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.     

Influence of solar UV radiation on the nitrogen metabolism in needles of Scots pine (Pinus sylvestris L.)

Needles of 20-year-old Scots pine (Pinus sylvestris L.) saplings were studied in an ultraviolet (UV) exclusion field experiment (from 2000 to 2002) in northern Finland (67 °N). The chambers held filters that excluded both UV-B and UV-A, excluded UV-B only, transmitted all UV (control), or lacked filters (ambient). UV-B/UV-A exclusion decreased nitrate reductase (NR) activity of 1-year-old needles of Scots pines compared to the controls. The proportion of free amino acids varied in the range 1.08-1.94% of total proteins, and was significantly higher in needles of saplings grown under UV-B/UV-A exclusion compared to the controls or UV-B exclusion. NR activity correlated with air temperature, indicating a “chamber effect”. The study showed that both UV irradiance and increasing temperature are significant modulators of nitrogen (N) metabolism in Scots pine needles.     

Applicability of MIEX®DOC process for organics removal from NOM laden water

The aim of this study was to evaluate applicability of ion exchange process for organics removal from Douro River surface water at the intake of Lever water treatment plant using magnetized ion exchange resin MIEX®. Qualitative analysis of the natural organic matter present in the surface water and prediction of its amenability to removal in conventional coagulation process were assessed. Results obtained in MIEX®DOC process kinetic batch experiments allowed determination of ion exchange efficiency in dissolved organic carbon (DOC), UV absorbing organics, and true color removal. The data were compared with the efficiencies of the conventional unit processes for organics removal at Lever WTP. MIEX®DOC process revealed to be more efficient in DOC removal than conventional treatment achieving the efficiencies in the range of 61–91 %, lowering disinfection by-products formation potential of the water. DOC removal efficiency at Lever WTP depends largely on the raw water quality and ranges from 28 % for water of moderated quality to 89 % of significantly deteriorated quality. In this work, MIEX®DOC process was also used as a reference method for the determination of contribution of anionic fraction to dissolved organic matter and selectivity of the unit processes at Lever WTP for its removal.     

An analysis of accidents caused by improper functioning of machine control systems.

The scope of this study covers events resulting from improper functioning of machine control systems. An accident model providing a basis for formulating a checklist for accident analysis has been developed. Data about 700 accidents were collected. An analysis has proved that in the group of accidents caused by improper functioning of machine control systems, serious accidents happened much more frequently as compared to the group of accidents with no relation to the control system. The reasons for the majority of incidents caused by improper performance of safety functions consist in the errors made by designers. In view of that, incorrect behaviour of a worker should be treated as a normal event instead of a deviation causing an accident.     

Synergy between visual and auditory signals and its influence on the follow-up regulation quality.

The study aimed at verifying a hypothesis that supporting a visual signal of regulation deviation with an auditory one could improve the quality of regulation; the operator would have better information on machine operation. A special simulator was applied to follow-up tracking with a manual lever which controlled vertical movements of a cursor on a monitor screen. Simultaneously with visual information on screen, the operator was provided with an auditory deviation signal of pre-determined characteristics. 33 young males underwent the test. It was found that supporting a visual signal with an auditory one resulted in an improvement in the regulation quality by 5-6%, which proved synergy between those signals. The results may be used in designing tele- and servo-mechanisms, especially for remote control machinery, e.g., inspection robots or micromanipulators controlled by operators in a follow-up system.     

Family and species as determinants modulating mineral composition of selected wild-growing mushroom species

It has been known since the 1970s that differences exist in the profile of element content in wild-growing mushroom species, although knowledge of the role of mushroom species/families as determinants in the accumulation of diverse element remains limited. The aim of this study was to determine the content of 63 mineral elements, divided into six separate groups in the fruit bodies of 17 wild-growing mushroom species. The mushrooms, growing in widely ranging types of soil composition, were collected in Poland in 2018. Lepista nuda and Paralepista gilva contained not only the highest content of essential major (531 and 14,800 mg kg⁻¹, respectively of Ca and P) and trace elements (425 and 66.3 mg kg⁻¹, respectively of Fe and B) but also a high content of trace elements with a detrimental health effect (1.39 and 7.29 mg kg⁻¹, respectively of Tl and Ba). A high content of several elements (Al, B, Ba, Bi, Ca, Er, Fe, Mg, Mo, P, Sc, Ti or V) in L. nuda, Lepista personata, P. gilva and/or Tricholoma equestre fruit bodies belonging to the Tricholomataceae family suggests that such species may be characterised by the most effective accumulation of selected major or trace elements. On the other hand, mushrooms belonging to the Agaricaceae family (Agaricus arvensis, Coprinus comatus and Macrolepiota procera) were characterised by significant differences in the content of all determined elements jointly, which suggests that a higher content of one or several elements is mushroom species-dependent.

Graphical abstract

     

Biological monitoring versus air monitoring strategies in assessing environmental-occupational exposure

Assessment of environmental and occupational exposure to chemicals can be performed with environmental monitoring (EM) and biological monitoring (BM). Biological monitoring was for a long time considered as a method complementary to environmental monitoring. At present this attitude is changing and in certain areas biological monitoring is applied as the method of choice for exposure and health-risk assessment. This paper examines advantages and disadvantages of those two approaches. In occupational settings environmental monitoring of exposure to VOCs seems to be superior to biological monitoring (possibility of simultaneous determination of components of mixtures, simple interpretation, possibility of evaluation of short-term exposure to local irritants). In the case of this group of compounds BM can be useful in selected cases such as evaluation of dermal absorption or efficiency of protective measures. In the case of metals both forms of monitoring can be used depending on the available methods for interpretation of results. BM of exposure may be considered as superior for evaluating the effects of exposure to lead, cadmium and mercury. However, quantitative evaluation of cancer risk after exposure to arsenic or chromium is possible only on the basis of determination in the air and the use of unit risk values. Both environmental and biological monitoring are useful for evaluation of occupational and environmental exposure to polycyclic aromatic hydrocarbons (PAHs). In certain areas such as evaluation of exposure to external tobacco smoking, cytostatic drugs, and pesticides, biological monitoring is the method of choice used for individual exposure assessment or tracing the trends of environmental exposure.     

Modelling deposition and air concentration of reduced nitrogen in Poland and sensitivity to variability in annual meteorology

The relative contribution of reduced nitrogen to acid and eutrophic deposition in Europe has increased recently as a result of European policies which have been successful in reducing SO(2) and NO(x) emissions but have had smaller impacts on ammonia (NH(3)) emissions. In this paper the Fine Resolution Atmospheric Multi-pollutant Exchange (FRAME) model was used to calculate the spatial patterns of annual average ammonia and ammonium (NH(4)(+)) air concentrations and reduced nitrogen (NH(x)) dry and wet deposition with a 5 km × 5 km grid for years 2002-2005. The modelled air concentrations of NH(3) and dry deposition of NH(x) show similar spatial patterns for all years considered. The largest year to year changes were found for wet deposition, which vary considerably with precipitation amount. The FRAME modelled air concentrations and wet deposition are in reasonable agreement with available measurements (Pearson's correlation coefficients above 0.6 for years 2002-2005), and with spatial patterns of concentrations and deposition of NH(x) reported with the EMEP results, but show larger spatial gradients. The error statistics show that the FRAME model results are in better agreement with measurements if compared with EMEP estimates. The differences in deposition budgets calculated with FRAME and EMEP do not exceed 17% for wet and 6% for dry deposition, with FRAME estimates higher than for EMEP wet deposition for modelled period and lower or equal for dry deposition. The FRAME estimates of wet deposition budget are lower than the measurement-based values reported by the Chief Inspectorate of Environmental Protection of Poland, with the differences by approximately 3%. Up to 93% of dry and 53% of wet deposition of NH(x) in Poland originates from national sources. Over the western part of Poland and mountainous areas in the south, transboundary transport can contribute over 80% of total (dry + wet) NH(x) deposition. The spatial pattern of the relative contribution of national sources to total deposition of NH(x) may change significantly due to the general circulation of air.