Long-term patterns in soil acidification due to pollution in forests of the Eastern Sudetes Mountains

Soil acidification was assessed in the Eastern Sudetes Mountains (Czech Republic) between 1941 and 2003, i.e. before and after the period of major industrial pollution (1950s-1990s). The twenty sites included in our study were distributed along a gradient of altitude ranging 1000 m. Values of pH have decreased in 80-90% of the pairs of samples after the six decades, on average by 0.7 for pH-H₂O and 0.6 for pH-KCl. Organic matter increased in the topsoil, probably reflecting a change in decomposition conditions. The most important finding is that the acidification varies along the joint gradient of altitude/tree layer composition, and displays a changing pattern in three soil horizons (A, B and C). Contrary to expectations, most acidified were soils in beech forests at lower elevations.     

Enantioselective effects of alpha-hexachlorocyclohexane (HCH) isomers on androgen receptor activity in vitro

Alpha-hexachlorocyclohexane (alpha-HCH), a part of the HCH pesticide mixture, is one of the most widespread persistent organic pollutants. Interestingly, only limited number of studies addressed the toxicity of alpha-HCH and the effects of its individual optical isomers have not been investigated in detail. In the present study we separated two alpha-HCH enantiomers by preparative HPLC and studied their activities towards androgen receptor (AR) using the MDA-kb2 cell line stably transfected with the luciferase reporter gene under the control of AR. There was no direct effect of alpha-HCH on AR but both isomers significantly suppressed the activity of AR in co-exposure with the natural ligand dihydrotestosterone in a concentration-dependent manner. One of the enantiomers appeared to be more active at lower concentration, which was also supported by the molecular modeling calculations with AR that showed a slight difference in estimated free energy of binding and inhibition constant between two enantiomers. Although studies with other pesticides demonstrated strong enantioselective differences in toxicity, the present research shows rather minor differences in modulations of AR by both alpha-HCH enantiomers. For the first time, enantioselective effects of alpha-HCH were demonstrated and the results suggest interaction with multiple regulatory events controlling the AR activity. Full elucidation of the toxicity mechanism will require further research.     

Phytotoxicity of low-weight carboxylic acids

Presence of low-weight carboxylic acids (LWCAs) can be the reason for phytotoxicity of green manures, treated bio-waste or digestates from biogas production applied to soils. As the phytotoxic concentrations of LWCA are poorly known, this work presents data on six acids (C(1)C(6): formic, acetic, propionic, butyric, valeric, and caproic). Phytotoxicity was measured in acute (72 or 120 h) and subchronic (21 d) assays for seed germination, seedling elongation, and plant growth for garden cress Lepidium sativum and ryegrass Lolium multiflorum. The dose-response relationship was modeled using Weibull model. Results showed a trend that toxicity of LWCA increases with the length of the carbon chain, formic acid (C(1)) being the least and caproic acid (C(6)) the most toxic. EC50 values in the acute seed germination of cress ranged between 1.9 and 4.2mM and for ryegrass between 1.8 and 6.4mM. In subchronic assays EC50 values for germination were in a range from 11 to 46mMkg(-1)dm for cress, and from 18 to 127 mM kg(-1) dm for ryegrass. EC50 values for early seedling growth of cress based on acute assays ranged from 0.7 to 2.3mM and that of ryegrass from 1.2 to 1.8mM. Range of EC50 values for shoot biomass of cress was between 8 and 40 mM kg(-1) dm and of ryegrass between 12 and 93 mM kg(-1) dm.     

Microbial biotransformation of aryl sulfanylpentafluorides

We report, for the first time, the biotransformation of potential pollutants bearing the pentafluorosulfanyl (SF₅-) functional group in a fungus and bacteria. Cunninghamella elegans transformed p-methoxy phenyl SF₅ via demethylation; Pseudomonas knackmussii and P. pseudoalcaligenes KF707 transformed amino-, hydroxyamino- and diamino- substituted phenyl SF₅, forming the N-acetylated derivatives as the main product. Cell-free extract of Streptomyces griseus transformed 4-amino-3-hydroxy-phenyl SF₅ to the N-acetylated derivative in the presence of acetyl CoA, confirming that an N-acetyltransferase is responsible for the bacterial biotransformations. Approximately 25 % of drugs and 30 % of agrochemicals contain fluorine, and the trifluoromethyl group is a prominent feature of many of these since it improves lipophilicity and stability. The pentafluorosulfanyl substituent is seen as an improvement on the trifluoromethyl group and research efforts are underway to develop synthetic methods to incorporate this moiety into biologically active compounds. It is important to determine the potential environmental impact of these compounds, including the potential biotransformation reactions that may occur when they are exposed to microorganisms.     

Thyroid ultrasound volume, structure and function after long-term high exposure of large population to polychlorinated biphenyls, pesticides and dioxin

We examined 2,046 adults (834 males and 1,212 females aged 20-75 years) from polluted district in East Slovakia (POLL) and two neighboring upstream and upwind located districts of background pollution (BCGR). By ultrasound we estimated the thyroid volume (ThV), hypoechogenicity (HYE), nodules and cysts. Serum levels of thyrotropin (TSH), thyroperoxidase antibodies (TPOab) and thyroglobulin were estimated by electrochemiluminiscent assay and these of 15 PCB congeners, p,p'-DDE, p,p'-DDT, hexachlorobenzene (HCB) and hexachlorocyclohexane by high-resolution gas chromatography. In 320 subjects also selected hydroxylated and methylsulfonated PCB metabolites, polychlorinated dibenzo-dioxins (PCDDs), -furans (PCDFs), five dioxin-like coplanar and eight mono-ortho PCB congeners were estimated. Urinary iodine was measured by automatic microplate method. Reciprocal positive association was found between three major POPs (PCBs, DDE and HCB), the levels of these and also PCDDs plus PCDFs in polluted area being considerably higher than in background pollution area. ThV in groups of males and females from POLL with high PCBs level was significantly higher (p<0.001 by t-test) then in age and sex matched groups from BCGR with low PCBs level. In 1,048 males and females aged <60 years with serum PCBs level >1,000 ng g(-1) lipid (median=1,756 ng g(-1)) a significant effect of age on ThV was found (p<0.01 by ANOVA), while in 921 respective subjects with PCBs level <1,000 ng g(-1) (median=661 ng g(-1)) it was not. These findings supported the view on the additional effect of PCBs on ThV other than that of age. Since the urinary iodine in both districts showed optimal range, any interfering effect of unsatisfactory iodine intake on ThV may be excluded. The frequency of autoimmune thyroiditis signs such as HYE, increased serum level of TPOab and TSH resulting in subclinical or overt thyroid hypofunction was positively associated with sex, age and organochlorine levels. The increase of such frequency in males with POPs levels was much more abrupt than that in females. No considerable differences in the frequency of thyroid nodules as related to PCBs level were found.     

Development of Lymantria dispar affected by manganese in food

We studied the response of gypsy moth (Lymantria dispar (Linnaeus) (Lepidoptera: Lymantriidae)) to the content of manganese in food in the laboratory breeding of caterpillars. The food of the caterpillars {Betula pendula Roth (Fagales: Betulaceae) leaves} was contaminated by dipping in the solution of MnCl₂·4H₂O with manganese concentrations of 0, 0.5, 5 and 10 mg ml^?1, by which differentiated manganese contents (307; 632; 4,087 and 8,124 mg kg^?1) were reached. Parameters recorded during the rearing were as follows: effect of manganese on food consumption, mortality and length of the development of caterpillars, pupation and hatching of imagoes. At the same time, manganese concentrations were determined in the offered and unconsumed food, excrements, and exuviae of the caterpillars, pupal cases and imagoes by using the AAS method. As compared with the control, high manganese contents in the food of gypsy moth caterpillars affected the process of development particularly by increased mortality of the first instar caterpillars (8 % mortality for caterpillars with no Mn contamination (T0) and 62 % mortality for subjects with the highest contamination by manganese (T3)), by prolonged development of the first–third instar (18.7 days (T0) and 27.8 days (T3)) and by increased food consumption of the first–third instar {0.185 g of leaf dry matter (T0) and 0.483 g of leaf dry matter (T3)}. The main defence strategy of the caterpillars to prevent contamination by the increased manganese content in food is the translocation of manganese into frass and exuviae castoff in the process of ecdysis. In the process of development, the content of manganese was reduced by excretion in imagoes to 0.5 % of the intake level even at its maximum inputs in food.     

The ethics of Google Earth: crossing thresholds from spatial data to landscape visualisation

‘Virtual globe’ software systems such as Google Earth are growing rapidly in popularity as a way to visualise and share 3D environmental data. Scientists and environmental professionals, many of whom are new to 3D modeling and visual communications, are beginning routinely to use such techniques in their work. While the appeal of these techniques is evident, with unprecedented opportunities for public access to data and collaborative engagement over the web, are there nonetheless risks in their widespread usage when applied in areas of the public interest such as planning and policy-making?     

Contrasting lead speciation in forest and tilled soils heavily polluted by lead metallurgy

The concentration trends and chemical fractionation of Pb was studied in eight tilled and forest soil profiles heavily polluted by Pb metallurgy in the Pribram district, Czech Republic. The highest Pb concentrations were observed in surface and subsurface horizons attaining 35,300 mg kg-1 in forest soils and 1233 mg kg-1 in tilled soils. Total Pb concentrations were one order of magnitude lower in tilled soil due to intensive ploughing and annual crop off-take. The results of the Tessier sequential extraction procedure showed the preferential binding of Pb in forest soils to operationally-defined exchangeable positions and soil organic matter (oxidisable fraction). The Pb exchangeable fraction is thought to correspond to weak electrostatic binding on the functional groups of organic matter. In tilled soil, Pb is predominantly bound to operationally-defined Fe and Mn oxides (reducible fraction). A comparison with the background Pb concentration values showed a strong contamination even in mineral horizons IIC and confirmed a strong vertical mobility of Pb within the soil profiles. The calculated mobility factors (MF) showed that up to 72% of Pb is mobile and bioavailable in forest soils. In contrast, the bioavailability of Pb in tilled soils was significantly lower as the MF accounted for up to 30%. In the most polluted horizon of forest soil profile, the X-ray powder diffraction (XRPD) analysis confirmed the presence of anglesite (PbSO4), derived likely from the smelter emissions.     

Dioxin-like and non-dioxin-like PCBs in human serum of Slovak population

In the present study, non-ortho, mono-ortho and other ortho-substituted PCB congeners were analysed in individual blood serum samples taken from healthy adults (196 males and 119 females) in the polluted area of the Michalovce district and in the background area of the Stropkov/Svidnik districts in Eastern Slovakia by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). The samples from general population living in villages and towns of two regions were taken between August 2001 and February 2002 within the project of the EC's 5th Framework Programme (PCBRISK, ). The medians of dioxin-like PCBs (dl-PCBs)--expressed as TEQs on lipid basis--of all males (24.7 pg g(-1) lipid) and females (21.4 pg g(-1) lipid) were comparable, but there was a significant difference between both of the areas studied. In the district of Michalovce, the medians of males (47.3 pg g(-1) lipid) and females (41.1 pg g(-1) lipid) were 2.3 times higher than in the area of the Stropkov/Svidnik districts. The medians of total non-dioxin-like PCB concentration were 1,835 and 1,033 ng g(-1) lipid in males and females, respectively. The data show a trend toward higher concentrations of both dl- and non-dioxin-like PCBs in the older age groups. The substantial increase was observed for the 60+ age group. PCB-126 was the most abundant non-ortho congener. PCBs-118 and 156 were the predominant mono-ortho congeners. They were quantitated in all samples analysed. Congeners 153, 138(+163), 180 and 170(+190) were the main contributors to total non-dioxin-like PCB concentrations. Mean mutual ratio HexaCBs:HeptaCBs:OctaCBs in the non-dioxin-like group was 37:50:1. The results of this study represent the overall information about the congener distribution of dioxin-like and non-dioxin-like PCBs in human serum blood of adult Slovaks.