LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

Methods for synthesis of nonabromodiphenyl ethers and a chloro-nonabromodiphenyl ether

Polybrominated diphenyl ethers (PBDEs) have been used extensively as brominated flame retardants (BFRs) in textiles, upholstery and electronics. They are ubiquitous contaminants in wildlife and humans. A low concentration of nonabrominated diphenyl ethers (nonaBDEs) is present in commercial DecaBDE and they are also abiotic and biotic debromination products of decabromodiphenyl ether (BDE-209). The objective of the present work was to develop methods for synthesis of the three nonaBDEs, 2,2',3,3',4,4',5,5',6-nonabromodiphenyl ether (BDE-206), 2,2',3,3',4,4',5,6,6'-nonabromodiphenyl ether (BDE-207) and 2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (BDE-208), with the intention of making them available as authentic standards for analytical, toxicological and stability studies, as well as studies regarding physical-chemical properties. Two methods were developed, one based on perbromination of phenoxyanilines and the other via reductive debromination of BDE-209 by sodium borohydride followed by chromatographic separation of the three nonaBDE isomers formed. An additional nonabrominated compound, 4'-chloro-2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (Cl-BDE-208), was also synthesized in the present work. Cl-BDE-208, prepared by the perbromination of 4-chlorodiphenyl ether, may be used as an internal standard in analysis of highly brominated diphenyl ethers. BDE-206, BDE-207, BDE-208 and Cl-BDE-208 were characterized by 1H NMR, 13C NMR, electron ionization mass spectra and by their melting points. The structures of all three nonaBDEs have been characterized previously by X-ray crystallography.     

Approximation and spatial regionalization of rainfall erosivity based on sparse data in a mountainous catchment of the Yangtze River in Central China

In densely populated countries like China, clean water is one of the most challenging issues of prospective politics and environmental planning. Water pollution and eutrophication by excessive input of nitrogen and phosphorous from nonpoint sources is mostly linked to soil erosion from agricultural land. In order to prevent such water pollution by diffuse matter fluxes, knowledge about the extent of soil loss and the spatial distribution of hot spots of soil erosion is essential. In remote areas such as the mountainous regions of the upper and middle reaches of the Yangtze River, rainfall data are scarce. Since rainfall erosivity is one of the key factors in soil erosion modeling, e.g., expressed as R factor in the Revised Universal Soil Loss Equation model, a methodology is needed to spatially determine rainfall erosivity. Our study aims at the approximation and spatial regionalization of rainfall erosivity from sparse data in the large (3,200 km²) and strongly mountainous catchment of the Xiangxi River, a first order tributary to the Yangtze River close to the Three Gorges Dam. As data on rainfall were only obtainable in daily records for one climate station in the central part of the catchment and five stations in its surrounding area, we approximated rainfall erosivity as R factors using regression analysis combined with elevation bands derived from a digital elevation model. The mean annual R factor (R _a) amounts for approximately 5,222 MJ?mm?ha^?1?h^?1?a^?1. With increasing altitudes, R _a rises up to maximum 7,547 MJ?mm ha^?1?h^?1 a^?1 at an altitude of 3,078 m a.s.l. At the outlet of the Xiangxi catchment erosivity is at minimum with approximate R _a?=?1,986 MJ?mm?ha^?1?h^?1?a^?1. The comparison of our results with R factors from high-resolution measurements at comparable study sites close to the Xiangxi catchment shows good consistance and allows us to calculate grid-based R _a as input for a spatially high-resolution and area-specific assessment of soil erosion risk.     

Life cycle modelling of fossil fuel power generation with post-combustion CO2 capture

Due to its compatibility with the current energy infrastructures and the potential to reduce CO₂ emissions significantly, CO₂ capture and geological storage is recognised as one of the main options in the portfolio of greenhouse gas mitigation technologies being developed worldwide. The CO₂ capture technologies offer a number of alternatives, which involve different energy consumption rates and subsequent environmental impacts. While the main objective of this technology is to minimise the atmospheric greenhouse gas emissions, it is also important to ensure that CO₂ capture and storage does not aggravate other environmental concerns. This requires a holistic and system-wide environmental assessment rather than focusing on the greenhouse gases only. Life Cycle Assessment meets this criteria as it not only tracks energy and non-energy-related greenhouse gas releases but also tracks various other environmental releases, such as solid wastes, toxic substances and common air pollutants, as well as the consumption of other resources, such as water, minerals and land use. This paper presents the principles of the CO₂ capture and storage LCA model developed at Imperial College and uses the pulverised coal post-combustion capture example to demonstrate the methodology in detail. At first, the LCA models developed for the coal combustion system and the chemical absorption CO₂ capture system are presented together with examples of relevant model applications. Next, the two models are applied to a plant with post-combustion CO₂ capture, in order to compare the life cycle environmental performance of systems with and without CO₂ capture. The LCA results for the alternative post-combustion CO₂ capture methods (including MEA, K⁺/PZ, and KS-1) have shown that, compared to plants without capture, the alternative CO₂ capture methods can achieve approximately 80% reduction in global warming potential without a significant increase in other life cycle impact categories. The results have also shown that, of all the solvent options modelled, KS-1 performed the best in most impact categories.     

Age dependency of high-affinity ouabain receptors and their magnetosensitivity

Age dependency of [³H]-ouabain binding, ⁴⁵Ca²⁺ eflux and its magnetosensitivity in rats’ brain cortex and heart muscle tissues were studied. Curves of dose-dependent [³H]-ouabain binding consisted of three components with different affinities (10⁻⁷–10⁻⁴ M (α₁); 10⁻⁹–10⁻⁷ M (α₂); and 10⁻¹¹–10⁻⁹ M (α₃)). These curves were also characterized by different dose-dependent kinetics. [³H]-ouabain binding with α₃ receptors in brain cortex and heart muscle tissues of young and adult animals had a dose-dependent character, while that in old ones had a dose-independent character. A 0.2 T static magnetic field (SMF) exposure had modulation effect on ouabain binding with α₁, α₂ and α₃ receptors in young rats, while in adult ones, only α₃ receptors were magnetosensitive. In old animals, SMF exposure had no significant effect on ouabain binding with α₃ receptors in brain cortex, while in heart muscle, it had inhibitory effect on it. Age-dependent effect of ouabain impact on ⁴⁵Ca²⁺ efflux showed that all concentrations of ouabain lead to inhibitory effect in young animals’ brain cortex and heart muscle (with the exception of 10⁻¹⁰ and 10⁻⁶ M), while in old ones, it had activation effect as compared with data received without ouabain. SMF exposure in young animals had activation effect on ⁴⁵Ca²⁺ efflux from brain cortex and heart muscle in data without ouabain, and in old rats, ⁴⁵Ca²⁺ efflux from brain cortex was magnetic insensitive. In old animals, SMF increased ⁴⁵Ca²⁺ efflux even after extra low concentration of ouabain. It is suggested that α₃ receptors having a crucial role in the regulation of Na⁺/Ca²⁺ exchange serve as age-dependent magnetosensors of excitable cells.     

Flicker Test as a Load Measurement During the Combined Effect of Heat and Noise

This study was a joint physiological and psychological experiment undertaken to determine changes in physiological and psychological human functions under the combined influence of heat, noise, and physical activity. Seven experimental situations were simulated in a climatic chamber with different configurations of three independent variables: heat (40 °C), noise (98 dB), and physical effort (30% of maximum volume of oxygen uptake—V0₂ max). Five psychological variables (critical flicker fusion—CFF, hand tremor, reaction time, subjective climate evaluation, and subjective evaluation of the given condition load) and two physiological variables (heart rate and rectal temperature) were monitored. Results indicate that CFF changed (increased) significantly when more than one experimental variable was applied. These changes coincided with significant changes in both subjective climate evaluation and subjective evaluation of a given condition load. There were no significant changes in psychomotor functions (hand tremor and reaction time). None of the observed physiological parameters were above the critical value. The results suggest that CFF can be treated as a psychophysical load indicator.     

Organochlorine pollutants in Scots pine needles--biological and site related variation within a forest stand

To study the biological variation in the content of some persistent organic pollutants, viz hexachlorobenzene (HCB), alpha- and gamma-hexachlorocyclohexane (alpha- and gamma-HCH), and 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane (DDT) were analysed in needles from Scots pine trees growing at an isolated peninsula south of Stockholm, Sweden. The concentration variations of each compound was evaluated by a nested analysis of variance (ANOVA) with sampling site specific compass direction, individual tree, and sampling height as factors. Two pair-wise post hoc tests were used to test significant results from the ANOVA. The hexachlorocyclohexanes showed no significant differences between sampling site, trees or sampling height. DDT concentration was significantly lower at the sampling site with the densest vegetation compared to at least three of the other sampling sites. HCB was significantly lower at the lowest sampling height (0.5 m).     

An experimental and numerical investigation into the impact of dissolution/precipitation mechanisms on CO2 injectivity in the wellbore and far field regions

Carbon dioxide capture and storage (CCS) technology is gaining credibility as the best short to medium term solution for significantly reducing net carbon emissions into the atmosphere. From a capacity point of view, deep saline aquifers offer the greatest potential for CO₂ storage. In this respect, well injectivity is considered a key technical and economical issue. Rock/fluid interactions – dissolution/precipitation of minerals, in particular carbonates – are currently considered as one of the principal reasons for wellbore injectivity changes in aquifers.This research investigated the mechanisms involved in injectivity losses through experimental and theoretical methods. The impact on injectivity of permeability changes occurring at various distances from the wellbore was studied using an idealised CO₂ injection well flow model. A new experimental set-up was used to investigate the effect on dissolution/precipitation mechanisms of the pressure and temperature changes that the fluid is subjected to as it advances from the wellbore.Numerical modelling of the injection wellbore has shown that changes in the petrophysical properties of the reservoir several metres away from the wellbore can still have a significant impact on injectivity. As indicated by the experimental research carried out, pressure and temperature gradients that exist inside the reservoirs may lead to re-precipitation in the far field, however no significant permeability and porosity changes were detected to suggest major losses of injectivity due to these effects.