A risk assessment by metal contamination in a river used for public water supply.

Aquatic ecosystems provide habitats for many organisms. Historically, riverbanks have always been inhabited and exploited for subsistence and navigation. The present study evaluates the contamination and ecological risks caused by potentially toxic elements in surface sediments of the Paraguaçu River, Bahia, Brazil. Seven sediments samples were collected, and eight heavy metals were determined employing inductively coupled plasma spectrometry mass (ICP-MS). The concentrations range as (mg kg-1) found were 6.78-18.68 for lead, 14.21-42.16 for zinc, 27.61-48.63 for nickel, 2.03-6.50 for chromium, 6.06-12.90 for vanadium, 5.99-13.33 for cupper, 1.25-3.19 for cobalt, and 79.52-286.08 for manganese. Nickel showed significant enrichment (EF: 5.75; 7.62, and 14.11), followed by zinc, which showed moderate enrichment (EF: 2.16; 2.19, and 4.52). These enrichment levels are possible of anthropogenic origin. When the pollution index (PI) was evaluated, the elements V, Ni, Zn, Mn, Co, and Cu were strongly polluted (PI ≥3). In general, the pollution index (PI), geoaccumulation index (Igeo), enrichment factor (EF), and potential ecological risk indices (Er and PERI) show that contaminated sediments have adverse effects on aquatic environments, especially for o Mn, Ni, Pb, V, and Zn.

Determination of Cu, Ni, Mn and Zn in diesel oil samples using energy dispersive X-ray fluorescence spectrometry after solid phase extraction using sisal fiber.

As a natural adsorbent, sisal (agave sisalana) fibers were used to extract Cu, Ni, Mn, and Zn from diesel oil samples for posterior determination (i.e., direct analytical measurements on the solid support) of the analytes by energy dispersive X-ray fluorescence spectrometry (EDXRF). In the proposed procedure, 0.2 g of sisal fiber was directly added to 5.0 mL of diesel oil contained in a glass tube. After 5 min of contact time, the mixture was filtered, and the collected fibers were oven-dried for 30 min at 70 °C. After drying, the analytes were quantified directly by EDXRF using the sisal fibers as a solid support. The calibration curves showed linear concentration ranges of 0.09-1.00, 0.12-1.00, 0.09-1.00, 0.06-1.0 µg g-1 for Cu, Ni, Mn, and Zn, respectively. The limits of detection (LOD) for Cu, Ni, Mn, and Zn were 0.03, 0.04, 0.03, and 0.02 µg g-1, respectively. The repeatability, evaluated by performing ten measurements at a concentration of 0.50 µg g-1 for each metal, with the results expressed in terms of the relative standard deviation (RSD), was 3.2, 6.5, 6.8, and 6.1% for Cu, Ni, Mn, and Zn, respectively. The results obtained by the proposed method were compared with the results obtained by a comparative method using inductively coupled plasma optical emission spectrometry, and both results showed good agreement. The proposed method was applied for Ni, Cu, Mn, and Zn determination in diesel oil samples collected from different gas stations.

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.

Sources and distribution of polycyclic aromatic hydrocarbons (PAHs) and organic matter in surface sediments of an estuary under petroleum activity influence, Todos os Santos Bay, Brazil.

The present study evaluated the origin and distribution of polycyclic aromatic hydrocarbons (PAHs) and the organic matter (OM) in the surface sediment of the São Paulo River estuary, Todos os Santos Bay (TSB), Brazil. The samples were collected in the rainy (CP1) and the dry (CP2) seasons. We analyzed the 16 PAHs from the United States Environmental Protection Agency (US EPA) priority pollutant list, total organic carbon (TOC), total nitrogen (N), and stable carbon isotope (δ13C). The total concentration of PAHs ranged from 11.45±1.28 to 1825.35±107.96ngg-1, while TOC ranged from 3.8 to 27.7gkg-1. CP1 showed the highest concentrations for all parameters. The δ13C ratio indicated terrigenous OM (-23.81 to -26.63‰). The TOC/N ratio (C/N) indicated transitional OM (12.32 to 24.39), in addition to the continental origin. The diagnostic ratios of PAHs origin revealed only pyrolytic source, although close to areas with a history of petroleum contamination.

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.

Phytoremediation in mangrove sediments impacted by persistent total petroleum hydrocarbons (TPH's) using Avicennia schaueriana.

This study evaluated the efficiency of Avicennia schaueriana in the implementation of phytoremediation compared with intrinsic bioremediation in mangrove sediments contaminated by total petroleum hydrocarbons (TPHs). The experiment was conducted for 3months at a pilot scale under conditions similar to a mangrove: the dynamics of the tides were simulated, and physical, chemical, microbiological and biogeochemical parameters were monitored. After the 90 days, it was found that the phytoremediation was more efficient in the degradation of the TPHs compared to bioremediation, reducing the initial concentration of 32.2-4.2 mg/g. A. schaueriana was also more efficient in mediating the degradation of different fractions of hydrocarbons, achieving a removal efficiency of 87%. The microbiological results consisted of a higher growth in the model with the plants, demonstrating the phytostimulation ability of the plants. Finally, the experiment showed that phytoremediation is a promising alternative in mangrove impacted by oil.