Official control of plant protection products in Poland: detection of illegal products

Market presence of illegal and counterfeit pesticides is now a global problem. According to data published in 2012 by the European Crop Protection Association (ECPA), illegal products represent over 10% of the global market of plant protection products. Financial benefits are the main reason for the prevalence of this practice. Counterfeit and illegal pesticides may contain substances that may pose a threat to the environment, crops, animals, and humans, inconsistent with the label and registration dossier. In Poland, action against illegal and counterfeit plant protection products is undertaken by the Main Inspectorate of Plant Health and Seed Inspection (PIORiN), the police, the prosecution, and the pesticide producers. Results of chemical analyses carried out by the Institute of Plant Protection - National Research Institute So?nicowice Branch, Pesticide Quality Testing Laboratory (PQTL IPP-NRI Sosnicowice Branch) indicate that a majority of illegal pesticides in Poland are detected in the group of herbicides. Products from parallel trade tend to have the most irregularities. This article describes the official quality control system of plant protection products in Poland and presents the analytical methods for testing pesticides suspected of adulteration and recent test results.     

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.     

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.     

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.     

Optimized yeast-based in vitro bioassay for determination of estrogenic and androgenic activity of hydroxylated / methoxylated metabolites of BDEs / CBs and related lipophilic organic pollutants

ABSTRACT

Persistent organic pollutants (POPs) are known to show endocrine disrupting (ED) activity, including interactions with hormone receptors. The aim of this work was to develop a bioassay applicable for evaluation of ED potency of highly lipophilic metabolites of POPs. To that end, a yeast-based bio-assay protocol was used. Estrogenic / androgenic activity of some native brominated biphenyl ethers (BDEs) / chlorinated biphenyls (CBs), and their hydroxylated / methoxylated metabolites was assessed. Since data (including potency compared to reference native hormones) obtained using different protocols vary, the possibility that yeast transforms POPs into some more potent compounds was first checked; it seems that no such transformation is important from the test applicability standpoint. The developed method was sensitive with EC50 values 6.5*10^?11 M and 4.5*10^?9 M calculated for E2 and DHT, respectively. Both CBs and BDEs show weak estrogenic activity negatively correlated with the degree of their halogenation, but their metabolites are significantly more potent xenohormones. 4-OH-2,2′,4′,6′-TeCB was the most potent estrogen receptor (ER) agonist among all tested compounds; its activity was only 1,000 times lower than that of native E2.     

Relevant parameters for assessing the environmental impact of some pyridinium, ammonium and pyrrolidinium based ionic liquids

Several physico-chemical properties relevant to determine the environmental impact of ionic liquids - aqueous solubility, octanol/water partition coefficient, chromatographically derived lipophilicity and infinite dilution diffusion coefficients in water - were measured in ionic liquids based on pyridinium, ammonium and pyrrolidinium cations with bis(trifluoromethylsulfonyl)imide anions. The influence of the presence of hydroxyl or ester groups in the physico-chemical properties of these liquids was checked. It appeared that the presence of functional oxygenated moieties reduces the lipophilicity of ionic liquids and so decreases the risk of bioaccumulation in environment.     

Mean annual (222)Rn concentration in homes located in different geological regions of Poland: first approach to whole country area

The paper presents the results of year-long measurements of radon (²²²Rn) concentration inside 129 buildings in Poland in relation to the geological conditions of their foundation. The authors took into account the division of the country into tectonic units, as well as the lithology of the rocks forming the bedrock of these buildings. As expected, the highest value of mean annual ²²²Rn concentration (845 Bq/m³) was recorded in a building situated in the area of the Sudetes, while the highest geometric mean (characteristic of the expected log-normal data distribution) was calculated based on measurements from buildings located within the East-European craton, in the area of Mazury-Podlasie monocline, where it reached 231 Bq/m³. Such results reflect geological conditions - the occurrence of crystalline rocks (especially U- and Ra-enriched granites and orthogneisses) on the surface in the Sudetes, and of young post-glacial sediments containing fragments of Scandinavian crystalline rocks, also enriched with U and Ra, in the area of Mazury-Podlasie monocline. However, the least expected result of the investigations was finding out that, contrary to the hitherto widespread belief, none of the major tectonic units of Poland can be excluded from the list of those containing buildings with mean annual ²²²Rn concentration exceeding 200 Bq/m³. The mean annual concentration of radon for all the buildings were much higher than the mean concentration value (49.1 Bq/m³) of indoor radon in Poland quoted so far. These results cast a completely new light on the necessity to perform measurements of radon concentration in residential buildings in Poland, no more with reference to small areas with outcrops of crystalline rocks (especially the Sudetes, being the Polish fragment of the European Variscan belt), but for all the major tectonic units within Poland.     

Carbon exchange between ecosystems and atmosphere in the Czech Republic is affected by climate factors

By comparing five ecosystem types in the Czech Republic over several years, we recorded the highest carbon sequestration potential in an evergreen Norway spruce forest (100%) and an agroecosystem (65%), followed by European beech forest (25%) and a wetland ecosystem (20%). Because of a massive ecosystem respiration, the final carbon gain of the grassland was negative. Climate was shown to be an important factor of carbon uptake by ecosystems: by varying the growing season length (a 22-d longer season in 2005 than in 2007 increased carbon sink by 13%) or by the effect of short- term synoptic situations (e.g. summer hot and dry days reduced net carbon storage by 58% relative to hot and wet days). Carbon uptake is strongly affected by the ontogeny and a production strategy which is demonstrated by the comparison of seasonal course of carbon uptake between coniferous (Norway spruce) and deciduous (European beech) stands.     

Identification of volatiles from Pinus silvestris attractive for Monochamus galloprovincialis using a SPME-GC/MS platform

Introduction

A myriad of volatile organic compounds (VOCs) released by terrestrial vegetation plays an important role in environmental sciences. A thorough chemical identification of these species at the molecular level is essential in various fields, ranging from atmospheric chemistry to ecology of forest ecosystems. In particular, the recognition of VOCs profiles in a context of plant?Cinsect communication is a key issue for the development of forest protection tools.

Purpose

This work was aimed at the development of a simple, robust and reliable method for the identification of volatiles emitted from plant materials, which can attract or deter pest insects. Specifically, volatiles emitted from the bark of Pinus sylvestris were studied, which might attract the black pine sawyer beetle Monochamus galloprovincialis??a serious pest of the tree and a vector of a parasitic nematode Bursaphelenchus xylophius.

Method

The volatiles from bark samples were collected using a solid-phase micro-extraction technique, and subsequently analysed by gas-chromatography/mass-spectrometry (GC/MS). The characterisation of the volatile fraction was based on the comparison with data in mass spectral libraries, and in most cases, with the available authentic standards. The identified compounds were screened against the available entomological data to select insect attractors.

Results

The identified components included terpenes (??-pinene, ?-3-carene, and para-cymenene), oxygenated terpenes (??-terpineol and verbenone), sesquiterpenes (??-longipinene, longifolene, E-??-farnesene, ??-cadinene and pentadecane), and diterpenes (manoyl oxide and (+)-pimaral). Of these, longifolene and (+)-pimaral are of particular interest as plausible attractors for the M. galloprovincialis beetle that might find application in the construction of insect bait traps.