Role of indigenous microorganisms and organics in the release of iron and trace elements from sediments impacted by iron mine tailings from failed Fundão dam.

After Fundão Dam failure in 2015, most of Gualaxo do Norte River in Doce River Basin in Brazil became silted by iron mining tailings consisting mainly of fine-grained quartz, hematite, and goethite. Previous work pointed to the possibility of reductive dissolution of iron and manganese from tailings, leading to mobilization of iron, manganese and trace elements. Several microorganisms were shown to reduce Fe(III) to Fe(II) and Mn(III, IV) to Mn(II) "in vitro", but their roles in mobilization of Fe and trace elements from freshwater sediments are poorly understood. In this work, bottom sediments and water collected in Gualaxo do Norte River were used to build anoxic microcosms amended with acetate, glucose or yeast extract, in order to access if heterotrophic microorganisms, either fermenters or dissimilatory Fe reducers, could reduce Fe(III) from minerals in the sediments to soluble Fe(II), releasing trace elements. The Fe(II) concentrations were measured over time, and trace elements concentrations were evaluated at the end of the experiment. In addition, minerals and biopolymers in bottom sediments were quantified. Results showed that organic substrates, notably glucose, fuelled microbial reduction of iron minerals and release of Fe(II), Mn, Ba, Al and/or Zn from sediments. In general, higher concentrations of organic substrates elicited mobilization of larger amounts of Fe(II) and trace elements from sediments. The results point to the possibility of mobilization of huge amounts of iron and trace elements from sediments to water if excess biodegradable organic matter is released in rivers affected by iron mine tailings.

Metal Bioaccumulation by the Neotropical Clam Anomalocardia flexuosa to Estimate the Quality of Estuarine Sediments.

This investigation evaluated the bioaccumulation potential of the tropical estuarine bivalve Anomalocardia flexuosa for trace metals. To this aim, chemical and sedimentological analyses and bioaccumulation tests were performed. The sediments were mainly composed by fine-sands and mud, with variable levels of organic matter and CaCO3. Muddy sediments from a depositional site (P2) presented the highest concentrations of metals, despite SEM/AVS not indicating bioavailability. Bioaccumulation factors showed high ratios for Cd, Ni, and Zn, while associations between the contents of mud, organic matter, CaCO3 and metals in sediments and tissues of A. flexuosa were indicated by a principal component analysis. The SEM/AVS was not effective to predict the bioavailability through dissolved metals. The results showed that contaminants were bioavailable, while the performed bioaccumulation test proved to be a reliable technique for assessing sediment contamination in estuarine regions. Moreover, A. flexuosa was considered an adequate test organism for bioaccumulation studies.

Metal accumulation in roadside soils of Rio de Janeiro, Brazil: impact of traffic volume, road age, and urbanization level.

Traffic-related metal emissions have become a global concern due to their deposition in roadside soils and potential hazardous effects. This study evaluates metal levels in soils adjoining four highways of Rio de Janeiro (Linha Vermelha, Via Dutra, BR-465, and Avenida Brasil), chosen for their diverse traffic volumes, age, and urban/rural settings. In addition to soil physicochemical properties, 11 elements (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V, and Zn) were assessed on samples collected at different distances from the road (1, 3, 5, 10, 15 m) and soil depths (0-15 and 15-30 cm). Moreover, the geoaccumulation index was also computed to infer the soil contamination extent. The results indicate that soil metal levels at each highway are highly dependent on factors like traffic volume, distance to road, other anthropogenic sources of pollution, and their rural or urban location. The highways with greater traffic volume, Linha Vermelha and Avenida Brasil (154,000 and 126,000 vehicles day-1, respectively), clearly presented the highest soil metal concentrations. Still, as stressed by the principal component analysis, traffic volume alone fails to explain the distribution of metals in soils neighboring these highways. Thus, factors like their urban setting and larger exposure to anthropogenic activities may play a pivotal role. On the other hand, soils from Via Dutra and BR-465, both on a rural backdrop, were mostly influenced by traffic as their metal levels decreased with increasing distances from the road. Comparison with reference and preventive values for Brazilian soils and the assessment of the geoaccumulation index have shown that concentrations of Pb and V have reached concerning thresholds at Linha Vermelha and Avenida Brasil.

Speciation analysis of inorganic arsenic in river water by Amberlite IRA 910 resin immobilized in a polyacrylamide gel as a selective binding agent for As(V) in diffusive gradient thin film technique.

In this study, a method is proposed for the selective retention of As(V) using diffusive gradient in thin film (DGT) samplers containing a strongly basic anion exchange resin (Amberlite IRA 910) supported on a polyacrylamide gel. In addition, the total arsenic content is determined by ferrihydrite gel discs. Subsequently, the concentration of As(III) was obtained by determining the difference between the total As and As(V). DGT experiments showed linear accumulation of As(V) (up to 280 ng) until a deployment time of 8 h deployment (R(2) > 0.99). The retention of As(V) was appropriate (97.9-112.3%) between pH 5 and 9. For a solution with an ionic strength ranging from 0.001 to 0.05 mol L(-1), the As(V) uptake ranged from 90-120%. The proposed method was applied for the speciation of arsenic in river water. For the analysis of spiked samples collected at the Furnas stream, the recoveries of total arsenic content ranged between 103.9% and 118.8%. However, the recoveries of As(III) and As(V) were 43.3-75.2% and 147.3-153.4%, respectively. These differences were probably because of the oxidation of As(III) to As(V) during deployments. For spiked samples collected at the Ribeirão Claro, the recoveries of dissolved As(III), As(V) and As(T) were 103.1%, 108.0% and 106.3%, respectively. Thus, the DGT technique with Amberlite IRA 910 resin as the binding phase can be employed for the in situ redox speciation of inorganic arsenic.

Heavy metals and health risk assessment of Brazilian artisanal cheeses.

Dairy products stand out as a food matrix susceptible to the contamination of heavy metals via cattle feed and environmental or processing conditions. Specifically, in the case of cheese, the concentrations can be further increased depending on the production process. The artisanal cheese market has been standing out, especially in Brazil, due to cultural and gastronomic reasons. Eight types of Brazilian artisanal cheese were analyzed for metal concentrations (chromium, copper, cadmium, lead, arsenic, and mercury, n = 80, 10 samples of each cheese) using inductively coupled plasma mass spectrometry. Based on the results, a health risk assessment was carried out, based on the determination of estimated daily intake, target hazard quotient (THQ), and hazard index (HI). Variable concentrations were observed between the types of cheese, but in all cases the THQ and HI values were less than 1, indicating an absence of potential risk in the consumption of artisanal cheeses in relation to the intake of heavy metals.

Geochemistry of intertidal sediment pore waters from the industrialized Santos-Cubatão Estuarine System, SE Brazil.

The geochemical composition of sediment pore water was investigated in comparison with the composition of sediment particles and surface water in an estuary within one of the most industrialized areas in Latin America (Santos-Cubatão estuarine system, SE Brazil). Pore and surface waters presented anomalously high levels of F(-), NH4(+), Fe, Mn and P due to two industrial point sources. In the summer, when SO(4)(2-)/Cl(-) ratios suggested an enhanced sulfate reduction, the higher dissolved levels observed in pore waters for some metals (e.g., Cu and Ni) were attributed to reductive dissolution of oxidized phases. Results evidenced that the risks of surface water concentration increase due to diffusion or advection from pore water are probably dependent on coupled influences of tidal pumping and groundwater inputs.

Organic Black Beans (Phaseolus vulgaris L.) from Rio de Janeiro State, Brazil, Present More Phenolic Compounds and Better Nutritional Profile Than Nonorganic.

Brazil is the world's third largest common bean (Phaseolus vulgaris L.) producer, and 60% of its population consumes this legume. Although organic farming is a sustainable alternative to nonorganic agriculture, its effect on chemical composition is still controversial. Therefore, the aim of this study was to investigate differences in the nutritional and phenolic compounds profiles between organically and nonorganically produced Brazilian black beans. Samples were obtained from the same harvest periods and from near geographical locations at metropolitan and coastal regions of Rio de Janeiro state, Brazil. No residues of 294 evaluated pesticides were detected in the samples. In both regions, organic beans had 17% fewer lipids, 10% less phytate and 20% more proteins when compared to nonorganic ones. Sixteen different phenolic compounds were identified as soluble and insoluble forms in black beans, with anthocyanins being the most abundant (on average, 66%). In both regions, soluble and total phenolic compounds contents in organic beans were consistently higher (on average, 25% and 28%, respectively) than in nonorganic ones. Our results show that organic farming improves the nutritional profile and increases the phenolic compounds content of black beans.

Persistence, bioaccumulation and vertical transfer of pollutants in long-finned pilot whales stranded in Chilean Patagonia.

Long-finned pilot whales (LFPW) are cetaceans with strong social groups often involved in mass strandings worldwide. However, these beachings occur for reasons that are not fully understood. In 2016, 124 LFPW were stranded on the Chilean Patagonian islands, offering a unique opportunity to obtain crucial information on the ecology, biology, and genetics of this population. In addition, we examined whether persistent organic pollutants (POPs) and trace elements (TEs) were responsible for this mass mortality. Stable isotopes (δ13C & δ15N) and genetic analyses were used to reconstruct the trophic ecology, social structure, and kinship of LFPW and compared to POPs and TEs levels found in LFPW. Mitochondrial DNA analyses on 71 individuals identified four maternal lineages within the stranded LFPW. Of these animals, 32 individuals were analyzed for a suite of POPs, TEs, and lipid content in blubber. The highest levels were found for ΣDDXs (6 isomers) (542.46 ± 433.46 ng/g, lw) and for total Hg (2.79 ± 1.91 mg/kg, dw). However, concentrations found in these LFPW were lower than toxicity thresholds and those reported for LFPW stranded in other regions. Evidence was found of ΣDDX, Σ7PCBs, and Cd bioaccumulation and maternal transfer of POPs in mother/offspring groups. Nevertheless, no clear relationship between contaminant concentrations and LFPW mortality was established. Further research is still needed to assess LFPW populations including conservations status and exposure to chemicals in remote areas such as Patagonia.

The anticancer drug perillyl alcohol is a Na/K-ATPase inhibitor.

The monoterpene perillyl alcohol (POH) is a drug used in the treatment of several malignant tumors, including gliomas. The present study defines a POH inhibitory effect on Na/K-ATPase activity from kidney and brain guinea pig extracts and from a human glioblastoma cell line. This inhibition showed a high degree of selectivity toward the kidney enzyme expressing, as do glioblastoma cells, the α(1) subunit. Kinetic studies with purified enzymes showed a noncompetitive POH inhibition profile to Na(+) and K(+) and an uncompetitive inhibition towards ATP. Furthermore, potassium activated p-nitrophenylphosfatase activity of these purified preparations was not inhibited by POH, suggesting that this drug, differently from the classical inhibitor ouabain, acted in the initial phase of the enzyme's catalytic cycle. We suggest that POH antitumor action could be linked to its Na/K-ATPase binding properties.

Distribution of copper in the vicinity of a deactivated mining site at Carajás in the Amazon region of Brazil.

In this work the re-fixation of mobilized copper (Cu) that was released from a deactivated pilot Cu ore dressing plant in the tropical rain forest at Southeastern Amazon (Carajás) was studied. Samples of top soils, decay leaf litter deposited on soils, roots and leaves of standing biomass were taken for the determination of Cu concentration in order to evaluate the distribution of it between different environmental compartments. In the sampling points near to the now extinct plant, total Cu concentrations in the soil reached an average value of 2140 microg g(-1) above the natural level of about 40 microg g(-1), being that bioavailable Cu estimated by DTPA method varied from 1.9 to 20.7% of this total. From the data was possible to calculate that the soil compartment is able to hold around 10 kg Cu/m(2) of ground. Roots of the standing biomass in that area hold around 17 g Cu/m(2), while the Cu content in leaves showed to be largely independent of the Cu level in the soil. Copper in the leaves was estimated as around 1g/m(2) of ground area. In turn, the decay leaf litter deposited on soil can hold about 1.6 g Cu/m(2). The terrestrial system surrounding the abandoned pilot plant demonstrated great buffer capacity to retain mobile Cu released by anthropogenic activities in the area.

Optimization of an open-focused microwave oven digestion procedure for determination of metals in diesel oil by inductively coupled plasma optical emission spectrometry.

This work reports the optimization of a focused microwave assisted procedure for the wet acid dissolution of diesel oil in order to allow the determination of metals in the samples by inductively coupled plasma optical emission spectrometry (ICP-OES). The dissolution process was monitored by measuring residual carbon content (RCC), also by ICP-OES, in the final solutions obtained after application of digestion program. All experimental work was performed using a commercial sample of diesel oil containing 85.74+/-0.13% of carbon. The initial dissolution program comprised three steps: (i) carbonization with H(2)SO(4); (ii) oxidation with HNO(3) and (iii) final oxidation with H(2)O(2). During work it was verified that the first step played an important role on the dissolution process of this kind of sample. It is therefore, necessary to give a detailed optimization of such step. Employing the optimized conditions it was possible to digest 2.5 g of diesel oil with a 40 min-heating program. At these conditions, residual carbon content was always lower than 5%. Optimized methodology was applied in the determination of metals in three diesel oil samples by ICP-OES. Recovery tests were also performed by adding 10 microg of metals, as organic standards, to the samples before digestion. Recovery percentages always higher than 90% were obtained for the metals of interest (Al, Cu, Fe and Ni), except for Zn, which presented recoveries between 70 and 78%.

Distinct histomorphology for growth arrest and digitate outgrowth in cultivated Haliclona sp. (Porifera: Demospongiae).

The use of sponges in biotechnological processes is limited by the supply problem, and sponge biomass production is becoming a current topic of research. The distinction between characteristics for growth and growth arrest is also important for environmental monitoring. In this study, we analyze the morphology of the digitate outgrowths from the sponge Haliclona sp. The sponge Haliclona sp. was successfully cultivated for 14 months in a closed system. The morphological characterization of growth arrest was performed after submitting explants to starvation-stress for approximately 2 weeks, to correlate morphology with growth and growth arrest. The digitate outgrowth showed three distinct regions: mature (MR), transition (TR) and immature (IR). Our data suggest a growth developmental program, with collagen fascicles guiding axial growth in IR, followed by progressive development of choanocyte chambers and large aquiferous systems at the more mature proximal region (choanosome). The intercalation of choanocyte chambers and small aquiferous systems inside collagen fascicles previously originated at the IR region can be responsible for thickening expansion and conversion of the collagen fascicles into columnar choanosome in MR. The growth arrest after starvation-stress assay showed morphological changes in the IR corroborating collagen in the extreme tip of the digitate outgrowth as an important role in guiding of axial growth of Haliclona sp. The identification of distinct morphologies for growth and growth arrest suggest a growth developmental program, and these data could be useful for further investigations addressing sponge biomass gain and environmental monitoring.

Sediment quality in a metal-contaminated tropical bay assessed with a multiple lines of evidence approach.

A sediment quality assessment was performed near to the main industrial source of metal contamination in Sepetiba Bay, Brazil, which represents one of the worst cases of trace metal contamination reported for coastal areas. Acute and chronic toxicity tests, benthic fauna community analysis and metal bioavailability evaluations were applied to identify risks to the benthic community. Significant amphipod mortality was observed close to the major pollution source and lower copepod fertility was observed for all stations. Equilibrium-partitioning and biotic-ligand models to predict pore water metal toxicity, which were based on acid-volatile sulfide (AVS) and organic carbon fraction (fOC) normalization approaches, suggested that metals are not likely to be available in sediment pore water. However, Cd, Pb and Zn concentrations were mainly (>50%) weakly bound to sediments, suggesting high potential bioavailability. Linking the chemical results with ecotoxicological responses, we observed that sediment-feeding organisms presented acute and chronic toxicities that were positively correlated to the metal concentrations in the sediments. Additionally, benthic fauna composition was dominated by tolerant species, revealing a trophic structure response to environmental contamination. These results reinforce the necessity of a multiple lines of evidence approach to establish sediment quality and to support environmental management decisions that are based on observed effects and potential extrapolation scenarios into the future.

Marking Triatoma brasiliensis, Triatoma pseudomaculata and Rhodnius nasutus Nymphs with Trace Elements: Element Persistence and Effects of Marking on Insect Mortality.

BACKGROUND: Field ecologists often rely on mark-release-recapture (MRR) experiments to estimate population dynamics parameters for a given species. In the case of a medically important taxon, i.e., a disease vector, inferences on species survival and dispersal rates are particularly important as they have the potential to provide insights into disease transmission dynamics in endemic areas. Medical entomologists have traditionally used fluorescent dusts to externally mark the cuticle of insects. However, dust marking is usually restricted to the adult life stage because immature insects lose the mark when they molt. METHODOLOGY/PRINCIPAL FINDINGS: We evaluated the efficacy of 13 trace elements in marking nymphs of three native Brazilian Chagas disease vectors: Triatoma brasiliensis, Triatoma pseudomaculata, and Rhodnius nasutus. Cr and Cu were detected in over 97% of T. brasiliensis (34/35 31/31 for Cr and Cu), while Cu and Mn were detected in more than 95% of T. pseudomaculata (29/29 for Cu and 28/29 for Mn) tested 120 days after marking. Only Mn marked over 90% of R. nasutus nymphs (38/41). Overall, trace elements had no negative effects on T. pseudomaculata longevity, but As-marked T. brasiliensis nymphs (p<0.01), and Cd-marked R. nasutus nymphs (p<0.01) had significantly shorter lifespan. CONCLUSIONS/SIGNIFICANCE: Previous evidence shows that there is little or no genetic differentiation between populations at the microgeographic level, which often precludes indirect estimations of dispersal capability based on genetic markers. In such situations, MRR studies are more suitable as they measure insect movement directly from one site to another, instead of effective migration (i.e. gene flow). The determination of a reliable and persistent marking method is the first step towards the development of meaningful ecological estimates through the application of MRR methodology. Here, we have identified trace elements that can be used for mark and recapture studies of three triatomine species in Brazil.

Flow injection/atomic absorption spectrometric determination of zineb in commercial formulations of pesticide based on slurry sampling.

This paper reports on a new strategy for the slurry sampling determination of dithiocarbamate pesticide zineb [[ethylenebis(dithiocarbamato)]zinc] employing a FIA system with a flame atomic absorption spectrometry detector. In the flow system, an on-line alkaline hydrolysis of the pesticide is performed, allowing the release of Zn(II) ions to the solution, which are easily detected by a flame AAS technique. Several parameters that could affect the performance of the analytical methodology were studied, such as the concentration of NH3(aq) used in the hydrolysis step, the effect of the presence of Triton X-100 on the sensitivity and precision, and the FIA parameters (carrier flow rate and mixing coil volume). Under optimized conditions, aqueous slurries containing 2.5 to 25 microg ml(-1) zineb provided good linear calibration fits. From the obtained data, a detection limit (3sigma) of 1.0 microg ml(-1) zineb was found and a repeatability of 2.7% was obtained from 12 measurements of a slurry containing 2.5 microg m(-1) zineb. On the other hand, a precision (reproducibility) of 7.8% was achieved from three determinations of a sample containing 128 mg g(-1) of the pesticide. Also, the developed system provides a sampling frequency of 72 h(-1).

Organic matter and pyritization relationship in recent sediments from a tropical and eutrophic bay.

The degree of pyritization (DOP) and the extension of metals incorporation into pyrite was investigated at Guanabara Bay sediments. Maximum concentrations of total organic carbon (TOC), total sulfur, biopolymers and viable bacteria cells were observed in silted stations close to discharge points of sewage and minimum concentrations at sandy stations at the entrance of the bay. Pyrite iron concentrations (Fepy) was always lower than the reactive iron and Fepy were below the detection limit at sandy stations. The same trend was found to metals, which its degree of pyritization was Mn=Cu>As=Co>Ni>Cd>Zn≫Pb>Cr. The bay gathers all required factors to sulfate reduction and pyrite formation, once the C:S ratio express the reduced tendency conditions, almost half of the TOC present in its sediments is labile and both reactive sulfur and iron are available. However the degree of trace metals pyritization did not exceed 20%, consistent with the median DOP (29%).

Direct determination of manganese in produced waters from petroleum exploration by Electrothermal Atomic Absorption Spectrometry using Ir-W as permanent modifier.

This present work reports the development and evaluation of a method for the direct determination of manganese in waters extracted during petroleum exploitation by Electrothermal Atomic Absorption Spectrometry (ET AAS) using Ir-W as permanent modifier. These waters, usually called produced waters, contain a wide range of organic and inorganic substances and are characterized by their high salinity. In order to achieve suitable experimental conditions for the method application, studies about the effect of operational variables (chemical modifier, pyrolysis and atomization temperatures) were performed, as well as the establishment of convenient calibration strategy. The best results were verified when the temperatures of pyrolysis and atomization were 1000°C and 2300°C, respectively, and using Ir-W as permanent modifier. The results showed that manganese can be determined by the standard addition method or employing external calibration with standard solutions prepared in the same salinity of the samples (with NaCl). Three real samples with salinities varying between 74 and 84‰ were successfully analyzed by the developed procedure. The limits of detection and quantification were 0.24 and 0.80 µg L(-1), respectively, in purified water, and 0.34 and 1.1 µg L(-1), respectively, in 0.4 mol L(-1) NaCl medium (approximately 23‰ salinity).

Evaluation of Cu potential bioavailability changes upon coastal sediment resuspension: an example on how to improve the assessment of sediment dredging environmental risks.

PURPOSE: Metal bioavailability-based sediment quality analysis, inferred from geochemical partitioning data, may contribute to improve sediment management policies. This is important because decision-making processes should not give similar priorities to sediments offering contrasting environmental risks associated to metal bioavailability. However, current uses of Sediment Quality Guidelines (SQGs) as interpretive tools to support decisions about dredging-related activities have not considered the changes in metal bioavailability upon sediment resuspension. METHODS: Sediments from a Cu-contaminated site in Guanabara Bay (Brazil) were submitted to 16-h resuspension experiments in estuarine water to assess the susceptibility of Cu mobilization to the dissolved phase and alteration in the solid phase partitioning between a potentially bioavailable (1 mol/l HCl-extractable) phase and concentrated HNO(3)-extractable phase. RESULTS: After sediment resuspensions, dissolved Cu levels became slightly lower (in a surface water-resuspension treatment) or slightly higher (in a bottom water-resuspension treatment). In both treatments, the 1 mol/l HCl-extractable solid phase concentrations changed from seven times lower to two times higher values than an SQG adopted in Brazilian legislation. This change was explained by a transition from concentrated HNO(3)-extractable phases to reactive HCl-extractable phases upon resuspension. CONCLUSIONS: An evaluation of metal susceptibility to present geochemical partitioning changes, as can be inferred from HCl-extractable fraction analyses before and after resuspension experiments, is recommended as an additional criterion to assess environmental risks of sediment dredging in relation to resuspension-sensitive metals, such as Cu.

On-line redox speciation analysis of antimony using l-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection.

L-proline was immobilized on controlled pore glass to study the ability of this material for the separation and preconcentration of Sb(III) and Sb(V). The substrate was packed in a minicolumn and incorporated in a flow injection system. The effluents of the on-line solid phase extraction (before and after elution) were directly coupled to the hydride generation inductively coupled plasma optical emission spectrometry system. The effect of pH, sample (and eluent) volume, flow rates of sample loading and elution on separation of Sb(III) e Sb(V) were evaluated. Our experiments demonstrated that Sb(V) was not retained and it was selectively determined during the loading step, while retained Sb(III) was determined after elution. The proposed system was also used for the selective preconcentration of Sb(III). In this case, a preconcentration factor of 11 and a limit of detection of 90 ng L(-1) for Sb(III) were achieved when 8 mL of sample were loaded into the column. The speciation analysis of inorganic Sb in river water and effluent samples was performed using the proposed method. The values obtained for total Sb (obtained by sum of Sb(III) and Sb(V)) were in good agreement with expected values. Recoveries of Sb(III) and Sb(V) in the river water Standard Reference Material 1640 (from National Institute of Standard and Technology) and spiked river waters were between 83 and 111%.

Direct determination of arsenic and antimony in naphtha by electrothermal atomic absorption spectrometry with microemulsion sample introduction and iridium permanent modifier.

This paper reports the determination of arsenic and antimony in naphtha by employing electrothermal atomic absorption spectrometry (ETAAS) as the analytical technique. In order to promote the direct determination of the analytes in the very volatile naphtha, the formation of a microemulsion with different surfactants (Triton X-100 and Brij-35) and different chemical modification strategies were tested. The results indicated that Triton X-100 is the best emulsification agent for naphtha in both As and Sb determination when it is employed at a concentration of 1% w/v in the microemulsion. Under these conditions, the microemulsion was stabile for at least 2 h. By using Brij-35 it was possible to achieve good stability only in the first 15 min. Among all chemical modification approaches investigated (Ir permanent modifier, W-Ir permanent modifier, and Pd modifier), the Ir permanent modifier provided better sensitivity for both analytes and allowed a higher pyrolysis temperature, which decreased the background signals at lower levels. Under the best conditions established in this work, an RSD of 4.6% (20 microg L(-1)) and a detection limit of 2.7 microg L(-1) were observed for arsenic. For antimony, an RSD of 4.0% (20 microg L(-1)) and a detection limit of 2.5 microg L(-1) were obtained. The accuracy of the procedure was assessed by analyzing spiked samples of naphtha from different origins.