Elena Martínez-Carballo

Effects of toasting procedures on the levels of polycyclic aromatic hydrocarbons in toasted bread

Some polycyclic aromatic hydrocarbons (PAHs), particularly those with a high molecular weight, have been classified as probably carcinogens to humans by the International Agency for Research on Cancer (IARC). The significance of the determination of PAHs is reflected by the special attention of the European Union, which is paying to regulate the maximum allowed levels of PAHs in foodstuffs such as smoked foods. Like other thermally processed foodstuffs, toasted bread can contain these carcinogenic chemicals, not only due to a contamination at source but also during toasting. In order to check PAHs generated from toasting in sandwich bread, several treatment conditions were evaluated: direct toasting (flame-toasting, coal-grilling or gas oven-toasting) or indirect toasting (electric oven-toasting). PAHs were extracted by solid-liquid extraction (SLE) and determined by liquid chromatography with fluorescence detection (LC-FD). Based on the results, the used toasted technique would strongly affect in PAH levels in the final product. No samples obtained by electric oven and toaster were polluted; otherwise the samples toasted by charcoal and flame grilling presented very important levels. Up to 350μg/kg of total PAHs were detected in toasted samples by wood flame. Differences between different ways of toasting could be ascribed to deposition of PAHs from smoke. Finally, several commercial toasted samples of bread were tested to determine PAHs. Overall, the PAH levels were very low. Benzo[a]pyrene ranged from no detectable to 0.23μg/kg.

Determination of quaternary ammonium herbicides in soils. Comparison of digestion, shaking and microwave-assisted extractions.

Very challenging analytical problems arise from the continuous introduction in agriculture of chemical pesticides. Particularly, diquat (DQ), paraquat (PQ) and difenzoquat (DF) are a difficult group of quaternary ammonium herbicides to analyze. This article reviews and addresses the most relevant analytical methods for determining the selected herbicides in soil. We discuss and critically evaluate procedures, such as digestion-based methods, shaking extraction and microwave-assisted extraction (MAE). Clean-up of extracts was performed by solid-phase extraction (SPE) using silica cartridges. Detection of these herbicides was carried out by liquid chromatography (LC) coupled to UV detection and mass spectrometry (MS) as confirmatory technique. Recoveries ranged from 98% to 100% by digestion, from no recovered to 61% by shaking, and from 102% to 109% by MAE with estimated quantification limits between 1.0 microg/kg and 2.0 microg/kg by digestion and 5.0 mug/kg and 7.5 microg/kg by MAE using LC/MS-MS as detection technique. The recoveries obtained under the optimum conditions are compared and discussed with those obtained from digestion extraction and MAE.

Removal of polycyclic aromatic hydrocarbons from organic solvents by ashes wastes.

Polycyclic aromatic hydrocarbons (PAHs) can be formed during the refinery processes of crude petroleum. Their removal is of great importance. The same happens with other organic solvents used for the extraction of PAHs (hexane, acetonitrile...), which can be polluted with PAHs. Kinetic and equilibrium batch sorption tests were used to investigate the effect of wood ashes wastes as compared to activated carbon on the sorption of three representative PAHs from n-hexane and acetonitrile. Mussel shell ashes were discarded for batch sorption experiments because they were the only ashes containing PAHs. The equilibrium time was reached at 16 h. Physical sorption caused by the aromatic nature of the compounds was the main mechanism that governed the PAHs removal process. Our investigation revealed that wood ashes obtained at lower temperature (300 degrees C) did not show any PAHs sorption, while ashes obtained at higher temperature (>500 degrees C) have adsorbent sites readily available for the PAH molecules. An increase in the molecular weight of PAHs has a strong effect on sorption wood ashes wastes. As low the wood ashes particle size as high the sorption of PAHs, as a result of differences in adsorbent sites. The performance of wood ash wastes vs. activated carbon to remove 10 PAHs from organic solvents is competitive in price, and a good way for waste disposal.

Occurrence and Downslope Mobilization of Quaternary Herbicide Residues in Vineyard-Devoted Soils

The aim of this study was to examine the fate of quaternary herbicides in soil deposits derived from erosion of vineyard-devoted soils. Herbicide occurrence in the crop soils was due to the farmer application inputs. Special attention should be paid to the presence of paraquat (PQ) in the studied vineyard-devoted soils. The major factor governing the sorption of PQ was the solid state organic fraction with the clay mineral content also making a significant contribution. The mobilization and transport of quats-enriched soil particles may generate downslope and downstream environmental problems that mainly affect detritivore ecology.

A Critical Review about Human Exposure to Polychlorinated Dibenzo-p-Dioxins (PCDDs), Polychlorinated Dibenzofurans (PCDFs) and Polychlorinated Biphenyls (PCBs) through Foods

Dioxins include polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and part of polychlorinated biphenyls (PCBs). Only the compounds that are chlorinated at the 2,3,7, and 8 positions have characteristic dioxin toxicity. PCDDs, PCDFs and PCBs accumulate in the food chain due to their high lipophilicity, high stability, and low vapor pressure. They are not metabolized easily; however their hydroxylated metabolites are detected in feces. They cause a wide range of endocrine disrupting effects in experimental animals, wildlife, and humans. Endocrine related effects of PCDDs, PCDFs and PCBs on thyroid hormones, neurodevelopment and reproductive development were referenced. In addition, some studies of contamination of foods, bioaccumulation, dietary exposure assessment, as well as challenges of scientific research in these compounds were reviewed.

Comparative performance of extraction strategies for polycyclic aromatic hydrocarbons in peats.

The assessment of historical trends in atmospheric deposition of organic contaminants by using peat samples has been reported on several occasions because these samples represent an almost ideal medium for recording temporal changes in organic contaminant deposition rates. The determination of polycyclic aromatic hydrocarbons (PAHs) in peat samples is complicated due to the high content of organic matter in peat, which affects both extraction efficiency and analytical quality. A rapid and simple method is proposed for the determination of 10 US Environmental Protection Agency indicator PAHs in complex matrices such as peat. This article reviews and addresses the most relevant analytical methods for determining PAHs in peat. We discuss and critically evaluate three different extraction procedures, such as ultrasound-assisted solvent extraction (UASE), shaking and pressurized liquid extraction (PLE). Clean-up of extracts was performed by solid-phase extraction using silica cartridges. Detection of the selected PAHs was carried out by high-performance liquid chromatography coupled with fluorescence detection for determination. Optimization of the variables affecting extraction by the selected extraction techniques was conducted, concluding that the UASE extraction method using hexane:dichloromethane (80:20) as extractant was robust enough to determine the selected PAHs in peat samples with estimated quantification limits between 0.050 and 3.5 microg/kg depending on the PAH. UASE did not demand sophisticated equipment and long extraction times. PLE involved sophisticated equipment and showed important variations in the results. The method proposed was applied to the determination of PAHs in peat samples from Xistral Mountains (Galicia, Spain).

Quaternary herbicides retention by the amendment of acid soils with a bentonite-based waste from wineries

The agronomic utility of a solid waste, waste bentonite (WB), from wine companies was assessed. In this sense, the natural characteristics of the waste were measured, followed by the monitoring of its effects on the adsorption/desorption behaviour of three quaternary herbicides in acid soils after the addition of increasing levels of waste. This was done with the intention of studying the effect of the added organic matter on their adsorption. The high content in C (294 g kg(-1)), N (28 g kg(-1)), P (584 mg kg(-1)) and K (108 g kg(-1)) of WB turned it into an appropriate amendment to increase soil fertility, solving at the same time its disposal. WB also reduced the potential Cu phytotoxicity due to a change in Cu distribution towards less soluble fractions. The adsorption of the herbicides paraquat, diquat and difenzoquat by acid soils amended with different ratios of WB was measured. In all cases, Langmuir equation was fitted to the data. Paraquat (PQ) and diquat (DQ) were adsorbed and retained more strongly than difenzoquat (DFQ) in the acid soil studied. However, the lowest retention of DFQ in an acid soil can be increased by amendment with organic matter through a solid waste from wineries, and it is enough for duplicate retention a dosage rate of 10t/ha. Anyway, detritivores ecology can still be affected. Detritivores are the organisms that consume organic material, and in doing so contribute to decomposition and the recycling of nutrients. The term can also be applied to certain bottom-feeders in wet environments, which play a crucial role in benthic ecosystems, forming essential food chains and participating in the nitrogen cycle.

A Critical Review about the Health Risk Assessment of PAHs and Their Metabolites in Foods

Polycyclic aromatic hydrocarbons (PAHs) are a family of toxicants that are ubiquitous in the environment. These contaminants generate considerable interest, because some of them are highly carcinogenic in laboratory animals and have been implicated in breast, lung, and colon cancers in humans. Dietary intake of PAHs constitutes a major source of exposure in humans. Factors affecting the accumulation of PAHs in the diet, their absorption following ingestion, and strategies to assess risk from exposure to these hydrocarbons following ingestion have received very little attention. This review, therefore, focuses on concentrations of PAHs in widely consumed dietary ingredients along with gastrointestinal absorption rates in humans. Metabolism and bioavailability of PAHs in animal models and the processes, which influence the disposition of these chemicals, are discussed. Finally, based on intake, disposition, and tumorigenesis data, the exposure risk to PAHs from diet is presented. This information is expected to provide a framework for refinements in risk assessment of PAHs.

The potential of solvent-minimized extraction methods in the determination of polycyclic aromatic hydrocarbons in fish oils

Fish oil has been identified as one of the most important contributors to the level of Persistent Organic Pollutants (POPs) in feed products. The determination of polycyclic aromatic hydrocarbons (PAHs) in fish oils is complicated due to the fat matrix, which affects both extraction efficiency and analytical quality. This article reviews and addresses two of the most relevant analytical methods for determining 11 mutagenic and carcinogenic PAHs, as well as two EPA indicator PAHs in fish oils. We discuss and critically evaluate two different extraction procedures, such as ultrasound-assisted solvent extraction (USAE) and ultrasound-assisted emulsification-microextraction (USAEME). Clean-up of extracts was performed by solid-phase extraction using C18 and glass columns containing silica gel and florisil for USAE or only C18 for USAEME. Detection of the selected PAHs was carried out by high-performance liquid chromatography coupled with fluorescence detection for determination. Optimization of the variables affecting extraction by the selected extraction techniques was conducted and recoveries ranged from 70% to 100% by USAE and from 70% to 108% by USAEME with estimated quantification limits between 0.020 and 2.6 μg/kg were achieved. Moreover, the applicability of the selected methods was evaluated by the analysis of real samples. To our knowledge, this is the first time that USAEME has been applied to the determination of PAHs in food matrices, such as oil fish samples. The methods proposed were applied to the determination of the target PAHs in fish samples from different countries, and it was found that the low PAH contamination of the selected fish oils could mainly occur by atmospheric sources.

Effect of Beer Marinades on Formation of Polycyclic Aromatic Hydrocarbons in Charcoal-Grilled Pork

The effect of marinating meat with Pilsner beer, nonalcoholic Pilsner beer, and Black beer (coded respectively PB, P0B, and BB) on the formation of polycyclic aromatic hydrocarbons (PAHs) in charcoal-grilled pork was evaluated and compared with the formation of these compounds in unmarinated meat. Antiradical activity of marinades (DPPH assay) was assayed. BB exhibited the strongest scavenging activity (68.0%), followed by P0B (36.5%) and PB (29.5%). Control and marinated meat samples contained the eight PAHs named PAH8 by the EFSA and classified as suitable indicators for carcinogenic potency of PAHs in food. BB showed the highest inhibitory effect in the formation of PAH8 (53%), followed by P0B (25%) and PB (13%). The inhibitory effect of beer marinades on PAH8 increased with the increase of their radical-scavenging activity. BB marinade was the most efficient on reduction of PAH formation, providing a proper mitigation strategy.