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1.
Sci Rep ; 14(1): 10240, 2024 May 03.
Article in English | MEDLINE | ID: mdl-38702364

ABSTRACT

This work presents the experimental assessment of a 20 mL batch reactor's efficacy in converting plastic and oil residues into biofuels. The reactor, designed for ease of use, is heated using a metallic system. The experiments explore plastic solubilization at various temperatures and residence times, employing a mixture of distilled water and ethylene glycol as the solvent. Initial findings reveal that plastic solubilization requires a temperature of 350 °C with an ethylene glycol mole fraction of 0.35, whereas 250 °C suffices with a mole fraction of 0.58. Additionally, the study includes a process simulation of a plant utilizing a double fluidized bed gasifier and an economic evaluation of the interesterification/pyrolysis plant. Simulation results support project feasibility, estimating a total investment cost of approximately $12.99 million and annual operating expenses of around $17.98 million, with a projected payback period of about 5 years.

2.
Mar Pollut Bull ; 198: 115842, 2024 Jan.
Article in English | MEDLINE | ID: mdl-38039579

ABSTRACT

This work reports assessing risks to human health resulting from mercury levels in sardines (Sardinella brasiliensis), which have been highly consumed by the low-income population from Salvador, Brazil. Mercury was determined using the Direct Mercury Analysis (DMA) in fifty-one commercially acquired samples in seventeen neighborhoods. The mercury content on a wet basis ranged from 0.023 to 0.083 µg g-1 for an average value of 0.039 µg g-1. The estimated weekly intake (EWI), target hazard quotient (THQ), and maximum safe consuming quantity (MSCQ) were used in the toxicological assessment, and all these indices denoted that this food does not pose any risks to the human health of the population that consumes it. The development of this work was very significant because most sardines sold in Salvador originate from Todos os Santos Bay, which has a history of mercury contamination.


Subject(s)
Mercury , Animals , Humans , Mercury/analysis , Brazil , Environmental Monitoring , Food Contamination/analysis , Risk Assessment , Fishes
3.
Mar Pollut Bull ; 192: 115083, 2023 Jul.
Article in English | MEDLINE | ID: mdl-37245321

ABSTRACT

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.


Subject(s)
Mercury , Water Pollutants, Chemical , Mercury/analysis , Brazil , Water Pollutants, Chemical/analysis , Rivers , Geologic Sediments/analysis , Risk Assessment , Environmental Monitoring
4.
Sci Rep ; 13(1): 4248, 2023 Mar 14.
Article in English | MEDLINE | ID: mdl-36918617

ABSTRACT

We investigated if pristine and functionalized fullerenes could be actual constituents of fine atmospheric aerosols. Comprehensive profiles of fullerenes from 1 µL extracts were made through matrix laser desorption ionization Time-of-Flight Mass Spectrometry (MALDI-MS) within a few minutes. The ion with m/z 720, corresponding to [C60]-•, was identified as fullerene after 1 µL of α-cyano-4-hydroxycinnamic acid matrix solution was spotted over the dried extracts. The ions with the m/z corresponding to C70, C76, C84, C100, C118, C128, and C130 were also attributed to other fullerene species detected within the samples. The ion m/z 878 was found to be the fullerene derivative diethyl methano[60]fullerene dicarboxylate. Since ions of fragmented fullerene molecules were not detected even at high laser energies, we considered the fullerenes' occurring as original constituents of real atmospheric particle matrices instead of being formed as artifacts of the laser action on samples. Therefore, this protocol would be helpful in the understanding of the distribution of either pristine or functionalized fullerenes in the environment and their participation in atmospheric chemistry under typical conditions, as well as its application in vitro and in vivo (eco)toxicity studies.

5.
Sci Total Environ ; 851(Pt 1): 157965, 2022 Dec 10.
Article in English | MEDLINE | ID: mdl-35952874

ABSTRACT

In the present study, the Hg levels in freshly collected polychaete species and their associated sediments were evaluated from Todos os Santos Bay, Northeastern Brazil. Additionally, it was also measured the Hg distribution along the annelids' body parts (anterior region, abdomen, and posterior region). Total Hg concentration was as follows: 13.6-144 µg kg-1 (Scolelepis chilensis, deposit feeder), 8.2-122 µg kg-1 (Laeonereis acuta, deposit feeder), 95-612 µg kg-1 (Armandia agilis, deposit feeder); 96.6-206 µg kg-1 (Lumbrineris sp., carnivorous), 75.3-112 µg kg-1 (Goniada echinulate, carnivorous), and 115-198 µg kg-1 (Branchiomma sp., suspension feeder). In turn, Hg levels in sediments ranged from 2.77 ± 0.24 to 6.38 ± 0.15 µg kg-1. Hg concentrations found in polychaete soft tissues were higher than those found in the sediments. Specific habits, feeding behavior, trophic level, and stressful environmental conditions are the main factors affecting the Hg levels in the species studied. The bioaccumulation factor (BAF), contamination factor (CF), and ecological risk assessment (Er) were calculated. The BAF values were higher than 1 for all studied species, indicating Hg bioaccumulation in the annelids, but the low levels of CF e Er showed those Hg levels present low to no significant ecological risk for the biota and benthonic organisms living in the sediments. Finally, no statistically significant difference was observed for Hg concentration levels along the polychaete body parts.


Subject(s)
Mercury , Polychaeta , Water Pollutants, Chemical , Animals , Atlantic Ocean , Bays , Environmental Monitoring , Geologic Sediments , Mercury/analysis , Water Pollutants, Chemical/analysis
6.
Food Chem ; 370: 131062, 2022 Feb 15.
Article in English | MEDLINE | ID: mdl-34537431

ABSTRACT

A simple method was developed to determine 14 endocrine-disrupting chemicals (EDCs) in bottled waters, based on dispersive micro-solid phase extraction (d-µ-SPE) and liquid chromatography-mass spectrometry (LC-MS). Extraction was optimized using 2 k-1 factorial and Doehlert experimental designs. Optimized conditions were 80 mg C18, 25 min extraction at 1000 rpm, and 6 min desorption time. Repeatability was below 17 % for all EDCs. LOD and LOQ varied from 1.60 ng L-1 (estradiol, E2) to 23.2 ng L-1 (dimethylphthalate, DMP) and from 5.33 ng L-1 (E2) to 77.3 ng L-1 (DMP). We found DMP and bisphenol A (BPA) in samples after the heat treatment. DMP was up to 58.7 µg L-1, while BPA was up to 1.34 µg L-1. Tolerance of daily intake (TDI) for DMP were 2.50-2.94 µg kg-1 day-1 (children) and 1.43-1.68 µg kg-1 day-1 (adults). TDI for BPA were 0.03-0.07 µg kg-1 day-1 (children) and 0.01-0.04 µg kg-1 day-1 (adults).


Subject(s)
Drinking Water , Endocrine Disruptors , Mineral Waters , Water Pollutants, Chemical , Benzhydryl Compounds/analysis , Child , Endocrine Disruptors/analysis , Humans , Solid Phase Extraction , Tandem Mass Spectrometry , Water Pollutants, Chemical/analysis
7.
Sci Total Environ ; 782: 146541, 2021 Aug 15.
Article in English | MEDLINE | ID: mdl-33839668

ABSTRACT

Microplastics (MPs) are emerging and ubiquitous contaminants which have been gaining prominence since the last decade to nowadays. This is due to their possible adverse effects in aquatic ecosystems as well as the huge amount of plastic waste exponentially generated around the globe. Plastics may be introduced either directly to water bodies or indirectly to the aquatic systems by being carried by the wind, from emissions of contaminated effluents, and soil leaching, among other processes. In turn, these debris may interact with organic and inorganic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and trace constituents, and with microorganisms. Although the abundance of microplastics from South Atlantic waters is among the highest found worldwide, the number of studies in these marine waters regarding MP contamination is still scarce. Additionally, there still are no consensus on the best sampling conditions, which may be underestimating MPs. In this way, adequate MPs studies regarding their distribution, exposure levels, chemical and biological interactions are highly suggested in order to better understand both environmental and human health potential risks. This review assessed advances in sampling, analytical methodologies, characterization and understanding of MP sources in these marine waters in comparison to data from other regions around the globe.

8.
J Chromatogr A ; 1639: 461781, 2021 Feb 22.
Article in English | MEDLINE | ID: mdl-33517136

ABSTRACT

A dispersive micro-solid phase extraction (d-µ-SPE) procedure was developed for the simultaneous extraction of 39 multiclass pesticides, containing a variety of chemical groups (organophosphate, organochlorine, pyrethroid, strobilurin, thiocarbamate, triazole, imidazole, and triazine), from water samples. A customized d-µ-SPE glass device was combined with a multi-tube platform vortex and a micro-desorption unit (Whatman Mini-UniPrep G2 syringeless filter), which allowed the unique simultaneous desorption, extract filtration, and injection. A simplex-centroid mixture design and Doehlert design were employed to optimize the extraction conditions. The optimized extraction conditions consisted of an extraction time of 30 min, an addition of 6.74 % of NaCl into 100 mL of water sample, and a desorption time of 24 min with 500 µL of EtAc. The procedure provided a low limit of detection (LOD), ranging from 0.51 ng L-1 (4,4-DDE) to 22.4 ng L-1 (dimethoate), and an enrichment factor ranging from 72.5 (dimethoate) to 200 (tebuconazole). The relative recoveries of the pesticides from spiked freshwater and seawater ranged from 74.2 % (endrin) to 123 % (molinate). The proposed procedure was applied to detect the presence of multiclass pesticides in environmental water samples. Three pesticides commonly applied in Brazil, namely, malathion, dimethoate, and lambda-cyhalothrin, were detected in concentrations ranging from

Subject(s)
Pesticides/analysis , Solid Phase Microextraction/instrumentation , Solid Phase Microextraction/methods , Water Pollutants, Chemical/analysis , Adsorption , Fresh Water/chemistry , Hydrocarbons, Chlorinated/analysis , Limit of Detection , Reproducibility of Results , Seawater/chemistry
9.
Talanta ; 217: 121033, 2020 Sep 01.
Article in English | MEDLINE | ID: mdl-32498836

ABSTRACT

This study presents the development and application of a new analytical methodology for determination of free- and bound-carbonyl compounds (CC) (as the CC themselves and as the hydroxyalkylsulfonic acids - HASA, respectively) in airborne particles. Free- and bound-CC determination were done through reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH) and analysis by UFLC-MS. The method was successfully validated, showing good figures for linearity (R2 ≥ 0.9937), sensibility (3 fg ˂ LOD ˂ 20 fg for methacrolein and heptanal, respectively) and repeatability (5.9% ˂ RSD ˂ 13%). The proposed method was successfully applied in real samples of inhalable atmospheric particulate matter (PM10) and urban dust certified reference material (SRM 1649 b). The main CC determined in the SRM 1649 b was formaldehyde (75.4 µg g-1 in the free form, and 1898 µg g-1 in the bound form). In addition, for the bound-CC form (HASA), concentrations were determined for acetaldehyde (60.3 µg g-1), acetone (20.5 µg g-1), acrolein (9.15 µg g-1), propionaldehyde (17.1 µg g-1) and valeraldehyde (12.2 µg g-1). For PM10 samples, formaldehyde (148 µg g-1) and acetaldehyde (28.9 µg g-1) were quantified as free aldehydes and as HASA (hydroxymethanelsulfonic acid and hydroxyethanesulfonic acid were 432 µg g-1 and 211 µg g-1, respectively). Other bound-CC were, on average, within 19.2 µg g-1 (acrolein) and 62.1 µg g-1 (valeraldehyde). For all samples, acetone, acrolein, propionaldehyde and valeraldehyde were quantified only as HASA (bound-CC). Therefore, we could identify and quantify six carbonyl compounds using the proposed method. It is worth mentioning the hydrolysis step was crucial for the correct quantification of the HASAs. This was, in turn, what enabled the quantification of a greater number of analytes in the airborne samples. Hence, this procedure was found to be comprehensive, precise, accurate and suitable to be employed for determination of free-CC and HASA (bound-CC) in atmospheric particulate samples.

10.
Sci Rep ; 10(1): 3465, 2020 02 26.
Article in English | MEDLINE | ID: mdl-32103055

ABSTRACT

In this work we report the occurrence of powerful mutagenic 3-nitrobenzanthrone (3-NBA), in addition to 18 polycyclic aromatic hydrocarbons (PAHs), 6 oxygenated PAHs and 27 nitrated PAHs in polychaete worms. Benzanthrone (BA), another important mutagenic polycyclic aromatic compound (PAC) also was detected in the samples. Polychaete annelids have great ecological relevance, being widely distributed in different environmental conditions, from intertidal zones up to seven thousand feet deep areas. They are abundantly found in both contaminated and uncontaminated areas and, therefore, used as indicators of the pollution status of a given area. As we know, so far, most of these PACs has not been previously reported in living organisms before. The 3-NBA concentrations determined in this study were within 0.11-5.18 µg g-1. Other relevant PACs such as PAHs, quinones and nitro-PAHs were found in maximum concentrations at 0.013 µg g-1 (coronene) to 11.1 µg g-1 (benzo[k]fluoranthene), 0.823 µg g-1 (9,10-phenenthrenequinone) to 12.1 µg g-1 (1,4-benzoquinone) and 0.434 (1-nitronaphthalene) µg g-1 to 19.2 µg g-1 (6-nitrobenzo[a]pyrene), respectively. Principal component analysis (PCA), ternary correlations and diagnostic ratios were employed in order to propose probable sources for PACs. Although statistical analysis preliminarily has indicated both pyrogenic and petrogenic contributions, petrogenic sources were predominant reflecting the impacts of petroleum exploration and intensive traffic of boats in the study area.


Subject(s)
Benz(a)Anthracenes/analysis , Mutagens/analysis , Polychaeta/chemistry , Polycyclic Aromatic Hydrocarbons/analysis , Animals , Benz(a)Anthracenes/isolation & purification , Benz(a)Anthracenes/metabolism , Environmental Monitoring , Gas Chromatography-Mass Spectrometry , Limit of Detection , Mutagens/metabolism , Polychaeta/metabolism , Polycyclic Aromatic Hydrocarbons/isolation & purification , Polycyclic Aromatic Hydrocarbons/metabolism , Principal Component Analysis , Solid Phase Extraction/methods , Sonication , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/isolation & purification , Water Pollutants, Chemical/metabolism
11.
Molecules ; 24(16)2019 Aug 15.
Article in English | MEDLINE | ID: mdl-31443290

ABSTRACT

Background. There is no gold standard method for human skin odor determination; several techniques can be applied to collect, extract, transfer, and detect human skin odors. However, none of these methods are suitable for field sampling of a large number of individuals. Objective. The present study aimed to develop a simple, fast, non-invasive, and low-cost method for such a purpose. Methods. Considering that hair from legs can act as a retention mesh of volatile organic compounds (VOCs), samples of leg hairs provided by healthy adult males were collected and solid-phase microextraction (SPME), in headspace (HS) mode, coupled to gas chromatography (GC) and mass spectrometry (MS) analysis of the samples was carried out. A pilot test was applied to detect five quality markers that are frequently reported in human skin odors. Then, several steps were performed for method standardization. The method was applied to 36 different individuals (3 sampled under laboratory conditions and 33 under field conditions), aiming to evaluate its applicability in both environments. Findings. A total of 49 VOCs were identified, and 73.5% of these have been reported in previous studies. Main Conclusions. Hair from legs can be considered an efficient tool for human skin odor sampling and a suitable and practical matrix for human skin odor profile determination by using HS-SPME/GC-MS.


Subject(s)
Hair/chemistry , Odorants/analysis , Skin/metabolism , Analysis of Variance , Gas Chromatography-Mass Spectrometry , Humans , Solid Phase Microextraction , Volatile Organic Compounds/analysis , Volatile Organic Compounds/chemistry , Volatile Organic Compounds/isolation & purification
12.
Sci Rep ; 9(1): 1, 2019 01 09.
Article in English | MEDLINE | ID: mdl-30626917

ABSTRACT

Polycyclic aromatic compounds (PACs) are known due to their mutagenic activity. Among them, 2-nitrobenzanthrone (2-NBA) and 3-nitrobenzanthrone (3-NBA) are considered as two of the most potent mutagens found in atmospheric particles. In the present study 2-NBA, 3-NBA and selected PAHs and Nitro-PAHs were determined in fine particle samples (PM 2.5) collected in a bus station and an outdoor site. The fuel used by buses was a diesel-biodiesel (96:4) blend and light-duty vehicles run with any ethanol-to-gasoline proportion. The concentrations of 2-NBA and 3-NBA were, on average, under 14.8 µg g-1 and 4.39 µg g-1, respectively. In order to access the main sources and formation routes of these compounds, we performed ternary correlations and multivariate statistical analyses. The main sources for the studied compounds in the bus station were diesel/biodiesel exhaust followed by floor resuspension. In the coastal site, vehicular emission, photochemical formation and wood combustion were the main sources for 2-NBA and 3-NBA as well as the other PACs. Incremental lifetime cancer risk (ILCR) were calculated for both places, which presented low values, showing low cancer risk incidence although the ILCR values for the bus station were around 2.5 times higher than the ILCR from the coastal site.

13.
Mar Pollut Bull ; 136: 248-256, 2018 Nov.
Article in English | MEDLINE | ID: mdl-30509805

ABSTRACT

Conventional methods for determination of polycyclic aromatic compounds (PACs) in sediments usually require large sample sizes (grams) and solvent volumes (at least 100 mL) through the employment of Soxhlet extraction, which is both time (hours) and energy consuming, among other disadvantages. We developed a new analytical protocol for the determination of PACs in sediments using microextraction, which requires small sample masses (25 mg), 500 µL of acetonitrile-dichloromethane mix and sonication for 23 min, followed by GC-MS analysis. The method was validated using the certified reference material SRM 1941b - NIST organic marine sediment, as well as internal deuterated standards. Seventeen PAHs, seven nitro-PAHs and one quinone were detected and quantified. The mean concentrations were 90.4 ng g-1 for PAHs, 179.2 ng g-1 for nitro-PAHs and 822.5 ng g-1 for quinones. The proposed method showed good sensitivity, linearity, precision and accuracy for the determination of PAC in sediments samples.


Subject(s)
Gas Chromatography-Mass Spectrometry/methods , Geologic Sediments/analysis , Polycyclic Aromatic Hydrocarbons/analysis , Water Pollutants, Chemical/analysis , Acetonitriles/chemistry , Brazil , Chemical Fractionation/methods , Methylene Chloride/chemistry , Nitrates/chemistry , Oxygen/chemistry , Polycyclic Aromatic Hydrocarbons/chemistry , Quinones/analysis , Reproducibility of Results , Rivers , Water Pollutants, Chemical/chemistry
14.
Talanta ; 179: 810-815, 2018 Mar 01.
Article in English | MEDLINE | ID: mdl-29310311

ABSTRACT

This work proposes a method for the determination of free and total sulfur(IV) compounds in coconut water samples, using the high-resolution continuum source molecular absorption spectrometry. It is based on the measurement of the absorbance signal of the SO2 gas generate, which is resultant of the addition of hydrochloric acid solution on the sample containing the sulfating agent. The sulfite bound to the organic compounds is released by the addition of sodium hydroxide solution, before the generation of the SO2 gas. The optimization step was performed using multivariate methodology involving volume, concentration and flow rate of hydrochloric acid. This method was established by the sum of the absorbances obtained in the three lines of molecular absorption of the SO2 gas. This strategy allowed a procedure for the determination of sulfite with limits of detection and quantification of 0.36 and 1.21mgL-1 (for a sample volume of 10mL) and precision expressed as relative standard deviation of 5.4% and 6.4% for a coconut water sample containing 38.13 and 54.58mgL-1 of free and total sulfite, respectively. The method was applied for analyzing five coconut water samples from Salvador city, Brazil. The average contents varied from 13.0 to 55.4mgL-1 for free sulfite and from 24.7 to 66.9mgL-1 for total sulfur(IV) compounds. The samples were also analyzed employing the Ripper´s procedure, which is a reference method for the quantification of this additive. A statistical test at 95% confidence level demonstrated that there is no significant difference between the results obtained by the two methods.


Subject(s)
Cocos/chemistry , Liquid-Liquid Extraction/methods , Sulfites/isolation & purification , Sulfur Dioxide/isolation & purification , Sulfur/chemistry , Water/chemistry , Brazil , Hydrochloric Acid/chemistry , Limit of Detection , Sodium Hydroxide/chemistry , Spectrophotometry, Atomic
15.
Sci Rep ; 7(1): 2267, 2017 05 23.
Article in English | MEDLINE | ID: mdl-28536439

ABSTRACT

The intensive use of pesticides such as herbicides, insecticides, fungicides and acaricides has been lead to ubiquitous contamination, being present not only in soils, water bodies and/or crops, but also in the atmosphere. Considering the massive amount of pesticides employed globally, together to their persistence, this may be an important concern regarding air quality and human health worldwide. In the present study we developed a green sensitive sample preparation method for determination of nine organophosphates, two pyrethroids, one carbamate, and one strobirulin in PM2.5 collected in a tropical coastal area in the Southern Hemisphere for the first time. Extraction of PM2.5 sample masses, as low as 206 µg, were performed in a miniaturized device using 500 µL of a mixture containing 18% acetonitrile in dichloromethane followed by sonication for 23 minutes and injection into GC-MS. A total of 12 pesticides were identified and quantified successfully, among them, eight banned pesticides. A risk assessment exposure and cancer risk for possible carcinogenic pesticides (bifenthrin, malathion, parathion and permethrin) were performed for exposure of adults, children and infants. Hazard Quotient and cumulative exposure for organophosphate and pyrethroid pesticides were less than 1, showing that cumulative risk is within acceptable range.

16.
Talanta ; 146: 166-74, 2016.
Article in English | MEDLINE | ID: mdl-26695248

ABSTRACT

A method has been developed for the determination of lead in biomass, bio-oil, pyrolysis aqueous phase, and biomass ashes by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) and direct solid or liquid sample analysis. All measurements were performed without chemical modifier and calibration could be carried out using aqueous standard solutions. A pyrolysis temperature of 800°C and an atomization temperature of 2200°C were applied. The limits of detection and quantification were, respectively, 0.5 µg kg(-1) and 2 µg kg(-1) using the analytical line at 217.001 nm and 6 µg kg(-1) and 19 µg kg(-1) at 283.306 nm. The precision, expressed as relative standard deviation, was between 3% and 10%, which is suitable for direct analysis. The lead concentrations found for the solid samples varied between 0.28 and 1.4 mg kg(-1) for biomass and between 0.25 and 2.3 mg kg(-1) for ashes, these values were much higher than those found for bio-oil (2.2-16.8 µg kg(-1)) and pyrolysis aqueous phase (3.2-18.5 µg kg(-1)). After the determination of lead in the samples, it was possible to estimate the relative distribution of this element in the fractions of the pyrolysis products, and it was observed that most of the lead present in the biomass was eliminated to the environment during the pyrolysis process, with a significant portion retained in the ashes.


Subject(s)
Biomass , Graphite/chemistry , Lead/analysis , Spectrophotometry, Atomic/methods , Reproducibility of Results , Temperature , Time Factors , Water/chemistry
17.
Talanta ; 146: 203-8, 2016 Jan 01.
Article in English | MEDLINE | ID: mdl-26695253

ABSTRACT

An analytical method for the determination of sulfur, as the tin mono-sulfide (SnS) molecule, in crude oil using high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS) has been developed. The molecular absorbance of the SnS has been measured using the wavelength at 271.624 nm and the crude oil samples were prepared as micro-emulsions due to their high viscosity. Several chemical modifiers (Ir, Pd, Ru, Zr) were tested and palladium was chosen, because it exhibited the best performance. The heating program was optimized by comparing the pyrolysis and vaporization curves obtained for an aqueous sulfur standard and a micro-emulsion of a crude oil certified reference material (CRM). The optimum pyrolysis and vaporization temperatures were found to be 600 and 2000°C, respectively. The limit of detection and the characteristic mass using micro-emulsion analysis of crude oil samples were 5.8 and 13.3 ng S. Accuracy and precision of the method has been evaluated using two crude oil CRM (NIST 2721 and NIST 2722), showing good agreement with the informed or certified values.

18.
An Acad Bras Cienc ; 87(2): 569-94, 2015.
Article in English | MEDLINE | ID: mdl-26131629

ABSTRACT

According to the demands of energy saving and carbon emission reduction, the water vs. energy nexus has become a major concern worldwide. Brazil occupies a singular position in the global energy system. A major portion of the Brazilian occupancies has electricity and the energy system expansion that, at first, possesses adequate means for supporting the economic growing may experience some turnovers. The Brazil determination through alternative fuels was a natural choice, given its large hydropower potential and land agricultural base. In the transportation sector Brazil has developed its energy matrix towards an important rate of ethanol and biodiesel. Although those fuels are low carbon emitter, they may probably not be an affordable alternative regarding land use, food security and water footprint. In this way, considering the recent advances in the exploration of oil from Pre-salt (9-15 million barrels) and the discovery of shale gas wells up to 245 tcf, together to unfavorable social and environmental issues associated to biofuels, the Brazilian energy matrix might turn back to the fossil fuels again. These represent challenges to the Brazilian policymakers and how they will be solved will reflect not only in Brazil but also to the world at large.

19.
Environ Monit Assess ; 187(1): 4123, 2015 Jan.
Article in English | MEDLINE | ID: mdl-25399121

ABSTRACT

The aim of this work was to evaluate the concentrations of polycyclic aromatic hydrocarbons (PAHs) in soils to which solid shale materials (SSMs) were added as soil conditioners. The SSMs were derived from the Petrosix pyrolysis process developed by Petrobras (Brazil). An improved ultrasonic agitation method was used to extract the PAHs from the solid samples (soils amended with SSMs), and the concentrations of the compounds were determined by gas chromatography coupled to mass spectrometry (GC-MS). The procedure provided satisfactory recoveries, detection limits, and quantification limits. The two-, three-, and four-ring PAHs were most prevalent, and the highest concentration was obtained for phenanthrene (978 ± 19 µg kg(-1) in a pyrolyzed shale sample). The use of phenanthrene/anthracene and fluoranthene/pyrene ratios revealed that the PAHs were derived from petrogenic rather than pyrogenic sources. The measured PAH concentrations did not exceed national or international limit values, suggesting that the use of SSMs as soil conditioners should not cause environmental damage.


Subject(s)
Environmental Monitoring , Polycyclic Aromatic Hydrocarbons/analysis , Refuse Disposal/methods , Soil Pollutants/analysis , Soil/chemistry , Brazil , Gas Chromatography-Mass Spectrometry , Incineration , Minerals/analysis
20.
Talanta ; 127: 140-5, 2014 Sep.
Article in English | MEDLINE | ID: mdl-24913868

ABSTRACT

The present paper describes the development of a method for the determination of copper in airborne particulate matter using slurry sampling and chemical vapor generation atomic absorption spectrometry (CVG AAS). Chemometric tools were employed to characterize the influence of several factors on the generation of volatile copper species. First, a two-level full factorial design was performed that included the following chemical variables: hydrochloric acid concentration, tetrahydroborate concentration, sulfanilamide concentration and tetrahydroborate volume, using absorbance as the response. Under the established experimental conditions, the hydrochloric acid concentration had the greatest influence on the generation of volatile copper species. Subsequently, a Box-Behnken design was performed to determine the optimum conditions for these parameters. A second chemometric study employing a two-level full factorial design was performed to evaluate the following physical factors: tetrahydroborate flow rate, flame composition, alcohol volume and sample volume. The results of this study demonstrated that the tetrahydroborate flow rate was critical for the process. The chemometric experiments determined the following experimental conditions for the method: hydrochloric acid concentration, 0.208 M; tetrahydroborate concentration, 4.59%; sulfanilamide concentration, 0.79%; tetrahydroborate volume, 2.50 mL; tetrahydroborate flow rate, 6.50 mL min(-1); alcohol volume, 200 µL; and sample volume, 7.0 mL. Thus, this method, using a slurry volume of 500 µL and a final dilution of 7 mL, allowed for the determination of copper with limits of detection and quantification of 0.30 and 0.99 µg L(-1), respectively. Precisions, expressed as RSD%, of 4.6 and 2.8% were obtained using copper solutions at concentrations of 5.0 and 50.0 µg L(-1), respectively. The accuracy was evaluated by the analysis of a certified reference material of urban particulate matter. The copper concentration obtained was 570±63 mg kg(-1), and the certified value was 610±70 mg kg(-1). This method was applied for the determination of copper in airborne particulate matter samples collected in two Brazilian regions of Bahia State, Brazil. The copper contents found varied from 14.46 to 164.31 ng m(-3).


Subject(s)
Air Pollutants/analysis , Copper/analysis , Particulate Matter/analysis , Air Pollutants/chemistry , Borohydrides/chemistry , Copper/chemistry , Hydrochloric Acid/chemistry , Particulate Matter/chemistry , Pentanols/chemistry , Spectrophotometry, Atomic , Volatilization
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