LC-MS/MS method validation for determination of selected neonicotinoids in groundwater for the purpose of a column experiment

The work was carried out to develop and validate a method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous detection and quantification of five neonicotinoid insecticides: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam in groundwater samples for the purpose of a further column experiment. This experiment will be used to analyze breakthrough curves of neonicotinoids under a saturated water flow to set transport parameters, where the reliability of the results of chemical analysis plays an important role. The validation was performed in a concentration range from 0.09?µg L^?1 to 100?µg L^?1 using an Infinity 1290 (Agilent, USA) chromatograph coupled with a QTrap 5500 mass spectrometer (Sciex, Canada). The calibration curves were obtained on the basis of the results of six standard solution analyses. Linearity was not lower than 0.998. The limit of detection was set at the lowest concentration which can be determined with an acceptable accuracy and precision. All pesticides had recoveries in the range 85–109% with relative standard deviation values less than 8.1%. The estimated measurement uncertainty did not exceed 30%, so the LC-MS/MS method fits for the intended purpose.     

Influence of type of MVC test on electromyography measures of biceps brachii and triceps brachii

Objective. This study aimed to investigate the amplitude and frequency measures of the electromyography (EMG) signal in agonistic and antagonistic muscles (biceps brachii, triceps brachii). Methods. Fifteen males (22.9?±?2.1 years old) took three isometric maximum voluntary contraction (MVC) tests. Two tests were typical MVC tests for biceps brachii and triceps brachii. The third was a test often used to obtain MVC for forearm muscles (arm and forearm hanging down). The EMG signal was recorded during three isometric MVC muscle contractions and during a relaxation test. Results. There were no differences in amplitude between relaxation and MVC antagonist in static contraction, with higher values for frequency measures in relaxation. When biceps brachii and triceps brachii act as antagonists in an MVC test, frequency measures present lower values than when the muscles act as agonists. Biceps brachii shows much lower amplitude than during an agonist MVC contraction with similar spectral measures. Triceps brachii presents much higher values of spectral measures than during an agonist MVC test. Conclusion. The type of exerted force, i.e., if a muscle acted as an agonist, antagonist or stabilizer, affects the relationship between the time and frequency domain measures.     

Tannery waste as a renewable source of nitrogen for production of multicomponent fertilizers with biostimulating properties

Environmental Science and Pollution Research - The studies presented in this work show that solid tannery waste-like shavings can be used as high-protein materials for fertilizer production...     

Accuracy assessment of a small-area method for estimating the spatial distribution of the degree of tree damage

Tree damage, gauged by the amount of defoliation, is one of the basic criteria used to determine treatments for protected and economic forests. Monitoring should include an assessment of the degree of tree damage in different spatial scales. Therefore, in addition to the commonly applied large-area methods, small-area methods should be used. The aim of the paper is to present the results of the accuracy assessment of a small-area method, proposed by Podlaski (2005) [Podlaski, R. (2005). Inventory of the degree of tree defoliation in small areas. Forest Ecology and Management, 215, 361–377], for monitoring the degree of tree damage. The degree of tree damage was shown in sub-blocks P₃ of the system of information on natural environment (SINUS). To estimate the spatial distribution of the degree of tree defoliation, survey sampling, based on simple random sampling with replacement (SRSWR), was used. The degree of damage to fir (Abies alba Mill.) and beech (Fagus sylvatica L.) was analysed in the Święty Krzyż forest section in the Świętokrzyski National Park. The maximum total estimation errors for the proportion of trees with a degree zero of damage, and with second and third degrees of damage together (for α = 0.05) were at most 30.8% for fir and 24.3% for beech trees. For standard, small-area evaluations, these are satisfactory values. In the Święty Krzyż forest section, the number of P₃ sub-blocks with 0.00–5.00% of undamaged trees and with 80.01–100.00% of moderately- or severely-damaged trees was significantly greater for fir than for beech. These results indicate that the fir population was unhealthier than the beech group in the study area. P₃ sub-blocks of the SINUS system, in which the proportion of the healthiest trees was highest, were situated at the forest margin, bordering on meadows and arable fields (in the case of fir) and forming dense patches consisting of several sub-blocks, or occurring singly in the whole study area (in the case of beech). The results show the significant differentiation of forest tree health in small areas.     

Short-term effects of dimethoate on metabolic responses in Chrysolina pardalina (Chrysomelidae) feeding on Berkheya coddii (Asteraceae), a hyper-accumulator of nickel

Berkheya coddii Roessler (Asteraceae) is a hyper-accumulator of nickel, which can be used in phytomining and phytoremediation. Chrysolina pardalina Fabricius (Chrysomelidae) is a phytophagous leaf beetle, which may be useful in controlling population levels of B. coddii after it has been introduced into a new habitat. The aim of this study was to investigate the response of C. pardalina to topical application of dimethoate. Data recorded included the activity of acetylcholinesterase (AChE), the concentration of glutathione (GSH), and the activity of selected enzymes connected with GSH metabolism. Assays were carried out several times during the first 24h after exposure to dimethoate. At the dosages used in this study, dimethoate was not as toxic as expected. AChE activity was significantly decreased 14 and 24h after application. GST activity was significantly decreased 24h after application. GSTPx activity was significantly decreased 2, 14 and 24h after application. GR activity was significantly increased 4h after application. GSH concentration was significantly increased 24h after application. Long-term exposure to high levels of nickel may have caused adaptive changes in the enzymes that enable C. pardalina to deal with other stressors, including organophosphate pesticides.     

Tradable Permit Systems: Considering Uncertainty in Emission Estimates

We simulate the market for emission permits by considering uncertainty in emission inventory reports. The approach taken in this analysis is to enhance the emissions reported in each region by a certain part of their uncertainty when compliance with the Kyoto targets is being proved. While this formulation is not new in the literature, we define the uncertainty component in a way that enables comparison with the approach of effective permits presented in Nahorski, Horabik, and Jonas (2007) Compliance and emissions trading under the Kyoto protocol: Rules for uncertain inventories, (this issue). We show and explain that the transformation to effective permits bears additional costs apart from those resulting from shifting the Kyoto targets.     

Determination of exposure to lead of subjects from southwestern Poland by human hair analysis

The aim of the present work was to investigate the exposure to lead from various sources by investigation of mineral composition of human scalp hair. The research was carried out on hair sampled from 267 young adults living in Wroc?aw (southwest Poland). The effect of the place of residence, diet, and lifestyle on lead content in hair was examined by inductively coupled plasma optical emission spectrometry (ICP-OES). Lead was determined at the wavelength 220.353 nm. These outcomes were reached by linking the results of lead level in hair with the results of questionnaire survey. The mean lead level in hair of the whole examined population was 2.01?±?2.10 mg kg^?1. Lead can enter the human body mainly by inhalation and gastrointestinal absorption. It was found that consuming cheese, fish, and lettuce caused increased level of lead in hair. On the other hand, drinking of milk, tea, coffee, or lemon resulted in decreased content of lead in hair. Additional source of exposure to lead could be cigarette smoking, distance to the traffic road, painting the walls, amalgam filling. Based on the results, it can be concluded that exposure to lead can occur mainly from eating habits and environmental exposure.     

Effect of long-term dietary lead exposure on some maturation and reproductive parameters of a female Prussian carp (Carassius gibelio B.)

Lead is reported to be an endocrine disruptor. In the current study, we exposed female Prussian carp to artificial feed, supplemented with five doses of dietary Pb (0, 1 (control), 8, 13, 24, and 49 mg/kg) over either a 24-month period or a 12-month period, followed by further 12 months where the fish were fed the control diet. Periodically, oocyte maturation, gonadosomatic index (GSI), ability to secret luteinizing hormone (LH) as well as gonad Pb concentrations were measured. It was found that the reproductive system of the female Prussian carp is not indifferent to chronic exposure to lead. The negative effect was manifested by a decrease in the GSI after 12 months despite the fact that a higher proportion of oocytes at more advanced maturity stages were concurrently observed. After 12 months of exposure, the effect on LH secretion varied according to the dose. In the group exposed to the lowest dose (8 mg/kg), LH decreased spontaneously, and in the groups exposed to the highest two doses (24 and 48 mg/kg), a significantly higher LHRH-A-stimulated LH secretion was observed. After 24 months of lead exposure, the effects on oocyte maturation and size and on GSI values were not pronounced. Analysis of the effect of lead exposure on LH secretion showed that the relationships were similar to those observed after 12 months but nonsignificant. During chronic a 24-month period exposure to Pb, Prussian carp female appears to acclimate to Pb doses used in the experiment. After 12 months of exposure and 12 months of depuration, the levels of spontaneous and stimulated LH secretion observed in all the groups were similar to the control, which is evidence that depuration eliminates the previously observed effects of exposure to lead. Lead is easily accumulated in the ovary, reaching a fivefold higher level (0.8 mg/kg tissue) compared to the control (0.15 mg/kg tissue), but after discontinuation of exposure, this organ is quickly depurated. The results indicate that environmental Pb can be a potent endocrine disruptor affecting ovarian steroidogenesis, gametogenesis, and ovulation, which may lead to adverse impacts on fish reproduction and population density and that female Prussian carp become resistant to the negative effects of lead with advancing age, and their organs cope by reaching a state of homeostasis.     

Trace metals content in soils along the state road 51 (northeastern Poland)

The aim of the study was to determine concentrations of some trace elements (lead, cadmium, chromium, and nickel) in soils along State Road 51 leading from Olsztyn to Olsztynek, northeastern Poland. The traffic flow had a significant effect on the content of heavy metals in soils lying along the road. Further away from the road, and under a lower traffic flow intensity, the amounts of contaminants originating from the motor traffic decreased. There was a pine forest growing by the road near Olsztyn, which served as a buffer zone for all the analyzed heavy metals. At all the sampling locations, the content of chromium was approximately the same as its natural concentration. The statistical analysis demonstrated that there was a strong negative correlation between the concentrations of nickel, lead, chromium, and cadmium in soils and the distance from the road. The biggest differences in the content of an individual element were determined for lead and the smallest ones—for cadmium. Emissions of trace elements depended on the differences in the traffic flow intensity, number, type, and speed of vehicles and on the atmospheric conditions as well as the distribution of buildings.