Bioavailability assessment of toxic metals using the technique "acid-volatile sulfide (AVS)-simultaneously extracted metals (SEM)" in marine sediments collected in Todos os Santos Bay, Brazil.

This paper reports the bioavailability of the metals (cadmium, copper, zinc, lead, and nickel) in sediment samples collected in seven stations from the São Paulo Estuary, Todos os Santos Bay, Brazil. The bioavailability was determined by employing the technique "acid-volatile sulfide (AVS) and simultaneously extracted metal (SEM)". The elements cadmium, copper, lead, and zinc were determined using differential pulse anodic stripping voltammetry (DPASV), while nickel was quantified utilizing electrothermal atomic absorption spectrometry (ET AAS). The accuracy of these methods was confirmed using a certified reference material of estuarine sediment (NIST 1646). The sulfide was quantified using potentiometry with selective electrode and the organic matter determination employing an indirect volumetric method using potassium dichromate and iron(II) sulfate solutions. The bioavailability of the metals was estimated by relationship between the concentration of AVS and the sum of the concentrations of the simultaneously extracted metals (ΣSEM), considering a significant toxicity when (ΣSEM)/(AVS) is higher than 1. The bioavailability values in the seven stations studied varied from 0.93 to 1.31 (June, 2014) and from 0.34 to 0.58 (September, 2014). These results demonstrated a critical condition of toxicity (bioavailability >1) in six of the seven sediment samples collected during the rainy season (June, 2014). In the other period (September, 2014), the bioavailability was always lower than 1 for all sediment samples collected in the seven stations. The individual values of the concentrations of the five metals were compared with the parameters PEL (probable effects level) and TEL (threshold effects level), which are commonly employed for characterization of ecological risk in environmental systems. This comparison revealed that all metals have concentrations lower than the PEL and only zinc and lead in some stations have contents higher than the TEL. The bioavailability evaluation and the concentrations achieved for the five elements in the sediments samples analyzed demonstrated that the ecosystem studied does not present an environmental risk.

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.

Determination and evaluation of the ecological risk of mercury in different granulometric fractions of sediments from a public supply river in Brazil.

This work reports the quantification of total mercury in sediments collected in periods with and without rain from the Joanes River, Bahia, Brazil. Determinations were made using Direct Mercury Analysis (DMA), the accuracy of which was confirmed with two certified reference materials. The highest total mercury concentrations were found at the sampling point close to commercial areas and large residential condominiums. On the other hand, the lowest levels were found in the site close to a mangrove region. The geoaccumulation index was applied to the total mercury results, evidencing low contamination in the region studied. The contamination factor showed that of the seven stations investigated, four samples collected in the rainy season showed moderate contamination. The results of the ecological risk assessment were utterly consistent with the contamination factor data. This study showed that the smaller sediment particles concentrate more mercury, corroborating what has been predicted by the adsorption processes.

Integrated assessment of mangrove sediments in the Camamu Bay (Bahia, Brazil).

Camamu Bay, an Environmentally Protected Area, may be affected by the pressures of tourism and oil exploration in the adjacent continental platform. The current quality of the mangrove sediments was evaluated by porewater bioassays using embryos of Crassostrea rhizophorae and by an analysis of benthic macrofauna and its relationships with organic compounds, trace metals and bioavailability. Porewater toxicity varied from low to moderate in the majority of the samples, and polychaetes dominated the benthos. The Grande Island sampling station (Station 1) presented more sandy sediments, differentiated macrobenthic assemblages and the highest metal concentrations in relation to other stations and guideline values, and it was the only station that indicated a possible bioavailability of metals. The origin of the metals (mainly barium) is most likely associated with the barite ore deposits located in the Grande and Pequena islands. These results may be useful for future assessment of the impact of oil exploration in the coastal region.

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.

Phytoremediation of polycyclic aromatic hydrocarbons (PAHs) in mangrove sediments using Rhizophora mangle.

A phytoremediation experiment was carried out in mesocosms to investigate the performance of Rhizophora mangle in the remediation of polycyclic aromatic hydrocarbons (PAHs) in mangrove sediment contaminated with crude oil. The water pH of the experiments (phytoremediation and natural attenuation) ranged from 4.9 to 8.4 at 0 and 90 days, respectively. The oxy-reduction potential (Eh) ranged from oxidising (108.0 mV, time 0) to reducing (approximately -110.0 mV, time 90) environments. Dissolved oxygen (DO) ranged from 5.7 mg L-1 (time 0) to 4.5 mg L-1 and 3.6 mg L-1 (time 90) in phytoremediation and natural attenuation, respectively. The sediments had silty texture and an average concentration of 5% organic matter (OM). Phytoremediation (60.76%) showed better efficiency in the remediation of the 16 PAHs compared to natural attenuation (49.57%). Principal component analyses showed a correlation between the concentrations of PAHs with pH, Eh, OM and DO in both experiments.

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.

Potential application of oil-suspended particulate matter aggregates (OSA) on the remediation of reflective beaches impacted by petroleum: a mesocosm simulation.

This paper presents the oil-suspended particulate matter aggregate (OSA) resulted from the interaction of droplets of dispersed oil in a water column and particulate matter. This structure reduces the adhesion of oil on solid surfaces, promotes dispersion, and may accelerate degradation processes. The effects of the addition of fine sediments (clay + silt) on the formation of OSA, their impact on the dispersion and degradation of the oil, and their potential use in recovering reflective sandy beaches were evaluated in a mesoscale simulation model. Two simulations were performed (21 days), in the absence and presence of fine sediments, with four units in each simulation using oil from the Recôncavo Basin. The results showed that the use of fine sediment increased the dispersion of the oil in the water column up to four times in relation to the sandy sediment. There was no evidence of the transport of hydrocarbons in bottom sediments associated with fine sediments that would have accelerated the dispersion and degradation rates of the oil. Most of the OSA that formed in this process remained in the water column, where the degradation processes were more effective. Over the 21 days of simulation, we observed a 40 % reduction on average of the levels of saturated hydrocarbons staining the surface oil.

Multivariate optimization of a procedure employing microwave-assisted digestion for the determination of nickel and vanadium in crude oil by ICP OES.

This work presents the optimization of a sample preparation procedure using microwave-assisted digestion for the determination of nickel and vanadium in crude oil employing inductively coupled plasma optical emission spectrometry (ICP OES). The optimization step was performed utilizing a two-level full factorial design involving the following factors: concentrated nitric acid and hydrogen peroxide volumes, and microwave-assisted digestion temperature. Nickel and vanadium concentrations were used as responses. Additionally, a multiple response based on the normalization of the concentrations by the highest values was built to establish a compromise condition between the two analytes. A Doehlert matrix optimized the instrumental conditions of the ICP OE spectrometer. In this design, the plasma robustness was used as chemometric response. The experiments were performed using a digested oil sample solution doped with magnesium(II) ions, as well as a standard magnesium solution. The optimized method allows for the determination of nickel and vanadium with quantification limits of 0.79 and 0.20µgg-1, respectively, for a digested sample mass of 0.1g. The precision (expressed as relative standard deviations) was determined using five replicates of two oil samples and the results obtained were 1.63% and 3.67% for nickel and 0.42% and 4.64% for vanadium. Bismuth and yttrium were also tested as internal standards, and the results demonstrate that yttrium allows for a better precision for the method. The accuracy was confirmed by the analysis of the certified reference material trace element in fuel oil (CRM NIST 1634c). The proposed method was applied for the determination of nickel and vanadium in five crude oil samples from Brazilian Basins. The metal concentrations found varied from 7.30 to 33.21µgg-1 for nickel and from 0.63 to 19.42µgg-1 for vanadium.

Distribution and ecotoxicology of bioavailable metals and As in surface sediments of Paraguaçu estuary, Todos os Santos Bay, Brazil.

Surface sediments collected in the intertidal zone of Paraguaçu estuary in July, 2013, were analyzed for organic matter, nitrogen, phosphorus, grain size fractions and partial concentrations of 16 metals. The USEPA 3051A method and ICP-OES and CV-AAS techniques were chosen to metal analysis. Pollution indices (EF, Igeo and PIN) and a comparison with sediment quality guidelines (UET, ERL, ERM, TEL and PEL of NOAA) were conducted in order to evaluate the potential metal impacts over the area. Principal Component Analysis (PCA) and Pearson correlation results showed the importance of organic matter content and the fine-grained fraction of sediments on the control of the bioavailable metals distribution. The Paraguaçu estuary already has anthropogenic enrichment relative to the background level, especially for Mn, whose values exceeded almost 30 times the background at one site (Mn: 1197.30 mg kg(-1)). However, metal levels are still below the reference values with the exception of Hg at one site (Hg: 0.25 mg kg(-1), exceeded TEL and ERL).

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.