to Suzuki-Miyaura reactions involving highly funtionalized reaction partners are demonstrated, all run using environmentally benign nanoreactors in water at ambient temperatures. Comparisons with existing state-of-the-art ligands and catalysts are discussed herein., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Anodic stripping voltammetry, a classical electroanalytical method has been optimized to analyze trace Pd(II) in active pharmaceutical ingredient matrices. The electroanalytical approach with an unmodified glassy carbon electrode was performed in both aqueous and 95% DMSO/5% water (95/5 DMSO/H2O) solutions, without pretreatment such as acid digestion or dry ashing to remove the organics. Limits of detection (LODs) in the presence of caffeine and ketoprofen were determined to be 11 and 9.6 μg g(-1), with a relative standard deviation (RSD) of 5.7% and 2.3%, respectively. This method is simple, highly reproducible, sensitive, and robust. The instrumentation has the potential to be portable and the obviation of sample pretreatment makes it an ideal approach for determining lost catalytic metals in pharmaceutical-related industries. Furthermore, the simultaneous detection of Pd(II) with Cd(II) and Pb(II) in the low μg L(-1) range indicates that this system is capable of simultaneous multi-analyte analysis in a variety of matrices., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Palladium contamination causes potential danger to the environment, and a study of its biological safety is still on the way. Here, a fluorescent and colorimetric probe (compound 1) containing oxime-ether for Pd(2+) has been developed. 1 can detect Pd(2+) in aqueous samples with high selectivity and sensitivity. 1 can also work well in biological samples, which gives access to detect Pd(2+) in an organism.