Downward migration of radiocaesium in organic soils across a transect in Scotland.

Following the accident at the Chernobyl nuclear power plant in 1986, radioactive materials including (137)Cs were distributed over large parts of the former Soviet Union and Europe. Due to the relatively long physical half-life of (137)Cs (30.1 y) measurable activity concentrations can still be observed in the natural environment. We have determined the depth distribution of (137)Cs from the testing of nuclear weapons in the atmosphere and Chernobyl, in eight highly-organic soils along an approximately east to west transect across the Central Highlands of Scotland. The (137)Cs activity concentrations in the soil profiles, corrected for radioactive decay to May 1986, were between 2.8 and 14.4 kBq m(-2). There were differences in the pattern of distribution of (137)Cs in the soil profiles. The mean migration depth of (137)Cs in the soil profiles was 12.2 cm with a range between 8.2 and 17.4 cm. Quantitative mineralogical analysis of the ash obtained after heating the soil to 400 °C indicated that clay minerals alone did not have a prime role in controlling the migration of (137)Cs down the profile.

Effect of clay content and wetting-and-drying on radiocaesium behaviour in a peat and a peaty podzol.

The interaction of radiocaesium with peat under two moisture regimes was studied in laboratory experiments and by growing ryegrass in pot experiments to simulate changing field moisture conditions. A peat untreated and treated with 5% by weight of clay containing 46% illitic minerals, and a peaty podzol naturally containing 4.5% mineral matter on a dry weight basis were contaminated with (134)Cs and incubated. The soils were exposed to 8 wetting-and-drying cycles or kept constantly wet during 40 days. Extraction of the peat with 1 M CH(3)COONH(4) (pH 7) repeated after each wetting-and-drying cycle indicated increasing (134)Cs fixation with time of incubation. The peat treated with clay showed a much higher (134)Cs fixation than that without clay. The pot experiment with the incubated soils showed a (134)Cs transfer to ryegrass of the same order for the peaty podzol as for the peat treated with clay. For the peat untreated with clay the (134)Cs transfer to ryegrass was much greater. Wetting-and-drying the peat, with or without clay, increased the overall yield of grass and the concentration and uptake of (134)Cs over 5 consecutive harvests. K-fertilisation increased the yield of plant material (except for the peat with added clay), decreased the concentration of (134)Cs, but had no significant effect (p=0.05) on the resultant uptake of (134)Cs. Mixing clay with the surface layer of organic soils appears to be an effective means of decreasing radiocaesium transfer to field crops in fallout situations.

Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS.

Newly developed methods involving an on-line combination of sedimentation field-flow fractionation-inductively coupled plasma-high resolution mass spectrometry (SdFFF-ICP-HRMS) have been used to study the distributions of extractable heavy metals in a soil which had been treated with sewage sludge contaminated with Cu or Pb. The relationship of these metals with other elements in the colloidal fraction was also investigated. The colloidal fraction from the soil was obtained by repeated gravitational sedimentation and extracted with 0.11 M acetic acid, 0.1 M hydroxylamine hydrochloride, 0.05 M ethylenediaminetetraacetic acid disodium salt (EDTA) or aqua regia to assess the potential availability of the metals Cu and Pb. Large proportions of the Cu and Pb were extracted by EDTA, approaching that removed by aqua regia, whereas < 10% of the aqua regia extractable metals were removed by acetic acid and hydroxylamine chloride. The distributions of the heavy metals, the major mineral forming element (Al) and the elements forming sesquioxides (Fe and Mn) within different size classes (0.05-1 microm) of the colloidal fraction were measured using SdFFF-ICP-HRMS before and after extraction with EDTA. This information provides an insight into the composition of the colloids and the distributions of metal contaminants. In the contaminated soil colloids, the concentration of Fe, Mn and Pb is greatest in the smaller particles (<0.2 microm). In contrast, the Cu concentration is constant over the size range studied. Iron oxide surface coatings probably play a significant role in Pb adsorption on soil particles, but may be less important for Cu. The combination of selective chemical extraction, SdFFF and ICP-HRMS provides a means of determining the distribution of potentially available heavy metals within the colloidal fraction of contaminated soils.

Stable isotope dilution-mass spectrometry for determining total selenium levels in plants, soils and sewage sludges.

Quantitation of selenium in plants, soils and sludges was achieved by isotope dilution-mass spectrometry using a benchtop instrument. Samples for analysis were spiked with (76)Se isotope solution. Plant material was digested on a heating block at 150 degrees C using a mixture of nitric acid and hydrogen peroxide. Selenium in soils and sludges was released by treatment with nitric acid followed by digestion with nitric and hydrofluoric acids. Selenium in the digests was reduced to Se(IV) with hydrochloric acid and derivatised with nitro-1, 2-phenylenediamine to 5'-nitropiazselenol. Analysis by gas chromatography-mass spectrometry using selected ion monitoring was validated using certified reference materials (CRMs) and gave results within the certified range with a low standard deviation. The CRMs plant (Chinese cabbage leaves) and soil (Chinese soil) were found to contain (+/-95% confidence limits) 0.091(+/-0.007) mug g(-1) and 1.67(+/- 0.04) mug g(-1)Se respectively. The certified values were 0.083(+/-0.008) mug g(-1) and 1.56(+/-0.12) mug g(-1) respectively. The selenium content of four different freely drained acid Scottish soils under grasslands was in the range 0.5-0.8 mug g(-1) air-dried soil. Sewage sludges were found to contain measurably more selenium than the soils, and samples of three sludges taken from sites in the UK contained between 1.1 and 3.5 mug g(-1) dry matter.

Extraction of ergosterol from peaty soils and determination by high performance liquid chromatography.

The ergosterol content of soil can be used as an indicator of fungal activity. A method has been developed for the extraction and determination of ergosterol in organic soils, as part of a study to assess the correlation between fungal activity and the sequestration of metal pollutants. The moisture content of the soil affected the extraction process. Four consecutive extractions with methanol removed >95% of the ergosterol that can be obtained from the fresh sample (63% moisture) by exhaustive extraction. By freeze drying the soils prior to extraction (a) up to 35% more ergosterol was extracted after a single extraction, (b) >90% of the recoverable ergosterol was collected in two extractions and (c) the repeatability of the extraction was improved. Storage of soil extracts in the absence of light prevents degradation of ergosterol. A previously reported method for determination of ergosterol by HPLC has been improved by modification of the eluant composition. With 46% methanol/46% acetonitrile/8% dichloromethane, ergosterol was eluted with good resolution approximately 8 min after injection of 20 mul of the extract. The detection limit of the HPLC method was 0.5 mug/ml ergosterol, equivalent to 0.06 mug/g in 25 g fresh soil. Changes in ergosterol contents of peaty soil treated with fungicide, and in samples of the peaty podzol and a humus iron podzol in the vicinity of fungal fruiting bodies, have been determined.

Determination of dissolved organic phosphorus in soil solutions by an improved automated photo-oxidation procedure.

An improved automated photo-oxidation procedure to determine dissolved organic phosphorus in soil solutions is described. Organically combined phosphorus is converted quantitatively to orthophosphate under UV radiation and an excess of dissolved oxygen. The orthophosphate is determined spectrophotometrically using the Murphy and Riley procedure, modified by increasing the concentration of ascorbic acid. Fluoride was added to the system to overcome potential interference when working with soil solution. The limit of detection was 0.64 mug/l. PO(4)(-3) -P and calibration was linear over the range studied (5-1000 mug/l. PO(4)(-3) -P).

Acquisition and analysis of GFAAS data.

Since its inception as an analytical technique some 30 years ago atomic absorption spectrometry has become a firmly established method for the analysis of trace metals. Graphite furnace atomic absorption spectrometry provides the analyst with the capability of analysis of solutions containing mug l(-1) levels of the analyte, but, because of the transient nature of the signals, a sophisticated approach to the data aquisition and handling of data is required. Most modern commercial graphite furnace atomic absorption spectrometers have built in microprocessors for this purpose but they often have limited capability for extensible user programs and limited data storage facilities. In this communication we describe the use of an Apple IIe microcomputer for the acquisition of data from a Pye Unicam SP9 graphite furnace atomic absorption spectrometer. Details of the interface which utilizes an in-house designed AD converter, and an overview of the Pascal and assembler programs employed are given. The system allows the user to record, store and dump the graphical display of the furnace signalsfor all analyses performed. Files containing details of peak height, and area are formatted on an eight-column spreadsheet. Details of sample type, concentrations of standards, dilutions and replication are entered from the keyboard. The calibration graph is constructed using a moving quadratic fit routine and the concentrations of the analyte in unknown solutions calculated. In addition to this, greater processing power and integration of the data into other analytical schemes can be achieved by exporting the data to other software packages and computers. Details of data transfer between the Apple IIe and an Amstrad PC 1512 are given. Some examples of the use of the system in the development of an analytical methodfor silver in plant material are given.