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.     

Die Beeinflussung der Bodenlösung durch Saugkerzen aus Ni-Sintermetall und Keramik

Influencing soil solution by suction cup material (Ni, ceramics) The influence of suction cup material (ceramics, Ni) on the chemical composition of the soil solution was tested in the laboratory by percolating soil solutions of different concentration (pH ～ 4.0). Ceramic cups of P 80 material can be used for the collection of soil solution and its determination for the concentrations of H, Na, K, NH₄, Ca, Mg, Mn, Al, S, Cl and NO₃. They can't be used to determine P-concentrations. The cups must be prepared and preconditioned by leaching large amounts of equilibrium soil solution which should not be oversaturated with respect to the solubility product of AlOHSO₄. The changes in the concentration of extracted soil solution when it passes through the cups depend upon the extracted volume. The lower the volume, the greater are the changes. Sintered Ni-cups show many severe disadvantages (decreasing permeability, insufficient resistence against acid solutions, large variability among single cups), and can only be used for cases where Na, Ca, K, and S are to be determined. Ceramic cups of the type ‘Czeratzki’ are comparable with those of P 80. However, they can only be used, when the concentrations don't vary too much and large amounts of water can be extracted.     

Aluminium contamination of acid soil solution isolated by means of porcelain suction cups: a reply to a paper by Hughes & Reynolds (1990) and an interpretation of aluminium release

Possible aluminium contamination of acid soil solutions isolated by use of porous porcelain suction cups (‘P.80 type’) was reported by Raulund-Rasmussen (1989). The aluminium release was explained by a proton-induced dissolution of cup material. Hughes & Reynolds (1990) suggested that the aluminium release and proton consumption could be explained by an ion-exchange reaction. In an attempt to understand the mechanism and thereby also the usefulness of suction cups, laboratory experiments were carried out to define mineralogical and chemical composition, stability under acid conditions, cation exchange capacity, and reactivity under conditions relevant to the field. The cups consisted of mullite and corundum (65% Al₂O₃) as shown by X-ray diffraction analysis. The cation exchange capacity of the cups was too low (0.65 μmol_c per cup) to explain the observed contamination of isolated soil solution. Ground cup material dissolved slowly in acid. Investigations on whole cups showed that aluminium release to acid test solutions depended on the time of exposure. It is concluded that porcelain suction cups may lead to contamination of isolated soil solution depending on: (i) the intake rate, (ii) the rinsing procedure before sampling, and (iii) the composition of the soil solution (pH and aluminium ion activity being important parameters).     

Schwermetall-Sorptionsverhalten einer Saugkerze aus porösem Borosilikatglas

Heavy metal sorption of a new developed porous borosilicate glass suction cup In relation to conventional ceramic P 80-suction cups, a porous borosilicate glass suction cup shows distinctly lower sorption and desorption regarding the heavy metals Pb and Cu.     

Measurement of redox potential inside a suction probe

Ceramic suction probes were combined with internal redox electrodes in order to reduce the deviation between site parallels, and to relate redox potential measurements directly to the solution analyzed chemically. In a laboratory experiment soil material was water‐saturated for 49 days and temporal changes of redox potential and pH outside and inside the ceramic suction probes were recorded. Furthermore, iron concentrations inside the ceramic cups were detected. Results indicate that a device combining ceramic suction probes and redox electrodes is in principal possible. However, the device used here could not reduce the deviation between site replications compared to free installed redox electrodes. Increasing iron concentrations due to decreasing redox potentials outside and inside the ceramic suction probes indicate that the soil water iron dynamic is at least partly measurable using this device.<?show $6#>     

Short Communication — Kurzmitteilung Siliziumcarbid — eine Alternative zur Aluminiumoxid‐Saugkerze?

Siliciumcarbide — is it an alternative to suction cups made of aluminumoxide? Siliziumcarbide (SiC) is a novel non‐oxide ceramic material. We tested differently preconditioned SiC and aluminum‐oxide ceramics (P80) with respect to their influence on the solution passing through. For this we used a cation standard, an anion standard and a soil solution. Both ceramics released considerable amounts of Na and Al. However, in most cases SiC showed better results for anions and dissolved organic carbon. Therefore it may be a promising task to improve the properties of SiC by minimizing sinter additives and optimized conditioning procedures, and develop improved suction cups.     

Effects of grazing strategy on limiting nitrate leaching in grazed grass‐clover pastures on coarse sandy soil

Urinations of ruminants on grazed pastures increase the risk of nitrate leaching. The study investigated the effect of reducing the length of the grazing season on nitrate leaching from a coarse sandy, irrigated soil during 2006–2007 and 2007–2008. In both years, precipitation was above the long‐term mean. The experiment was initiated in a 4‐yr‐old grass‐clover sward in south Denmark. Three treatments were as follows grazing only (G), spring cut followed by grazing (CG) and both spring and autumn cuts with summer grazing (CGC). Nitrate leaching was calculated by extracting water isolates from 80 cm depth using ceramic suction cups. Because of considerable variation in measured nitrate concentrations, the 32 installed suction cups per treatment were insufficient to reveal differences between treatments. However, weighted nitrate leaching estimations for G, CG and CGC showed estimated mean nitrate N concentrations of 23, 19 and 13 mg/L for an estimated proportion area occupied by urine patches of 0.33, 0.26 and 0.16, respectively. Thus, N concentrations in G and CG exceeded the EU limit of 11.3 mg N/L. Under the prevailing conditions, the time of urination did not appear important. The estimated background leaching calculated from suction cups presumably not situated under urine patches resulted in mean nitrate N concentrations of 2.6 mg/L.     

Ionic contents of leachate from grassland soils: a comparison between ceramic suction cup samples and drainage

Abstract. Ceramic suction cups were used to obtain samples of soil solution from permanently grazed swards receiving 200 kg N/ha/y. The suction cups were installed in 1 ha plots at 10, 30 and 60 an depth in a poorly drained, heavy clay soil in S. W. England. The plots were hydrologically isolated from each other by perimeter drains which channelled surface runoff water into v-notch weirs. In one treatment, artificial drainage by a system of field and mole drains also converged to outfalls through v-notch weirs, which enabled samples to be taken. Nitrate and a range of other ionic constituents were examined over a 12 month period in soil solutions taken from the suction cups and compared with leachate obtained from the field drains and surface channels. Field drain samples frequently exceeded the EC limit of 11.3 mg nitrate-N/1, but concentrations in suction cups obtained during the same period did not, and were up to ten-fold less. Although correlations for ions were found between different sampling depths and drainage samples, no clear patterns emerged. It was concluded that suction cups were inappropriate for the determination of the overall leaching losses in this soil type, but provided useful data on changes in ionic concentrations which occurred in different soil horizons through to drainage outfalls.     

Novel micro–suction‐cup design for sampling soil solution at defined distances from roots

Micro–suction cups made of nylon membranes and polyacrylic tubes with planar geometry of the membrane were designed for repeated sampling of rhizosphere solution at defined distances from a root monolayer. Adsorption tests revealed that the materials used (nylon membrane, polyacrylic tube) have little influence on the concentration of heavy metals in the sample solution, whereas some organic acids are partly retained by the suction cup. A sampling protocol was developed for collecting extremely small solution volumes (i.e., droplets of 28.3±2.46 μl) for subsequent measurements of trace elements using ICP‐SFMS. A homogeneity test showed that soil‐solution concentrations of Ca, K, Mg, and Ni could be reproduced independent of the suction‐cup position in a rhizobox experiment without plants. In a similar experiment, the rhizobox was planted with the Ni hyperaccumulator Thlaspi goesingense. Compared to more distant soil layers, an increase of Ni and a concurrent decrease of Ca, K, and Mg at 1 mm distance from the root plane was found. These changes can be related to plant uptake and mobilization processes. Our results show that the novel micro–suction cups are a valuable tool for elucidating rhizosphere processes.     

Aluminium contamination and other changes of acid soil solution isolated by means of porcelain suction-cups

Comparison was made between the chemical composition of soil solutions isolated by means of a suction method using porcelain cups and by centrifugation. The soil solutions were isolated from three depths of field plots, where the soil (Typic Haplohumod) had been subjected to various pretreatments.
The cups were made of mullite and corundum as shown by X-ray diffraction analysis. The material when powdered had a cation exchange capacity of about 10meq kg⁻¹. Solutions with similar ionic strengths were obtained by the two methods, but the cups were found to release substantial amounts of Al and to adsorb H, Ca, K, Na and organic matter.
After the cups had been placed in the soil for more than 7 months, calculations suggested that the Al activity in cup solutions was controlled by amorphous gibbsite. This amorphous material was probably produced by proton-induced decomposition of part of the cup material. It is concluded that such cups are improper for isolation of soil solution from acid soils.     

Einbaubedingte Gefügeänderungen in der Bodenzone um keramische Saugkerzen

Soil fabric changes due to the installation of ceramic suction cups Samples from different sites containing ceramic suction cups with the surrounding soil were taken. After embedding and hardening in polyester resin polished blocks and thin sections were prepared. Soil zones up to 2 cm wide around the cups show up as more or less influenced. Former interaggregate or channel voids disappear. Clay coatings or infillings are smeared over into reoriented streaks. These features appear in dependence upon the predominant grain size distribution. In medium to fine grained soils the said zone is superimposed by a concentric system of fine cracks forming scaly shaped lamellae in perpendicular orientation around the cups. In coarse grained soils the extent of displacement and regrouping of sand grains is hardly visible. Piercing through a banded fabric (B_t-Band), a striking side and downward displacement of grains became obvious. In all cases a flushed silt or fine sand sludge works well to improve the soil/cup contact.     

Micro-scale variation of solid-phase properties and soil solution chemistry in a forest podzol and its relation to soil horizons

In order to evaluate micro-scale heterogeneities 55 micro suction cups were placed in an array at 15 mm intervals in a profile face of a cambic podzol. The chemistry of soil solution (mineral anions, pH, UV absorption as a measure for DOC) was compared with solid-phase properties from soil samples (2 cm³ volume), which had surrounded the suction cups. Sequential extraction techniques (water, NF₄Cl, hydroxylamin-hydrochloride, citrate-bicarbonate, oxalate, dithionite-citrate-bicarbonate) and base titrations were applied to characterize the solid phase. Although the average soil solution concentrations between horizons often differed significantly, the spatial distributions of pH and SO₄^2? did not correlate with soil horizon borders. Even if concentration isolines and soil horizon borders were parallel, marked concentration gradients could be observed within individual soil horizons. The less intense the interaction between solute ion and soil matrix, the greater was the variation in solution concentration within a soil horizon. For the soil solid phase only a weak correlation of slow buffer reactions to soil horizons was found. The distribution of extractable Fe and Al was typical for a podzol profile, however, with very steep gradients within single soil horizons. Except for pH, which was related mainly to citrate-bicarbonate extractable aluminium, no solid-phase characteristic showed a clear correlation with soil solution chemistry.     

Verlagerung und Dispersion von Chlorid-, Bromid-, Nitrat- und SulfatTracern in zwei typischen Auenböden

Translocation and dispersion of chloride, bromide, nitrate and sulfate tracers in two typical Fluvi-Eutric Cambisols Chloride, bromide, nitrate and sulfate were applied as tracers on two weakly to moderately acidic Fluvi-Eutric Cambisols. The soil solution was sampled by ceramic suction cups down to a soil depth of 180 cm. At definite time intervals also soils material was taken from different depth to produce the soil saturation extract. The concentrations of the non-adsorbed anions chloride, bromide and nitrate were very similar in the suction cup solutions and in the saturation extracts, whereas the concentrations of the weakly adsorbed sulfate partially showed considerable differences. Obviously both methods extract in acid soils different fractions of the dissolved sulfate. By comparison of marked sulfate peaks with those of chloride, bromide or nitrate, which occur at the same time in different soil depth, a Kd value of 0.16 1/kg can be calculated for the Ap horizon and of 0.02 1/kg for the subsurface horizons of one Fluvi-Eutric Cambisol. Values of the dispersivity of the different horizons were estimated by varying the values of the dispersivity reported in the literature until the best fit of the simulated anion depth distribution to the measured values was found. The estimated dispersivities varied between 1.0 cm in the Ap horizon and 1.8 and 10.0 cm in the subsurface horizons.     

Sorption of trace metals by suction cups of aluminium oxide,ceramic and plastics

The sorption properties of ceramic, aluminium oxide and plastic suction cups in respect to trace metals (Be, Cd, Co, Cu, Mn, Ni, Pb, Zn) were compared in laboratory and field experiments. The sorption effect is determined by the level of the cation exchange capacity of the cup material, the pH-value of the soil solution, the content of dissolved organic carbon, the sampling rate and the sampled volume. Sorption was generally negligible only in case of cobalt, manganese and nickel. At low pH-values no retention of trace metals occurred with the exception of lead in the aluminium oxide and the ceramic cups. At pH-values of about 8 cadmium and zinc were strongly sorbed only by aluminium oxide and ceramic cups whereas beryllium, copper and lead were markedly sorbed at this pH-range by all cup types. These results are only valid for the boundary conditions used. Whenever a suction cup's suitability is in doubt it should be tested after a conditioning procedure using realistic boundary conditions.     

The desorption solution — an alternative approach to measure water soluble ions in soils

Although the composition of the soil solution has important ecological information, there is no general consensus for obtaining and analyzing of the soil solution. This study presents an alternative procedure to obtain the soil solution and determine all relevant anions and cations. The soil samples are taken with an auger. 10—20 g of field moist soil are desorbed in a pressure chamber at 170 kPa (pF 3.2), with a cellulose acetate membrane filter (∅︁ < 0.45 μm) as capillar bridge between the interior and exterior of the chamber. The desorption procedure is performed at 4°C for 24 hours and yields up to 1.0 ml soil solution, depending on the actual water potential. If more soil solution is needed, the soil may be replaced by another aliquot of the same sample. 0.15 ml of soil solution is sufficient for analysing all cations and anions, which account quantitatively for the ion balance with a capillary electrophoresis. Compared with suction cups, ion concentrations in desorption solutions are, although generally lower, in the same order of magnitude. The advantage of this method is that no field equipment is needed, apart from the auger. Even in heterogeneous forest soils, water soluble ions can be monitored with a high spatial resolution and without any dilution effects, which are common in the most laboratory methods. The problem of lacking spatial representativity in stationary lysimeter stations is also overcome. Additionally it is possible to obtain and analyze soil solutions in a suction range where suction cups fail.     

Mikroskalige Variabilität der Bodenlösungschemie - Ergebnisse eines Laborversuchs zum Vergleich von Standard- und Mikro-Saugkerzen

Microscalic variability of soil solution chemistry - results of a laboratory experiment comparing standard - with micro suction cups In a laboratory experiment with an undisturbed soil column, the chemistry of soil solution collected by a standard suction cup (Ø 2 cm) was compared with that of 20 micro suction cups (Ø I mm) installed in the same soil depth. The standard cup showed comparable concentrations of inorganic anions with the soil column leachate, because preferably the main water paths of the soil column were sampled. In contrast, about 30 % of the micro suction cups sample soil compartments that have a different solution chemistry. In these cases the differences between standard and micro suction cups decrease in the order nitrate, chloride, sulfate. Standard suction cups seem to be the right sampling device for the investigation of element fluxes through soil. To get information about plant availability of ions they are inadequate, due to their dimension. Here micro suction cups are more appropriate, because their dimension is comparable to plant roots.     

Zusammensetzung und Speziierung der Bodenlösung eines mit Schwermetallen belasteten kalkreichen Bodens

Composition and Speciation of Soil Solution collected in a Heavy Metal polluted calcareous Soil Close to a brass foundry, which had emitted heavy metal containing dusts for over 80 years, soil water was collected in the topsoil (18 cm) and in the subsoil (40 cm) of a severely polluted Calcic Fluvisol by means of polyethylen suction cups over a period of 2 years. The total metal content of the topsoil (extracted with 2M HNO₃ at 100 °C for 2 hours) was 38 nmol g^?1, 24 μmol g^?1, and 25 μmol g^?1 for Cd, Cu, and Zn, respectively. The mean heavy metal concentrations of the soil solution were 0.5 mol L^?1, 300 nmol L^?1, and 200 nmol L^?1 in the topsoil and 0.6 nmol L^?1, 90 nmol L^?1, and 30 nmol L^?1 in the subsoil for Cd, Cu, and Zn, respectively. Solubility calculations showed that the soil solutions were undersaturated with respect to heavy metal carbonates as well as to hydroxides. It seems that the heavy metal concentration is determined by sorption processes rather than by precipitation. The composition of the soil solution has been shown to be governed by the presence, of calcite, by the soil temperature and by the partial pressure of CO₂ in the soil air. The pCO₂ in the soil air (in both depths) has been estimated at 2 mbar during the winter term and at 20 mbar during the summer term. A corresponding increase of the concentration of macroelements (Ca, Mg, Na) as well as of total dissolved carbonate and of dissolved organic matter (DOC) has been measured in the summer half year. No significant seasonal variations of the heavy metal concentrations were detected and no correlations with concentrations of other components could be found.     

Sickerwassergewinnung mittels Saugkerzen – eine Literaturstudie

Sampling seepage water with suction cups – a literature study The article presents a literature study concerning the sampling of seepage water with suction cups. It gives a general view about construction and materials of different types of suction cups as well as proposals for the installation and arrangement of sampling equipments. Furthermore the article deals with questions related to the release or the sorption of substances by the cup material. Other problems like the influence of the applied suction on the concentration of the solutants in the seepage water sample and the potential field around the suction cup are discussed.     

Evaluation of porous ceramic cups for monitoring soil-water aluminium in acid soils: comment on a paper by Raulund-Rasmussen (1989)

Following recent observations by Raulund-Rasmussen (1989) implicating A1 contamination of soil solutions isolated by suction-cup samplers, A1 release from porous ceramic cups in acid solutions was investigated. In our studies a flush of Al, followed by a gradual decrease in leaching over successive extractions was observed. The amount of Al released was retarded by the presence of 37 μmol dm^?3 of A1 in solution. Gibbsite solubility controls were not observed; all solutions isolated by the cups were undersaturated with respect to amorphous gibbsite. The cups evaluated in this study are appropriate for sampling acidic soil solution, provided they are suitably pretreated and then equilibrated in the field before use.     

Comparisons of methods for measuring the leaching of mineral nitrogen from arable land

Comparisons were made between 1988 and 1991 to evaluate three methods of estimating the leaching of mineral nitrogen (N) from unstructured freely draining sandy loam and loamy sand soils. The studies compared the drainage patterns and quantities of N (almost exclusively nitrate) leached from monolith lysimeters with those estimated from ceramic suction cups and soil core extracts. The latter two methods gave direct measurements of the mineral N concentrations in drainage, but required an estimate of the drainage volume calculated from meteorological observations and evapotranspiration equations to give total N leached. A bromide tracer was also used to confirm conclusions from nitrate leaching studies. There was a delay in the onset of drainage from free draining lysimeters because they lack the subsoil matric potential of field soils. However, total annual drainage measured by lysimeters or calculated from meteorological observations was similar, providing that return to field capacity was correctly identified in the field soil. During the first year there were discrepancies between methods which were attributed to soil disturbance during lysimeter and/or ceramic cup installation. In the second and third years of the experiment, estimates of N leaching losses using the lysimeters and ceramic cups were in good agreement. Nitrate concentrations in soil solution at a depth of 130 cm measured from soil core extracts were smaller than found by the other methods during the second year and the peak concentrations were significantly different (P<0.05). However, total overwinter N leached was not significantly different. Thus, while lysimeters and cups can be used to quantify leaching losses on unstructured, free draining soils if used correctly, the use of soil core extracts is questionable.