Débora A. Azevedo

Monitoring of priority pesticides and other organic pollutants in river water from Portugal by gas chromatography-mass spectrometry and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) were optimized and applied for the trace-level determination of 42 priority pesticides and 33 priority organic pollutants from European Union Directive EC 76/464. First, off-line solid-phase extraction of 200 ml of river water using an OASIS solid-phase extraction cartridge, followed by GC-MS was used. Next, selected samples that were positive to GC-MS were analyzed by LC-APCI-MS in order to detect further polar byproducts or to improve the determination of previously detected polar analytes. The transformation products of triazine pesticides like deethylatrazine (DEA) and deisopropylatrazine (DIA) and compounds such as diuron and several chlorophenols were positively identified by LC-APCI-MS. The present methodology has also been used for searching for new analytes not included in the EC 76/464 list, like Irgarol, DEA and DIA. In addition it was applied to target pollutants in 43 river water samples from Portugal during a pilot survey from April to July 1999. Atrazine followed by simazine and 2,4,6-trichlorophenol were the most ubiquitous compounds detected in this area. The levels detected of the different compounds were in the range of: 0.01-2.73 microg/l, 0.05-0.74 microg/l, 0.02-1.65 microg/l, 0.02-5.43 microg/l, 0.01-0.40 microg/l, 0.01-0.26 microg/l, 0.02-0.61 microg/l, 0.01-3.90 microg/l, 0.01-1.24 microg/l, 0.02-2.3 microg/l, 0.01-0.13 microg/l and 0.01-0.5 microg/l for atrazine, simazine, terbuthylazine, alachlor, metolachlor, Irgarol, propanil; tributhylphosphate, diuron, 2,4,6-trichlorophenol, deisopropylatrazine and deethylatrazine, respectively.

Composition of extractable organic matter in aerosols from urban areas of Rio de Janeiro city, Brazil

Abstract The hydrocarbon compositions of atmospheric particulate matter from urban areas of Rio de Janeiro city have been studied to assess the different pollution levels. Samples were acquired using a standard high-volume air sampler (Hi-Vol), extracts were prepared and fractionated into aliphatic and aromatic compounds. High-resolution gas chromatography and GC coupled to mass spectrometry (GC–MS) were used for the analysis of the organic matter. The results show that all samples contain n-alkanes, but the distributions are different for each sample, reflecting both the biogenic (vascular plant wax input) and fossil fuel contamination sources (vehicular exhaust). The fossil fuel biomarkers, hopanes and steranes, were also observed in all samples except in the Tijuca Forest, which is a mountain forest in the midst of the sea-level city. A decrease in the level of pollution was observed in the sequence for Reboucas Tunnel>Cinelândia (downtown)>Quinta da Boa Vista Park>Tijuca Forest, as expected from the traffic density. Unfortunately, all sites are polluted mainly from vehicular emissions, but at different degrees, with the lowest levels in Tijuca Forest.

Organic geochemistry of geographically unrelated tasmanites

Abstract The biomarker analysis of three tasmanite rock samples from Tasmania, Alaska and Brazil showed an unusually high tricyclic terpane concentration relative to hopanes and steranes. A possible product-precursor relationship is advanced, associating Tasmanaceae alage with these tricyclic terpanes. These results support the search of possible precursor molecules in present day organisms which may be taxonomically related to these algae.

Analysis of phytoestrogens, progestogens and estrogens in environmental waters from Rio de Janeiro (Brazil).

The environment is currently exposed to a large variety of man-made chemicals (e.g. for industrial, medicinal use) which have potential adverse effects to its ecological status. In addition, the densely populated areas represent local high emissions of those chemicals leading to more aggravating consequences. Estrogenic compounds that end-up in environmental water directly affect living organisms by interfering with their endocrine metabolism. The assessment of their presence in the environment requires sensitive and selective analytical methods. Nineteen estrogenic compounds belonging to different classes (5 free estrogens, 6 conjugated estrogens, 3 progestogens and 5 phytoestrogens) have been studied. The analytical methodology developed is based on solid phase extraction followed by liquid chromatography tandem mass spectrometry and has been applied to study the occurrence of the above mentioned analytes in environmental waters from the state of Rio de Janeiro (Brazil). Due to insufficient infra-structure in this region, waste waters are released onto the environment without or with incomplete previous treatment. The results show that high levels of the phytoestrogens daidzein, coumestrol and genistein of up to 366 ng/L and progesterone of up to 47 ng/L could be found in river water. Estrogens and their conjugated derivatives were detected in the lower ng/L range up to 7 ng/L. The main estrogens estrone, estradiol and the synthetic ethinyl estradiol could not be detected. The developed method showed overall good performance with recoveries above 80% (with one exception), limits of detection < or =2 ng/L, good linearity and reproducibility.

Occurrence of nonylphenol and bisphenol-A in surface waters from Portugal

The occurrence of the endocrine disruptor compounds, such as 4-nonylphenol isomers and bisphenol A was determined in surface water samples from Portugal. The analytical method used involved the preconcentration of 200 mL of water sample by solid phase extraction (SPE) using a OASIS (Waters) cartridge, followed by Gas Chromatography-Mass Spectrometry (GC/MS) determination. Recoveries and limits of detection of 4-nonylphenol isomers and bisphenol-A were 73 % and 119 %, respectively, 0.01 mg L-1 and 0.002 mg L-1. The method was applied to the determination of these estrogenic pollutants in river and coastal waters during three months (August-October/1999). The total samples analyzed were 135. Concentrations of 4-nonylphenol isomers and bisphenol-A ranged from 0.03-30 mg L-1 and 0.07-4.0 mg L-1, respectively. Only in two river samples, concentrations of 4-nonylphenol isomers were above 10 mg L-1 and bisphenol-A were above 2 mg L-1. These values can cause estrogenic effects in fish and these sampling points require further investigation in order to verify the maintenance of these levels.

Novel series of tricyclic aromatic terpanes characterized in Tasmanian tasmanite

Abstract A novel series of tricyclic ring-C monoaromatic terpanes and a minor group of tricyclic diaromatic terpanes were characterized in Tasmanian tasmanite. The monoaromatic series ranges from C18 to C40, with a homolog distribution pattern similar to the geologically ubiquitous tricyclic terpane series. The diaromatic compounds are comprised of the C17-C19 homologs. The occurrence of these aromatic compounds in an immature sediment (Ro = 0.3–0.4%) indicates an early diagnetic origin or possibly a direct biological input. The implications of these findings to the search for the precursors of these biomarkers is discussed. A minor series of aromatic des-A-triterpenoid hydrocarbons from biodegraded terrestrial lipids is also present.

Chemical characterization of bio-oils using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

The liquid product obtained via the biomass flash pyrolysis is commonly called bio-oil or pyrolysis oil. Bio-oils can be used as sources for chemicals or as fuels, primarily in mixtures or emulsions with fossil fuels. A detailed chemical characterization of bio-oil is necessary to determine its potential uses. Such characterization demands a powerful analytical technique such as comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS). Limited chemical information can be obtained from conventional gas chromatography coupled mass spectrometry (GC-MS) because of the large number of compounds and coelutions. Thus, GC×GC-TOFMS was used for the individual identification of bio-oil components from two samples prepared via the flash pyrolysis of empty palm fruit bunch and pine wood chips. To the best of our knowledge, few papers have reported comprehensive two-dimensional gas chromatography (GC×GC) for bio-oil analysis. Many classes of compounds such as phenols, benzenediols, cyclopentenones, furanones, indanones and alkylpyridines were identified. Several coelutions present in the GC-MS were resolved using GC×GC-TOFMS. Many peaks were detected for the samples by GC-MS (~166 and 129), but 631 and 857 were detected by GC×GC-TOFMS, respectively. The GC×GC-TOFMS analyses indicated that the major classes of components (analytes>0.5% relative area) in the two bio-oil samples are ketones, cyclopentenones, furanones, furans, phenols, benzenediols, methoxy- and dimethoxy-phenols and sugars. In addition, esters, aldehydes and pyridines were found for sample obtained from empty palm fruit bunch, while alcohols and cyclopentanediones were found in sample prepared from pine wood chips indicating different composition profiles due to the biomass sources. The elucidation of the composition of empty fruit bunch and pine wood chips bio-oils indicates that these oils are suitable for the production of value-added chemicals. The high quantity of phenol in the bio-oil of empty palm fruit bunch is of interest because phenol isolated from the bio-oil could provide an alternative to the phenol obtained from petroleum. The anhydrosugars found mainly in the bio-oil sample of pine wood chips can be isolated and fermented to produce ethanol or lipids. GC×GC-TOFMS can be used to increase the knowledge of the chemical composition of bio-oils allowing the improved usage of this attractive renewable energy source in bio-fuels.

Identification and seasonal variation of atmospheric organic pollutants in Campos dos Goytacazes, Brazil

Abstract Organic aerosol samples collected during a 1 year study at three sites in the city of Campos dos Goytacazes, Rio de Janeiro, Brazil, were examined by gas chromatography and gas chromatography–mass spectrometry. Samples were acquired using a standard high-volume air sampler (Hi-Vol); extracts prepared and fractionated into aliphatic, aromatic and polar compounds. These compounds were quantified and their seasonal ambient concentration patterns discussed. High winter and low summer concentrations were observed for retene, polycyclic aromatic hydrocarbons and total suspended particulate matter (TSP), with a seasonal (winter) peak for all compounds studied. The higher concentrations observable from May to September may result from crop burning processes, which occur in the sugarcane plantations, mainly during this part of the year. The studied sites may be considered unpolluted as concentrations of benzo[a]pyrene and benzene were lower than the regulation lower limits. On the other hand, two sites were considered polluted by TSP determination.

Distribution of polycyclic aromatic hydrocarbons in surface sediments and waters from Guanabara Bay, Rio de Janeiro, Brazil

Polycyclic aromatic hydrocarbons (PAHs) were identified and quantified in sediment and water samples from 12 sites in the north-northeast region of the Guanabara Bay. The samples were analyzed by GC-MS to assess the degree of contamination by monitoring the affected ecosystem after an oil spill that occurred in January 18, 2000. Total PAH concentrations ranged from 77 to 7,751 µg kg-1 dry weight in surficial sediment samples and from not detected to 1592 ng L-1 in water samples. The majority of sediment samples were classified as highly contaminated (total PAH > 500 µg kg-1) while for water samples the concentration of PAHs was not sufficiently high to induce acute toxicity to aquatic organisms. In comparison with other coastal areas, PAH concentrations in Guanabara Bay are relatively high. The ratios of low molecular weight/high molecular weight (LMW/HMW) PAHs, phenanthrene/anthracene and benzo[a]anthracene/chrysene, are sensitive indicators of the origin of PAH pollution, which have shown to be mostly from fuel combustion in the Guanabara Bay.

Analysis of Priority Pesticides and Phenols in Portuguese River Water by Liquid Chromatography-Mass Spectrometry

SummaryThe determination of selected pesticides and phenols in Portuguese river water samples was carried out from April to September, 1999. The method involved 200 mL samples taken by offline, solid phase extraction by OASIS polymeric cartridges followed by liquid chromatography-atmospheric pressure, chemical ionization-mass spectrometry (LC-APCI-MS). Recoveries of pesticides were 50–96% and 72–120% for the Platform and HP 1100 instruments, respectively. Chlorophenols gave recoveries of 60–91%. Triazines and transformation products like desethylatrazine (DEA) and desisopropylatrazine (DIA) and compounds such as diuron and chlorophenols were positively identified by LC-APCI-MS. The levels detected of the different compounds varied from 0.01–2.61 μg L−1, the most frequently detected compounds being, atrazine, simazine, terbuthylazine, alachlor, metolachlor, Irgarol, diuron, 2,4,6-trichlorophenol, desisopropylatrazine and desethylatrazine.