Simultaneous Determination of Multi-Class Pesticide Residues and PAHs in Plant Material and Soil Samples Using the Optimized QuEChERS Method and Tandem Mass Spectrometry Analysis.

New analytical approaches to the simultaneous identification and quantification of 94 pesticides and 13 polycyclic aromatic hydrocarbons (PAHs) in five representative matrices (pepper, apple, lettuce, wheat, and soil) were developed. The analyses were based on gas chromatography coupled with triple quadrupole tandem mass spectrometry (GC-MS/MS). The procedure was optimized by changing the solvent used during the extraction, from acetonitrile to the acetone: n-hexane mixture at a volume ratio of 1:4 (v/v), as well as the use of a reduced amount of water during the extraction of compounds from cereals. An additional modification was the use of florisil instead of GCB in the sample cleanup step. A full method validation study was performed, at two concentration levels (LOQ and 1000 × LOQ), which showed satisfactory results for all analytes from the PAHs group, with recoveries ranging from 70.7-115.1%, and an average RSD of 3.9%. Linearity was tested in the range of 0.001-1.000 mg/kg and showed coefficients of determination (R2) ≥ 0.99 for all PAHs. Satisfactory recovery and precision parameters (LOQ and 100 × LOQ) were achieved for almost all analytes from the pesticide group in the range of 70.1-119.3% with the mean RSD equal to 5.9%. The observed linearity for all analytes in the concentration range of 0.005-1.44 mg/kg was R2 ≥ 0.99, with the exception of famoxadone, chizalofop-p-ethyl, prothioconazole, spirodiclofen, tefluthrin, and zoxamid. The extended uncertainties were estimated, using a top-down approach of 9.9% (average) and 15.3% (average) for PAHs and pesticides samples, respectively (the coverage factor k = 2, the 95% confidence level). Ultimately, the method was successfully applied to determine pesticide residues in commercial samples of fruit, vegetables and grain, and soil samples for PAHs, which were collected from selected places in the Podkarpacie region. A total of 38 real samples were tested, in which 10 pesticides and 13 PAHs were determined. Proposed changes allow us to shorten the sample preparation time (by 20%) and to reduce the consumption of organic solvents (by 17%). The use of florisil for sample cleanup, instead of GCB, improves the recovery of compounds with flat particles.

The dynamics of pyrethroid residues and Cyp P450 gene expression in insects depends on the circadian clock.

A circadian clock may underlie pesticide resistance mechanisms in organisms that are very important for humans, for example, in the honey bee (Apis mellifera). Using the gas chromatography, we evaluated the daily variability in the λ-cyhalothrin degradation rate in bodies of guards and forager bees, Apis mellifera. Additionally, using the RT-qPCR method, we studied expression levels of selected cytochrome P450 genes after exposure to λ-cyhalothrin. During 48-h-tests, we exposed bees to λ-cyhalothrin at four crucial times of the day: at 04:30 a.m., 11:30 a.m., 06:30 p.m., and 11:30 p.m. The results obtained indicate that in bees the intensity of the λ-cyhalothrin degradation is the highest during first 6 h after intoxication, when it disappeared at the rate of 14.29% h-1, 11.43% h-1, 13.15% h-1, and 12.50% h-1 in bees treated at noon, sunset, midnight, and sunrise, respectively. In the later period (6-48 h of the experiment), the degradation stopped and its rate did not exceed 1.0% h-1. In the control group of bees we demonstrated that the increase in the Cyp9Q1 and Cyp9Q3 expression was the highest during the experiments started at 04:30 a.m., while the highest elevation in the Cyp9Q2 expression was observed in the group for which the experiments started at 11:30 p.m.In intoxicated honey bees, the highest increase in the Cyp9Q1 expression occurred in the group treated with the pesticide at 11:30 a.m. In the case of genes encoding Cyp9Q2 and Cyp9Q3, the highest rise in the expression took place at 06:30 p.m.The obtained results indicate that honey bees activate detoxifying mechanisms partly protecting them against the effects of hazardous substances absorbed from the environment more efficiently during foraging than at other times of the day.

Characteristics of Dietary Fatty Acids Isolated from Historic Dental Calculus of the 17th- and 18th-Century Inhabitants of the Subcarpathian Region (Poland).

Dental calculus analysis can be a valuable source of archaeological knowledge, since it preserves not only microbial and host biomolecules but also dietary and environmental debris, as well as metabolic products likely originating from dietary and craft activities. Here we described GC-MS analysis of a set of historic dental calculus samples from the front teeth of the mandibles of seven individuals found in 17th- and 18th-century graves in the city of Rzeszow, located in South-eastern Poland. We have found that only saturated fatty acids, which are characteristic for fats of animal origin, were present in the tested samples. Our preliminary results indicate that the diet of modern-period inhabitants of Rzeszow was rich in animal products, such as meat and dairy products.

Assessment of risk to honey bees and honey consumers resulting from the insect exposure to captan, thiacloprid, penthiopyrad, and λ-cyhalothrin used in a commercial apple orchard.

Samples of leaves, flowers, soil, pollen, bee workers, bee brood, honey, and beeswax were collected to assess the possibility of a transfer of captan, thiacloprid, penthiopyrad, and λ-cyhalothrin from apple trees of Idared variety to honey bee (Apis mellifera) hives. Chemical analyses were performed using the Agilent 7890 Gas Chromatograph equipped with the Micro-cell Electron Capture Detector. It was found that significant amounts of penthiopyrad, the active ingredient of Fontelis 200 SC, were present in leaves, flowers, pollen, bee workers, and beeswax. Simultaneously, captan was present in the brood, worker bees, and honey samples. Significant levels of the captan residues were also detected on the soil surface. In honey samples, captan residue levels exceeded the acceptable standard, reaching 160% of its maximum residue level. However, in no case the amounts of captan, thiacloprid, penthiopyrad, and λ-cyhalothrin ingested with honey by an adult consumer exceeded the level of 0.02% of the acceptable daily intake. Despite the trace amounts of pesticide residues in honey samples collected during the field trial, bee honey consumption can be considered safe. An adult consumer can safely consume about 16 kg of honey.

Treating honey bees with an extremely low frequency electromagnetic field and pesticides: Impact on the rate of disappearance of azoxystrobin and λ-cyhalothrin and the structure of some functional groups of the probabilistic molecules.

The purpose of these laboratory tests was to assess the impact of 50 Hz EMF (electromagnetic field) on the disappearance of azoxystrobin (active ingredient (AI) of Amistar 250 SC) and λ-cyhalothrin (AI of Karate Zeon 050 CS) in the body of honey bees (Apis mellifera) and the structure of some functional groups of the probabilistic molecules in their organisms. Amistar 250 SC (an azoxystrobin-based fungicide; ABF) and Karate Zeon 050 CS (a λ-cyhalothrin-based insecticide; CBI) are plant protection products (PPPs) applied to bee-pollinated-crops. Chromatographic methods were used to assess the rate of AI disappearance. EMF affected the rate of disappearance of azoxystrobin and λ-cyhalothrin in bees within 6 h of intoxication. When these substances were used separately their disappearance in the presence of EMF slowed from 12.6% to 10.5% h-1 and from 9.2% to 4.8% h-1, respectively, and accelerated when used in a mixture, from 14.1% to 14.7% h-1 and from 9.3% to 11.5% h-1 respectively. Fourier Transform Infrared (FTIR) spectroscopy was used to analyze changes in the functional groups of the probabilistic molecules of the tested bees. To obtain the information about the spectra variations we used the Principal Component Analysis. It has been shown, that EMF statistically significantly interferes with amide I and II, symmetric PO32- group from DNA, RNA and phospholipids vibrations. It also increased the number of changes of functional groups of the probabilistic molecules caused by ABF, but at the same time limited the changes in the functional groups studied in bees treated with CBI and a mixture containing both of them. In addition, exposure to EMF in bees treated with fungicide or insecticide, separately, and with both preparations caused differences (p < 0.05) in the secondary structure of proteins compared to controls. The obtained results indicate that EMF may affect the rate of metabolism and the detoxification process of pesticides in bees, depending on the AI of PPPs, applied individually or together. However, further detailed research is required to explain the mechanism of EMF as a detoxification modulator.

Influence of a Commercial Biological Fungicide containing Trichoderma harzianum Rifai T-22 on Dissipation Kinetics and Degradation of Five Herbicides in Two Types of Soil.

Biological crop protection is recommended to be applied alternately or together with chemical one, to protect human health from the excessive use of toxic pesticides. Presence of microorganisms can influence the concentration of chemical pollutants in soil. The aim of this study is to estimate the influence of a commercial biological fungicide containing Trichoderma harzianum Rifai T-22 on dissipation kinetics and degradation of five herbicides belonging to different chemical classes: clomazone, fluazifop-P-butyl, metribuzin, pendimethalin, and propyzamide, in two types of soil. Results of the study revealed that T. harzianum T-22 influences pesticide degradation and dissipation kinetics of the non-persistent herbicides: clomazone, fluazifop-P-butyl, and metribuzin. In soil with a higher content of nitrogen, phosphorus, and organic matter, degradation increased by up to 24.2%, 24.8%, and 23.5% for clomazone, fluazifop-P-butyl, and metribuzin, respectively. In soil with lower organic content, degradation was on a low level, of 16.1%, 17.7%, and 16.3% for clomazone, fluazifop-P-butyl, and metribuzin, respectively. In our study, the addition of the biological preparation shortened herbicide dissipation half-lives, from 0.3 days (2.9%) for fluazifop-P-butyl, to 18.4 days (25.1%) for clomazone. During the degradation study, no significant differences were noticed for pendimethalin, belonging to persistent substances. Biological protection of crops can modify pesticide concentrations and dissipation rates. On one hand, this may result in the reduced effectiveness of herbicide treatments, while on the other, it can become a tool for achieving cleaner environment.

Influence of Bacillus subtilis and Trichoderma harzianum on Penthiopyrad Degradation under Laboratory and Field Studies.

In plant protection, biological preparations are used alternately with chemical pesticides. The applied microorganism can influence the concentration of chemical substances. Laboratory and field studies were conducted to assess the influence of Bacillus subtilis and Trichoderma harzianum on the penthiopyrad concentration. In laboratory studies, the effectiveness of penthiopyrad degradation by B. subtilis was approximately 5% during 14 days of the experiment. For penthiopyrad treated with T. harzianum strains, the degradation effectiveness ranged from 34.2% on Day 3 to 56.9% on Day 14. In experiments testing the effects of mixed culture of microorganisms, the effectiveness of penthiopyrad degradation ranged from 23.7% on Day 3 to 29.1% on Day 14. After treatment of apple trees of Gala and Golden Delicious varieties with a biological preparation, a maximum degradation of penthiopyrad of 20% was found in both varieties. Samples of apples were prepared by the quick, easy, cheap, effective, rugged and safe (QuEChERS) method, and penthiopyrad was analyzed by gas chromatography with a mass detector. A determined value of the chronic exposure to penthiopirad was 1.02% of the acceptable daily intake, both for children and for adults. The acute exposure amounted to 7.2% and 1.9% of the acute reference dose for children and adults, respectively. These values were considered to be acceptable and not threatening to health.

A Non-Vector Approach to Increase Lipid Levels in the Microalga Planktochlorella nurekis.

Microalgae are freshwater and marine unicellular photosynthetic organisms that utilize sunlight to produce biomass. Due to fast microalgal growth rate and their unique biochemical profiles and potential applications in food and renewable energy industries, the interest in microalgal research is rapidly increasing. Biochemical and genetic engineering have been considered to improve microalgal biomass production but these manipulations also limited microalgal growth. The aim of the study was the biochemical characterization of recently identified microalgal strain Planktochlorella nurekis with elevated cell size and DNA levels compared to wild type strain that was achieved by a safe non-vector approach, namely co-treatment with colchicine and cytochalasin B (CC). A slight increase in growth rate was observed in twelve clones of CC-treated cells. For biochemical profiling, several parameters were considered, namely the content of proteins, amino acids, lipids, fatty acids, ß-glucans, chlorophylls, carotenoids, B vitamins and ash. CC-treated cells were characterized by elevated levels of lipids compared to unmodified cells. Moreover, the ratio of carotenoids to chlorophyll a and total antioxidant capacity were slightly increased in CC-treated cells. We suggest that Planktochlorella nurekis with modified DNA levels and improved lipid content can be considered to be used as a dietary supplement and biofuel feedstock.

Physicochemical Parameters of Real Wastewater Originating from a Plant Protection Products Factory and Modification of the QuEChERS Method for Determination of Captan.

The aim of this study was the modification and application of the QuEChERS method for the preparation and purification of samples in order to determine the level of captan in real wastewater originating from a plant protection products factory which was characterized by a significant content of organic substances [Chemical Oxygen Demand (COD) = 856 ± 128 mg O2/L and Total Organic Carbon (TOC) = 62 ± 9 mg/L]. The optimization of the method consisted of the selection of solvents used for the extraction of captan from wastewater and also sorbents used to purify the extracts by the dispersion of a solid phase extraction technique (dSPE). Two steps were used: extraction and clean-up. In the extraction step, acetonitrile was replaced by anacetonitrile:acetone mixture. In the clean-up step by the dSPE, five sorbents were tested: Florisil®, aluminum oxide (Al2O3), zirconium oxide (ZrO2), silicon oxide (SiO2) and PSA (primary and secondary amine). Concentrations of captan in wastewater extracts were determined by gas chromatography (GC) combined with electron capture detection (µECD). The best recovery parameters and precision of the method were obtained for samples purified using ZrO2 (recovery 98% and precision expressed as relative standard deviation RSD 8%) and Florisil® (recovery 96%, RSD 9%). Limits of detection (LOD) and quantification (LOQ) for determination of captan in diluted extract of wastewater were 0.003 and 0.01 mg/L, respectively. Matrix effects were in the range of -69% to -44% for samples purified by ZrO2 and Florisil®, respectively. The modified and optimized method was applied for fast and simple determination of captan levels in real industrial wastewater samples, in which the concentration of captan in diluted extract was determined to be 4.0±0.3 mg/L.

Transfer of the Active Ingredients of Some Plant Protection Products from Raspberry Plants to Beehives.

Plant protection products (PPPs) have been found increasingly in the environment. They pose a huge threat to bees, contributing to honeybee colony losses and consequently to enormous economic losses. Therefore, this field investigation was designed to determine whether their active ingredients (AIs) were transferred from raspberry plants to beehives located in the immediate neighbourhood of the crop and to what extent they were transferred. Every week for 2 months, samples of soil, raspberry leaves, flowers and fruits, worker bees, honeybee brood, and honey were collected and analysed for the presence of propyzamide, chlorpyrifos, iprodione, pyraclostrobin, boscalid, cypermethrin, difenoconazole, azoxystrobin, and pyrimethanil residues. Five of these substances were found in the worker bee bodies. Chlorpyrifos, applied to only the soil through the irrigation system, also was detected in the brood. A small amount of boscalid was noted in the honey, but its residues did not exceed the maximum residue level. For chlorpyrifos, boscalid, and pyrimethanil, a positive correlation between the occurrence of PPPs in the crops and the beehives was found. Statistical methods confirmed that the application of PPPs on a raspberry plantation, as an example of nectar-secreting plants, was linked to the transfer of their AIs to beehives.

Assessment of boscalid and pyraclostrobin disappearance and behavior following application of effective microorganisms on apples.

The aim of this study is to assess the disappearance of boscalid (IUPAC name: 2-chloro-N-[2-(4-chlorophenyl)phenyl]pyridine-3-carboxamide) and pyraclostrobin (IUPAC name: methyl N-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-N-methoxycarbamate) residues in apple fruit, and to verify whether an organic fertilizer enriched with strains of antagonistic microorganisms can reduce pesticide residue levels. Field trials were conducted in a commercial orchard on apples of the Gloster variety, during 21 days after the treatment with Bellis 38 WG and the subsequent application of Zumba Plant formulation containing Bacillus spp., Trichoderma spp. and Glomus spp. In control samples, the decrease rate of boscalid and pyraclostrobin residue levels followed an exponential function, described by formulae Rt = 0.2824e-0.071t and Rt = 0.1176e-0.060t, with the coefficient of determination of r2 = 0.8692 and r2 = 0.9268, respectively. These levels dropped to half (t1/2) of their initial values after 9.8 and 11.5 days, respectively. The treatment with Zumba Plant resulted in a reduction in boscalid and pyraclostrobin residue levels by 52% and 41%, respectively. The results of this study are of importance for horticulture sciences and for producers of apples using plant protection products (PPPs).

The transfer of active ingredients of insecticides and fungicides from an orchard to beehives.

This investigation was undertaken to determine whether active ingredients (AIs) of currently recommended plant protection products (PPPs) could be transferred to beehives from apple and pear trees. A field trial was carried out with apple trees of Ligol and Idared variety, and pear trees of Conference variety. For pest and diseases control of fungal origin, recommended PPPs were applied. Samples of flowers from the above-mentioned varieties of fruit trees, of bees, brood and honey from beehives located in their direct neighborhood were collected regularly and analyzed for the presence of lambda-cyhalothrin (an insecticide) and cyprodinil, captan, fluopyram, kresoxim-methyl, penthiopyrad and trifloxystrobin (fungicides). In samples of flowers of Ligol variety, fluopyram residues (on average 0.621 µg single flower-1) were at the highest levels, whereas in samples of pear flowers of Conference variety, and in flowers of Idared variety, captan residues (on average, respectively, 0.705 and 165.7 µg single flower-1). In samples of bees and honey, residues of five AIs were detected, and in brood six AIs, whereby in each case captan residues prevailed, respectively, up to 585.2, 51.52 and 126.5 µg kg-1 bees and honey. In the honey, significantly larger residues of captan were found out than maximum residue level (MRL) for this AI - 103.04% MRL. In the case of any AI, the daily intake did not exceed 0.002% acceptable daily intake (ADI).

Behavior of fluopyram and tebuconazole and some selected pesticides in ripe apples and consumer exposure assessment in the applied crop protection framework.

The supervised field trials were conducted in a commercial apple orchard in 2016. The trials were an attempt to determine a model for dissipation and toxicological evaluation of fluopyram, tebuconazole, captan, tetrahydrophthalimide (THPI), pirimicarb, spirodiclofen, and boscalid residues detected in fruit of Red Jonaprince, Lobo, and Gala varieties immediately before harvest. The analysis also covered amounts of pesticides still present in remnants of calyx in Lobo and Gala varieties immediately before harvest. Laboratory samples of ripe apples were collected within 14 days of the treatment. Levels of pesticide residues detected in the samples changed at a constant exponential rate, and the residue levels found in ripe apples of Red Jonaprince, Gala, and Lobo varieties immediately before harvest were below maximum residue levels (MRL). Overall, captan residues in remnants of calyx were at a level of 22.3% for the Gala variety and 9.3% for the Lobo variety. Likewise, the long-term daily intake of the detected substances by a Polish adult consumer was low, ranging from 0.02% ADI for pirimicarb to 0.72% ADI for captan.

Occurrence and estimation of pesticide residues in edible minor crops in southeastern Poland in 2013-2014.

This paper presents the results of official control of pesticide residues in minor crops collected in southeastern Poland in 2013-2014. Compliance of used pesticides with applicable law was also verified, and determined residues were compared to maximum residue levels (MRLs) provided for in Regulation (EC) No. 395/2005. A total of 583 samples of 25 different types of fresh fruit and vegetables were analyzed for pesticide residues. Pesticide residues were detected in 158 samples (27.1 % of the analyzed samples). According to the European Commission Health & Consumer Protection Directorate-General (SANCO) guidelines document, MRL violations were understood as cases where a residue level exceeded the MRL after the uncertainty of the method (50 %) was considered. MRL violations were found in four samples. The usage of unauthorized pesticides was detected in 5.8 % of analyzed samples. Substances banned in Poland were found in two samples. Fungicides were the most frequently detected group of pesticides. Pesticide residues were most commonly found in fruit samples (19.4 % of all analyzed samples), mainly in gooseberry, redcurrant, and huckleberry. The majority of samples were compliant with MRLs, which means that they were suitable for trade.

Occurrence of pesticide residues in fruiting vegetables from production farms in south-eastern region of Poland

Background: Considering the fact that pesticides are commonly used in agriculture, continuous monitoring of these substances in food products is of great significance. Residues of these substances can be present in crops after harvest. Objective: The aim of this study was to evaluate presence of pesticide residues in fruiting vegetables from production farms in south-eastern region of Poland in 2012­2015. Material and methods: 138 samples were tested using accredited test methods. The monitoring programme covered determination of 242 pesticides. The tests covered tomato, cucumber and pepper crops. The test results were interpreted in accordance with criteria included in the European Commission recommendations published in the document SANCO/12571/2013 (now superseded by Document SANTE 2015), as well as on a basis of the maximum residue levels in force in the EU Member States. Results: Pesticide residues were found in 47 samples, representing 34% of all tested samples. 17 active substances were found, belonging to fungicides and insecticides. Azoxystrobin (38%), boscalid (28%) and chlorothalonil (21%) were most commonly found in fruiting vegetables testing samples. Non-compliances related to use of plant protection product not authorized for protection of a given crop were observed in 6% of analysed samples. However, pesticide residues of fruiting vegetables in quantities that exceed the maximum residue levels (NDP, ang. MRLs), as well as substances which use for plant protection is forbidden were no found. Conclusions: Crops monitoring is used to determine to what extent such products are contaminated with pesticide residues, and ensures protection of customer health.

Pesticide residues in raw agricultural products from the south-eastern region of Poland and the acute risk assessment.

BACKGROUND: The use of pesticide leads to the increase in quantity and quality of yields, but may also result in presence of toxic contaminants in food products. OBJECTIVE: The aim of this study was to evaluate presence of pesticide residues in raw agricultural products from the south-eastern region of Poland, to verify their compliance with the maximum residue levels' (MRLs) as specified in the EU regulations concerning products present in the market, and to assess the acute risk related to consumption of these products. MATERIAL AND METHODS: Samples of raw agricultural products were obtained from production farms as a part of an official premarket monitoring of pesticide residues conducted on behalf of the Ministry of Agriculture and Rural Development, implemented in cooperation with the regional Inspectorates of Plant Health and Seed Inspection. The scheduled tests covered determination of 243 chemicals included in residue definitions for purposes of pesticide residues monitoring in or on food of plant origin (229 pesticides). RESULTS: In 2015, a total of 328 samples of raw commodities collected from the south-eastern region of Poland were analysed for the presence of pesticide residues. Pesticide residues were detected in 84 samples (25.6%), while in 7 samples (2.1%) they exceeded MRLs. Violations of MRLs concerned 2 samples of Peking Cabbage, 3 samples of dill, 1 sample of raspberry and 1 sample of spinach. The pesticide residues were most often found in: fruit (38.3% of all fruit samples), herbs (35.3%) and vegetables (20.0%). The assessed acute exposure did not exceed the 100% acute reference dose (ARfD) in any sample. CONCLUSIONS: Monitoring of pesticide residues in the agricultural crops prevents penetration of products with MRLs exceeded or containing unacceptable pesticide residues into the market, thus protecting consumers' health. KEY WORDS: pesticide residues, agricultural products, risk assessment, multiresidue method.

Pesticide residues in stone fruits from the south-eastern region of Poland in 2012-2104.

BACKGROUND: Peaches, sour cherries, nectarines, apricots, plums and cherries are fruit commonly known as "stone fruit". Their nutritional properties namely, vitamins, minerals, fiber and numerous microelements, make them a very important component of human diet. As fruit trees can be attacked by numerous diseases and pests, chemical protection of these crops is used. Therefore, it is important that the relevant governmental agencies or institutions ensure correct application of pesticides. OBJECTIVE: The aim of the study was to evaluate the occurrence of pesticide residues in stone fruits south-eastern region of Poland in 2012-2014 in order to provide data to estimate health risk to consumers. MATERIAL AND METHODS: Validated analytical methods based on liquid / liquid extraction coupled with gas chromatography with electron capture and nitrogen phosphorus detection (GC-ECD/NPD) and spectrophotometry (dithiocarbamates residues) were used for the analysis. 92 samples of stone fruits were tested for the presence of pesticide residues. RESULTS: 13 of all samples (14%) contained pesticide residues. 7 active substances were detected, including 5 fungicides: boscalide, bupirimate, difenoconazole, dithiocarbamates and captan, and 2 insecticides: cypermethrin and pirimicarb. In the analysed samples, the use of not recommended plant protection products in orchard crops were found. However, neither maximum residue levels (MRLs) recommended by the Regulation (EC) No 396/2005 were exceeded nor pesticides being unapproved by the Regulation (EC) No 1107/2009 detected in the analysed samples. CONCLUSIONS: Lack of plant protection products for control specific diseases or pests in crops results in the use of formulations not recommended for use in certain orchard crops. On a basis of results reported in previous years it can be concluded that occurrence of pesticide residues in stone fruit samples dropped significantly.

Pesticide residues in berries harvested from South-Eastern Poland (2009-2011).

BACKGROUND: Poland is a leading grower/producer of berries in Europe that are either eaten raw or processed. As well as berries this includes fruit such as grapes, strawberries and other small fruits. Testing for the presence of active substances in Plant Protection Products, (PPP), in such fruit is however important, as part of measures taken to minimise human intake. OBJECTIVE: To determine the incidence of pesticide residues in berries harvested from South-Eastern Poland in 2009-2011. MATERIAL AND METHODS: . Chromatographic separation followed by analytical detection was performed on 250 samples of various test fruits using an accredited methodology: GC/ECD/NPD, together with spectrophotometric detection wherever necessary, according to PN-EN ISO/IEC 17025. As part of previous monitoring, 126 active substances were identified in 2009, 132 in 2010 and 153 in 2011; levels were compared to Maximum Residue Limits (MRLs). RESULTS;. Analyses showed that 46.4% of samples contained PPPs of which 4% exceeded the MRL. The most were found in raspberries, (58.8% of all tested), followed by 58.3% redcurrants, and gooseberries as well as 50% grapes. The most frequently found active substances of PPPs were pyrimethanil (15.6%), dithiocarbamates (12.4%), procymidone (8%), cyprodinil (5.6%) and difenoconazole (5.2%). The highest MRL exceedances were found in blackcurrants. Testing also revealed many examples of pesticides not recommended for the protection of specific crops: propiconazole in gooseberries, cyprodinil, flusilazole, iprodione, pyrimethanil in blackcurrants and folpet and captan in raspberries. Furthermore, active substances whose use in PPPs have been forbidden since 2008 were also detected, ie. endosulfan in blackcurrants and strawberries, fenitrothion in black and red currants as well as procymidone in raspberries, blackcurrants and strawberries. These data are consistent to those obtained from the whole of Poland and the European Union (EU). CONCLUSIONS: Most pesticides were present in raspberries, redcurrants, gooseberries and grapes of which fungicides were the most frequently detected. These results are in keeping with other similar studies.

The role of focal infections in the pathogenesis of psoriasis and chronic urticaria.

INTRODUCTION: The Focal Infection Theory, originally presented at the beginning of the 20(th) century, postulates that systemic diseases can be caused by microorganisms that arise from the focus of infection. Foci of infections have been described as sinuses, adenoids, tonsils, teeth, genitourinary tract, gall bladder and kidneys. A focus of infection is defined as the area that can occur in any part of the body, contains a pathogen (microorganism) and is usually asymptomatic. There are discordant opinions about the role of focal infections in the pathogenesis of psoriasis and urticaria. AIM: To establish whether there is a higher incidence of focal infections in patients with chronic urticaria and psoriasis. MATERIAL AND METHODS: We retrospectively reviewed 129 patients with a history of psoriasis and chronic urticaria: 58 women and 71 men treated in the Department of Dermatology of the Jagiellonian University Medical College in Krakow. RESULTS: In the analyzed group, 11 patients had a dental consultation, 58 - laryngological consultation and 29 women had a gynecological consultation. The most common examples of focal infection were tonsillitis, upper respiratory tract infections, sinusitis, dental caries and genitourinary tract infections. Aggravating factors were similar to previously described. CONCLUSIONS: A high incidence of focal infections in patients with psoriasis and urticaria suggests that infections may play a significant role in the pathogenesis of these skin disorders. Treatment of infection foci may play the key role in the remission of skin changes.

Microplastics - An emerging contaminants for algae. Critical review and perspectives.

In recent decades, micro- and nanoplastics (MNPs) became persistent contaminants of emerging concern to the environment. These xenobiotic are found in all components of environment, including living organisms. Ubiquitous contamination of aquatic ecosystems with these pollutants is studied worldwide. In aquatic ecosystems, algae are important primary producers providing nutrients for a wide range of species, so they play a fundamental role in maintaining the balance of the marine ecosystem. Thus, the toxic effect of pollutants on algae can have a negative impact on organisms at higher trophic levels. The microplastic toxic effect on algae is studied by many researches, leading to many different conclusions due to different experimental designs. The polymer type is an important parameter, as it influences the growth rate, the photosynthetic pigments content, and the oxidative stress. Polystyrene is considered more toxic than other types of microplastics. Studies show that plastics of a smaller size and with a positive surface charge have a higher toxic effect on algae. MNPs toxicity to algae strongly depends on their concentration, and becomes more severe as its level increase. Moreover, size and concentration of plastic particles influence changes in reactive oxygen species and the enzymatic antioxidant activity. MNPs are also a vector for other environmental pollutants. Effects of pollutant-MNPs complexes are more often found to be antagonistic than synergetic, in consequence of toxic substance adsorption on the MNPs surface and their lower bioavailability to algae. The aim of this review was to summarize effects and impacts of microplastics and coexisting pollutants on algal populations, on the basis of currently available literature.