RESUMO
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.
Assuntos
Platina , Ródio , Brasil , Monitoramento Ambiental , Estuários , Paládio/análise , Platina/análise , Ródio/análiseRESUMO
Abstract A novel series of platinum (II) complexes was synthesized and the complexes were evaluated for their in vitro cytotoxicity against four human cancer cells lines. Five platinum complexes showed activity against at least one tumor cell line. Complexes 3 and 6 were promising, being active, at micromolar concentrations, against all the assayed tumor cell lines. Compound 3 was selected for further studies in mice with Ehrlich solid tumors and it was able to reduce the rate of tumor growth significantly during the first seven days. However, at the end of the experiments, there was no significant difference between the group of animals treated with 3 and the control group. The low solubility of the compound in the assay conditions can explain, at least in part, these results.
Assuntos
Animais , Masculino , Feminino , Ratos , Platina/análise , Ensaios de Seleção de Medicamentos Antitumorais/instrumentação , Testes Imunológicos de Citotoxicidade/classificação , Carcinoma de Ehrlich/classificação , Citotoxinas/efeitos adversosRESUMO
The increase in platinum (Pt) in the airborne particulate matter with size ≤2.5 µm (PM2.5) in urban environments may be interpreted as result of the abrasion and deterioration of automobile catalyst. Nowadays, about four million vehicles in Mexico City use catalytic converters, which means that their impact should be considered. In order to evaluate the contribution of Pt to environmental pollution of the metropolitan area of Mexico City (MAMC), airborne PM2.5 was collected at five different sites in the urban area (NW, NE, C, SW, SE) in 2011 during April (dry-warm season), August (rainy season) and December (dry-cold season). Analytical determinations were carried out using a ICP-MS with a collision cell and kinetic energy discrimination. The analytical and instrument performance was evaluated with standard road dust reference material (BCR-723). Median Pt concentration in the analyzed particulate was is 38.4 pg m(-3) (minimal value 1 pg m(-3) maximal value 79 pg m(-3)). Obtained Pt concentrations are higher than those reported for other urban areas. Spatial variation shows that SW had Pt concentration significantly higher than NW and C only. Seasonal variation shows that Pt median was higher in rainy season than in both dry seasons. A comparison of these results with previously reported data of PM10 from 1991 and 2003 in the same studied area shows a worrying increase in the concentration of Pt in the air environment of MAMC.
Assuntos
Poluentes Atmosféricos/análise , Monitoramento Ambiental , Material Particulado/análise , Platina/análise , Cidades , Poeira/análise , Espectrometria de Massas/métodos , México , Tamanho da Partícula , Estações do AnoRESUMO
Over the last years, investigations on the increase of platinum (Pt), palladium (Pd), and rhodium (Rh) levels in urban environments of big cities all over the world - especially to catalytic converters emissions - have been grown up enormously. São Paulo City is the 6th largest megacity in the world having about 20 million inhabitants and an ever increasing seven million motor vehicle fleet. In spite of this, there has never been an investigation regarding Pt, Pd, and Rh levels in the city. In the present study, Pt, Pd, and Rh concentrations were determined in soils adjacent to seven main high-density traffic avenues in the metropolitan region of São Paulo City. Inductively coupled plasma mass spectrometry was employed - after ultrasound-assisted aqua regia leaching - as analytical technigue. The results showed concentration levels up to 378 ng g(-1) for Pd, 208 ng g(-1) for Pt, and 0.2 to 45 ng g(-1) for Rh. These levels are much higher than those considered for the geochemical background of soils, indicating a catalytic converter source. Due to the different Pt/Pd/Rh ratio in Brazilian automobile catalytic converters, lower levels of Pt/Pd ratios compared with other similar studies were observed. The obtained results are the first data for monitoring Pt, Pd, and Rh pollution in São Paulo City soils.
Assuntos
Monitoramento Ambiental , Paládio/análise , Platina/análise , Ródio/análise , Poluentes do Solo/análise , Brasil , Cidades , Humanos , Veículos Automotores , Solo/químicaRESUMO
This work describes a route for platinum recovery from spent commercial Pt and PtSnIn/Al(2)O(3) catalysts using strong basic mesoporous and macroporous anion exchange resins (Cl(-) form). The catalysts were leached with aqua regia (75 °C, 20-25 min). Platinum adsorption was influenced by the presence of other metals which form chlorocomplexes (tin, indium) and also base metals (aluminum). However, it was possible to overcome this fact by a sequential desorption procedure. Aluminum was selectively removed from the resins by elution with 3 mol L(-1) HCl. Platinum was desorbed passing 1 mol L(-1) Na(2)S(2)O(3) (pH 9). Tin was removed by elution with 0.1 mol L(-1) ascorbic acid. Indium was removed using 0.1 mol L(-1) EDTA as eluent. Desorption efficiency exceeded 99% for all metals. Metals were recovered in high yields (>98 wt%).
Assuntos
Cloretos/análise , Índio/análise , Platina/análise , Estanho/análise , Adsorção , Alumínio/análise , Resinas de Troca Aniônica , Ânions , Ácido Ascórbico/química , Catálise , Ácido Edético/química , Concentração de Íons de Hidrogênio , Metais/análise , Modelos QuímicosRESUMO
Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⻹, 0.013 ng g⻹ and 0.030 ng g⻹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, <0.010-1.011 ng g⻹; Pt, 0.016-2.734 ng g⻹; and Rh, 0.063-1.298 ng g⻹. Data on 7 areas were similar suggesting that no specific source, for example traffic or anthropogenic activity, influenced directly the metal concentrations in Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas.
Assuntos
Poluentes Ambientais/análise , Irídio/análise , Líquens/química , Platina/análise , Ródio/análise , Argentina , Monitoramento AmbientalRESUMO
Automotive exhaust gases from vehicles using catalytic converters were filtered through cellulose filter papers to collect suspended particles expulsed along with the engine's escape fumes. A specially designed sample collector was used for supporting the filter papers during collection. The collector was manufactured from a new car's exhaust pipe. A cellulose circular paper filter, 11 cm diameter, was attached to one end of the pipe and kept centered by pressing it against the borders of the pipe by means of a perforated aluminum cap, slightly wider than the pipe, used to cover this end of the collector. Filter papers loaded with the solid particles were acid-digested using a modified domestic microwave oven to bring the solid material into solution. The resulting solutions were analyzed for Pt by graphite furnace atomic absorption spectrometry (GF-AAS) and for Pd and Rh by inductively coupled plasma (ICP-OES). Results indicate that concentration of these analytes in the particulate is higher for new vehicles, having new catalytic converters, than for old ones. Maximum Pd, Pt and Rh in the samples analyzed were found to be 5.36, 12.60 and 1.03 microg g(-1), respectively.
Assuntos
Paládio/análise , Platina/análise , Rênio/análise , Espectrofotometria Atômica/métodos , Emissões de Veículos/análiseRESUMO
The reaction of 2-acetylthiophene thiosemicarbazone (2-HATT) and 2-acetylthiophene 4-phenylthiosemicarbazone (2-HAT-4-FT) with Pd(COD)Cl(2) (COD = 1,5-cyclooctadiene) and trans-Pt(2)PEt(3)Cl(4) yielded four new metal complexes: [Pd(2-HATT)Cl(2)] (1), [Pd(2-ATT)(2)] (2), [Pd(2-AT-4-FT)Cl] (3) and [Pt(2-ATT)(PEt(3))Cl] (4). Apart from compound 3 all the others were characterised by (1)H and (13)C{(1)H} NMR, infrared spectroscopy, and elemental analysis. Multinuclear NMR experiments of (31)P{(1)H} and (195)Pt{(1)H} of complex 4 have revealed that the ligand 2-HATT behaves as a bidentate chelating agent towards Pd(COD)Cl(2) and trans-Pt(2)PEt(3)Cl(4) whereas ligand 2-HAT-4-FT forms a tridentate chelating complex with Pd(COD)Cl(2).
Assuntos
Paládio/química , Platina/análise , Platina/química , Espectrofotometria/métodos , Tiofenos/química , Tiossemicarbazonas/química , Ligantes , Espectroscopia de Ressonância Magnética , Modelos Químicos , Compostos Organometálicos/química , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , Tiossemicarbazonas/síntese químicaRESUMO
Vehicular traffic is the main source of platinum group elements (PGEs) in highly populated urban areas like Buenos Aires where a traffic density of 1,500,000 vehicles day(-1) (corresponding to 7,500 vehicles km(-2)) is estimated. Since there is no information on the levels of PGEs in Buenos Aires, a pilot study was undertaken to ascertain the amount of two major PGEs, namely Pt and Rh, in the atmosphere of this city. To this end, 49 samples of PM-10 particulate matter were collected during 7 days in seven representative sampling sites located downtown Buenos Aires and spread over an area of about 30 km(2). The collection of particulate matter was performed on ash-free glass-fiber filters using high volume samplers with PM-10 sampling heads. Filters loaded with the particulate matter were subjected to microwave (MW)-assisted acid digestion using a combination of HNO(3), HF and HClO(4). The resulting solutions were evaporated and then diluted with 0.1 mol l(-1) HCl. Analyses were performed by sector field inductively coupled plasma-mass spectrometry (SF-ICP-MS) and special attention was paid to the control of mass interferences. Statistical analysis was performed on the experimental data obtained for the element concentrations taking also into account local meteorological data for the monitored period. The highest concentrations of Pt and Rh were detected at two sites (Hospital Alemán and Casa Rapallini) located in streets with traffic consisting mostly of passenger cars. The Pt content (in pg m(-3)) in airborne particulate matter was found to vary from 2.3 to 47.7, with a mean value of 12.9+/-7, and that of Rh from 0.3 to 16.8, with a mean value of 3.9+/-2.8. These concentrations are by far below the levels for which adverse health effects might be expected to occur, i.e., around 100 ng m(-3). On the other hand, monitoring of PGEs should be carried out in a systematic fashion to detect possible dramatic increases from today's levels.
Assuntos
Aerossóis/análise , Poluentes Atmosféricos/análise , Platina/análise , Ródio/análise , Argentina , Cidades , Monitoramento Ambiental , Humanos , Saúde Pública , Medição de Risco , Emissões de Veículos/análiseRESUMO
Automobile exhaust catalysts using platinum group elements (PGE) have been mandatory on new cars in the Mexico City Metropolitan Area (MCMA) since 1991. Platinum, Pd, Rh, Ir, and Os concentrations and the isotopic composition of Os were determined in PM10 samples from the MCMA. Samples were prepared by isotope dilution NiS fire assay, and analysis was performed by magnetic sector ICP-MS using a single collector instrument for Pt, Pd, Rh, and Ir analysis and a multicollector instrument for Os analysis. Pt, Pd, and Rh concentrations at a downtown location (Merced) increased from < or =1.7 pg of Pt m(-3), 2.7 (4.0) pg of Pd m(-3), and 1.2+/-0.9 pg of Rh m(-3) in 1991 to 9.6 +/- 1.8 pg of Pt m(-3), 10.2+/-1.8 pg of Pd m(-3), and 2.8 +/-0.6 pg of Rh m(-3) in 2003. Concentrations at five sites in MCMA in 2003 averaged 9.3+/-1.9 pg of Pt m(-3), 11+/-4 pg of Pd m(-3), and 3.2+/- 1.0 pg of Rh m(-3). In contrast, Ir and Os concentrations and Os isotopic composition remained relatively constant and were 0.08+/-0.04 pg of Ir m(-3), 0.030 +/-0.007 pg of Os m(-3), and 0.60+/-0.04, respectively, in the MCMA in 2003. Elevated Pt, Pd, and Rh concentrations in the MCMA are attributed to automobile catalysts. A Pt-Pd-Rh concentration peak in 1993 suggests that early catalysts emitted a larger amount of PGE, possibly due to factors inherent in the technology or the use of inappropriate gasoline. Therefore, this study suggests that the current introduction of automobile catalysts in developing countries may result in elevated PGE concentrations if it is not accompanied by infrastructures and policy measures supporting their efficient use.