Peter Englmaier

Comparison of the element composition in several plant species and their substrate from a 1 500 000-km2 area in Northern Europe

Leaves of 9 different plant species (terrestrial moss represented by: Hylocomium splendens and Pleurozium schreberi; and 7 species of vascular plants: blueberry, Vaccinium myrtillus; cowberry, Vaccinium titis-idaea; crowberry, Empetrum nigrum; birch, Betula pubescens; willow, Salix spp.; pine, Pinus sylvestris and spruce, Picea abies) have been collected from up to 9 catchments (size 14-50 km2) spread over a 1500000 km2 area in Northern Europe. Soil samples were taken of the O-horizon and of the C-horizon at each plant sample site. All samples were analysed for 38 elements (Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Sc, Se, Si, Sn, Sr, Th, Tl, U, V, Y, Zn and Zr) by ICP-MS, ICP-AES or CV-AAS (for Hg-analysis) techniques. The concentrations of some elements vary significantly between different plants (e.g. Cd, V, Co, Pb, Ba and Y). Other elements show surprisingly similar levels in all plants (e.g. Rb, S, Cu, K, Ca, P and Mg). Each group of plants (moss, shrubs, deciduous and conifers) shows a common behaviour for some elements. Each plant accumulates or excludes some selected elements. Compared to the C-horizon, a number of elements (S, K, B, Ca, P and Mn) are clearly enriched in plants. Elements showing very low plant/C-horizon ratios (e.g. Zr, Th, U, Y, Fe, Li and Al) can be used as an indicator of minerogenic dust. The plant/O-horizon and O-horizon/C-horizon ratios show that some elements are accumulated in the O-horizon (e.g. Pb, Bi, As, Ag, Sb). Airborne organic material attached to the leaves can thus, result in high values of these elements without any pollution source.

Influence of extreme pollution on the inorganic chemical composition of some plants

Leaves of nine different plant species (terrestrial moss: Hylocomium splendens and Pleurozium schreberi, blueberry: Vaccinium myrtillus, cowberry: Vaccinium vitis-idaea, crowberry: Empetrum nigrum, birch: Betula pubescens, willow: Salix spp., pine: Pinus sylvestris, and spruce: Picea abies) have been collected from up to nine catchments (size 14-50 km2) spread over a 1,500,000 km2 area in northern Europe. Additional soil samples were taken from the O-horizon and the C-horizon at each plant sample site. All samples were analysed for 38 elements (Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Sc, Se, Si, Sn, Sr, Th, Tl, U, V, Y, Zn, and Zr) by ICP-MS, ICP-AES or CV-AAS (Hg) techniques. One of the 9 catchments was located directly adjacent (5-10 km S) to the nickel smelter and refinery at Monchegorsk, Kola Peninsula, Russia. The high levels of pollution at this site are reflected in the chemical composition of all plant leaves. However, it appears that each plant enriches (or excludes) different elements. Elements emitted at trace levels, such as Ag, As and Bi, are relatively much more enriched in most plants than the major pollutants Ni, Cu and Co. The very high levels of SO2 emissions are generally not reflected by increases in plant total S-content. Several important macro-(P) and micro-nutrients (Mn, Mg, and Zn) are depleted in most plant leaves collected near Monchegorsk.

Element levels in birch and spruce wood ashes — green energy?

Production of wood ash has increased strongly in the last ten years due to the increasing popularity of renewable and CO(2)-neutral heat and energy production via wood burning. Wood ashes are rich in many essential plant nutrients. In addition they are alkaline. The idea of using the waste ash as fertiliser in forests is appealing. However, wood is also known for its ability to strongly enrich certain heavy metals from the underlying soils, e.g. Cd, without any anthropogenic input. Concentrations of 26 chemical elements (Ag, As, Au, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, La, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Sr, Ti, and Zn) in 40 samples each of birch and spruce wood ashes collected along a 120 km long transect in southern Norway are reported. The observed maximum concentrations are 1.3 wt.% Pb, 4.4 wt.% Zn and 203 mg/kg Cd in birch wood ashes. Wood ashes can thus contain very high heavy metal concentrations. Spreading wood ashes in a forest is a major anthropogenic interference with the natural biogeochemical cycles. As with the use of sewage sludge in agriculture the use of wood ashes in forests clearly needs regulation.

The performance of moss, grass, and 1- and 2-year old spruce needles as bioindicators of contamination: A comparative study at the scale of the Czech Republic

Moss (Pleurozium schreberi), grass (Avenella flexuosa), and 1- and 2-year old spruce (Picea abies) needles were collected over the territory of the Czech Republic at an average sample density of 1 site per 290km(2). The samples were analysed for 39 elements (Ag, Al, As, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Hg, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, Pb, Pr, Rb, S, Sb, Se, Sn, Sr, Th, Tl, U, V, Y and Zn) using ICP-MS and ICP-AES techniques (the major nutrients Ca, K, Mg and Na were not analysed in moss). Moss showed by far the highest element concentrations for most elements. Exceptions were Ba (spruce), Mn (spruce), Mo (grass), Ni (spruce), Rb (grass) and S (grass). Regional distribution maps and spatial trend analysis were used to study the suitability of the four materials as bioindicators of anthropogenic contamination. The highly industrialised areas in the north-west and the far east of the country and several more local contamination sources were indicated in the distribution maps of one or several sample materials. At the scale of the whole country moss was the best indicator of known contamination sources. However, on a more local scale, it appeared that spruce needles were especially well suited for detection of urban contamination.

Biogeochemical plant-soil interaction: variable element composition in leaves of four plant species collected along a south-north transect at the southern tip of Norway.

Leaves from four different plant species (birch, willow, juniper, and heather) together with samples of the soil O and C horizons were collected at 44-46 sites along a south-to-north transect extending inland for 200 km from the southern tip of Norway. The transect covers one of the steepest vegetation gradients on Earth, crossing six vegetation zones. Juniper and heather are evergreen, and preferably exclude potentially toxic elements to avoid their accumulation in assimilating tissues, birch and willow shed their leaves in autumn together with the load of potentially toxic elements, and thus can tolerate the uptake of such elements. The plant leaves show the highest concentrations for B, Ca, K, Mg, Mn, P, Rb and S. In the soil O-horizon Ag, Au, As, Bi, Cu, Ge, Hg, In, Pb, Sb, Se, Sn, Te and W are enriched with respect to the C-horizon, whilst Mn and Rb are depleted. Cadmium, Sr and Zn are enriched in willow and Cs, Na and Tl in heather. In terms of concentration gradients from the coast inland, two different patterns are detected: 1) short range with an almost exponential decrease of concentrations from the coast, which appears to be typical for seaspray-related element input, and 2) long range with an almost linear decrease of concentrations with distance from the coast. These patterns differ among the four species, even for one and the same element. Inter-element correlation is different from material to material. Along the transect each of the different plants at the same site individually adapts to the available element combination. High linear correlations in the plants occur between the lanthanides (La, Ce, Y), and interestingly, between P and Ti. The plant/soil system appears highly non-linear and self-regulated.

A strong enrichment of potentially toxic elements (PTEs) in Nord-Trøndelag (central Norway) forest soil.

Analysis of soil C and O horizon samples in a recent regional geochemical survey of Nord-Trøndelag, central Norway (752 sample sites covering 25,000 km2), identified a strong enrichment of several potentially toxic elements (PTEs) in the O horizon. Of 53 elements analysed in both materials, Cd concentrations are, on average, 17 times higher in the O horizon than in the C horizon and other PTEs such as Ag (11-fold), Hg (10-fold), Sb (8-fold), Pb (4-fold) and Sn (2-fold) are all strongly enriched relative to the C horizon. Geochemical maps of the survey area do not reflect an impact from local or distant anthropogenic contamination sources in the data for O horizon soil samples. The higher concentrations of PTEs in the O horizon are the result of the interaction of the underlying geology, the vegetation zone and type, and climatic effects. Based on the general accordance with existing data from earlier surveys in other parts of northern Europe, the presence of a location-independent, superordinate natural trend towards enrichment of these elements in the O horizon relative to the C horizon soil is indicated. The results imply that the O and C horizons of soils are different geochemical entities and that their respective compositions are controlled by different processes. Local mineral soil analyses (or published data for the chemical composition of the average continental crust) cannot be used to provide a geochemical background for surface soil. At the regional scale used here surface soil chemistry is still dominated by natural sources and processes.

Trimethylsilyl-ester pflanzlicher säuren und ihre anwendung in der gaschromatographie: Darstellung, kinetik der silylierung und einflüsse verschiedener lösungsmittel auf ausbeute und stabilität der derivate

Abstract Trimethylsilyl esters of plant acids and their application in gas-liquid chromatography. Preparation, kinetics of silylation and solvent effects on quantitative reaction and stability of the derivatives. Gas-liquid chromatographic separation of phosphate and organic acids in plant extracts as trimethylsilyl (TMS) derivatives is usually carried out in relatively high boiling solvents (pyridine, dimethylformamide) using internal standards which undergo no reaction with the silylating agent. It is shown that acetone is advantageous to conventional solvents concerning boiling point, dissolving of the acids and the fact that extremely anhydrous conditions are not needed. Moreover, the reproducibility of results in essentially better for most compounds than with pyridine. An internal standard forming TMS derivatives compensates for variable reaction conditions and permits the analysis of samples over an extended period of time, since its derivatives are subjected to a similar decomposition as the substances analysed. Butylmalonate met all these requirements. The kinetics of the silylation reaction and the decomposition of the derivatives were investigated for phosphate and a lot of biologically interesting plant organic acids.

Nitrate analysis by gas-liquid chromatography using the nitration of 2,4-dimethylphenol in sulphuric acid

Abstract Nitration of aromatic compounds in a sulphuric acid medium as a method for nitrate determination has been studied by gas chromatography. 2,4-Dimethylphenol was used as reactant because it is highly reactive and can only form a single nitro- derivative. Its concentration and that of sulphuric acid during nitration were optimized. The yield of the toluene extraction method employed was determined and found to be satisfactory. No degradation of the reaction product in the samples was found within 72 h. The detection limit was 0.1 ppm. Concentrations from 1 to 100 ppm and higher can be quantitatively detected without dilution.

Carbohydrate metabolism of salt-tolerant fructan grasses as exemplified with Puccinellia peisonis

Summary The physiological role of carbohydrates, particularly of water-soluble fructose polymers (fructans), in metabolism was studied in Puccinellia peisonis, a salt-tolerant, caespitose grass growing at the banks of salty pools (“Lacken”) in the Seewinkel area (Burgenland, Austria). High resolution steric exclusion chromatography (SEC) made it possible to determine the molecular-weight distribution of the homologous fructan series and to quantify the individual components. The seasonal changes in the concentration of free monosaccharides, sucrose, oligo- and polyfructans (in 4 fractions with increasing molecular weight) and starch, which always occurred in small quantities, were studied in relation to the plants phenology. Results showed that high-molecular fructans (with a degree of polymerization, DP of more than 18) mainly served as storage components, whereas fructose oligomers, similar to the raffinose series in many dicotyledonous species, provided resistance to freezing. Fructose and sucrose contributed much to the osmotic potential of the plant, which as most monocotyledonous species is highly efficient in excluding excess ions from the substrate. The resulting osmotic values, however, are too low to bridge dry periods in summer. In such cases decomposition of the water-soluble fructans may lead to a rapid increase of the osmotic potential. Moreover, the possible role of low molecular-weight fructans (with DP 7 to 10) as effectors of osmoregulation is discussed. The multiform functions of a polymeric series of simple carbohydrates may help to explain the success of Poaceae in growing on dry biotopes.

The effects of emersion on soluble carbohydrate accumulations in Hippuris vulgaris L.

Abstract The influence of emersion on carbohydrate accumulation in Hippuris vulgaris L. was studied by comparing the carbohydrate levels of fully submersed plants with those of plants producing emergent shoots. In all plant fractions, the dominant component was stachyose. It reached levels up to 34.6% dry matter. In both growth forms the green submersed parts contained between 2.12 (submersed plants) and 2.41 (plants with emergent apices) times more soluble carbohydrate, respectively, than the corresponding basal white parts. Another pool of carbohydrates was located in the emergent parts: the carbohydrate level of plants with emergent apical sections was about 8 times that of submersed plants. Emergent plants stored about 7 times more carbohydrate in the green submersed parts and 6.2 times more in the basal white parts than fully submersed plants. Thus the effects of direct access to atmospheric sources of CO 2 , and the lack of any attenuation of irradiance by backscattering or absorbance in the water, achieved by aerial stems, are clearly evident in the different carbohydrate contents of submersed and emergent Hippuris plants.