Changes in the heavy metal and nutrient contents of dried feather mosses during long-term storage

This study measured heavy metal and nutrient concentrations of two feather mosses during the periods of dry storage. Samples (Hylocomium splendens, Pleurozium schreberi) were collected in the nationwide moss surveys carried out on the permanent sample plots of the 8th Finnish National Forest Inventory in 1985–86, 1990, 1995 and 2000. A small amount of each moss sample was analyzed soon after collection, and the remainder was dried and stored at the Paljakka environmental specimen bank (ESB). The 108 stored samples from 27 plots were reanalyzed in 2008. Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) and nutrients (Ca, K, Mg, P) were determined and compared for each survey year. Overall, Fe, Pb and Cr concentrations decreased, and Cu concentrations increased significantly during storage. The greatest decrease was observed in samples from plots where their initial concentrations were the highest. Changes in the concentrations of Cd, Ni and Zn were less pronounced. The loss of heavy metals is likely due to drying when cell membranes rupture and some of the surface material is lost. K, P and, to some extent, Mg concentrations increased during storage, whereas Ca did not change significantly. Nutrient increase is probably due to their movement from older to younger growths during the initial phase of drying. Ca is mostly bound to cell walls and is not easily released. Results emphasize the importance of establishing the intended use of a stored moss prior to sampling, in order to select and optimize an appropriate storage technique.     

Deposition of gamma emitters from Chernobyl accident and their transfer in lichen–soil columns

Lichen–soil column samples were taken from several locations in the Southern Finland between 1986 and 2006. Columns were divided into three parts, upper lichen, lower lichen and underlying soil, and their gamma emitting radionuclides, ¹³⁴Cs, ¹³⁷Cs, ¹⁰³Ru, ⁹⁵Zr, ¹⁰⁶Ru, ^110mAg, ¹²⁵Sb and ¹⁴⁴Ce, were measured with gamma spectrometry. Deposition values were calculated as Bq/m² for each sampling site. Distribution of various radionuclides in the three compartments as a function of time was determined. Both effective and ecological half-lives of all radionuclides were calculated for upper lichen, whole lichen and whole lichen–soil column. A linear relation was derived between the physical half-lives and effective half-lives for whole lichen and for whole lichen–soil column. Reindeer meat activity concentrations of various radionuclides and ensuing radiation doses to reindeer-herding people were also estimated for a hypothetical case where a similar high radioactive pollution, as was taken place in the Southern Finland, would have occurred in the reindeer-herding areas in the Finnish Lapland.     

Arsenic and other toxic elemental contamination of groundwater, surface water and soil in Bangladesh and its possible effects on human health

The problems of contamination caused by arsenic (As) and other toxic metals in groundwater, surface water and soils in the Bengal basin of Bangladesh have been studied. Altogether 10 groundwater, seven surface water and 31 soil samples were collected from arsenic-affected areas and analysed chemically. The geologic and anthropogenic sources of As and other toxic metals are discussed in this paper. The chemical results show that the mean As concentrations in groundwater in the Char Ruppur (0.253mg As L^–1), Rajarampur (1.955mg As L^–1) and Shamta areas (0.996mg As L^–1) greatly exceed the WHO recommended value, which is 0.01mg As L^–1. The concentrations of As in groundwater are very high compared to those in surface water and in surface soil in the three (As-affected) areas studied. This indicates that the source of As in groundwater could be bedrock. The relatively high concentrations of Cr, Cu, Ni, Pb and Zn in surface water, compared to world typical value, are due to the solubility of metal ions, organometalic complexes, coprecipitation or co-existance with the colloidal clay fraction. In the soil, the elevated concentrations of As, Cr, Cu, Ni, Pb and Zn are due to their strong affinity to organic matter, hydrous oxides of Fe and Mn, and clay minerals.     

Molecular orbital studies on brominated diphenyl ethers. Part I--conformational properties

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants and quantities in the environment are on the rise. Because they are structurally related to polychlorinated biphenyls and also to thyroid hormones, there is serious concern that PBDEs may pose a danger to human health. Knowledge of their conformational properties is key to assessing their environmental fate and risk. The conformational properties of PBDEs were investigated by quantum chemical methods including semiempirical self-consistent field molecular orbital (SCF-MO), ab initio SCF-MO and density functional theory (DFT). Conformational analyses of model congeners 2,2',4,6'-tetrabromodiphenyl ether and 2,3,4,4',5,6-hexabromodiphenyl ether, based on energy maps calculated by semiempirical AM1 method, may indicate that all PBDE congeners except those with the tetra-ortho-bromination are conformationally flexible (or soft) due to low energy barriers for interconversion of stable conformers. The results of the conformational analyses are in conformity with recently published X-ray crystallographic data. For comparison with the results of the semiempirical method, higher level ab initio and DFT models were applied as well. The optimized geometries all lie well inside low energy regions on the maps and thus also ascertain the semiempirical calculations. According to computed geometric parameters and net atomic charges, the model B3LYP/3-21G* seemed to give better results than B3LYP/6-31G* and HF/6-31G*.     

Molecular orbital studies on brominated diphenyl ethers. Part II--reactivity and quantitative structure-activity (property) relationships

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic reactions of BDEs was predicted. Furthermore, satisfactory quantitative structure-activity (property) relationship (QSAR and QSPR) models were derived to calculate gas chromatographic and ultraviolet spectral properties and luciferase induction activities from the AM1-computed electronic parameters.     

Deposition of gamma emitters from Chernobyl accident and their transfer in lichen-soil columns

Lichen-soil column samples were taken from several locations in the Southern Finland between 1986 and 2006. Columns were divided into three parts, upper lichen, lower lichen and underlying soil, and their gamma emitting radionuclides, (134)Cs, (137)Cs, (103)Ru, (95)Zr, (106)Ru, (110m)Ag, (125)Sb and (144)Ce, were measured with gamma spectrometry. Deposition values were calculated as Bq/m(2) for each sampling site. Distribution of various radionuclides in the three compartments as a function of time was determined. Both effective and ecological half-lives of all radionuclides were calculated for upper lichen, whole lichen and whole lichen-soil column. A linear relation was derived between the physical half-lives and effective half-lives for whole lichen and for whole lichen-soil column. Reindeer meat activity concentrations of various radionuclides and ensuing radiation doses to reindeer-herding people were also estimated for a hypothetical case where a similar high radioactive pollution, as was taken place in the Southern Finland, would have occurred in the reindeer-herding areas in the Finnish Lapland.     

Biological and photochemical degradation rates of diethylenetriaminepentaacetic acid (DTPA) in the presence and absence of Fe(III)

The environmental fate of ethylenediaminetetraacetic acid (EDTA) has been extensively studied, while much less is known about the environmental behaviour of diethylenetriaminepentaacetic acid (DTPA). In this study, it was confirmed that DTPA is persistent toward biodegradation. The biodegradability of DTPA was investigated in the absence and in the presence of Fe(III) by using CO2 evolution test and Manometric respirometry test. The CO2 evolution and oxygen uptake of iron-free (DTPA was added as free acid) and Fe(III)DTPA were less than in inoculum blank. Possible inhibitor effect was analysed by testing biodegradation of sodium benzoate with and without iron-free or Fe(III)DTPA in the Manometric respirometry test. Only slight inhibition was observed when DTPA was added as free acid. Photodegradation of iron-free DTPA and Fe(III)-DTPA complex was studied by using sunlight and UV radiation at the range 315-400 nm emitted by black light lamps. The results indicate that DTPA added as free acid degrades photochemically in humic lake water. Fe(III)DTPA was shown to be very photolabile in humic lake water in the summer; the photochemical half-life was below one hour. Photodegradation products were identified by the mass spectrometric technique (GC-MS). It was shown that photodegradation of Fe(III)DTPA does not result in total mineralization of the compound. Diethylenetriaminetetraacetic acid, diethylenetriaminetriacetic acid, ethylenediaminetriacetic acid, N,N'- and/or N,N-ethylenediaminediacetic acid, iminodiacetate, ethylenediaminemonoacetic acid and glycine were identified as photodegradation products of Fe(III)DTPA. Based on these observations, we propose a photodegradation pathway for Fe(III)DTPA.     

Photodegradation of new amino acid derivatives suitable for chelating agents in pulp bleaching applications

The purpose of this study was to evaluate photodegradabilities of the following new low-nitrogen chelating agents: N-bis[(carboxymethoxy)ethyl]glycine (compound 1), N-bis[(1,2-dicarboxyethoxy)ethyl]glycine (compound 2) and N-bis[(1,2-dicarboxyethoxy)ethyl]aspartic acid (compound 3). At first photodegradation of these chelating agents as uncomplexed Na-compound 1–3 and Cu(II) complexes were tested, both in lake and distilled water, by exposing them to near-UV region radiation at the range of 315–400 nm. Uncomplexed Na-compounds 2 and 3 were selected to sunlight exposure experiments carried out in lake and distilled water. Compound 3 was also tested in sunlight as Cu and Ca complexes in both solutions. Photodegradation of Na₆-compound 3 in distilled water was studied by exposing it to radiation at the wavelength of 253.7 nm. Photodegradation products were analysed by means of GC-MS (gas chromatography with mass selective detector).

The results demonstrated that compound 1 was quite photostable even as Cu complex while compounds 2 and 3 were found to be photodegradable. Over 90% reduction of compound 3 was achieved during one week and 80% reduction of compound 2 in two weeks' time when they were added as Na salt to lake water and exposed to sunlight. Compound 3 as Cu complex degraded totally in the sunlight in less than one week. In the case of compound 3, the degradation rate decreased depending on the counter cation in the order Cu > Na  Ca. The study demonstrated that photodegradation of Na₆-compound 3 does not result in total mineralization of the compound. A photodegradation pathway for Na₆-compound 3 is proposed.     

Electromagnetic irradiation exposure and its bioindication – An overview

Man made electromagnetic irradiation and fields cover now the globe due to the recent extensive propagation of mobile telephony. The increased load affects animals and also plants. Especially birds have been studied. Humans are also sensitive. They are good bioindicators as epidemiological methods are available. Humans can also report symptoms which cannot be directly measured with presently available technologies. The nonionizing irradiation can as the ionizing one break the DNA, damage proteins, even increase the blood brain barrier permeability, disturb the night rest, cause fatigue and hormonal disturbances. An increase of the tumours of human head has been described in correlation with the long term mobile phone use and on that side more exposed. The regulations covering mobile telephony are already about two decades old and need re-evaluation. The multitude of irradiation and the interaction of the different wavelength exposures, i.e., frequency sensitivity is poorly known at present. We should not forget the comparative studies of different species especially those which rely in their lives on electromagnetic orientation physiology. Some countries have issued warnings on the exposures of children. The producers of mobile technology have recently warned the users not to keep those devices in active stage in skin contact.