Mikrosondenuntersuchungen an unterschiedlich stark mit Schwermetallen belasteten Böden. 2. Gehalte an Schwermetallen und anderen Elementen in Huminstoffaggregationen,Streustoffen und Holzkohlepartikeln

Electron microprobe studies on soil samples with varying heavy metal contamination. 2. Contents of heavy metals and other elements in aggregations of humic substances, litter residues and charcoal particles EMA point analysis show that the organic matter constituents of heavy metal contaminated soils are highly enriched with heavy metals. The maximal trace element accumulation were for Cu up to 13,000 mg/kg, for Zn up to 48,000 mg/kg, for Cd up to 2,100 mg/kg and for Pb up to 193,000 mg/kg. The affinity for the accumulation of the different heavy metals in aggregations of humic substances can be described by the sequence Cu > Pb ? Cd > Zn ? Ni > Co. In very strongly acidified humic top soil horizons the Pb and Cd accumulation in the organic matter constituents is in competition with the accumulation in Fe and Mn oxides. The heavy metal contents (especially of Cu) of the organic matter are often correlated with the content of organically bound calcium. The EMA results also show that high heavy metal amounts occur in combination with Ca-accumulations in the epidermis and the outer bark parenchym of decayed roots. EMA point analysis of the interior of fungus sclerotias show that sclerotias can contain high amounts of heavy metals, in particular lead (up to 49,700 mg Pb/kg). From statistical results of EMA point analysis follows that lead and other heavy metals attached to humic substances are not only bound as metal organic complexes but also as organic metal phosphate complexes. Also charcoal particles of polluted soils contain high amounts of heay metals. The accumulation affinity is quite similar to that of humic substances.     

Extraktion von Schwermetallen aus Böden mit Ionenaustauscherharz

Extraction of Heavy Metals from Soils by Ion Exchangers The aim of this investigation was to optimize an extraction method for the analysis of available heavy metals (Cd, Cu, Pb, Zn) in soils. LEWATIT was used as an ion exchanger (IEX) which absorbs heavy metals specificly. A special extraction vessel with two chambers was developed to recover the IEX from the soil solution. Nitric acid was used for the desorption of heavy metals from the ion exchanger. The described method measures water soluble and exchangeable ions as well as acid soluble heavy metals. The amount of acid soluble heavy metals can be regulated by conditioning the IEX with K⁺. Using an IEX conditioned with 30% K⁺, the maximum change of pH in the soil solution was 2 units. This is the same range of acidity changes occuring in the rhizosphere of plants by nutrient uptake. The extract contains no organic compounds. Thus the co-determination of stabil organic complexes is excluded. Accordingly, this method is also feasible for the investigation of forest soils with humic layers.     

Fracht an chemischen Elementen in den Niederschlägen im Solling

Loading of chemical elements in precipitation at the Solling For the period 1969–1976 (NH₄, NO₃: 1971–1976) monthly values of concentrations and flows of the ions NH₄, H, Na, K, Ca, Mg, Fe, Mn, Al, Cl, NO₃, SO₄, P and organic bound N in precipitation are passed on. From the correlations between elements the following main ion sources are concluded: sea water (Na, Cl), combustion processes (SO₄, NO₃, NH₄), lime dust after dissolution by H₂SO₄ and HNO₃ (Ca, Mg), soil dust after dissolution by H₂SO₄ and HNO₃ (Al, Fe), leaching from plants (K, NO₃, SO₄, Mg, Ca), biogenic contaminations (P, organic N, K, NH₄, NO₃). Seasonal variations in the concentrations are most evident for Na and Cl, less for NH₄, SO₄ and NO₃. During the measuring period the flux of NH₄ is significantly increased; for H and SO₄, less for NH₄, Mg, Ca and Fe, the increasing trend was interrupted in winter 1973/74 (oil crisis). Consequences for sampling are discussed.     

Gehalte an Haupt- und Nebenelementen in Konkretionen aus Oberböden von Marschen – Untersuchungen mit einer Mikrosonde

Contents of major and trace elements in concretions of surface samples from marsh soils – Electron microprobe analysis The amounts of 14 elements (Ti, Fe, Mn, Si, Al, Ca, and P, S, Co, Ni, Cu, Zn, Cd, Pb) in concretions of four A horizons of marsh soils were determined by electron microprobe analysis on thin sections. According to the major element compositions the following types of concretions can be distinguished: Ti-Fe(-Mn) concretions (31–39% Ti; 18–29% Fe; 0,3–5,5% Mn); Fe(-Mn) concretions (31–58% Fe; ≤ 1,8% Mn); Fe-Si(-Mn) concretions (6–28% Fe; 8–42% Si; ≤ 5% Mn); Mn-Fe and Mn-Fe-Si concretions (16–40% Mn; 2–9% Fe; 2–15% Si). The formation of Ti-Fe(-Mn) concretions can be explained by adsorption of Fe²⁺ ions under reducing conditions on surfaces of Ti minerals followed by oxidation to Fe(III) oxide. In this way pseudorutile may be formed. Concretions with high Fe and/or Mn content often contain occlusions of carbonates, silicates and/or SiO₂ (bioopal) which may act as nuclei for their growth. Redox processes in marsh soils result in the formation of concretions with dominating Fe or Mn accumulation. Among the group of trace elements, P and S (like Ti and Si) reach their highest concentrations in Fe rich concretions (up to 54.000 mg P/kg and 4.200 mg S/kg). The accumulation of these elements is obviously influenced by anion competition, especially of P and Si, and probably also Ti. Likewise, high amounts of Pb were found in Fe(-Mn) concretions (up to 12.000 mg/kg). Co, Ni, Zn, and Cd show the highest amounts in Mn rich concretions (Co up to 3.400; Ni 1.800; Zn 13.200; Cd 1.000 mg/kg). Cu is also accumulated in some concretions (up to 1140 mg/kg) but no clear affinity to one of the different types of concretions was found.     

Adsorptionsisothermen als Regelgrößen beim Transport von Schwermetallen in Böden

Adsorption isotherms as regulators controlling heavy metal transport in soils The adsorption and desorption of Pb²⁺ and Cd²⁺ from equilibrium solutions with heavy metal contents up to 5000 μg/1 were determined in bulk experiments for soil samples from an acid Braunerde developed in loess loam, taken from the humic surface layer of the mineral soil (0–10 cm) and from the subsoil fairly free from organic matter (30–40 cm). Pb and Cd in solutions were determined by flameless atomic absorption spectroscopy. Pb was more strongly retained in the solid phase than Cd, and higher amounts of heavy metals were retained in the humic surface soil than in the subsoil free of organic matter. In the case of Pb adsorption/desorption showed slight hysteresis in the subsoil. The quantity/intensity (Q/I) relationships found in the experiments could be described by the Freundlich equation. The Q/I-relationships were substituted in the general transport equation. With a simulation model the transport of Pb and Cd through the soil with vertical water flow was calculated by the use of the Continuous Simulation Programming Language (CSMP). Two different cases were considered: a small, continuous increase in the heavy metal input of the soil surface, and a high, instantaneous peak input. Simulation of the transport and distribution mechanisms induced by the inputs over a period of 10 years showed strong retention of lead in the surface layer and consequently a strong damping of the concentration peak in the soil solution. In contrast, cadmium is distributed more quickly over the whole profile, yet the concentration peak in the solution phase is, too, damped considerably in the surface layer by temporary retention in the solid phase. The results of the simulation runs are in accordance with the situation in real soils where often strong accumulation of Pb is found in the top soil, while Cd is accumulated only slightly.     

Verhalten von Schwermetallen in Böden 1. Untersuchungen zur Schwermetallmobilität

Behaviour of heavy metals in soils. 1. Heavy metal mobility 158 soil samples with widely varying composition were analysed for their total, EDTA, DTPA and CaCl₂ extractable contents of Cd, Zn, Mn, Cu and Pb. By means of single and multiple regressions the relations between the different heavy metal fractions and the pH, organic carbon and clay content were considered. The correlations between the total, EDTA and DTPA extractable contents are very close, whereas the CaCl₂ extractable contents are not or only weakly correlated with these fractions. According to these statistical results the former fractions are considered to be the total quantity (total content) and the reactive quantity (EDTA and DTPA extractable contents) of the heavy metals, whereas the CaCl₂ extractable fraction represents the mobile fraction of the heavy metals in soils. The multiple regressions show that the mobile content of heavy metals is closely correlated with each of the quantity fractions and with soil pH. In the same way the proportion of the mobile fraction (in %) of the total, EDTA and DTPA extractable heavy metal content of the soil samples is closely related to the soil pH. Hereby the proportion of the mobile content of the various elements increases in the pH range 6,5 - 3 below element-specific threshold pH values (in brackets) in the order Cd (6,5) > Mn (5,7) > Zn (5,3) > Cu (4,5) > Pb (3,5). In the pH range 6,5 - 7,5 mainly Cu and to a lesser degree also Pb show an increasing mobility due to the influence of soluble organic substances.     

Einfluß unterschiedlicher Gehalte an organischer Bodensubstanz auf das Konsistenzverhalten verschiedener Mineralbodensubstrate

Effect of organic matter content on the consistency of several mineral substrates The effect of organic matter content on the consistency of soils different in texture was investigated. The shifts of the values of the consistency limits towards higher moisture contents are explained by different organic matter contents. The consistency limits of plasticity and liquidity. were significantly dependent on the content of organic matter.     

Simulation von Stickstoff-Austrägen aus Lysimetern

Simulation of nitrogen leaching out of lysimeter tanks Leaching of nitrogen species under different crops and fertilizing patterns through 3 years was simulated with the model LEACHM and compared to observed data from lysimeter tanks. This model simulates not only leaching, but also mobilization, denitrification and volatilization of ammonia. Our aim was to simulate processes which are difficult to observe and to check the capability of the model to predict N-leaching. We tried to estimate as many parameters as possible on the basis of model-independent investigations. We were able to find a parameter set to simulate observed data over three years including different crops quite well. Slow reactions as for instance mineralization of organic matter require data from at least 3 years to determine reliable parameter values. A problem which should be solved in future is the prediction of real evapotranspiration of any crop using pan evaporation data.     

Ökologische Gruppierung von Böden nach ihrem chemischen Bodenzustand

Ecological grouping of soils according to their chemical soil state On the base of the solubility of carbonic acid, calcium carbonate, as well as the oxidic compounds of Al and Fe existing in soils, the following buffer ranges are defined and separated from each other by pH values in the soil solution: Carbonic acid/Carbonate buffer range (pH 6.2 to 8.6), Carbonic acid/Silicate buffer range (pH 5.0 to 6.2), Exchanger buffer range (pH 4.2 to 5.0), Aluminium buffer range (pH 2.8 to 4.2), Iron buffer range (pH 2.4 to 3.8). The buffer capacities are calculated and literature indications regarding buffer rates are compiled. The characteristical chemical soil state is demonstrated for the various buffer ranges with aid of a soil collection. With increasing soil acidification the Ca/Al mole ratio in fine roots decreases from values > 1 to values around 0.3; this is taken as evidence for increasing disposition for Al-toxicity. It is suggested to attach soil horizons to buffer ranges on the base of pH(H₂O) measurements made on field fresh samples. The measurement of pH in salt solution is taken as measure for the amplitude of the chemical soil state in case of H-ion or salt stress.     

Zur Anreicherung von Schwermetallen in Böden und Kulturpflanzen durch praktische Klärschlammdüngung

The accumulation of heavy metals in soils and crops by practical sewage sludge application An accumulation of cadmium, lead, zinc and copper was found in some soils and crops after sewage sludge application as compared with same soils and plants not fertilized with sewage sludge. In the soils the heavy metals mainly were accumulated in the Ap-horizons. The displacement into subsoils was small, in spite of the good permeability of the sandy soils investigated. Relatively the mobility of zinc and cadmium in soils was most distinct. Within the plants the accumulation of the heavy metals was strongest in the roots, however also evident in the shoots of rye, barley and oats. Zinc and copper was concentrated in the grains, too. On the meadow-land an accumulation of the elements investigated was found in the blades of rye grass (Lolium perenne L.).     

Natürlicher gehalt und anthropogene anreicherung von Schwermetallen in den Sedimenten von Elbe, Eider, Trave und Schwentine

The sediments of four rivers in Northern Germany were analysed for heavy metals. 371 sediment samples were taken from 24 investigation sites of the rivers Elbe, Eider, Trave and Schwentine and from North Sea tidal flat areas. Within each investigation site strong positive relationships exist between the heavy metal contents and the contents of the fine size fractions < 2 μm and < 20 μm of the sediments. To compare the metal contents in the sediments from different areas, differences in grain size were eliminated by computing the metal contents for a clay content of 25% by means of regression equations.The fluvial sediments at a few inland investigation sites, as well as the tidal flat sediments are not detectably polluted with heavy metals. Their metal contents could be used as background values for computing enrichment factors of polluted fluvial deposits.Sediments from the river Elbe in and upstream of the port of Hamburg, and from some parts of the rivers Eider and Trave near industrial and densely populated districts, are highly enriched with heavy metals. The highest enrichment factors are for Hg 85, Cd 56, Pb 37, Cu 34, Zn 29, As 19, Cr 6, Ni 4 and Co 3 times the background values.The ecological importance of the heavy metal contents in the sediments is discussed.     

Die Bestimmung von selektiv freisetzbarem Kalium in Parabraunerde aus Löß und Pelosol aus Gipskeuper-Tonmergeln

The determination of preferentially releasable potassium in hapludalf from loess and chromudert from gipskeuper clay marl Octadecylammonium-chloride (ODA)-extractable potassium and interlayer potassium (K_ZW), exchanged after thermal dissociation of adsorbed NH₄, were determined on particle size fractions of soils from gipskeuper clay marl (typic chromudert) and loess sediments (shallow hapludalf). The extraction by ODA is a diffusion controlled K-exchange process. This is shown by the increase of K-release at small sample quantity and K-concentration in the extraction solution. The ODA-potassium supplies (= Biotit-K) of the two typic chromudert were significantly higher than that of the shallow hapludalf (34000 and 30000 kg/ha vs. 22000 kg/ha, to a depth of 55 cm). Biotit-K was highest in the 2-6μm-fraction for both soils. The smaller the particle size, the larger were the amounts of K_ZW In the clay fractions of all samples they reached between 70 and 80% of total K (K_t). XRD-data give evidence of different mineral genesis processes between the two types of sediments. This is supported by the K_ZW-values of the particle-size fractions. The selectively releaseable interlayer potassium is associated with wedge shaped layers of illite. It can be differentiated from the bulk interlayer potassium by its preferential extractability in the first 3 to 5 heating treatments. This potassium quantity is, on an average, 22% of total clay interlayer potassium.     

Ermittlung des Spannungszustandes von Böden aus Werten des Eindringwiderstandes von Sonden

Evaluation of the soil consolidation state by using data from penetration resistance probes Penetration resistance data (EW) from handdriven equipment are easily obtainable because the equipment is simple, cheap, and easily carriable. Measurements are performed quickly without extensive destruction of the site. It is the only method to measure soil strength directly and in situ. Therefore, it is worthwhile to propose an interpretation of the results in order to obtain more conclusive statements on the structural soil state. The procedure applied in our study consists in assigning EW values to the principal stress σ_x and in using an auxiliary construction for the vertical component (σ_z ) as a function of penetration depth. The EW value obtained at the final soil depth is assumed to represent stresses at rest, i.e., K₀ = σ_x/σ_z = 1. Drawing a straight line from this point towards the origin of the coordinates EW and soil depth supplies values of the hydrostatic condition for each depth; e.g., values for σ_z are available for each depth. The coefficient for the equivalent stress at rest (K_0E) per depth can now be calculated simply by comparing the measured EW values with the assumed (hydrostatic) vertical depth function of EW. From a total volume of 29 sets of EW versus depth relations, means and standard deviation of K_0E are presented for arable and forest soils from central Europe. K_0E of forest soils tends to be close to 1 showing approximately normal compaction. In arable sites, K_0E > 2 prevail, indicating precompation. These results confirm the general feasibility of the approach to evaluate the compaction state of soil from EW data. Examples are given to show the K_0E characteristics for special cases of mechanical stress situations.     

Adsorption von Pflanzenschutzmitteln und DOC an Saugkerzen aus Glas und Keramik

Sorption of pesticides and DOC on glass and ceramic suction cups Suction cups are widely used for the sampling of soil solution. Due to sorption and desorption processes the concentration of dissolved substances in the samples may vary considerably depending on the material of the suction cups. In order to minimize these losses, a new glass suction cup was developed. In laboratory studies, aqueous solutions of pesticides and DOC were percolated through both types of suction cups; the concentration of pesticides and DOC in the percolates was examined. The pesticides pendimethaline, terbuthylazine, metolachlor and chlortoluron were tested at concentrations of 2, 20, and 200 μg 1⁻¹. The average losses due to sorption by the suction cups were 10% (1.1—31%) for the ceramic cups and 3.1% (0—11%) for the glass cups. Sorption effects increased with increasing hydrophobicity of the pesticides and decreasing pesticide concentrations. Thus, at a concentration of 2 μg 1⁻¹ ceramic cups sorbed 31% of pendimethaline compared with 7.7% in the case of glass cups. Corresponding tests with soilborne DOC solutions yielded comparable results. Ceramic suction cups adsorbed up to 50% of the DOC input concentration, while glass cups retarded 2.4% on average. These results are especially noteworthy because soilborne dissolved organic substances are effective sorbents and carriers for pesticides. The new type of glass suction cups may help to improve the results of pesticide field studies and, in consequence, the assessment and prediction of the leaching behavior of pesticides.     

Bestimmung von Mikronährstoffen und Schwermetallen in Böden mit dem Verfahren der Elektro‐Ultrafiltration (EUF) durch Zugabe von DTPA

With the electro–ultrafiltration (EUF) technique, the plant availability of several plant nutrients in soils can be characterized. The basic principle of EUF is that an electric field is induced using platinum electrodes. Ions in the soil suspension move either to the cathode or to the anode and are filtrated through ultra‐membrane filters. In the standard EUF procedure, two extractions steps are used: 30 min at 20°C and 5 min at 80°C. However, the determination of micronutrients and heavy metals with the standard EUF procedure is not possible, because the solubility of these elements in water is low and most of the watersoluble elements are precipitated when passing the platinum electrodes. The addition of DTPA, a well known complexing agent, during a third EUF fraction (5 min at 80°C) enables extraction of micronutrients and heavy metals. Highest concentrations in the 33 soils of the study were found for iron, followed by zinc, manganese, lead, copper, and nickel. Lower concentrations were obtained for cobalt, chromium, cadmium, and molybdenum. For two soils, the EUF/DTPA procedure was compared to CaCl₂/DTPA and EDTA soil extraction methods, showing that higher or comparable amounts were found with CaCl₂/DTPA and much higher amounts with the EDTA method. These results reveal that the EUF/DTPA technique in principle can be used for the determination of plant‐available micronutrients and heavy metals. However, in a next step the relationship between EUF/DTPA‐extractable elements and their availability for plants needs to be quantified.