Geochemical variations in aeolian mineral particles from the Sahara-Sahel Dust Corridor

The Sahara-Sahel Dust Corridor runs from Chad to Mauritania and expels huge amounts of mineral aerosols into the Atlantic Ocean. Data on samples collected from Algeria, Chad, Niger, and Western Sahara illustrate how corridor dust mineralogy and chemistry relate to geological source and weathering/transport history. Dusts sourced directly from igneous and metamorphic massifs are geochemically immature, retaining soluble cations (e.g., K, Na, Rb, Sr) and accessory minerals containing HFSE (e.g., Zr, Hf, U, Th) and REE. In contrast, silicate dust chemistry in desert basins (e.g., Bodélé Depression) is influenced by a longer history of transport, physical winnowing (e.g., loss of Zr, Hf, Th), chemical leaching (e.g., loss of Na, K, Rb), and mixing with intrabasinal materials such as diatoms and evaporitic salts. Mineral aerosols blown along the corridor by the winter Harmattan winds mix these basinal and basement materials. Dusts blown into the corridor from sub-Saharan Africa during the summer monsoon source from deeply chemically weathered terrains and are therefore likely to be more kaolinitic and stripped of mobile elements (e.g., Na, K, Mg, Ca, LILE), but retain immobile and resistant elements (e.g., Zr, Hf, REE). Finally, dusts blown southwestwards into the corridor from along the Atlantic Coastal Basin will be enriched in carbonate from Mesozoic-Cenozoic marine limestones, depleted in Th, Nb, and Ta, and locally contaminated by uranium-bearing phosphate deposits.     

Sequestration of pyrrolizidine alkaloids by larvae ofTellervo zoilus (Lepidoptera: Ithomiinae) and their role in the chemical protection of adults against the spiderNephila maculata (Araneidae)

Summary Life stages of the primitive Australian ithomiine butterflyTellervo zoilus and its larval hostplant, the apocynaceous vineParsonsia straminea, were quantitatively assayed for pyrrolizidine alkaloids (PAs). PAs were found in all stages, mainly as N-oxides, being most concentrated in larvae and freshly-emerged adults. Although adults feed at various confirmed PA sources this probably does not compensate for losses, as wild-caught adults had considerably lower concentrations of PAs. The main alkaloid present in both freshly-emerged adults and in leaves of the host-plant was lycopsamine (1b), stored by butterflies in the N-oxide form. Its presence in higher proportion, in relation to intermedine (1a), in larvae, pupae and adults ofTellervo in relation to the host-plants suggests the inversion of intermedine to lycopsamine by the insects. No 14-member ring macrocyclic PAs were detected in either food-plant or butterflies. Several other PAs were found in wild-caught adults reflecting visits to other PA sources. PAs were also found in high concentrations in freshly-emerged individuals of the danaineEuploea core bred onParsonsia straminea. Wild-caughtDanaus affinis had high PA levels acquired from adult feeding. Freshly emergedEuploea raised onIschnocarpus frutescens andDanaus raised onIschnostemma carnosum (both PA-free) were preyed on by the orb weaving spiderNephila maculata, and showed no PAs. In all cases where PAs were present, most butterflies were liberated, usually cut out of the web unharmed, byNephila. The spider's response was not closely linked to PA concentration, however, and may also depend on hunger levels and previous experience with PA-containing butterflies. All control and other non-PA containing butterflies were consumed although rejection of some body parts of freshly-emergedDanaus affinis suggests that compounds other than PAs may be involved.     

Trace gas emissions from German agriculture as obtained from the application of simpler or default methodologies

For the assessment of emission inventories matching pairs of activities (emission explaining variables) and emission factors are used. Simpler and detailed methodologies are proposed within the emission inventory handbooks. The data sets needed to serve the detailed methodologies have not been at public disposal so far. Therefore, this paper investigates the applicability of simpler methodologies to the statistical data sets of activities officially available in Germany. The statistical data base for the assessment of emissions from fertilised soils is adequate if one assumes that fertilisers sold in one financial year are applied in the same year. For grassland, statistical data describing the actual management do not exist. Lack of nitrogen inputs with crop residues and due to nitrogen fixation make it impossible to deduce the respective emissions. The assessment of indirect emissions due to reactions of leached nitrogen is also impossible. For extensively managed grasslands, data concerning fertiliser application or grazing are missing when calculating emissions. The determination of emissions from organic soils presupposes the knowledge of both the area concerned and the degree of mineralisation which has been attained at the time of the inventory. The results of the biennial animal census meet the requirements of the simpler methodologies. However, the assumptions made to evaluate the mean emission factors are not correct in many cases, as far as animal performance, housing, storage and application of animal excreta are concerned. The simpler methodologies are biassed, as the emission factors are (Northwest) European means. Changes in the raising of statistical data make the construction of meaningful time-series difficult.     

Practical considerations for addressing uncertainties in monitoring bulk deposition

The assessment of the deposition of both wet (rain and cloud) and dry sedimenting particles is a prerequisite for estimating element fluxes in ecosystem research. Many nations and institutions operate deposition networks using different types of sampler. However, these samplers have rarely been characterized with respect to their sink properties. Major errors in assessing bulk deposition can result from poor sampling properties and defective sampling strategies. Relevant properties are: sampler geometry and material, in particular the shape of the rim; sink properties for gases and aerosols; and microbial transformations of the collected samples. An adequate number of replicates allows the identification of samples which are contaminated, in particular by bird droppings. The paper discusses physical and chemical properties of the samplers themselves. The dependence of measurement accuracy on the number of replicates and the sampling area exposed is discussed. Recommendations are given for sampling strategies, and for making corrections and substitution of missing data.     

Monitoring and modelling of biosphere/atmosphere exchange of gases and aerosols in Europe

Monitoring and modelling of deposition of air pollutants is essential to develop and evaluate policies to abate the effects related to air pollution and to determine the losses of pollutants from the atmosphere. Techniques for monitoring wet deposition fluxes are widely applied. A recent intercomparison experiment, however, showed that the uncertainty in wet deposition is relatively high, up to 40%, apart from the fact that most samplers are biased because of a dry deposition contribution. Wet deposition amounts to about 80% of the total deposition in Europe with a range of 10-90% and uncertainty should therefore be decreased. During recent years the monitoring of dry deposition has become possible. Three sites have been operational for 5 years. The data are useful for model development, but also for model evaluation and monitoring of progress in policy. Data show a decline in SO(2) dry deposition, whereas nitrogen deposition remained constant. Furthermore, surface affinities for pollutants changed leading to changes in deposition. Deposition models have been further developed and tested with dry deposition measurements and total deposition measurements on forests as derived from throughfall data. The comparison is reasonable given the measurement uncertainties. Progress in ozone surface exchange modelling and monitoring shows that stomatal uptake can be quantified with reasonable accuracy, but external surface uptake yields highest uncertainty.     

Simple biotoxicity tests for evaluation of carbonaceous soil additives: establishment and reproducibility of four test procedures

Biochar derived from pyrolysis has received much attention recently as a soil additive to sequester carbon and increase soil fertility. Hydrochar, a brown, coal-like substance produced via hydrothermal carbonization, has also been suggested as a beneficial soil additive. However, before soil application, both types of char need to be tested for potential toxic effects. The aim of this study was to develop simple, inexpensive, and easy-to-apply test procedures to identify negative effects of chars but not to provide false-negative results. The following tests, based partly on ISO norm biotoxicity test procedures, were chosen: (i) cress germination test for gaseous phytotoxic emissions; (ii) barley germination and growth test; (iii) salad germination test; and (iv) earthworm avoidance test for toxic substances. Test reproducibility was ensured by carrying out each test procedure three times with the same biochar. Several modifications were necessary to adapt the tests for biochars/hydrochars. The tested biochar did not induce negative effects in any of the tests. In contrast, the beet-root chip hydrochar showed negative effects in all tests. In an extension to the regular procedure, a regrowth of the harvested barley shoots without further nutrient additions yielded positive results for the hydrochar, which initially had negative effects. This implies that the harmful substance(s) must have been degraded or they were water soluble and leached. Tests with a biochar and hydrochar showed that the proposed modified quick-check test procedures provide a fast assessment of risks and effects of char application to soils within a short period of time (<2 wk).     

Pyrrolizidine alkaloids and pentacyclic triterpene saponins in the defensive secretions of Platyphora leaf beetles

Summary. Field collected exocrine defensive secretions of nine neotropical Platyphora species were analyzed for the presence of plant acquired pyrrolizidine alkaloids (PAs) and pentacyclic triterpene saponins. All species secrete saponins. In addition, five species feeding on Tournefortia (Boraginaceae), Koanophyllon (Asteraceae, tribe Eupatorieae) and Prestonia (Apocynaceae) were shown to sequester PAs of the lycopsamine type, which are characteristic for species of the three plant families. The PA sequestering species commonly store intermedine, lycopsamine and their O^3′-acetyl or propionyl esters as well as O⁷- and O⁹-hydroxyisovaleryl esters of retronecine. The latter as well as the O^3′-acyl esters were not found in the beetles’ host plants, suggesting the ability of the beetles to esterify plant derived retronecine and intermedine or its stereoisomers. Despite the conformity of the beetles’ PA patterns, considerable inconsistencies exist regarding the PA patterns of the respective host plants. One host plant was devoid of PAs, while another contained only simple necines. Since the previous history of the field collected beetles was unknown this discrepancy remains obscure. In contrast to the Palearctic chrysomeline leaf beetles, e.g. some Oreina species which ingest and store PAs as their non-toxic N-oxides, Platyphora leaf beetles absorb and store PAs as the toxic free base (tertiary PA), but apparently avoid to accumulate PAs in the haemolymph. This suggests that Chrysolina and Platyphora leaf beetles developed different lines of adaptations in their parallel evolution of PA mediated chemical defense. Received 30 November 2000; accepted 5 February 2001     

Differential sorption behaviour of aromatic hydrocarbons on charcoals prepared at different temperatures from grass and wood

Naturally occurring charcoals are increasingly being recognized as effective sorbents for organic compounds. In this study we investigated the sorption of benzene and toluene in single-sorbate and bi-sorbate systems on different types of charcoals produced in laboratory, employing the batch sorption technique. Air dried plant materials from Phalaris grass (Phalaris tuberosa) and Red Gum wood (Eucalyptus camadulensis) were combusted under limited oxygen supply at 250 degrees C, 450 degrees C, and 850 degrees C. The resulting charcoals were characterized for their specific surface areas, total cation content, and pore size distributions (pore size distribution only for wood combusted at 450 degrees C and 850 degrees C). For the materials treated at 850 degrees C not only the surface area, microporosity, and total amount of sorbed sorbate increased markedly, but also the non-linearity of the sorption isotherm. The pore size distributions and surface areas as well as an indifferent sorption behaviour and competition effects for both sorbates indicated that pore filling mechanisms were the dominating processes governing the sorption on these microporous, high temperature treated materials. For the materials treated at lower temperatures the affinity of toluene was higher compared to that of benzene. In the bi-sorbate system the overall uptake of benzene increased. These phenomena might be due to the stronger hydrophobicity of toluene, and to a varying potential for swelling of the matrix and pore deformation by the two sorbates. The significantly lower sorption capacity of the Phalaris-derived material compared to the Red Gum charcoal correlated with its smaller surface area and higher cation content.