Studying sulfur functional groups in Norway spruce year rings using S L-edge total electron yield spectroscopy.

Profiles of the major sulfur functional groups in mature Norway spruce wood tissue have been established for the first time. The big challenge was the development of a method suitable for sulfur speciation in samples with very low sulfur content (<100 ppm). This became possible by synchrotron X-ray absorption spectroscopy at the sulfur L-edge in total electron yield (TEY) detection mode with thin gold-coated wood slices. Functional groups were identified using sulfur compound spectra as fingerprints. Latewood of single year rings revealed metabolic plausible sulfur forms, particularly inorganic sulfide, organic disulfide, methylthiol, and highly oxidized sulfur. Form-specific profiles with Norway spruces from three different Swiss forest sites revealed high, but hitherto little-noticed, sulfur intensities attributable to natural heartwood formation and a common, but physiologically unexpected maximum around year ring 1986 with trees from the industrialized Swiss Plateau. It is hypothesized whether it may have resulted from the huge reduction in sulfur emissions after 1980 due to Swiss policy. Comparison with total S content profiles from optical emission spectroscopy underlined the more accurate and temporally better resolved TEY data with single wood year rings and it opened novel insights into the wood cell chemistry.

A 700-year paleoecological record of boreal ecosystem responses to climatic variation from Alaska.

Recent observations and model simulations have highlighted the sensitivity of the forest-tundra ecotone to climatic forcing. In contrast, paleoecological studies have not provided evidence of tree-line fluctuations in response to Holocene climatic changes in Alaska, suggesting that the forest-tundra boundary in certain areas may be relatively stable at multicentennial to millennial time scales. We conducted a multiproxy study of sediment cores from an Alaskan lake near the altitudinal limits of key boreal-forest species. Paleoecological data were compared with independent climatic reconstructions to assess ecosystem responses of the forest tundra boundary to Little Ice Age (LIA) climatic fluctuations. Pollen, diatom, charcoal, macrofossil, and magnetic analyses provide the first continuous record of vegetation fire-climate interactions at decadal to centennial time scales during the past 700 years from southern Alaska. Boreal-forest diebacks characterized by declines of Picea mariana, P. glauca, and tree Betula occurred during the LIA (AD 1500-1800), whereas shrubs (Alnus viridis, Betula glandulosa/nana) and herbaceous taxa (Epilobium, Aconitum) expanded. Marked increases in charcoal abundance and changes in magnetic properties suggest increases in fire importance and soil erosion during the same period. In addition, the conspicuous reduction or disappearance of certain aquatic (e.g., Isoetes, Nuphar, Pediastrum) and wetland (Sphagnum) plants and major shifts in diatom assemblages suggest pronounced lake-level fluctuations and rapid ecosystem reorganization in response to LIA climatic deterioration. Our results imply that temperature shifts of 1-2 degrees C, when accompanied by major changes in moisture balance, can greatly alter high-altitudinal terrestrial, wetland, and aquatic ecosystems, including conversion between boreal-forest tree line and tundra. The climatic and ecosystem variations in our study area appear to be coherent with changes in solar irradiance, suggesting that changes in solar activity contributed to the environmental instability of the past 700 years.

Pinpointing the source of a lunar meteorite: implications for the evolution of the Moon.

The lunar meteorite Sayh al Uhaymir 169 consists of an impact melt breccia extremely enriched with potassium, rare earth elements, and phosphorus [thorium, 32.7 parts per million (ppm); uranium, 8.6 ppm; potassium oxide, 0.54 weight percent], and adherent regolith. The isotope systematics of the meteorite record four lunar impact events at 3909 +/- 13 million years ago (Ma), approximately 2800 Ma, approximately 200 Ma, and <0.34 Ma, and collision with Earth sometime after 9.7 +/- 1.3 thousand years ago. With these data, we can link the impact-melt breccia to Imbrium and pinpoint the source region of the meteorite to the Lalande impact crater.

Interaction of sulfate assimilation with carbon and nitrogen metabolism in Lemna minor.

Cysteine synthesis from sulfide and O-acetyl-L-serine (OAS) is a reaction interconnecting sulfate, nitrogen, and carbon assimilation. Using Lemna minor, we analyzed the effects of omission of CO(2) from the atmosphere and simultaneous application of alternative carbon sources on adenosine 5'-phosphosulfate reductase (APR) and nitrate reductase (NR), the key enzymes of sulfate and nitrate assimilation, respectively. Incubation in air without CO(2) led to severe decrease in APR and NR activities and mRNA levels, but ribulose-1,5-bisphosphate carboxylase/oxygenase was not considerably affected. Simultaneous addition of sucrose (Suc) prevented the reduction in enzyme activities, but not in mRNA levels. OAS, a known regulator of sulfate assimilation, could also attenuate the effect of missing CO(2) on APR, but did not affect NR. When the plants were subjected to normal air after a 24-h pretreatment in air without CO(2), APR and NR activities and mRNA levels recovered within the next 24 h. The addition of Suc and glucose in air without CO(2) also recovered both enzyme activities, with OAS again influenced only APR. (35)SO(4)(2-) feeding showed that treatment in air without CO(2) severely inhibited sulfate uptake and the flux through sulfate assimilation. After a resupply of normal air or the addition of Suc, incorporation of (35)S into proteins and glutathione greatly increased. OAS treatment resulted in high labeling of cysteine; the incorporation of (35)S in proteins and glutathione was much less increased compared with treatment with normal air or Suc. These results corroborate the tight interconnection of sulfate, nitrate, and carbon assimilation.

Flux control of sulphate assimilation in Arabidopsis thaliana: adenosine 5'-phosphosulphate reductase is more susceptible than ATP sulphurylase to negative control by thiols.

The effect of externally applied L-cysteine and glutathione (GSH) on ATP sulphurylase and adenosine 5'-phosphosulphate reductase (APR), two key enzymes of assimilatory sulphate reduction, was examined in Arabidopsis thaliana root cultures. Addition of increasing L-cysteine to the nutrient solution increased internal cysteine, gamma-glutamylcysteine and GSH concentrations, and decreased APR mRNA, protein and extractable activity. An effect on APR could already be detected at 0.2 mm L-cysteine, whereas ATP sulphurylase was significantly affected only at 2 mm L-cysteine. APR mRNA, protein and activity were also decreased by GSH at 0.2 mm and higher concentrations. In the presence of L-buthionine-S, R-sulphoximine (BSO), an inhibitor of GSH synthesis, 0.2 mm L-cysteine had no effect on APR activity, indicating that GSH formed from cysteine was the regulating substance. Simultaneous addition of BSO and 0.5 mm GSH to the culture medium decreased APR mRNA, enzyme protein and activity. ATP sulphurylase activity was not affected by this treatment. Tracer experiments using (35)SO(4)(2-) in the presence of 0.5 mm L-cysteine or GSH showed that both thiols decreased sulphate uptake, APR activity and the flux of label into cysteine, GSH and protein, but had no effect on the activity of all other enzymes of assimilatory sulphate reduction and serine acetyltransferase. These results are consistent with the hypothesis that thiols regulate the flux through sulphate assimilation at the uptake and the APR step. Analysis of radioactive labelling indicates that the flux control coefficient of APR is more than 0.5 for the intracellular pathway of sulphate assimilation. This analysis also shows that the uptake of external sulphate is inhibited by GSH to a greater extent than the flux through the pathway, and that the flux control coefficient of APR for the pathway, including the transport step, is proportionately less, with a significant share of the control exerted by the transport step.