Fates of chlorimuron-ethyl were investigated in barren soils and farm soils for the purpose of better understanding of its persistence in fields and offering valid parameters for its eco- risk assessment. The degradation of chlorimuron-ethyl occurred mainly by chemical processes and fitted well to the first order kinetic models, with degradation rate constant k of 0.021 +/- 0.002 and 0.033 +/- 0.005, and half lives t(1/2) of 32.7 and 21.4 in barren soils and farm soils, respectively. k negatively, while t(1/2) positively correlated with K-OC and pH at a significant level of p<0.05. The persistence of chlorimuronethyl was caused by the adsorption to soil organic matter.

The substantial amounts of iron taken up by plants give rise to unstimulated formation of iron oxide particles inside their photosynthetic organs which, given the presence of ample reductants such as glucose. contain Fe(II) and thus are ferro(or ferri-)magnetic (magnetite Fe3O4). Besides this, other (heavy and light) metals are absorbed by plants both from aerosol deposited on leaves and via the roots. Since the uptake rates of different metals are linked by biochemical factors, it should be feasible to correlate magnetic signals from leaves/needles which are due to magnetite to the burden of other, toxic heavy metals. If this be proven, there are ramifications for biomonitoring escaping the need and expenses of traditional analytics. In this paper, thermodynamic and biochemical (bioinorganic) requirements for magnetite formation and doing this kind of biomonitoring are discussed.1 If given in sufficiently high doses, all heavy metals (HM) are toxic of course, but THM referred to those which are hazardous when given in small amounts. but over a longer period of time. E.g. for being neurotoxic.2 Bidentate ligands bind to one single metal ion via two different atoms.3 Effect or impact indicators/monitors are organisms that demonstrate specific or unspecific effects in response to exposure to a certain element or compound or a number of substances (MARKERT, 2008).4 It is important to note, that all considerations given in this paper are made under the assumption, that the magnetic signal of the vegetation species originate from the magnetic-like phases formed inside the plant tissues. However we used in recently published studies (JORDANOVA et al., 2008, 2009) non-washed material. which means, that the largest contribution of the magnetic signal derives from dust particles, which are mechanically attached to the surface of the plant investigated. Therefore, an unwashed plant can be handled as a "dust collector" of atmospheric fallout measurements.

The International Atomic Energy Agency (IAEA) organized a co-ordinated research project (CRP) on "Validation and application of plants as biomonitors of trace element atmospheric pollution analysed by nuclear and related techniques" involving 14 participating countries. The CRP's objective was to identify appropriate bioindicators for local and/or regional application and validate them for general air pollution monitoring. Activities included quantification studies, research into spatial and time resolution for particular organisms, and physiological studies. A number of suitable bioindicators were identified in different parts of the globe and tested during the CRP Sampling strategies were reviewed and the recommended approach adopted by the group. Appropriate sample preparation procedures were assessed and harmonised to the degree allowed by different geographic and climatic conditions in the participating countries. Two interlaboratory comparison exercises were carried out on lichen and moss materials. Results confirmed definite improvement in analytical performance of the participating laboratories, but also revealed possible inconsistencies due to different sample processing procedures. Several monitoring surveys were carried out and consequently pollution maps drawn for extended areas or countries. Overall results confirmed applicability of lower plants for assessing the degree of atmospheric pollution and provided several countries with effective monitoring tools not used before.

Two different tributyltin (TBT)-induced virilisation phenomena in prosobranch snails – intersex in Littorina littorea and imposex in Nucella lapillus – are compared in order to facilitate their simultaneous use in geographical large scale effect monitoring surveys. Imposex in dogwhelks is a more sensitive biomarker and should be used in areas that are only slightly or moderately contaminated with TBT (ambient TBT concentrations < 2.0 ng as Sn l-1). The assessment of intersex intensities in periwinkle populations has considerable advantages in areas with higher TBT concentrations and should be used also wherever dogwhelks are absent irrespective of the TBT exposure level. The intersex index (ISI) and vas deferens sequence (VDS) index are proposed as the most suited parameters for effect monitoring purposes. The geographical uniformity of intersex and imposex is analysed and proven for the coasts of Ireland, France, and Germany. A relative loss of TBT sensitivity in females can be found, but to a varying extent in both species. The implications of this result for biological TBT effect monitoring programmes are discussed in light of the fact that intersex and imposex have both been found to be irreversible. Because it is the objective of these programmes to assess current TBT contaminations and resulting biological effects, only relatively young specimens should be considered in the sampling strategy.

The interferences from Cd, Cu, Hf, Pb, Sr, Zn, Zr and Y on the inductively coupled plasma quadrupole mass spectrometry (ICP-MS) determination of Pt, Pd, Rh, Ru and Ir in geological (Pt-ore SARM-7, abundance range for platinum metals 0.07–3.74μg/g) and environmental samples (sediment JSd-2 abundance range for Pt and Pd 0.0167–0.021μg/g; road dust and plant sample) are evaluated using model solutions, real samples and comparison to inductively coupled plasma atomic emission spectrometry (ICP-AES) results. Pt, Rh, Ru and Ir can be determined usually after introduction of corrections for the interference in all investigated materials though in sediments the direct determination of Pt might be a problem depending on the actual Hf concentrations. The direct determination of Pd (after microwave-assisted acid digestion) is possible in ores using all investigated isotopes (105Pd, 106Pd, 108Pd), in plants using 108Pd and correction for the interferences of Zr, Mo and Cd, and not possible in sediments and road dust. Therefore, we developed a procedure for isolation of Pd using its diethyl-dithio-carabamate (DDTC) complex. The detection limits for Pt, Pd and Ir are 0.015ng/g, and for Ru and Rh 0.03ng/g.

Using ICP-MS and ICP-AES platinum group elements (Pt, Pd, Rh, Ru and Ir) and Ce, La, Nd, Pb and Zr have been determined in street dust, Taraxacum officinale (dandelion), Plantago lanceolata (plantain), Lolium multiflorum (annual ryegrass), Rhytidiadelphus squarrosus (moss) and Vascellum pratense (mushrooms) collected along highways and streets in Germany during 1999. Among the plants Taraxacum officinale (dandelion) reflects most adequately the pollution with the investigated elements matching the results from street dust. A strong positive correlation between all elements determined in the plants is established. Transfer factor for Pt between soil and plants has been determined in an agricultural experiment ranging between 0.004 and 0.008 for two types of soils.

The effects of two suspected endocrine-disrupting chemicals, the xeno-androgens triphenyltin (TPT) and tributyltin (TBT), were investigated in a new whole-sediment biotest with the freshwater mudsnail Potamopyrgus antipodarum (Gastropoda, Prosobranchia). Artificial sediments were spiked with seven concentrations, ranging from 10 to 500 microg nominal TPT-Sn/kg dry weight and TBT-Sn/kg dry weight, respectively. We analyzed the responses of the test species after two, four, and eight weeks exposure. For both compounds, P. antipodarum exhibited a sharp decline in the number of embryos sheltered in its brood pouch in a time- and concentration-dependent manner in comparison to the control sediment. The number of new, still unshelled embryos turned out to be the most sensitive parameter. The lowest-observed-effect concentration (LOEC) was equivalent to the lowest administered concentration (10 microg/kg of each test compound) for most parameters and thus no no-observed-effect concentration (NOEC) could be established. The calculation of effect concentrations (EC10) resulted in even lower values for both substances (EC10 after eight weeks for unshelled embryos: 0.03 microg TPT-Sn/kg, EC10 after four weeks for unshelled embryos: 0.98 microg TBT-Sn/kg). Our results indicate that P. antipodarum is highly sensitive to both endocrine disruptors TPT and TBT at environmentally relevant concentrations.

Forest burning for pastures in tropical areas represents an important component of biogeochemical cycles. In order to provide information concerning chemical modifications after forest burning, in this local study the total contents of 29 elements in topsoils were analyzed when forest is changed to pasture land. The work was carried out in 1999 in Rondĵnia state (Brazilian Amazon Basin) focussing on a native forest site and four neighboring pastures established in 1987, 1983, 1972 and 1911 after forest conversion. Chemical fingerprint graphs of the pasture soils related to the forest soil illustrated mainly higher contents for the vast majority of macro- and micro nutrients, but for other elements as well (e.g. Ba, Sr, Cr, Ni, V or Pb). Also increases of pH levels were measured in all pastures, which remained higher than the forest values for decades. After initial increases of most of the elements in pasture of 1987 the decreases of some macro elements (e.g. C, N, K, Mg, S) in pasture 1983 as well as again the enhanced levels in pasture 1972 and 1911 suggest both a persistent leaching of these elements and a function of pasture age where external element inputs exceed outputs. Ash deposition, accumulation of organic matter, animal excreta as well as natural soil conditions are discussed as influencing factors on the element contents of the original forest and the pasture soils. Nevertheless, in this particular area continuous pasturing after forest clearing primarily enriched the soils in elements.

Industrial emissions of lanthanides to aquatic ecosystems increase, but knowledge of the environmental fate of these metals is limited. Here we focus attention upon the distribution of lanthanides in freshwater ecosystems, describing lanthanide partitioning between sediment, water and biota. Since lanthanides are often used as oxidation-state analogues for actinides, their distribution can reflect long-term behaviour of the radioactive transuranics. Concentrations of all 14 naturally occurring lanthanides were measured by ICP-MS in Sago pondweed (Potamogeton pectinatus), common duckweed (Lemna minor), seven different mollusc species (tissue and shell), two sediment fractions (< 2 mm and < 63 microm), surface water and sediment pore water from five locations in The Netherlands. In all samples, the typical 'saw-tooth' lanthanide pattern was observed, which implies that lanthanides are transported as a coherent group through aquatic ecosystems. Typical deviations from this pattern were found for Ce and Eu and could be explained by their redox chemistry. The variation in concentrations in abiotic fractions was limited, i.e. within one order of magnitude. However, variations of up to three orders of magnitude were observed in biotic samples, suggesting different affinities among organisms for lanthanides as a group, with significant differences only among molluscs and pondweed samples in relation to sampling location. For P. pectinatus it was shown that pore water was the most important lanthanide source, and for snails, food (plants) seems to be the dominant lanthanide source. Lanthanides were not equally distributed between mollusc shell and tissue and the ratio of lanthanide concentrations in shell and tissue were dependent on the sampling location. Shells contained much lower concentrations and were relatively enriched in Eu, and to a lesser extent in Ce. Bioconcentration factors for lanthanides in plants and snails relative to surface water were typically between 10000 and 100000 l x kg(-1) dry matter, while sediment-water partition coefficients were between 100000 and 3000000 l x kg(-1) dry matter. There was a low extent of biomagnification in the plant-to-snail system, with a maximum biomagnification factor of 5.5. Many distribution coefficients displayed a slight decrease with atomic number. This can be attributed to the general increase in ligand stability constants with atomic number, keeping the heavier lanthanides preferentially in solution.

Leaf samples of tropical trees, i.e. Dryobalanops lanceolata (Kapur paji), Dipterocarpaceae and Macaranga spp. (Mahang), Euphorbiaceae were analyzed for 21 chemical elements. The pioneer Macaranga spp. exhibited higher concentrations for the majority of elements compared to the emergent species of Dryobalanops lanceolata, which was attributed to the higher physiological activity of the fast growing pioneer species compared to emergent trees. Lead showed rather high concentrations in several samples from the Bakam re-forestation site. This is suggested to be caused by emissions through brick manufacturing and related activities in the vicinity. A comparison of Dryobalanops lanceolata samples collected in 1993, 1995 and 1997 in the Lambir Hills National Park revealed that certain heavy metals, i.e. Co, Cu, Mn, Ni, Pb and Ti showed higher values in 1997 compared to the previous years, which could indicate an atmospheric input from the haze caused by the extensive forest fires raging in Borneo and other parts of Southeast Asia.

The concentrations of lanthanoids, Be, Bi,Ga, Te, Tl, Th and U have been determined using ICP-MS for 100 standardized samples of poplar leaves collected from the territory of Bulgaria. The investigated elements are log-normally distributed on the territory. Using cluster analysis of the analytical data the samples were grouped according soil type on which the plants are growing.

Four digestion procedures for microwave dissolution of soils and sediments are investigated. Accurate results (accuracy better than 10%) for lanthanides, Be, Bi, Te, Th, U and Y are obtained only after an overnight stay with a mixture of 2 ml 48% HF and 2 ml 65% HNO3 and afterwards stepwise microwave digestion with 1 ml 48% HF and 10 ml 5% H3BO3. Only As is not be to be determined by this procedure due to significant interferences from Eu, Nd and Sm. For all other elements, accurate results are obtained by all four procedures.

The possibilities of inductively coupled plasma mass spectrometry (ICP-MS) (choice of isotopes, instrument optimisation) for the determination of lanthanoids, and some heavy and toxic elements in plants are discussed. A variety of plant certified materials (NIST-SRM-1515, NIST-SRM-1547, NIST-SRM-1573a, NIST-SRM-1575, GBW 08504, GBW 08505) are analysed and the elements: As, Be, Bi, Cd, Ce, Co, Cr, Cu, Dy, Er, Eu, Ga, Gd, Ho, La, Lu, Nd, Ni, Pb, Pr, Rb, Sm, Sr, Th, Te, Th, Tl, U, V, Y, Yb and Zn are determined. The comparison with certified values and literature values indicated that ICP-MS is a very promising method for the instrumental determination of Be, lanthanoids, Th and U and other elements at ng/g level in plants.

The foliar concentrations of 11 heavy metals were analyzed in 20 tree species from a mixed dipterocarp forest in the Lambir Hills National Park near Miri, Sarawak, Malaysia. The concentrations within the species differed considerably. All elements except Cu occurred in lower concentrations in overstory species than in understory species. A comparison of the overall mean concentrations to the “reference plant” proposed by Markert (Markert, B., 1996. Instrumental Element and Multi-element Analysis of Plant Samples — Methods and Applications, 2nd ed. Wiley, New York) revealed substantial differences. Ni showed a remarkable positive deviation (311%) while the deviation of 3160% found for Co was striking. This was attributed to the accumulative characteristics for Co exhibited by four species, Santiria mollis, Koilodepas laevigatum, Trigonostemon sp. nov. aff. ionthocarpus and Allantospermum borneense. The nickel concentrations appeared to be somewhat elevated in the majority of species. This corresponds with the results of a study conducted in mountain rain forest in Sri Lanka (Jayasekera, R., 1993. Concentrations of selected heavy metals in different compartments of a mountain rain forest ecosystem in Sri Lanka. In: Markert, B. (Ed.), Plants as Biomonitors. VCH Publishers, Weinheim, pp. 613–622). The highest nickel concentration was exhibited by T. sp. nov. aff. ionthocarpus with a mean of 22.10 mg/kg dry weight. While the manganese concentrations were rather high in the majority of species, Dryobalanops lanceolata and Memecylon paniculatum exhibited low concentrations with 52.77 and 30.20 mg/kg dry wt., respectively. Cr, Fe, Pb, V and Zn occurred in rather low concentrations through all species. Particularly the examined species of Euphorbiaceae were found to accumulate rather high concentrations of certain heavy metals indicating accumulative characteristics. Due to their specific environment, trees from tropical forest might have a rather different chemistry from trees in the Northern Hemisphere.

Stoichiometric Network Analysis (SNA), originally developed by the Canadian chemist Bruce L. Clarke during the 1970s, provides a most efficient means of reducing the background topology of complex interaction networks to some skeleton topology around which systems dynamics can be understood without jeopardising insight into complex dynamics by over- or miss-simplification. Since it focuses on the corresponding autocatalytic (AC) features of a feedback system as those which control overall behaviour to some extent, SNA deals with reaction kinetics in and beyond chemistry, e.g. with nuclear reactions. It is therefore quite straightforward to apply this manner of simplification, which in turn is supported by a number of mathematical theorems on systems behaviour and properties of AC cycles, to biological systems although their 'full' complexity may not even be assessed in the yet rare cases of complete genetic sequencing. Assuming there is a relationship between the kinds of metal or metalloid species and key biological/biochemical transformations to be promoted with their aid--this relationship being the subject of bio-inorganic chemistry--and that biochemistry is, in effect, about systems which can reproduce and thus behave autocatalytically, one can expect SNA to yield formally sound statements on basic features of biology and biochemistry too. If we sum up the facts and considerations concerning essentiality or possible essentiality in a biological system of elements (Markert, 1994), this means joining the triangular representation of BSE, including statements on (the degree of biological) evolution and aggregation levels, to SNA treatment of autocatalysis within hierarchical systems from metalloenzymes to entire biocoenoses. Arguments using preferred cluster sizes and aggregation tendencies from coordination chemistry are then employed to circumscribe possible functions within the BSE. They are also extended to metals hitherto not known to be essential, such as tellurium or scandium.

The determination of the residual water content by thermal methods and especially by Karl Fischer titration in a candidate reference material of the European Commission (candidate CRM 679 cabbage powder) is described and discussed.

In the years 1995 and 1996 the atmospheric deposition of elements in the EuroRegion Neisse (ERN) was determined in a biomonitoring project using mosses. The mosses Pleurozium schreberi and Polytrichum formosum were chosen as biomonitors because of their wide distribution in the area studied. The moss samples were analysed by ICP-MS and ICP-OES for their concentrations of 37 chemical elements. The results were shown in the form of maps. The data from the moss monitoring project served as a basis for determining those elements in the deposited material that promote the occurrence of disease. This was done by correlating the figures for the various diseases with the appropriate element concentrations in the mosses. Indications were found that a connection exists between the thallium content of mosses and the occurrence of cardiovascular disease and between Ce, Fe, Ga and Ge levels in the mosses and the incidence of diseases of the respiratory system.

A sensitive method for the determination of phytochelatins in plant matrices by pre-column derivatization with monobromobimane (mBrB) and high-performance liquid chromatography (HPLC) on reversed phases and fluorescence-detection has been developed and applied to cucumber sprouts (Cucumis sativus) treated with cadmium and to the water moss fontinalis antipyretica (Cd in environmentally-relevant concentrations). Whereas phytochelatins were found in the Cd-treated sprouts, no phytochelatins were detected in Fontinalis antipyretica.

The detoxification mechanisms of the aquatic moss, Fontinalis antipyretica Hedw., exposed to Cr was analyzed. In addition, the influence of Cr salts (as Cr nitrate, chloride and potassium bichromate) on these mechanisms has also been studied. The activity of antioxidant enzymes superoxide dismutase (SOD, EC 1.15.1.1.), catalase (EC 1.11.1.6.), ascorbate peroxidase (APX, EC 1.11.1.11.), guaiacol peroxidase (GPX, EC 1.11.1.7.) and glutathione reductase (GR, EC 1.6.4.2.) increased in plants treated with Cr concentrations ranging from 6.25 × 10−5 to 6.25 mM when given as Cr(NO3)3. Antioxidant enzymes responded to the other two salts CrCl3 and K2Cr2O7 only with Cr concentrations higher than 6.25 × 10−2 mM. Glutathione level and GSSG/GSH ratio also responded to Cr exposure but no dose–effect relationship could be observed. Moreover, two unknown thiol compounds were observed in mosses exposed to the highest Cr concentrations. Effects on chlorophyll contents and chlorophyll a/b ratios were also shown even at low Cr concentrations. Our results indicated that environmentally realistic concentrations of Cr could lead to impairment of the cellular activity towards F. antipyretica and that Cr(III), when present as a nitrate salt, was as harmful as Cr(VI).