Application of different chromatographic techniques and chemometric analysis in authenticity testing of plant protection products containing azoxystrobin as an active substance

Azoxystrobin (methyl(2E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy] phenyl}-3-methoxyacrylate) is an active ingredient used to protect crops against fungal diseases. The experience of the Polish control laboratory indicates relatively frequent cases of counterfeit plant protection products (PPPs) containing this active substance. The present study aimed to use chemometric methods to model chemical fingerprints obtained by different chromatographic techniques to verify the original formulation of PPPs containing the active substance azoxystrobin. The pesticides used in the study came from different sources (including stores and warehouses), were manufactured at a different time and came from different production batches. The results obtained with the HPLC-DAD and HS-GC-MS techniques were then modeled using principal component analysis (PCA) and soft independent modeling by class analogy (SIMCA) classifier. The proposed approach has been confirmed as useful for verifying the authenticity of PPPs and can be used in the routine control testing of SC pesticides containing azoxystrobin.     

Characterization of PM10 and PM2.5 and associated heavy metals at the crossroads and urban background site in Zabrze, Upper Silesia, Poland, during the smog episodes

The concentrations of seven heavy metals (Cd, Cr, Cu, Fe, Mn, Ni, and Pb) associated with PM10 and PM2.5 at the crossroads and the background sites have been studied in Zabrze, Poland, during smog episodes. Although the background level was unusually elevated due to both high particulate emission from the industrial and municipal sources and smog favorable meteorological conditions, significant increase of the concentration of PM2.5 and PM10 as well as associated heavy metals in the roadside air compared to the urban background has been documented. The average daily difference between the roadside and corresponding urban background aerosol concentration was equal to 39.5 μg m^???3 for PM10 and 41.2 μg m^???3 for PM2.5. The highest levels of the studied metals in Zabrze appeared for iron carried by PM10 particles: 1,706 (background) and 28,557 ng m^???3 (crossroads). The lowest concentration level (in PM10) has been found for cadmium: 7 and 77 ng m^???3 in the background and crossroads site, respectively. Also the concentrations of heavy metals carried by the fine particles (PM2.5) were very high in Zabrze during the smog episodes. Concentrations of all studied metals associated with PM10 increased at the roadside compared to the background about ten times (one order) while metals contained in PM2.5 showed two to three times elevated concentrations (except Fe—five times and Cr—no increase).     

The impact of land use and season on the riverine transport of mercury into the marine coastal zone

In Mediterranean seas and coastal zones, rivers can be the main source of mercury (Hg). Catchment management therefore affects the load of Hg reaching the sea with surface runoff. The major freshwater inflows to the Baltic Sea consist of large rivers. However, their systems are complex and identification of factors affecting the outflow of Hg from its catchments is difficult. For this reason, a study into the impact of watershed land use and season on mercury biogeochemistry and transport in rivers was performed along two small rivers which may be considered typical of the southern Baltic region. Neither of these rivers are currently impacted by industrial effluents, thus allowing assessment of the influence of catchment terrain and season on Hg geochemistry. The study was performed between June 2008 and May 2009 at 13 sampling points situated at different terrain types within the catchments (forest, wetland, agriculture and urban). Hg analyses were conducted by CVAFS. Arable land erosion was found to be an important source of Hg to the aquatic system, similar to urban areas. Furthermore, inflows of untreated storm water discharge resulted in a fivefold increase of Hg concentration in the rivers. The highest Hg concentration in the urban runoff was observed with the greatest amount of precipitation during summer. Moderate rainfalls enhance the inflow of bioavailable dissolved mercury into water bodies. Despite the lack of industrial effluents entering the rivers directly, the sub-catchments with anthropogenic land use were important sources of Hg in the rivers. This was caused by elution of metal, deposited in soils over the past decades, into the rivers. The obtained results are especially important in the light of recent environmental conscience regulations, enforcing the decrease of pollution by Baltic countries.     

Aerosol residence times and changes in radioiodine-131I and radiocaesium-137 Cs activity over Central Poland after the Fukushima-Daiichi Nuclear reactor accident

The first detectable activities of radioiodine (131)I, and radiocaesium (134)Cs and (137)Cs in the air over Central Poland were measured in dust samples collected by the ASS-500 station in the period of 21(st) to 24(th) of March, 2011. However, the highest activity of both fission products, (131)I and (137)Cs: 8.3 mBq m(-3) and 0.75 mBq m(-3), respectively, were obtained in the samples collected on 30(th) March, i.e.～18 days after the beginning of the fission products' discharge from the damaged units of the Fukushima Daiichi Nuclear Power Plant. The simultaneously determined corrected aerosol residence time for the same samples by (210)Pb/(210)Bi and (210)Pb/(210)Po methods was equal to 10 days. Additionally, on the basis of the activity ratio of two other natural cosmogenic radionuclides, (7)Be and (22)Na in these aerosol samples, it was possible to estimate the aerosol residence time at ～150 days for the solid particles coming from the stratospheric fallout. These data, as well as the differences in the activity size distribution of (7)Be and (131)I in the air particulate matter, show, in contrast to the Chernobyl discharge, a negligible input of stratospheric transport of Fukushima-released fission products.     

Remediation aspect of microbial changes of plant rhizosphere in mercury contaminated soil

Phytoremediation, an approach that uses plants to remediate contaminated soil through degradation, stabilization or accumulation, may provide an efficient solution to some mercury contamination problems. This paper presents growth chamber experiments that tested the ability of plant species to stabilize mercury in soil. Several indigenous herbaceous species and Salix viminalis were grown in soil collected from a mercury-contaminated site in southern Poland. The uptake and distribution of mercury by these plants were investigated, and the growth and vitality of the plants through a part of one vegetative cycle were assessed. The highest concentrations of mercury were found at the roots, but translocation to the aerial part also occurred. Most of the plant species tested displayed good growth on mercury contaminated soil and sustained a rich microbial population in the rhizosphere. The microbial populations of root-free soil and rhizosphere soil from all species were also examined. An inverse correlation between the number of sulfur amino acid decomposing bacteria and root mercury content was observed. These results indicate the potential for using some species of plants to treat mercury contaminated soil through stabilization rather than extraction. The present investigation proposes a practical cost-effective temporary solution for phytostabilization of soil with moderate mercury contamination as well as the basis for plant selection.     

Vertical distribution of heavy metals in grain size fractions in sedimentary rocks: Mosina–Krajkowo water well field, Poland

The paper presents the results of heavy metals determination in samples of sedimentary rocks from the Mosina-Krajkowo water well field (Poland). The concentration of heavy metals was analysed by type of rock (sand, gravel, warp, silt, till, and clay). Variation of heavy metal concentrations with depth was studied taking into account the age series of the rocks (fluvial sediments of the modern Warta River valley, sediments of the Baltic Glaciation, tills of the Middle-Polish Glaciation, sediments of the Masovian Interglacial (Holstein), tills of the Poznań series) and granulometric fractions. The grain sizes considered included: >2.0, 2.0-1.0, 1.0-0.5, 0.5-0.25, 0.25-0.1, 0.1-0.063, and <0.063 mm. The concentrations of the heavy metals studied were found to change with the type of rock, age series, and granulometric fraction. The levels of the metals were determined by the technique of atomic absorption spectrometry with flame atomisation (F-AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES).     

Probability of misclassifying biological elements in surface waters

Measurement uncertainties are inherent to assessment of biological indices of water bodies. The effect of these uncertainties on the probability of misclassification of ecological status is the subject of this paper. Four Monte-Carlo (M-C) models were applied to simulate the occurrence of random errors in the measurements of metrics corresponding to four biological elements of surface waters: macrophytes, phytoplankton, phytobenthos, and benthic macroinvertebrates. Long series of error-prone measurement values of these metrics, generated by M-C models, were used to identify cases in which values of any of the four biological indices lay outside of the “true” water body class, i.e., outside the class assigned from the actual physical measurements. Fraction of such cases in the M-C generated series was used to estimate the probability of misclassification. The method is particularly useful for estimating the probability of misclassification of the ecological status of surface water bodies in the case of short sequences of measurements of biological indices. The results of the Monte-Carlo simulations show a relatively high sensitivity of this probability to measurement errors of the river macrophyte index (MIR) and high robustness to measurement errors of the benthic macroinvertebrate index (MMI). The proposed method of using Monte-Carlo models to estimate the probability of misclassification has significant potential for assessing the uncertainty of water body status reported to the EC by the EU member countries according to WFD. The method can be readily applied also in risk assessment of water management decisions before adopting the status dependent corrective actions.