L. Comellas

Analysis and fate of aliphatic hydrocarbons, linear alkylbenzenes, polychlorinated biphenyls and polycyclic aromatic hydrocarbons in sewage sludge-amended soils

Abstract Different extraction and clean-up methods for the multi-residue determination of aliphatic hydrocarbons (AHCs), linear alkylbenzenes (LABs), polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in sewage sludge-amended soil were investigated. Soxhlet extraction with dichloromethane and actived silica gel clean-up provided the best results. HRGC with FID detection, HRGC with ECD detection, and HPLC with a programmable fluorescence detection, performed accurate identification and quantification of AHCs and LABs, PCBs and PAHs, respectively. The evolution of the pollutants in sludged soil has been monitored for a 594-day period. Results indicated that AHCs, LABs and low-molecular-mass PAHs were susceptible to loss processes, whereas high-molecular-mass PAHs and PCBs were persistent.

Comparison of various extraction and clean-up methods for the determination of polycyclic aromatic hydrocarbons in sewage sludge-amended soils☆

Abstract Different extraction and clean-up methods for the determination of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge-amended soil were investigated. Soxhlet plus saponification extraction and silica gel clean-up provided the best results. HPLC with a programmable fluorescence detector performed accurate identification and quantification of PAHs. The initial PAH concentrations in sewage sludge-amended soil ranged from 8 ng/g for benzo[a]fluoranthene to 93 ng/g for phenanthrene, with a total PAH concentration of 417 ng/g. The weathering of PAHs in sludged soil was monitored for a 141-day period. The results indicated that low-molecular-mass PAHs were susceptible to abiotic and biotic loss processes.

Extraction and clean-up methods for improvement of the chromatographic determination of polychlorinated biphenyls in sewage sludge-amended soils : elimination of lipids and sulphur

Abstract Different extraction and clean-up methods for the determination of polychlorinated biphenyls (PCBs) in sewage sludge-amended soil were investigated. Soxhlet extraction with hexane-acetone (41:59) and simultaneous elimination of sulphur, with recently precipitated copper, and Florisil cartridge clean-up provided the best results. High-resolution GC with electron-capture detection achieved accurate identification and quantification of the PCBs. Initial pollutant concentrations in soil amended with sewage sludge ranged from 0.5 to 94 ng/g for PCB congeners. The weathering of the PCBs in sludged soil was monitored for a 168-day period. The results indicated that PCBs were persistent.

Separation of non-ortho polychlorinated biphenyl congeners on pre-packed carbon tubes. Application to analysis in sewage sludge and soil samples

The analysis of planar (non-ortho) polychlorinated biphenyls (PCB) by HRGC-ECD or HRGC-HRMS requires a fractionation step to avoid the interferences of the bulk of PCB, usually in much higher concentration than the planar ones. In this paper, a new method, based on the fractionation of PCB on SPE commercial tubes pre-packed with Carbopack B, has been developed. After the extract has been applied on the stationary phase, the bulk of PCD are eluted with 15 ml of hexane (fraction I), mono-ortho PCB with 20 ml of hexane/toluene 99:1 (fraction II) and planar PCB with 20 ml of toluene (fraction III) in a station under vacuum. The method has been validated: accuracy (expressed as recovery in %) is >70% and precision (expressed as % RSD) is <20% considering changes of day, analyst and batch of tubes. The method is linear in the range studied. Other advantages are that the method is simple, rapid and it can be easily automated. The application of this separation to the determination of planar PCB in fly-ash extracts from an intercalibration exercise and to sewage sludge, sediment and soil samples has been successful. In addition, this method removes hydrocarbons from the planar PCB fraction and allows its concentration to very small volumes.

Analysis of dioxin-like compounds in vegetation and soil samples burned in Catalan forest fires. Comparison with the corresponding unburned material

Only a few data are reported about the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in forest fires. However, the inventories of sources undertaken by several European and American countries consider natural fires as a possible source of PCDD/F and, in some cases, as one of the most important. In our work we have analysed vegetation and soil samples burned in four forest fires which happened in Catalonia in the summer of 1998. The concentration of dioxin-like compounds (PCDD/F, non-ortho polychlorinated bi-phenyls (PCB) and mono-ortho PCB) has been compared to the concentration present in the corresponding unburned material collected in places near the fires but not affected. The results of this preliminary study show very low concentrations in all the samples, both burned and unburned. Although a change in the profile (proportional increase of tetrachlorinated congeners in PCDD/F) is observed in burned samples compared to unburned ones, the absolute values of concentration decrease in most samples. Therefore, natural fires seem not to be an important source of dioxin-like compounds. These results will be confirmed with air emissions measurements in future studies.

Application of the new C18 speedisks™ to the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans in water and effluent samples

A recently introduced disk for solid-phase extraction of pollutants from water (C18 Speedisk) has been tested for the analysis of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). The complete procedure of analysis has been validated with spiked deionized water. The accuracy, expressed as recovery for the sum of 2,3,7,8-substituted congeners. is 92% and the precision, expressed as the RSD of reproducibility, is 5.8%. The limit of detection (LOD), using 2 l of water, is 4.2 pg/l (0.6 pg ITEQ/l) for the sum of 2,3,7,8-substituted congeners. Actually, the C18 Speedisks have substituted the use of other C18 membrane disks in our laboratory because they allow the fast and efficient analysis of samples with high content of suspended material and reduce the time of elution of free-particulate samples. These disks have been successfully applied to the analysis of water from different sources and with very different physical and chemical characteristics: seawater, rain water, an industrial effluent, a landfill leachate and the inlet and chlorinated and non-chlorinated outlet water from a wastewater treatment plant.

Study of evolution of PCDD/F in sewage sludge-amended soils for land restoration purposes.

The evolution of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in sewage sludge-amended soils used in the restoration of degraded lands, like quarries, has been studied. Two experiments were performed: one in the lab, under controlled conditions, and another in a quarry. Two different doses of sewage sludge were applied in both experiments (with two types of application in the quarry experiment) and the evolution of the amended soils were compared with that of the respective control soils (without addition of sewage sludge). The samples were analyzed with a previously validated method by HRGC HRMS after the extraction and the necessary clean-up steps. The results reveal that polluted sewage sludge increases PCDD/F concentration in soils and that these compounds are persistent in the matrix after long periods of time.

Toxicogenetic monitoring in urban cities exposed to different airborne contaminants

Microparticles found in the air may be associated with organic matter that contains several compounds, such as Polycyclic Aromatic Hydrocarbons (PAHs) and nitro-PAHs, and may pose a significant risk to human health, possibly leading to DNA mutations and cancers. This study associated genotoxicity assays for evaluating human exposure with the atmospheric air of two urban areas in southern Brazil, that received different atmospheric contributions. Site 1 was under urban-industrial influence and the other was a non-industrial reference, Site 2. Organic extracts from the airborne particulate matter were tested for mutagenicity via the Salmonella/microsome assay and analyzed for PAH composition. Cells samples of people residing in these two cities were evaluated using the comet and micronucleus assay (MN).Concentrations of the individual PAHs ranged from 0.01 ng/m(3) (benzo[a]anthracene) to 5.08 ng/m(3) (benzo[ghi]perylene). As to mutagenicity analysis of airborne, Site 1 presented all the mutagenic responses, which varied from 3.2±1.22 rev/m(3) (TA98 no S9) to 32.6±2.05 rev/m(3) (TA98, S9), while Site 2 ranged from negative to minimal responses. Site 1 presented a high quantity of nitro and amino derivatives of PAHs, and peaked at 56.0±3.68 rev/μg (YG1024 strain). The two groups presented very low DNA damage levels without intergroup difference. Although Site 1 presented high mutagenic responses in the air samples, high PAH levels, healthy people exposed to this environment did not show significative damage in their genetic material. However, the evaluation of different environmental and genetic damage in such population is necessary to monitor possible damages.

Salmonella mutagenicity assessment of airborne particulate matter collected from urban areas of Rio Grande do Sul State, Brazil, differing in anthropogenic influences and polycyclic aromatic hydrocarbon levels.

Urban areas are both major sources and major targets of air pollution. The atmospheric environment receives diverse chemical substances, including genotoxic agents that may affect human health. The purpose of this study was to evaluate and compare the atmospheric quality in two urban areas in Rio Grande do Sul State (Brazil), under the influence of greater (Site 1) or lesser (Site 2) anthropogenic sources. Polycyclic aromatic hydrocarbons (PAHs) of environmental interest were quantified and the Salmonella/microsome assay was used for the measurement of mutagenicity. Organic compounds extracted from the airborne particulate matter were analyzed by high-performance liquid chromatography (HPLC) to detect PAHs of interest (known or possible carcinogens). The organic extracts were also tested for mutagenic and cytotoxic activity in the Salmonella/microsome assay with strains TA98, TA100, YG1021 and YG1024, with or without S9 activation. At Site 1, benzo[ghi]perylene (BghiP) and indeno[1,2,3-cd]pyrene (IP) were found at higher concentrations and mutagenicity (revertants per μg extract) varied from 1.0±0.25 (TA98, no S9) to 5.2±0.45 (TA98, S9). At Site 2, BghiP and IP were present in larger amounts and the mutagenic responses ranged from 0.6 to 3.7 revertants per μg (both in TA98, S9). The occurrence of BghiP and IP may be related to vehicular emissions. These and the other PAHs studied, as well as the nitro compounds, may contribute to the mutagenicity found in these airborne particles.

Two-dimensional thin-layer chromatographic method for the analysis of ochratoxin A in green coffee.

A low-cost thin-layer chromatographic method has been developed for the presumptive measurement of ochratoxin A (OTA) at 5 microg/kg in green coffee beans. The analytical method consisted of extracting OTA by shaking the beans with a mixture of methanol and aqueous sodium bicarbonate solution, which was then purified by liquid-liquid partition into toluene. OTA was separated by normal-phase two-dimensional thin-layer chromatography and detected by visual estimation of fluorescence intensity under a UV lamp at 365 nm. The chromatography solvents were toluene-methanol-formic acid (8:2:0.03) for the first development and petroleum ether-ethyl acetate-formic acid (8:10:1) for the second dimension development. This method was tested with uncontaminated green coffee bean samples spiked with an OTA standard at four different concentrations (5, 10, 20, and 30 microg/kg). The method is rapid, simple, and very easy to implement in coffee-producing countries. It is highly selective and does not involve the use of chlorinated solvents in the sample extraction step. This inexpensive method has been applied to different types of green coffee samples from various countries (Zimbabwe, Brazil, India, Uganda, Colombia, and Indonesia) and different manufacturers, and no OTA below the detection limit of 5 microg/kg was detected in any samples analyzed.