Determination of Cu, Ni, Mn, and Pb in diesel oil samples using reversed-phase vortex-assisted liquid-liquid microextraction associated with energy dispersive X-ray fluorescence spectrometry.

A method was developed based on reversed-phase vortex-assisted liquid-liquid microextraction (RP-VALLME) combined with energy dispersive X-ray fluorescence (EDXRF) spectrometry for the determination of Cu, Mn, Ni, and Pb in diesel oil samples. In this procedure, a nitric acid solution was used as the extraction phase to isolate analytes from organic samples. After a centrifugation step, the aqueous phase was added dropwise to a filter paper disc for EDXRF determinations. The following variables were optimized: type of extraction phase solution, concentration of the extraction phase, stirring time, and sample volume. Some instrumental parameters were also evaluated: atmospheric condition, irradiation energy, and irradiation time. Using 100 µL of a 0.075 mol L-1 nitric acid solution as the extraction phase for a sample volume of 5.0 mL and a stirring time of 45 s, the limits of detection were 14, 8, 10, and 7 µg L-1 for Cu, Mn, Ni, and Pb, respectively. The enrichment factors obtained were 34 (Cu), 62 (Mn), 59 (Ni), and 64 (Pb). The precisions, expressed as relative standard deviations (RSDs, %), were calculated from ten replications of the experiment under optimized conditions using standard solutions containing 200 µg L-1 and 400 µg L-1 of all four analytes and ranged between 2.1 and 6.4%. The results of recovery tests ranged from 87 to 112%. The proposed procedure was efficiently applied to the determination of the four analytes in diesel oil samples. The results were compared with those obtained by inductively coupled plasma optical emission spectrometry (ICP-OES) after sample digestion, and no significant differences were found.

Environmental disaster in the northeast coast of Brazil: Forensic geochemistry in the identification of the source of the oily material.

The characterization of petroleum or its products spilled in the environment in relation to its source rocks is an important tool to assist in the resolution of issues of environmental impact and legal responsibility since it clarifies the possible region or the producing country of that type of petroleum. This article analyzes the application of analytical techniques for petroleum geochemistry to identify the type and origin of oily material collected from beaches in Northeast Brazil in 2019. Samples of the oily material collected on the beaches in the states of Bahia and Sergipe were analyzed and for comparison purposes, samples of crude oils produced in Brazil, Middle East, Nigeria and Venezuela were also analyzed. The analytical results showed that the oily material that reached the beaches has geochemical characteristics compatible with those of the Venezuelan oil, indicating it was severely weathered or a product made with heavy oil produced.

Spatial distribution and concentration assessment of total petroleum hydrocarbons in the intertidal zone surface sediment of Todos os Santos Bay, Brazil.

The primary objective of this study was to investigate the concentrations and spatial distribution of the total petroleum hydrocarbons (TPHs) in the intertidal zone surface sediment of Todos os Santos Bay, Brazil, to assess the distribution and degree of contamination by TPHs, measure the level of TPH degradation in the surface sediment, and identify the organic matter sources. The surface sediment used in this study was collected in 50 stations, and TPHs, isoprenoid alkanes (pristane and phytane), and unresolved complex mixture (UCM) were analyzed by gas chromatography with a flame ionization detector. The total concentrations ranged from 0.22 to 40,101 µg g(-1) dry weight and showed a strong correlation with the total organic carbon (TOC) content. The highest TPH concentrations were observed in samples from the mangrove sediments of a river located near a petroleum refinery. Compared with other studies in the world, the TPH concentrations in the intertidal surface sediment of Todos os Santos Bay were below average in certain stations and above average in others. An analysis of the magnitude of UCM (0.11 to 17,323 µg g(-1) dry weight) and the ratios nC17/Pr and nC18/Ph suggest that an advanced state of oil weathering, which indicates previous contamination. The molar C/N ratios varied between 5 and 43, which indicate organic matter with a mixed origin comprising marine and continental contributions.

Assessment of carcinogenic heavy metal levels in Brazilian cigarettes.

Several studies have associated high cancer incidence with smoking habits. According to IARC, lead (Pb), cadmium (Cd), arsenic (As), nickel (Ni), and chromium (Cr) are carcinogenic to humans. These metals are present in cigarettes and their levels vary according to geographical region of tobacco cultivation, fertilizer treatment, plant variety etc. This study aims to assess these metal levels in cigarettes commercialized in Brazil. Three cigarettes of each 20 different brands were individually weighed, the tobacco filling removed, and homogenized. After desiccation, samples were subjected to microwave-assisted digestion. Analyses were performed by graphite furnace atomic absorption spectrometry. Mean levels for Pb, Cd, As, Ni, and Cr were, respectively, 0.27 ± 0.054, 0.65 ± 0.091, 0.09 ± 0.024, 1.26 ± 0.449, and 1.43 ± 0.630, in micrograms per gram of tobacco. No correlation was observed between Cd and any other metal analyzed. A mild correlation (r = 0.483, p < 0.05) was observed between Pb and Cr levels. Strong significant (p < 0.01) correlations were observed between Ni and Cr (r = 0.829), Ni and As (r = 0.799), Ni and Pb (r = 0.637), and between Cr and As (r = 0.621). Chromium and Ni levels were significantly higher in cigarettes from a multinational manufacturer. Our results show a high variability in heavy metal levels in cigarettes, representing an important exposure source of smokers and passive smokers to carcinogenic substances.

Relationship of metal content and bioavailability with benthic macrofauna in Camamu Bay (Bahia, Brazil).

Camamu Bay (Bahia, Brazil) is an Environmental Protected Area with mangroves of economic and ecological importance. The objective of this study was to elucidate, through the distribution of the benthic macrofauna and its relationships with trace metals and bioavailabilty, if the current quality of the mangrove sediments of Camamu Bay is acceptable for the protection of aquatic life. Seven sampling stations were selected as representative of the meso-littoral region of Camamu Bay. It was found 581 macrobenthic organisms distributed in 38 species. The highest values of metals occurred at stations located in areas that influenced by barite extraction, while the lowest concentrations were found in areas with relatively lower anthropogenic influence. Analysis of acid volatile sulphide and simultaneously extracted metals showed the occurrence of the ratio SEM/AVS >1, indicative of possible bioavailability of metals, at only one station. The results suggested that Camamu Bay is a nearly pristine area.

Determination of total arsenic and arsenic (III) in phosphate fertilizers and phosphate rocks by HG-AAS after multivariate optimization based on Box-Behnken design.

In the present paper, a procedure for the determination of total arsenic and arsenic (III) in phosphate fertilizers and phosphate rocks by slurry sampling (SS) with hydride generation atomic absorption spectrometry (HG-AAS) is proposed. Arsenic (III) is determinated directly and total arsenic is determinated after reduction reaction. The procedure was optimized for the flow rate of NaBH(4), NaBH(4) and hydrochloric acid concentrations using a full two-level factorial and also a Box-Behnken design. Slurry preparation with hydrochloric acid in an ultrasonic bath allowed the determination of arsenic (III) with limits of detection and quantification of 0.1 and 0.3 microg L(-1), respectively. The precision of results, expressed as relative standard deviation (RSD), was always lower than 3%. The accuracy of this method was confirmed by analysis of certified sediment reference materials, while the procedure also allows for calibration using aqueous external standards. This method (SS/HG-AAS) was used to determine total arsenic and arsenic (III) in two phosphate rock samples and two phosphate fertilizer samples. In these samples, total arsenic concentrations varied from 5.2 to 20.0 mg kg(-1), while As (III) concentrations varied from 2.1 to 5.5 mg kg(-1), in agreement with published values. All samples were also analyzed using acid digestion/HG-AAS. Both, a paired t-test and a linear regression model demonstrated no significant difference (95% CL) between the results obtained using these two sample preparation procedures.