This study presents monitoring data on the spatial and temporal occurrence of pesticide residues in arable soils of the Czech Republic and relates it to soil properties, pesticide usage and data on application provided by farmers. In total, 34 soils were sampled during 2014-2017, amounting to 136 samples which were analyzed for 60 pesticides and four transformation products. Conazole fungicides were frequently present in soils above the limit of quantification and/or above the 0.01 mg/kg threshold. Of the other pesticide types, the herbicides diflufenican, chlorotoluron, metolachlor, pendimethalin and terbuthylazine, fungicides azoxystrobin, carbendazim, fenpropidin, fenpropimorph and prochloraz and the insecticide methoxyfenozide were found in ≥20% of soils in at least one sampling campaign. Soils typically (>50%) contained 2-7 residues with a maximum of 14. For the 136 samples, 116 different mixtures were identified. The occurrence of pesticides was driven by their annual usage, their half-lives in soil, and their hydrophobicity. A comparison of the monitoring data and pesticide application data provided by farmers revealed that 63% of the applied pesticides are not likely to persist until the following growing season while up to 69% of pesticide residues found in soils could be inherited from the previous growing season(s).
- MeSH
- aniliny MeSH
- fungicidy průmyslové analýza MeSH
- herbicidy analýza MeSH
- insekticidy analýza MeSH
- látky znečišťující půdu analýza MeSH
- monitorování životního prostředí * MeSH
- pesticidy analýza MeSH
- půda chemie MeSH
- rezidua pesticidů analýza MeSH
- triaziny MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
Chlorotriazine herbicides (CTs) are widely used pest control chemicals. In contrast to groundwater contamination, little attention has been given to the circumstances of residue formation of parent compounds and transformation products in soils. Seventy-five cultivated floodplain topsoils in the Czech Republic were sampled in early spring of 2015, corresponding to a minimum of six months (current-use terbuthylazine, TBA) and a up to a decade (banned atrazine, AT and simazine, SIM) after the last herbicide application. Soil residues of parent compounds and nine transformation products were quantified via multiple residue analysis using liquid chromatography - tandem mass spectrometry of acetonitrile partitioning extracts (QuEChERS). Using principal component analysis (PCA), their relation to soil chemistry, crops and environmental parameters was determined. Of the parent compounds, only TBA was present in more than one sample. In contrast, at least one CT transformation product, particularly hydroxylated CTs, was detected in 89% of the sites, or 54% for banned triazines. Deethylated and bi-dealkylated SIM or AT residues were not detectable. PCA suggests the formation and/or retention of CT hydroxy-metabolite residues to be related to low soil pH, and a direct relation between TBA and soil organic carbon, and between deethyl-TBA and clay or Ca contents, respectively, the latter pointing towards distinct sorption mechanisms. The low historic application of simazine contrasted by the high abundance of its residues, and the co-occurrence with AT residues suggests the post-ban application of AT and SIM banned triazines as a permitted impurity of TBA formulations as a recent, secondary source. The present data indicate that topsoils do not contain abundant extractable residues of banned parent chlorotriazines, and are thus likely not the current source for related ground- and surface water contamination. In contrast, topsoils might pose a long-term source of TBA and CT transformation products for ground and surface water contamination.
- MeSH
- biodegradace MeSH
- herbicidy analýza metabolismus MeSH
- látky znečišťující půdu analýza metabolismus MeSH
- podzemní voda chemie MeSH
- půda chemie MeSH
- rezidua pesticidů analýza metabolismus MeSH
- triaziny analýza metabolismus MeSH
- zemědělství * MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
Capillary isotachophoresis (ITP) is an electrophoretic technique offering high sensitivity due to permanent stacking of the migrating analytes. Its combination with electrospray-ionization mass-spectrometric (ESI-MS) detection is limited by the narrow spectrum of ESI-compatible components but can be compensated by experienced system architecture. This work describes a methodology for sensitive analysis of hydroxyderivatives of s-triazine herbicides, based on implementation of the concepts of moving-boundary isotachophoresis and of H+ as essential terminating component into cationic ITP with ESI-MS detection. Theoretical description of such kind of system is given and equations for zone-related boundary mobilities are derived, resulting in a much more general definition of the effective mobility of the terminating H+ zone than used so far. Explicit equations allowing direct calculation for selected simple systems are derived. The presented theory allows prediction of stacking properties of particular systems and easy selection of suitable electrolyte setups. A simple ESI-compatible system composed of acetic acid and ammonium with H+ and ammonium as a mixed terminator was selected for the analysis of 2-hydroxyatrazine and 2-hydroxyterbutylazine, degradation products of s-triazine herbicides. The proposed method was tested with direct injection without any sample pretreatment and provided excellent linearity and high sensitivity with limits of detection below 100ng/L (0.5nM). Example analyses of unspiked and spiked drinking and river water are shown.
- MeSH
- atrazin analogy a deriváty analýza chemie MeSH
- elektrolyty chemie MeSH
- herbicidy analýza chemie MeSH
- hmotnostní spektrometrie s elektrosprejovou ionizací * MeSH
- izotachoforéza * MeSH
- látky znečišťující životní prostředí analýza MeSH
- sladká voda chemie MeSH
- voda chemie MeSH
- Publikační typ
- časopisecké články MeSH
This review focuses on the estrogenic activity of the benzonitrile herbicides – bromoxynil, chloroxynil, dichlobenil and ioxynil and their microbial metabolites – acids (such as 3,5-dibromo-4-hydroxybenzoic acid and its amide). Some of their metabolites are very persistent. The estrogenic activity of the benzonitrile herbicides and their metabolites were studied using the mutant strain of Saccharomyces cerevisiae BMA64-1A. However, their estrogenic activity was not proved.
- MeSH
- beta-galaktosidasa MeSH
- biodegradace MeSH
- biotransformace MeSH
- endokrinní disruptory * analýza MeSH
- fenoly analýza MeSH
- herbicidy * analýza MeSH
- kultivační techniky MeSH
- lidé MeSH
- luciferasy MeSH
- reportérové geny * MeSH
- Saccharomyces cerevisiae MeSH
- testy genotoxicity MeSH
- testy toxicity MeSH
- Check Tag
- lidé MeSH
This work presents the development of a fully automated flow-batch analysis (FBA) system as a new approach for on-line preconcentration, photodegradation and fluorescence detection in a lab-constructed mixing chamber that was designed to perform these processes without sample dispersion. The system positions the mixing chamber into the detection system and varies the instrumental parameters according to the required photodegradation conditions. The developed FBA system is simple and easily coupled with any sample pretreatment without altering the configuration. This FBA system was implemented to photodegrade and determine the fluorescence of the degradation products of metsulfuron methyl (MSM), a naturally non-fluorescent herbicide of the sulfonylurea׳s family. An on-line solid phase extraction (SPE) and clean up procedure using a C18 minicolumn was coupled to the photodegradation-detection mixing chamber (PDMC) that was located in the spectrofluorometer. An enrichment factor of 27 was achieved. Photodegradation conditions have been optimized by considering the influence of the elution solvent on both the formation of the photoproduct and on the fluorescence signal. Under optimal conditions, the calibration for the MSM determination was linear over the range of 1.00-7.20 µg L(-1). The limit of detection (LOD) was 0.28 µg L(-1); the relative standard deviation was 2.0% and the sample throughput for the entire process was 3h(-1). The proposed method was applied to real water samples from the Bahía Blanca׳s agricultural region (Bahía Blanca, Buenos Aires, Argentina). This method obtained satisfactory recoveries with a range of 94.7-109.8%.
- MeSH
- arylsulfonany analýza MeSH
- extrakce na pevné fázi MeSH
- fluorescenční spektrometrie MeSH
- fotochemie metody MeSH
- fotolýza MeSH
- herbicidy analýza MeSH
- kalibrace MeSH
- koncentrace vodíkových iontů MeSH
- látky znečišťující vodu analýza MeSH
- limita detekce MeSH
- reprodukovatelnost výsledků MeSH
- sulfonylmočovinové sloučeniny analýza MeSH
- světlo MeSH
- technologie zelené chemie MeSH
- voda chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
The effects of a 90 day simazine exposure at concentrations of 0.06 (reported concentration in Czech rivers), 1, 2, and 4 μg L⁻¹ were assessed in one-year-old common carp (Cyprinus carpio L.). Its influence on biometric parameters, hematology, blood biochemistry, liver biomarkers, and histology was investigated. Biometric parameters of common carp exposed to simazine at 0.06 μg L⁻¹ showed no differences from untreated fish. Simazine concentrations of 1, 2, and 4 μg L⁻¹ caused significant (p<0.01) increase of hepatosomatic indices relative to controls. Hematological profiles showed significant (p<0.01) decrease in leukocyte count relative to controls at all concentrations. Biochemical profiles of common carp exposed to simazine at all concentrations showed significant (p<0.01) increase in activity of alkaline phosphatase. In addition, at concentrations of 1 and 2 μg L⁻¹, there was a significant increase in alanine aminotransferase (p<0.05), and, at 4 μg L⁻¹, a significant increase in total protein (p<0.05), albumins (p<0.05), and alanine aminotransferase (p<0.05) compared with controls. Renal histology revealed severe hyaline degeneration of the epithelial cells of caudal kidney tubules in fish at all exposure levels compared to controls. Chronic exposure of common carp to simazine caused significant shifts in hematological, biochemical, and biometric profiles, and histopathological changes. The results of this study indicate that chronic exposure of simazine has altered multiple physiological indices in fish hematology and biochemistry, which potentially may be a biomarker of simazine toxicity; however, before these parameters are used as special biomarkers for monitoring residual simazine in aquatic environment, more detailed experiments in laboratory need to be performed in the future.
- MeSH
- alanintransaminasa metabolismus MeSH
- alkalická fosfatasa metabolismus MeSH
- biologické markery metabolismus MeSH
- chování zvířat účinky léků MeSH
- herbicidy analýza toxicita MeSH
- játra účinky léků metabolismus patologie MeSH
- kapři metabolismus fyziologie MeSH
- řeky chemie MeSH
- simazin analýza toxicita MeSH
- vystavení vlivu životního prostředí analýza MeSH
- vztah mezi dávkou a účinkem léčiva MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
OBJECTIVES: 2,3,7,8-tetrachloro-dibenzo-p-dioxin (TCDD) is a highly toxic persistent environmental contaminant, classified as a human carcinogen affecting any target organ. The mechanism of carcinogenesis by TCDD is unclear as TCDD shows a lack of direct genotoxicity. Experimental studies also support the role of oxidative stress in TCDD neurotoxicity and vascular dysfunction. The aim was to investigate markers of oxidative/nitrosative stress and inflammation using non-invasive methods in subjects who got ill due to severe occupational exposure to TCDD in the years 1965-1968. METHODS: In 11 TCDD-exposed patients, and 16 controls, the analysis of following oxidative products of lipids, proteins and nucleic acids in plasma, urine and exhaled breath condensate (EBC) was performed: 8-iso-prostaglandin F2α (8-isoprostane), 4-hydroxy-trans-2-nonenale (HNE), malondialdehyde (MDA), o-tyrosine (o-Tyr), 8-hydroxyguanosine (8-OHG), 8-hydroxy-2´-deoxy-guanosine (8-OHdG), 5-hydroxymethyluracil (5-OHMeU). In addition, nitric-oxide-tyrosine (NO-Tyr) and leukotriene (LT) B4, C4, D4, and E4 were detected by liquid chromatography-mass spectrometry/mass spectrometry (LC-ESI-MS/MS). TCDD was measured by HRGC/HRMS, body lipid content by densitometry. Single-photon emission spectrometry (SPECT) of the brain was performed and compared with the findings of the patients in 2008. RESULTS: Mean TCDD plasma level in 2010 was 175 ± 162 pg/g lipids (population level about 2 pg/g), total TCDD content in the body 5.16 ± 4.62 mg. Reduction of cerebral blood flow in SPECT progressed in 8 patients, finding was stable in 2 subjects, and improvement occurred in 1 patient. In the EBC, 10 from 12 markers (all except LT D4 and LT E4), were significantly increased in the patients (p<0.05). In the urine, 7 markers were significantly higher than in the controls (p<0.05): 8-isoprostane, MDA, HNE, LT C4, LT E4, o-Tyr and NO-Tyr. In plasma, only NO-Tyr and 8-OHG were elevated (p<0.05). CONCLUSION: NO-Tyr was increased in all matrices in dioxin-exposed patients. EBC is not limited to lung disorders as the markers of oxidative stress and inflammation were elevated in EBC of patients with normal lung functions. TCDD-induced oxidative stress and inflammation markers can be detected non-invasively in the EBC and urine in the follow-up of the highly-exposed patients. Their prognostic value, however, needs to be elucidated.
- MeSH
- analýza moči metody MeSH
- biochemická analýza krve metody MeSH
- biologické markery analýza krev moč MeSH
- chemický průmysl MeSH
- herbicidy analýza krev MeSH
- lidé středního věku MeSH
- lidé MeSH
- osmolární koncentrace MeSH
- oxidační stres fyziologie MeSH
- polychlorované dibenzodioxiny analogy a deriváty analýza krev MeSH
- pracovní expozice analýza MeSH
- reaktivní formy dusíku analýza krev metabolismus moč MeSH
- reaktivní formy kyslíku analýza krev metabolismus moč MeSH
- senioři MeSH
- studie případů a kontrol MeSH
- upregulace MeSH
- Check Tag
- lidé středního věku MeSH
- lidé MeSH
- mužské pohlaví MeSH
- senioři MeSH
- ženské pohlaví MeSH
- Publikační typ
- časopisecké články MeSH
- hodnotící studie MeSH
- práce podpořená grantem MeSH
Polar organic compound integrative samplers (POCIS) in combination with instrumental techniques such as LC-MS-MS were previously used to monitor environmental pollutants but the performance of alternative immunochemical methods such as ELISA (enzyme-linked immunosorbent assay) has been explored less. In the present study, POCIS technology was applied to surface water sampling in the Czech Republic, and ELISA was used as a detection technique for the herbicide atrazine. In the first study, 28 samples from streams around small municipal waste water treatment plants (WWTPs) were collected using two different devices (POCISpest and POCISpharm) over the course of 21 days. Elevated atrazine concentrations (up to 25 ng per POCIS) were found in samples down-stream of WWTPs. This observation was also confirmed in another two year study (4 sampling periods) investigating 7 river sites around a major city of Brno as well as the inlet and outlet of the city's WWTP. High atrazine levels were systematically determined at the outlet from the WWTPs (120-605 ng per POCIS). A decreasing trend in the atrazine concentrations in rivers around the city of Brno has been observed, with the highest levels observed within the first sampling period in spring 2007 (100-600 ng per POCIS, with an extreme value of 2760 ng per POCIS). Results of the atrazine ELISA were closely correlated with LC-MS/MS, which confirmed good applicability of ELISA as a cost-effective screening tool.
- MeSH
- atrazin analýza MeSH
- chemické látky znečišťující vodu analýza MeSH
- chemické znečištění vody statistika a číselné údaje MeSH
- ELISA MeSH
- herbicidy analýza MeSH
- monitorování životního prostředí přístrojové vybavení metody MeSH
- sladká voda chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
In this research, the adsorption of two herbicides, alachlor (ALA) and terbuthylazine (TBA), on granular activated carbon (GAC) in the presence of well-characterized peptide fraction of cellular organic matter (COM) produced by cyanobacterium Microcystis aeruginosa was studied. Two commercially available GACs were characterized using nitrogen gas adsorption and surface charge titrations. The COM peptides of molecular weight (MW) < 10 kDa were isolated and characterized using MW fractionation technique and high-performance size exclusion chromatography (HPSEC). The effect of surface charge on the adsorption of COM peptides was studied by means of equilibrium adsorption experiments at pH 5 and pH 8.5. Electrostatic interactions and hydrogen bonding proved to be important mechanisms of COM peptides adsorption. The adsorption of ALA and TBA on granular activated carbon preloaded with COM peptides was influenced by solution pH. The reduction in adsorption was significantly greater at pH 5 compared to pH 8.5, which corresponded to the increased adsorption of COM peptides at pH 5. The majority of the competition between COM peptides and both herbicides was attributed to low molecular weight COM peptides with MW of 700, 900, 1300 and 1700 Da.
- MeSH
- acetamidy analýza chemie MeSH
- adsorpce MeSH
- chemické látky znečišťující vodu analýza chemie MeSH
- dřevěné a živočišné uhlí chemie MeSH
- herbicidy analýza chemie MeSH
- kinetika MeSH
- Microcystis chemie MeSH
- odpad tekutý - odstraňování metody MeSH
- peptidy chemie MeSH
- povrchové vlastnosti MeSH
- triaziny analýza chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Optimum conditions are described for the determination of micromolar and submicromolar concentrations of herbicides Acifluorphen, Oxyfluorphen and Nitrophen by differential pulse voltammetry (DPV) on non-toxic solid silver amalgam electrode with modified meniscus in Britton-Robinson buffers at different pH. The detection limits are in the range 10-6-10-7 mol L-1. DPV determination of Acifluorphen in BR buffer at pH 2 using a carbon paste electrode was developed with a detection limit of 5·10-7 mol L-1.
