Microwave/SPME method to quantify pesticide residues in tomato fruits

A new analytical method using focused microwave-assisted extraction (FMAE), coupled with solid phase micro-extraction (SPME), has been elaborated to determine 25 pesticides used in tomato cultivation. Microwave energy was used for a fast and controlled heating of solvent to selectively extract compounds. Calibration curves were plotted from blank tomato samples spiked at different concentrations with standards. A linear response was obtained between 10 and 1000 μ g/Kg for pyrethroids and between 0.1 and 5000 μ g/Kg for other compounds. For all studied substances, the resulting correlation coefficient (r²) was greater than 0.99. Limits of detection (LOD) and quantification (LOQ) were measured lower than 8 and 25 μ g/Kg, respectively. The relative standard deviation (RSD) was determined below 15% for all pesticides. Field incurred tomato samples were used to validate the new FMAE/SPME method. Observed analysis results by using this technique were in good agreement compared to those obtained by two accredited trading laboratories using traditional methods. Four tomato samples, bought in a local market, were also tested with the FMAE/SPME method.     

Cytochrome c adducts with PCB quinoid metabolites

Polychlorinated biphenyls (PCBs) are a group of 209 individual congeners widely used as industrial chemicals. PCBs are found as by-products in dye and paint manufacture and are legacy, ubiquitous, and persistent as human and environmental contaminants. PCBs with fewer chlorine atoms may be metabolized to hydroxy- and dihydroxy-metabolites and further oxidized to quinoid metabolites both in vitro and in vivo. Specifically, quinoid metabolites may form adducts on nucleophilic sites within cells. We hypothesized that the PCB-quinones covalently bind to cytochrome c and, thereby, cause defects in the function of cytochrome c. In this study, synthetic PCB quinones, 2-(4′-chlorophenyl)-1,4-benzoquinone (PCB3-pQ), 4-4'-chlorophenyl)-1,2-benzoquinone (PCB3-oQ), 2-(3′, 5′-dichlorophenyl)-1,4-benzoquinone, 2-(3′,4′, 5′-trichlorophenyl)-1,4-benzoquinone, and 2-(4′-chlorophenyl)-3,6-dichloro-1,4-benzoquinone, were incubated with cytochrome c, and adducts were detected by liquid chromatography-mass spectrometry (LC-MS) and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI TOF). Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was employed to separate the adducted proteins, while trypsin digestion and liquid chromatography-tandem mass spectrometry (LC-MS/MS) were applied to identify the amino acid binding sites on cytochrome c. Conformation change of cytochrome c after binding with PCB3-pQ was investigated by SYBYL-X simulation and cytochrome c function was examined. We found that more than one molecule of PCB-quinone may bind to one molecule of cytochrome c. Lysine and glutamic acid were identified as the predominant binding sites. Software simulation showed conformation changes of adducted cytochrome c. Additionally, cross-linking of cytochrome c was observed on the SDS-PAGE gel. Cytochrome c was found to lose its function as electron acceptor after incubation with PCB quinones. These data provide evidence that the covalent binding of PCB quinone metabolites to cytochrome c may be included among the toxic effects of PCBs.     

The effects of 3,3′,4,4′-tetrabromobiphenyl on rats fed diets containing a constant level of copper and varying levels of molybdenum

Copper (Cu) metabolism is altered in rats fed diets high in molybdenum (Mo) and low in Cu. This 10-week study was carried out to examine the effects of supplemental Mo (7.5–240 μg/g diet) on male Sprague–Dawley rats fed diets adequate in Cu (5 μg/g diet) and to determine the susceptibility of Mo-treated animals to the environmental pollutant 3,3′,4,4′-tetrabromobiphenyl (TBB). After 7 weeks of dietary treatment, half of the rats in each group received a single IP injection of TBB (150 μM/kg bw), while the other half received the corn oil vehicle. Rats sacrificed at 10 weeks showed no effects of Mo on growth, feed efficiency, or selected organ or tissue weights. Dose-dependent effects on plasma Mo (0–5.1 μg/mL), plasma Cu (0.95–0.20 μg/mL), and bone Cu (3.4–10 μg/g) in control through the high dose were found. Cu sequestration in the bone of Mo-treated rats is a new finding. TBB treatment resulted in dramatic weight loss and loss of absolute organ mass. Relative organ weights were increased, except for the thymus. TBB altered the concentrations of certain amino acids. Compared to control rats, this polybrominated biphenyl congener significantly decreased plasma Cu and ceruloplasmin at higher concentrations of dietary Mo and promoted the process of plasma Cu decrease by Mo, suggesting a combined effect.     

Dietary antioxidants (selenium and N-acetylcysteine) modulate paraoxonase 1 (PON1) in PCB 126-exposed rats

Environmental pollutants polychlorinated biphenyls (PCBs), especially dioxin-like PCBs, cause oxidative stress and associated toxic effects, including cancer and possibly atherosclerosis. We previously reported that PCB 126, the most potent dioxin-like PCB congener, not only decreases antioxidants such as hepatic selenium (Se), Se-dependent glutathione peroxidase, and glutathione (GSH) but also increases levels of the antiatherosclerosis enzyme paraoxonase 1 (PON1) in liver and serum. To probe the interconnection of these three antioxidant systems, Se, GSH, and PON1, we examined the influence of varying levels of dietary Se and N-acetylcysteine (NAC), a scavenger of reactive oxygen species (ROS) and precursor for GSH synthesis, on PON1 in the absence and presence of PCB 126 exposure. Male Sprague–Dawley rats, fed diets with differing Se levels (0.02, 0.2, or 2 ppm) or NAC (1 %), were treated with a single intraperitoneal injection of corn oil or various doses of PCB 126 and euthanized 2 weeks later. PCB 126 significantly increased liver PON1 mRNA, protein level and activity, and serum PON1 activity in all dietary groups but did not consistently increase thiobarbituric acid levels (thiobarbituric acid reactive substances, TBARS), an indicator of lipid oxidation and oxidative stress, in liver or serum. Inadequate (high or low) dietary Se decreased baseline and PCB 126-induced aryl hydrocarbon receptor (AhR) expression but further increased PCB 126-induced cytochrome P450 1A1 (CYP1A1) expression, the enzyme believed to be the cause for PCB 126-induced oxidative stress. In addition, a significant inverse relationship was observed not only between dietary Se levels and PON1 mRNA and PON1 activity but also with TBARS levels in the liver, suggesting significant antioxidant protection from dietary Se. NAC lowered serum baseline TBARS levels in controls and increased serum PON1 activity but lowered liver PON1 activities in animals treated with 1 μmol/kg PCB 126, suggesting antioxidant activity by NAC primarily in serum. These results also show an unexpected predominantly inverse relationship between Se or NAC and PON1 during control and PCB 126 exposure conditions. These interactions should be further explored in the development of dietary protection regimens.     

Thymol as an alternative to pesticides: persistence and effects of Apilife Var on the phototactic behavior of the honeybee Apis mellifera

Thymol is a natural substance increasingly used as an alternative to pesticides in the fight against the Varroa destructor mite. Despite the effectiveness of this phenolic monoterpene against Varroa, few articles have covered the negative or side effects of thymol on bees. In a previous study, we have found an impairment of phototaxis in honeybees following application of sublethal doses of thymol—lower or equal to 100 ng/bee—under laboratory conditions. The present work shows the same behavioral effects on bees from hives treated with Apilife Var®, a veterinary drug containing 74 % thymol, with a decrease in phototactic behavior observed 1 day after treatment. Thus, thymol causes disruption of bee phototactic behavior both under laboratory conditions as well as in beehives. The bee exposure dose in treated hives was quantified using gas chromatography coupled to mass spectrometry (GC–MS), giving a median value of 4.3 μg per body 24 h after treatment, with 11 ng in the brain. The thymol level in 20 organic waxes from hives treated with Apilife Var® was also measured and showed that it persists in waxes (around 10 mg/kg) 1 year after treatment. Thus, in the light of (1) behavioral data obtained under laboratory conditions and in beehives, (2) the persistence of thymol in waxes, and (3) the high load on bees, it would appear important to study the long-term effects of thymol in beehives.     

Resilience and Challenges of Marine Social–Ecological Systems Under Complex and Interconnected Drivers

In this paper, we summarize the contributions made by an interdisciplinary group of researchers from different disciplines (biology, ecology, economics, and law) that deal with key dimensions of marine social–ecological systems. Particularly, the local and global seafood provision; the feasibility and management of marine protected areas; the use of marine ecosystem services; the institutional dimension in European fisheries, and the affordable models for providing scientific advice to small-scale fisheries. This Special Issue presents key findings from selected case studies around the world available to educators, policy makers, and the technical community. Together, these papers show that a range of diverse ecological, economic, social, and institutional components often mutually interact at spatial and temporal scales, which evidence that managing marine social–ecological systems needs a continuous adaptability to navigate into new governance systems.     

Spatial trends of organochlorinated pesticides,polychlorinated biphenyls,and polybrominated diphenyl ethers in Atlantic Anguillid eels

The bioaccumulation of lipophilic contaminants such as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) can result in a reduction in fitness and spawner quality in eels and may be a factor in Anguillid sp. population declines. Contaminant concentrations in eels have been studied extensively in Europe, but data for American eels are severely lacking. Concentrations of PCBs, OCPs, and PBDEs were determined in American eel from eastern Canada and New York, USA, along with European eel from Belgium. Principal component analysis revealed that eels captured in the St. Lawrence estuary were a mixture of upstream migrants from the St. Lawrence River watershed, and fish captured in local tributaries. Contaminant concentrations were dependent on origin, related to the local environment, and were lower than historic values. In Canada, concentrations of OCPs and PCBs in eel tissues were below the Canadian human consumption guidelines for contaminants in fish, indicating that the current risk to consumers is low. However, concentrations of PCBs, total DDT, and mirex in eels from L. Ontario and the upper St. Lawrence R. were above Great Lakes guidelines for the protection of piscivorous predators. Concentrations of penta-BDE homologs exceeded the Canadian guideline for environmental quality in over half of the eels in this study, but concentrations of the other homolog groups were below the guideline.     

Evaluation of a portable nephelometer against the Tapered Element Oscillating Microbalance method for monitoring PM(2.5)

Monitoring personal exposure to particle matter (PM(2.5)) in ambient air requires performing measurements using portable monitors. In this work, the portable nephelometer SidePak? AM510 Personal Aerosol Monitor manufactured by TSI Inc. was evaluated against a Tapered Element Oscillating Microbalance (TEOM) equipped with a Filter Dynamics Measurements System (FDMS). Conventionally, the SidePak is calibrated with respect to the Arizona Road Test Dust and then multiplied by an environmental calibration factor to yield mass concentration. To adapt this calibration to specific field conditions, we present an implementation of this calibration by introducing a growing factor correction which takes into account relative humidity and the dry and wet portions of the refractive index estimated from TEOM-FDMS measurements. PM(2.5) sampling with several SidePaks AM510 was carried out in background and rural sites in the Po Valley (Italy). Modeled SidePak data were plotted vs. reference TEOM-FDMS data which show a good agreement.