Pesticide burial grounds in Poland: a review

Obsolete pesticides were stored in Poland from the middle sixties until the late eighties of the 20th century mostly in underground disposal sites, called "pesticide burial grounds" or "pesticide tombs". The total amount of pesticide waste and packaging materials disposed of in these landfills exceeded 20000 Mg. Typically, the content of a pesticide tomb was dominated by organochlorine pesticides (comprising 10-100% of the total waste volume) with DDT as the prevailing compound. Other pesticide types, such as phosphoroorganic, carbamate insecticides, dinitrophenols, phenoxyacids, and inorganic compounds were stored in smaller quantities, usually not exceeding 10-20% of the total waste volume. With the growing awareness of the threats that these landfills posed to the environment, the first inventory for the whole country was made in 1993 and remediation was initiated in 1999. The total amount of waste, which had to be removed from the known pesticide tombs (hazardous substances, contaminated soils, construction materials etc.) was about 100000 Mg. According to the National Waste Management Plan, the reclamation of pesticide tombs was assumed to have been finished by the end of 2010, however, this goal has not been achieved. The aim of this review is to present a historical perspective of pesticide burial grounds in Poland with an emphasis on their creation, function, inventory, and remediation. Based on unpublished reports, and other published materials of limited availability written in Polish, this review may serve as a source of information for representatives of other countries, where remediation of pesticide burial grounds is still in progress. The experience gained over a ten-year period, when restoration of pesticide tombs was implemented in Poland, reveals that there are many obstacles to this action arising not only from technical, but also from economic and social issues.     

Atmospheric nitrogen fluxes at the Belgian coast: 2004–2006

Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel).The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m^?2 d^?1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m^?2 d^?1, respectively.Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.9–1.4 mg N m^?2 d^?1. Generally, the contribution of aerosol NH₄⁺ was more significant in the medium and fine particulate fractions than that of aerosol NO₃^?, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (～15%) to the total N-budget.Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m^?2 d^?1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH₄⁺ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 2–2.5-times higher than in other campaigns.     

Monitoring of the total content of polycyclic aromatic hydrocarbons (PAHs) in arable soils in Poland

The paper provides comprehensive information on the level of contamination of arable soils in Poland with polycyclic aromatic hydrocarbons (PAHs). Extensive monitoring studies were carried out to determine the content of the 16 priority PAHs in 216 soil samples collected in 2005 throughout arable lands (0-20 cm layer) in Poland. Locations of sampling points reflected the differences in regional industrialisation and urbanisation as well as in the characteristics of soils. The content of Sigma16PAHs ranged from 80 to 7264 microg kg(-1) with a median of 395 microg kg(-1) and with a dominance of 4-6 rings hydrocarbons (74% of total PAHs). Soil properties affected the PAHs content to a limited extend. The organic matter content was the only parameter correlated significantly (although weakly) with the concentrations of Sigma16PAHs; the strength of this relationship was more pronounced in soils with elevated OM content. The various molecular markers pointed to a prevailing pyrogenic origin of the PAHs in Polish arable soils, with minor contribution from liquid fuels combustion and traffic emissions. Two different Polish systems for classification of agricultural soils (providing for the content of Sigma9PAHs and Sigma13PAHs) indicate that the percentage of contaminated arable soils in Poland does not exceed 10%. Multivariate methods enabled an evaluation of spatial trends in Sigma16PAHs concentrations, an identification of regions with very low PAHs content (East part of the country), and a recognition of small industrial/urbanised areas of higher risk.     

The effects of cadmium or zinc multigenerational exposure on metal tolerance of Spodoptera exigua (Lepidoptera: Noctuidae)

The effects of ten generational zinc or cadmium pre-exposure on metal tolerance among beet armyworm Spodoptera exigua individuals were compared. These effects were assessed in animals from the 11th generation, reared on a diet either uncontaminated or contaminated with metal (cadmium or zinc). The survival rate of larvae and the degree of metal accumulation (in larvae, pupae and moths; among larval organs: gut and fat body) were analysed. Catalase, superoxide dismutase and glutathione transferase activity in larval organs of individuals subjected to different metal treatments were also measured. Animals transferred from control rearing to metals (cadmium or zinc) in the 11th generation, as well as those from multigenerational zinc treatment, but not from multigenerational cadmium treatment, had a significantly lower survival rate than control animals. Insects from the groups with the high metal treatment had high bioaccumulation factors (above 3.7 and 2.3 following cadmium and zinc, respectively). Cadmium (but not zinc) pre-exposure had a significant effect on metal accumulation in larvae. Multigenerational metal pre-exposure seemed to have mainly a negative effect on glutathione transferase activity in the gut of larvae from the 11th generation, in the case of the individuals exposed to metal other than that used in pre-exposure treatment or kept in control conditions. However, in the case of zinc pre-exposure, such effect was only apparent when zinc was replaced by cadmium. The long-term effect of cadmium on catalase activity in larvae was found.     

Multi-elemental analysis of Lentinula edodes mushrooms available in trade

ABSTRACT

The present study investigated the content of 62 elements in the fruiting bodies of Lentinula edodes (Shiitake mushroom) cultivated commercially in Poland on various substrates from 2007–2015. The general mean content (mg kg^?1 dry weight (DW)) of the studied elements ranked in the following order: K (26,335) > P (11,015) > Mg (2,284) > Ca (607) > Na (131) > Zn (112) > Fe (69) > Mn (33) > B (32) > Rb (17) > Cu (14.5) > Al (11.2) > Te (2.9) > As (1.80) > Cd (1.76) > Ag (1.73) > Nd (1.70) > Sr (1.46) > Se (1.41) > U (1.11) > Pt (0.90) > Ce (0.80) > Ba (0.61) > Co (0.59) > Tl (0.58) > Er (0.50) > Pb (0.42) > Li (0.40) > Pr (0.39) > Ir (0.37) > In (0.35) > Mo (0.31) > Cr (0.29) > Ni (0.28) > Sb (0.26) > Re (0.24) > Ti (0.19) > Bi (0.18) > Th (0.12) > La (0.10) = Pd (0.10) > Os (0.09) = Zr (0.09) > Rh (0.08) > Ho (0.07) > Ru (0.06) > Sm (0.04) = Eu (0.04) = Tm (0.04) > Gd (0.03) > Sc (0.02) = Y (0.02) > Lu (0.01) = Yb (0.01) = V (0.01). The contents of Au, Be, Dy, Ga, Ge, Hf, and Tb were below the limits of detection (0.02, 0.02, 0.01, 0.01, 0.01, 0.01, 0.02 mg kg^?1 respectively). The concentrations of Al, As, B, Ba, Ca, Cd, Cr, Er, Fe, In, Lu, Mn, Nd, Sr, Ti, Tm, and Zr were comparable over the period the mushrooms were cultivated. The study revealed that Lentinula edodes contained As and Cd at levels potentially adverse to human health. This highlights the need to monitor these elements in food products obtained from this mushroom species and ensure that only low levels of these elements are present in cultivation substrates.     

Comparison of two sample preparation methods for analysis of organochlorine pesticides residues in fish muscle

The aim of this study was to compare recoveries of organochlorine pesticides (heptachlor, α-HCH, β-HCH, γ-HCH, op'-DDD, pp'-DDD, pp'-DDE, op'-DDT, pp'-DDT) from fish muscle dried by two alternative methods: (i) grinding with anhydrous sodium sulphate and (ii) freeze drying. Pesticide residues content was determined by gas chromatography-mass spectrometry (GS-MS) method. For four pesticides (γ-HCH, α-HCH, heptachlor and pp;-DDD) in four of five fish species, higher recoveries were obtained from the freeze-dried samples. For five remaining pesticides, correlations between fish species and drying method were not found. The results of this study do not clearly indicate which drying method caused lower losses of analytes. Recoveries from the freeze-dried samples ranged from 69.9 to 117.6 %, while recoveries from the samples ground with sodium sulphate varied from 64.4 to 126.7 %. Either of the methods gave satisfactory recoveries and they both can be used interchangeably.     

Distribution patterns of PAHs and trace elements in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from different forest communities: a case study, south-central Poland

Twenty samples of the moss species Hylocomium splendens and Pleurozium schreberi were collected at 10 sites of the Holy Cross Mountains (south-central Poland) and analyzed for 16 polycyclic aromatic hydrocarbons and 33 elements. The ring sequence of PAHs in the moss samples is: 4 (92-1040 ng x g(-1))>3 and 5 (21-272 ng x g(-1))>6 (<5-131 ng x g(-1)). H. splendens accumulates PAHs more effectively than P. schreberi, and therefore the former may be regarded as a better bioindicator of PAHs. No correlation was found between concentrations of PAHs and elements. However, both H. splendens and P. schreberi shows different bioaccumulative capabilities depending on the plant communities. The mosses growing in the dry pine forest Cladonio-Pinetum reveal higher levels of Fe, Na, Sr, Ti, Cr, Mo, Ni, V and higher mean concentrations of summation operator16 PAHs, whereas those from the continental coniferous forest Querco roboris-Pinetum are highlighted by elevated levels of B, Ca, K, Mg, Mn, P, Rb and Sb and lower mean concentrations of summation operator16 PAHs. These differences seem to be brought about by a higher biodiversity of the second forest type and its higher productivity that favors more effective cycling of elements.     

Impact of agriculture and land use on nitrate contamination in groundwater and running waters in central-west Poland

Protected areas due to their long-term protection are expected to be characterized by good water quality. However, in catchments where arable fields dominate, the impact of agriculture on water pollution is still problematic. In Poland, recently, the fertilization level has decreased, mostly for economic reasons. However, this applies primarily to phosphorus and potassium. In order to evaluate the impact of agriculture on water quality in a protected area with a high proportion of arable fields in the aspect of level and type of fertilization, complex monitoring has been applied. The present study was carried out in Wielkopolska National Park and its buffer zone, which are protected under Natura 2000 as Special Areas of Conservation and Special Protection Areas. The aim of the study were (1) to assess the impact of agriculture, with special attention on fertilization, on groundwater, and running water quality and (2) to designate priority areas for implementing nitrogen reduction measures in special attention on protected areas. In our study, high nitrogen concentrations in groundwater and surface waters were detected in the agricultural catchments. The results demonstrate that in the watersheds dominated by arable fields, high nitrogen concentrations in groundwater were measured in comparison to forestry catchments, where high ammonium concentrations were observed. The highest nitrogen concentrations were noted in spring after winter freezing, with a small cover of vegetation, and in the areas with a high level of nitrogen application. In the studied areas, both in the park and its buffer zone, unfavorable N:P and N:K ratios in supplied nutrients were detected. Severe shortage of phosphorus and potassium in applied fertilizers is one of the major factors causing leaching of nitrogen due to limited possibilities of its consumption by plants.     

Significance of the long-term biomonitoring studies for understanding the impact of pollutants on the environment based on a synthesis of 25-year biomonitoring in the Holy Cross Mountains,Poland

This review presents compiled results of complex biomonitoring studies that have been conducted in the Holy Cross Mountains, south-central part of Poland, since the 1990s. The significance of these studies results from several aspects: (i) a number and a variety of plant organisms used, e.g., mosses, lichens, coniferous and deciduous trees, and their tissues (wood, bark, needles, leaves, the aboveground parts of several vascular plants); (ii) applications of a broad scope of instrumental methods aiming at determining major and trace elements (including rare earth elements), organic compounds (PAHs, PCBs, phenols), and stable sulfur isotopes (δ³⁴S); and (iii) different methodological and environmental issues addressed. The comparison and interpretation of results derived from seventeen sampling campaigns carried out between 1994 and 2017 are a valuable source of information on the following: (i) bioaccumulative properties of organisms used in air quality monitoring, (ii) identification and variations of local and regional pollution sources and geochemical landscape patterns and processes over years, and (iii) establishing environmental factors that variously affected chemical composition of plants growing under physiological stress, including roadside vegetation and plants from acid mine drainage areas.