Monitoring the impact of sulphur with the Austrian Bioindicator Grid

In Austria, the impact of sulphur has been assessed since 1985 with the help of the Austrian Bioindicator Grid on 760 sample plots with Picea abies as the main tree species (90%). The annual sampling allows a precise evaluation of the temporal and regional development of the impact of sulphur on the basis of legal standards. Despite the reduction of SO2 emissions in Austria, the legal standard is still exceeded on 8% of the plots. These plots are mainly located near large Austrian emittors, but also in areas affected by transboundary sulphur emissions from neighbouring countries. The present paper describes how the Bioindicator Grid can be applied for the control of legal requirements to enact effective clean air measures in Austria and take supportive measures that reduce the impact of sulphur from emittors in neighbouring countries.     

Trace elements and microbiological parameters in farmed Nile tilapia with emphasis on muscle,water, sediment and feed

Fish may bioaccumulate contaminants from the aquatic environment and extend them to the food chain provoking risks to human health. This study evaluated the microbiological parameters of the pond´s water and trace elements concentrations in samples of water, sediment, feed and muscle of farmed Nile tilapia used for human consumption in southern Brazil. A total of 240 fish were collected from 12 tilapia farms. Sediment, tank water and dry ration used in the animals' diet were collected for analysis. Analysis were performed by Energy Dispersion X-ray Fluorescence (EDXRF), Inductively Coupled Plasma Mass Spectrometer (ICP-MS), Induced Coupled Plasma Optical Emission Spectrometer (ICP-OES), and Atomic Absorption Spectrometer (AAS-VGA). In addition, the microbiological analysis of the water was carried out. The concentrations of Se, I, Fe, Cu and Zn in fish muscle were higher than the recommended by the Brazilian legislation, considering the advised daily intake for adults. The arsenic element had concentrations above the limit stipulated by the present Brazilian legislation, observed in all samples of muscle, sediment and tank water highlighting a possible environmental and fish contamination by the toxic element. Moreover, the arsenic concentration in the water presented a positive correlation (ρ?=?0.33) with arsenic in the muscle, suggesting that tilapia is a good environmental bioindicator, once they properly reflect the levels of arsenic in the water. It is suggested to perform an arsenic speciation for quantification of the inorganic form and accurate assessment of the degree of toxicity in the muscle samples and risks it can bring to human health. Regarding the other potentially toxic elements (Hg, Pb and Cd), and microbiological analysis of water it was verified that the consumption of the fish in question does not raise risks, since the values are within a quality benchmark established by law. The concentration of total and fecal coliforms in pond´s water in the facilities was in agreement with the microbiological indexes required by the legislation of CONAMA class II. Western region presented the lowest concentrations of fecal coliforms when compared to the other regions. There was no significant difference in the microbiological counts of total heterotrophic bacteria, Vibrio spp. and Pseudomonas spp. among the regions.     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.     

Determination of microbiological contamination,antibacterial and antioxidant activities of natural plant hazelnut (Corylus avellana L.) pollen

The aim of our study is to determine microbial contamination, antibacterial and antioxidant activities of 14 pollen samples of Corylus avellana collected from different locations in Slovakia. Microbiological analysis was carried out in two steps: microbiological assays and studies of antibacterial activity of pollen extracts. The antimicrobial properties of pollen extracts were carried out with the disc-diffusion method. Methanol (70%), ethanol (70%) and distilled water were used for pollen extracts. Five strains of bacteria such as gram-negative (Salmonella enterica subsp. enterica CCM 3807, Escherichia coli CCM 2024, and Yersinia enterocolitica CCM 5671) and gram-positive (Staphylococcus aureus CCM 2461 and Bacillus thuringiensis CCM 19T) were tested. Antioxidant activity of pollen extracts was determined by the DPPH method. Bacterial analysis includes the determination of the total bacterial count ranged from 4.08 to 4.61 log CFU g^?1, mesophilic aerobic bacteria ranged from 3.40 to 4.89 log CFU g^?1, mesophilic anaerobic bacteria ranged from 3.20 to 4.52 log CFU g^?1, coliform bacteria ranged from 3.30 to 4.55 log CFU g^?1, yeasts and filamentous fungi ranged from 3.00 to 3.56 log CFU g^?1. Microscopic filamentous fungi Aspergillus spp., Alternaria spp., Penicillium spp., Cladosporium spp., Rhizopus spp., and Paecylomyces spp. were isolated from hazelnut pollen. Yersinia enterocolitica was the most sensitive strain among ethanolic and methanolic pollen hazelnut extracts. Staphylococcus aureus was the most sensitive strain against aqueous hazelnut pollen extracts. We determined the following sensitivity against ethanol pollen extracts respectively: Yersinia enterocolitica?>?Salmonella enterica?>?Staphylococcus aureus?>?Bacillus thuringiensis?>?Escherichia coli. Methanol pollen extracts had shown following sensitivity: Yersinia enterocolitica?>?Salmonella enterica?>?Escherichia coli?>?Staphylococcus aureus?>?Bacillus thuringiensis. Aqueous extracts had shown the following sensitivity: Staphylococcus aureus?>?Salmonella enterica?>?Escherichia coli?>?Bacillus thuringiensis?>?Yersinia enterocolitica. Hazelnut pollen extracts have over 82% antioxidant capacity in samples from non-urban zones. An elevated level of antioxidant potential in the pollen is determined by its biological properties conditioned by biologically active substances. DPPH method allowed characterizing pollen as a source of antioxidants.     

Carbon monoxide emission rates from roasted whole bean and ground coffee

Carbon monoxide (CO) emitted from roasted coffee is a potential occupational respiratory exposure hazard to workers within the coffee industry. The current study objective was to estimate CO emission factors from commercially available roasted whole bean and ground coffee measured in loose form, not packaged, and to assess the utility of CO monitoring in nonventilated storage spaces such as within coffee roasting and packaging facilities, transport vessels, and cafés. Determinants affecting CO emissions from coffee were investigated, including form (whole bean vs. ground), roast level (light, medium, medium-dark, dark), and age (time since the package was opened). CO emission factors were estimated for roasted coffee samples from a variety of manufacturers purchased from local grocery stores and online. Emission tests were performed on 36 brands of coffee, some with more than one sample per brand and with various roast levels. Decaying source equations or smoothing functions were fitted to the CO concentration measurements. Maximum observed emission factors at the peak of the predicted concentration curve were adjusted by the time required to reach the maximum CO concentration and reported as emission factors (EF_buildup). Ground coffee had a significantly increased EF_buildup (P < 0.0001) compared with whole bean. Roast level did not significantly affect emissions for whole bean (P = 0.72) but did for ground (P < 0.001) coffee. For ground coffee, medium-dark and dark roasts had significantly higher emissions than medium and light roasts. Worst-case emission factors from commercially available whole bean and ground coffee measured in loose form, not packaged, showed that roasted coffee can rapidly emit CO. CO concentrations should be monitored in storage spaces in service and manufacturing facilities as well as transport vessels to ensure exposures do not exceed occupational exposure limits. Storage spaces may need to be ventilated to control CO concentrations to safe levels.

Implications: Emission rates of carbon monoxide (CO) from roasted coffee showed that unventilated or underventilated storage spaces should be monitored and ventilated, if necessary, to control CO concentrations to safe levels.     

Predicting logP of pesticides using different software

We compared experimental and calculated logP values using a data set of 235 pesticides and experimental values from four different sources: The Pesticide Manual, Hansch Manual, ANPA and KowWin databases. LogP were calculated with four softwares: HyperChem, Pallas, KowWin and TOPKAT. Crossed comparison of the experimental and calculated values proved useful, especially for pesticides. These are harder to study than simpler organic compounds. Structurally they are complex, heterogeneous and similar to drugs from a chemical point of view. They offer an interesting way to verify the goodness of the different methods. Other studies compared several logP predictors using a single set of experimental values taken as a reference. Here we discuss the utility of the different logP predictors, with reference to experimental data found in different databases. This offers three advantages: (1) it avoids bias due to the assumption that one single data set is correct; (2) a given predictor can be developed on the same data set used for evaluation; (3) it takes account of experimental variability and can compare it with the predictor's variability. In our study Pallas and KowWin gave the best results for prediction, followed by TOPKAT.     

Development of a microscale emission factor model for particulate matter for predicting real-time motor vehicle emissions

The U.S. Environmental Protection Agency's National Exposure Research Laboratory is pursuing a project to improve the methodology for modeling human exposure to motor vehicle emissions. The overall project goal is to develop improved methods for modeling the source through the air pathway to human exposure in significant exposure microenvironments. Current particulate matter (PM) emission models, particle emission factor model (used in the United States, except California) and motor vehicle emission factor model (used in California only), are suitable only for county-scale modeling and emission inventories. There is a need to develop a site-specific real-time emission factor model for PM emissions to support human exposure studies near roadways. A microscale emission factor model for predicting site-specific real-time motor vehicle PM (MicroFacPM) emissions for total suspended PM, PM less than 10 microm aerodynamic diameter, and PM less than 2.5 microm aerodynamic diameter has been developed. The algorithm used to calculate emission factors in MicroFacPM is disaggregated, and emission factors are calculated from a real-time fleet, rather than from a fleet-wide average estimated by a vehicle-miles-traveled weighting of the emission factors for different vehicle classes. MicroFacPM requires input information necessary to characterize the site-specific real-time fleet being modeled. Other variables required include average vehicle speed, time and day of the year, ambient temperature, and relative humidity.     

A study on emission of phthalate esters from plastic materials using a passive flux sampler

Phthalate esters are used as plasticizer in many plastics, and several studies have shown their toxicity. Phthalate esters are gradually emitted over time, and so it is conceivable that they pose a significant health risk. This study aims to investigate the temperature dependence of the emissions of various phthalate esters and to estimate the health risks of these emissions at various temperatures. A passive-type sampler was developed to measure the flux of phthalate esters from the surface of plastic materials. With this sampler, we examined three widely used plastic materials: synthetic leather, wallpaper and vinyl flooring. The observed maximum emissions of diethyl phthalate, dibutyl phthalate, and diethylhexyl phthalate (DEHP) from these materials at 20°C were 0.89, 0.77, and 14 μg m⁻² h⁻¹, respectively. Emissions at 80°C were 2.8, 4.5×10², and 1.5×10³ μg m⁻² h⁻¹, respectively. The results showed this temperature dependence is determined primarily by the type of phthalate ester and less so by the type of material. The estimation from the results of temperature dependence indicated the concentration of DEHP in a vehicle left out in the sunshine during the day can exceed the recommended levels of Japan Ministry of Health, Labour and Welfare.     

Regional differences in the occurrence of understorey species reflect nitrogen deposition in Swedish forests

Possible links between the occurrence of Vaccinium myrtillus, V. vitis-idaea and Deschampsia flexuosa and rates of nitrogen deposition were investigated in 557 coniferous forest stands. In areas with high N-deposition, V. myrtillus was less frequent, less abundant and more susceptible to the leaf pathogen Valdensia heterodoxa than in areas with lower levels of N-deposition. The occurrence of V. vitis-idaea was also strongly negatively correlated with increasing N-deposition, but no such trend was found for D. flexuosa. In regions with high N-deposition, V. myrtillus was more common in stands dominated by Scots pine than in stands dominated by Norway spruce. This was not the case in regions with lower levels of N-deposition. The patterns observed accord with results from N-addition experiments that demonstrate significant effects on vegetation, caused by N-deposition. The data suggest that even low rates of N-deposition may decrease the abundance of the most dominant species in coniferous forest ground flora.