Determination of priority pesticides in water samples combining SPE and SPME coupled to GC–MS. A case study: Suquía River basin (Argentina)

This study reports a combined method using solid phase extraction (SPE), followed by solid phase microextraction (SPME) to concentrate different pesticides, including chlorinated, organophosphorus, triazines, pyretroids and chloroacetamides, present at trace levels in water samples. Identification and quantification was carried out by gas chromatography coupled to Mass Spectrometry (GC–MS). The optimized methodology showed LOQs at ng L^?1 levels (ranging 0.2–3.5 ng L^?1) in addition to acceptable precision and robustness (recoveries ranged 63–104%, RSD from 4% to 23%), presenting a novel method to reach trace levels, similar to that obtainable using EC detector, with structural confirmation by MS during the analysis of a wide range of environmental pollutants.This method was applied to the study of temporal and spatial distribution of pesticides in the Suquía River basin (Córdoba-Argentina). As expected, highest levels of agrochemicals were observed in areas with intensive agricultural practices, being atrazine (max. = 433.9 ng L^?1), alpha-cypermetrine (max. = 121.7 ng L^?1) and endosulfan sulfate (max. = 106.7 ng L^?1) predominant. In urban areas, the prevalent pesticide was alpha-cypermethrine. These results draw attention to the need of pesticide monitoring programs in rivers, considering both urban and rural sections.     

Levels and risks of particulate-bound PAHs in indoor air influenced by tobacco smoke: a field measurement

Considering tobacco smoke as one of the most health-relevant indoor sources, the aim of this work was to further understand its negative impacts on human health. The specific objectives of this work were to evaluate the levels of particulate-bound PAHs in smoking and non-smoking homes and to assess the risks associated with inhalation exposure to these compounds. The developed work concerned the application of the toxicity equivalency factors approach (including the estimation of the lifetime lung cancer risks, WHO) and the methodology established by USEPA (considering three different age categories) to 18 PAHs detected in inhalable (PM₁₀) and fine (PM_2.5) particles at two homes. The total concentrations of 18 PAHs (Σ_PAHs) was 17.1 and 16.6 ng m^?3 in PM₁₀ and PM_2.5 at smoking home and 7.60 and 7.16 ng m^?3 in PM₁₀ and PM_2.5 at non-smoking one. Compounds with five and six rings composed the majority of the particulate PAHs content (i.e., 73 and 78 % of Σ_PAHs at the smoking and non-smoking home, respectively). Target carcinogenic risks exceeded USEPA health-based guideline at smoking home for 2 different age categories. Estimated values of lifetime lung cancer risks largely exceeded (68–200 times) the health-based guideline levels at both homes thus demonstrating that long-term exposure to PAHs at the respective levels would eventually cause risk of developing cancer. The high determined values of cancer risks in the absence of smoking were probably caused by contribution of PAHs from outdoor sources.     

Importance of sulfate reducing bacteria in mercury methylation and demethylation in periphyton from Bolivian Amazon region

Sulfate reducing bacteria (SRB) are important mercury methylators in sediments, but information on mercury methylators in other compartments is ambiguous. To investigate SRB involvement in methylation in Amazonian periphyton, the relationship between Hg methylation potential and SRB (Desulfobacteraceae, Desulfobulbaceae and Desulfovibrionaceae) abundance in Eichhornia crassipes and Polygonum densiflorum root associated periphyton was examined. Periphyton subsamples of each macrophyte were amended with electron donors (lactate, acetate and propionate) or inhibitors (molybdate) of sulfate reduction to create differences in SRB subgroup abundance, which was measured by quantitative real-time PCR with primers specific for the 16S rRNA gene. Mercury methylation and demethylation potentials were determined by a stable isotope tracer technique using ²⁰⁰HgCl and CH₃²⁰²HgCl, respectively. Relative abundance of Desulfobacteraceae (<0.01-12.5%) and Desulfovibrionaceae (0.01-6.8%) were both highly variable among samples and subsamples, but a significant linear relationship (p < 0.05) was found between Desulfobacteraceae abundance and net methylmercury formation among treatments of the same macrophyte periphyton and among all P. densiflorum samples, suggesting that Desulfobacteraceae bacteria are the most important mercury methylators among SRB families. Yet, molybdate only partially inhibited mercury methylation potentials, suggesting the involvement of other microorganisms as well. The response of net methylmercury production to the different electron donors and molybdate was highly variable (3-1104 pg g⁻¹ in 12 h) among samples, as was the net formation in control samples (17-164 pg g⁻¹ in 12 h). This demonstrates the importance of community variability and complexity of microbial interactions for the overall methylmercury production in periphyton and their response to external stimulus.     

Evaluation of carbon degradation during co-composting of exhausted grape marc with different biowastes

In this work the carbon biodegradation of exhausted grape marc (EGM) combined with other organic wastes using the turned pile composting system was studied. Four different piles were made of EGM in Pile 1, EGM mixed with cow manure and straw (CMS) in Pile 2, EGM mixed with municipal solid waste (MSW) in Pile 3 and EGM mixed with grape stalks (GS) in Pile 4. The results obtained were modelled to determine the main kinetic and stoichiometric parameters. Regarding to the rate constants of the composting processes they were increased from 0.033d(-1), the value obtained when EGM was composted alone, to 0.040 and 0.044d(-1) when MSW and GS were added, respectively as co-substrates. However, the addition of CMS reduced the rate constant. About the biodegradable carbon fractions, it was observed that the co-composting reduced significantly the remanent carbon concentration after composting in all the piles whilst increased the readily biodegradable carbon fractions from 35, the value obtained when EGM was composted alone, to 50 and 60%, respectively when MSW or GS were added. As regards the temperature profiles, only Piles 1 and 4 achieved thermal hygienization values and about the nitrogen losses, the lowest percentage of nitrogen loss took place when GS were added, because of its optimum pH and C/N initial ratio. Thus, though any of these wastes could be used for co-composting with EGM, the use of GS as co-substrate and bulking agent for the co-composting process of EGM was recommended.     

Concentrations of PCDD/PCDFs in plasma of subjects living in the vicinity of a hazardous waste incinerator: follow-up and modeling validation

In 2007, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs) were determined in plasma of non-occupationally exposed subjects living near the only hazardous waste incinerator (HWI) in Spain (Constantí, Tarragona County, Catalonia). These data were compared with the levels found in two previous surveys performed in 1998 (baseline) and 2002. The current mean PCDD/PCDF concentration in plasma was 9.36pg I-TEQg(-1) of lipid (range: 1.76-23.44pg I-TEQg(-1) of lipid). It means a significant reduction of the mean PCDD/PCDFs levels in plasma in comparison to the concentrations found in 1998 and 2002 (27.01 and 15.70pg I-TEQg(-1) of lipid, respectively). This important decrease agrees well with the notable reduction in the dietary intake of PCDD/PCDFs recently noted for the population of the same area (210.1pg I-TEQd(-1), 63.8pgWHO-TEQd(-1), and 27.8pgWHO-TEQd(-1), in 1998, 2002 and 2007, respectively). The current data were also used to predict theoretical PCDD/PCDF concentrations in plasma by executing a single-compartment empirically-based pharmacokinetic model on the basis of the daily intake of these pollutants by the local population.     

Effect of the organic loading rate on the performance of anaerobic acidogenic fermentation of two-phase olive mill solid residue

A study of the effect of the organic loading rate (OLR) on the anaerobic acidogenic fermentation of two-phase olive mill solid residue (OMSR) derived from fruits with a low ripening index was carried out in a laboratory-scale completely stirred tank reactor at mesophilic temperature (35 degrees C). Eight experimental runs were carried out at OLRs of 3.2, 5.6, 7.4, 9.6, 11.0, 12.9, 14.0 and 15.1g T-COD/ld, which were equivalent to hydraulic retention times of 50.0, 28.8, 21.8, 16.9, 14.7, 12.4, 11.5 and 10.7d, respectively. The experimental results obtained demonstrated that the optimum value of OLR for the acidogenic fermentation process was 12.9 g T-COD/ld, for which a maximum production of acetic acid was achieved. It was found that inhibition of the process occurred at OLRs higher than 12.9 g T-COD/ld. This was characterized by a significant decrease in the acetic acid concentration in the effluent and an increase in the concentration of other volatile acids that may affect the methanogenic step. The process inhibition was also characterized by the plateau in the curves of the effluent substrate concentration versus the OLR applied. It was found that a first-order kinetics satisfactorily described the influence of non-acetic acid soluble organic matter concentration (S-COD( *)) on the rate of soluble organic matter conversion to acetic acid (R(S-COD)( *)), and the influence of acetic acid concentration (AcH) on the rate of acetic acid production (R(AcH)), while a potential equation type adequately described the influence of acetic acid concentration on the volumetric hydrogen production (R(ACH) ). The kinetic constant for soluble organic matter removal was 0.145 d(-1), while the constant for acetic acid formation was found to be 0.075 d(-1).