Spatial variability and temporal trends in water-use efficiency of European forests.

The increasing carbon dioxide (CO2 ) concentration in the atmosphere in combination with climatic changes throughout the last century are likely to have had a profound effect on the physiology of trees: altering the carbon and water fluxes passing through the stomatal pores. However, the magnitude and spatial patterns of such changes in natural forests remain highly uncertain. Here, stable carbon isotope ratios from a network of 35 tree-ring sites located across Europe are investigated to determine the intrinsic water-use efficiency (iWUE), the ratio of photosynthesis to stomatal conductance from 1901 to 2000. The results were compared with simulations of a dynamic vegetation model (LPX-Bern 1.0) that integrates numerous ecosystem and land-atmosphere exchange processes in a theoretical framework. The spatial pattern of tree-ring derived iWUE of the investigated coniferous and deciduous species and the model results agreed significantly with a clear south-to-north gradient, as well as a general increase in iWUE over the 20th century. The magnitude of the iWUE increase was not spatially uniform, with the strongest increase observed and modelled for temperate forests in Central Europe, a region where summer soil-water availability decreased over the last century. We were able to demonstrate that the combined effects of increasing CO2 and climate change leading to soil drying have resulted in an accelerated increase in iWUE. These findings will help to reduce uncertainties in the land surface schemes of global climate models, where vegetation-climate feedbacks are currently still poorly constrained by observational data.

Reduced climate sensitivity of carbon, oxygen and hydrogen stable isotope ratios in tree-ring cellulose of silver fir (Abies alba Mill.) influenced by background SO2 in Franconia (Germany, Central Europe).

The climate sensitivity of carbon (δ(13)C), oxygen (δ(18)O) and hydrogen (δ(2)H) isotope signatures in tree-ring cellulose of Abies alba Mill. from a marginally industrialized area of Franconia (Germany) was analysed for the last 130 years. All isotopes preserve climatic signals up to c. 1950 AD. After 1950 we observe a clear reduction in climate sensitivity of δ(13)C and δ(2)H while δ(18)O - climate relations remain well pronounced. Nevertheless statistical tests implied that SO2 background emissions of West Germany had influenced isotope signatures long before 1950. The relationships between isotope values and concentrations of SO2, dust, O3 and NO2 at the regional level during the period 1979-2006 indicate that δ(13)C and δ(18)O were influenced primarily by SO2. The impact of SO2 on δ(2)H was negligible, but the observed reduction of climate sensitivity may be caused by synergic influences. The results have significant implications if isotope signatures from tree-rings from anthropogenic influenced regions are used to reconstruct past climate.

Routine hydrogen isotope measurement of cellulose nitrate by high-temperature pyrolysis--reference materials and precision.

The determination of isotope ratios of non-exchangeable hydrogen in tree-ring cellulose is commonly based on the nitration of wood cellulose followed by online high-temperature pyrolysis and isotope ratio mass spectrometry measurement of cellulose nitrate samples. The application of this method requires a proper calibration using appropriate reference materials whose delta(2)H values have been reliably normalized to the V-SMOW/SLAP scale. In our study, we achieve this normalization by a direct alternating measurement of reference waters (V-SMOW and SLAP) and three cellulose nitrates chosen as reference materials. For that purpose, both water and solid organic samples are introduced into the pyrolysis reactor by silver capsule injection. The analytical precision of the water measurement using the capsule method is +/-1.5 per thousand. The hydrogen isotopic composition of three cellulose nitrate standards measured ranges from -106.7 to -53.9 per thousand. The standard deviation of the calculated means from five measurement periods of those standards is better than 1 per thousand. Twenty-four different measurements of the hydrogen isotope composition of cellulose nitrate were evaluated in order to assess the precision of the described method. We obtained an analytical precision of +/-3.0 per thousand as representative for the 95% confidence interval applicable for routine measurements of cellulose nitrate samples. Evidence was found for significant differences in the behavior of cellulose nitrate and PE foil during the pyrolitic conversion that emphasizes the need for a proper calibration of the routine measurements. This calibration can only be successful if the reference materials used have a very similar chemical composition and undergo the same preparation procedure as the samples.

Wood cellulose preparation methods and mass spectrometric analyses of delta13C, delta18O, and nonexchangeable delta2H values in cellulose, sugar, and starch: an interlaboratory comparison.

Interlaboratory comparisons involving nine European stable isotope laboratories have shown that the routine methods of cellulose preparation resulted in data that generally agreed within the precision of the isotope ratio mass spectrometry (IRMS) method used: +/-0.2 per thousand for carbon and +/-0.3 per thousand for oxygen. For carbon, the results suggest that holocellulose is enriched up to 0.39 per thousand in 13C relative to the purified alpha-cellulose. The comparisons of IRMS measurements of carbon on cellulose, sugars, and starches showed low deviations from -0.23 to +0.23 per thousand between laboratories. For oxygen, IRMS measurements varied between means from -0.39 to 0.58 per thousand, -0.89 to 0.42 per thousand, and -1.30 to 1.16 per thousand for celluloses, sugars, and starches, respectively. This can be explained by different effects arising from the use of low- or high-temperature pyrolysis and by the variation between laboratories in the procedures used for drying and storage of samples. The results of analyses of nonexchangeable hydrogen are very similar in means with standard deviations between individual methods from +/-2.7 to +/-4.9 per thousand. The use of a one-point calibration (IAEA-CH7) gave significant positive offsets in delta2H values up to 6 per thousand. Detailed analysis of the results allows us to make the following recommendations in order to increase quality and compatibility of the common data bank: (1) removal of a pretreatment with organic solvents, (2) a purification step with 17% sodium hydroxide solution during cellulose preparation procedure, (3) measurements of oxygen isotopes under an argon hood, (4) use of calibration standard materials, which are of similar nature to that of the measured samples, and (5) using a two-point calibration method for reliable result calculation.

Microwave-supported preparation of alpha-cellulose for analysis of delta13C in tree rings.

The microwave technique is found to be very applicable for the preparation of alpha-cellulose from wood samples and can be recommended for analyzing the stable carbon isotopes in tree rings. At a reaction temperature of 80 degrees C, the extraction time can be decreased from 36 h to 15 min. Microwave-supported prepared cellulose contains more amorphous constituents, resulting in a relatively higher reactivity and amenability for a following nitration with regard to determination of nonexchangeable hydrogen. The delta18O values of microwave-enhanced extracted cellulose remain significantly lighter than reference values, possibly as a result of an increased oxygen isotope exchange between bleaching solution and cellulose under conditions of high energy input. Therefore, this technique cannot be recommended for oxygen isotope analyses in wood cellulose.