Dual carbon and oxygen isotopes in Siberian tree rings as indicator of millennia sunshine duration changes.

The current lack of information on past summer sunshine duration variability from annually resolved palaeoclimatological archives is hindering progress in the understanding and modelling of the earth climate system. We show that a combination of tree-ring carbon and oxygen isotopes from Siberia provides robust information on summer sunshine duration, which we use for an annual 1505-year reconstruction of July sunshine duration variability (1,5K-SIB-JSDR). We found that the Medieval maximum is 56 % higher than the average over 1505 years. Rapid and drastic decreases in sunshine duration up to 60 % correspond to major stratospheric volcanic eruptions. Grand Solar Minima and total sunspot numbers are also well preserved in the 1,5K-SIB-JSDR. Coherency with a global air temperature composite and spring Arctic Oscillation indicate that a large-scale climate signal is retained in our sunshine reconstruction.

Uncoupling of stomatal conductance and photosynthesis at high temperatures: mechanistic insights from online stable isotope techniques.

The strong covariation of temperature and vapour pressure deficit (VPD) in nature limits our understanding of the direct effects of temperature on leaf gas exchange. Stable isotopes in CO2 and H2 O vapour provide mechanistic insight into physiological and biochemical processes during leaf gas exchange. We conducted combined leaf gas exchange and online isotope discrimination measurements on four common European tree species across a leaf temperature range of 5-40°C, while maintaining a constant leaf-to-air VPD (0.8 kPa) without soil water limitation. Above the optimum temperature for photosynthesis (30°C) under the controlled environmental conditions, stomatal conductance (gs ) and net photosynthesis rate (An ) decoupled across all tested species, with gs increasing but An decreasing. During this decoupling, mesophyll conductance (cell wall, plasma membrane and chloroplast membrane conductance) consistently and significantly decreased among species; however, this reduction did not lead to reductions in CO2 concentration at the chloroplast surface and stroma. We question the conventional understanding that diffusional limitations of CO2 contribute to the reduction in photosynthesis at high temperatures. We suggest that stomata and mesophyll membranes could work strategically to facilitate transpiration cooling and CO2 supply, thus alleviating heat stress on leaf photosynthetic function, albeit at the cost of reduced water-use efficiency.

Updating the dual C and O isotope-Gas-exchange model: A concept to understand plant responses to the environment and its implications for tree rings.

The combined study of carbon (C) and oxygen (O) isotopes in plant organic matter has emerged as a powerful tool for understanding plant functional responses to environmental change. The approach relies on established relationships between leaf gas exchange and isotopic fractionation to derive a series of model scenarios that can be used to infer changes in photosynthetic assimilation and stomatal conductance driven by changes in environmental parameters (CO2 , water availability, air humidity, temperature, nutrients). We review the mechanistic basis for a conceptual model, in light of recently published research, and discuss where isotopic observations do not match our current understanding of plant physiological response to the environment. We demonstrate that (1) the model was applied successfully in many, but not all studies; (2) although originally conceived for leaf isotopes, the model has been applied extensively to tree-ring isotopes in the context of tree physiology and dendrochronology. Where isotopic observations deviate from physiologically plausible conclusions, this mismatch between gas exchange and isotope response provides valuable insights into underlying physiological processes. Overall, we found that isotope responses can be grouped into situations of increasing resource limitation versus higher resource availability. The dual-isotope model helps to interpret plant responses to a multitude of environmental factors.

Climate impacts on tree-ring stable isotopes across the Northern Hemispheric boreal zone.

Boreal regions are changing rapidly with anthropogenic global warming. In order to assess risks and impacts of this process, it is crucial to put these observed changes into a long-term perspective. Summer air temperature variability can be well reconstructed from conifer tree rings. While the application of stable isotopes can potentially provide complementary climatic information over different seasons. In this study, we developed new triple stable isotope chronologies in tree-ring cellulose (δ13Ctrc, δ18Otrc, δ2Htrc) from a study site in Canada. Additionally, we performed regional aggregated analysis of available stable isotope chronologies from 6 conifers' tree species across high-latitudinal (HL) and - altitudinal (HA) as well as Siberian (SIB) transects of the Northern Hemispheric boreal zone. Our results show that summer air temperature still plays an important role in determining tree-ring isotope variability at 11 out of 24 sites for δ13Ctrc, 6 out of 18 sites for δ18Otrc and 1 out of 6 sites for δ2Htrc. Precipitation, relative humidity and vapor pressure deficit are significantly and consistently recorded in both δ13Ctrc and δ18Otrc along HL. Summer sunshine duration is captured by all isotopes, mainly for HL and HA transects, indicating an indirect link with an increase in air and leaf temperature. A mixed temperature-precipitation signal is preserved in δ13Ctrc and δ18Otrc along SIB transect. The δ2Htrc data obtained for HL-transect provide information not only about growing seasonal moisture and temperature, but also capture autumn, winter and spring sunshine duration signals. We conclude that a combination of triple stable isotopes in tree-ring studies can provide a comprehensive description of climate variability across the boreal forest zone and improve ecohydrological reconstructions.

Modern aridity in the Altai-Sayan mountain range derived from multiple millennial proxies.

Temperature and precipitation changes are crucial for larch trees growing at high-elevation sites covered by permafrost in the Altai-Sayan mountain range (ASMR). To contextualize the amplitude of recent climate fluctuations, we have to look into the past by analyzing millennial paleoclimatic archives recording both temperature and precipitation. We developed annually resolved 1500-year tree-ring cellulose chronologies (δ13Ccell, δ18Ocell), and used these new records to reconstruct the variability in local summer precipitation and air temperature. We combined our new local reconstructions with existing paleoclimatic archives available for the Altai. The data show a strong decreasing trend by ca. 49% in regional summer precipitation, along with a regional summer temperature increase towards the twenty-first century, relative to the preceding 1500 years. Modern dry conditions (1966-2016 CE) in the ASMR are the result of simultaneous summer warming and decreased precipitation. Our new reconstructions also demonstrate that climate change in the ASMR is much stronger compared to the global average.

Spring arctic oscillation as a trigger of summer drought in Siberian subarctic over the past 1494 years.

Rapid changes in the hydrological and temperature regimes over the past decades at the northern latitudes enhance significantly permafrost degradation accelerating carbon release, increase the frequency of drought events and extensive wildfires. However, the mechanisms and dynamics driving drought events and their influence on Siberian forests are currently the subject of numerous research activities. Newly developed and annually resolved stable carbon and oxygen isotope chronologies of larch tree-ring cellulose (δ13Ccell and δ18Ocell) for the period 516-2009 CE allowed the reconstruction of July precipitation and Arctic Oscillation (AO) in May, respectively. Unprecedented drought events occurred towards twentieth-twenty-first centuries as indicated by the July precipitation reconstruction. Positive AO phases in May were most pronounced during the second part of the first millennium, but also increased in frequency in the modern period of the twentieth-twenty-first centuries. Negative AO phases are associated with cold anomalies and show a remarkable decrease in the nineteenth century caused by a series of major volcanic eruptions. Our findings help explaining the increased frequency of Siberian forest fires over the past decades in Central Siberia consistent with a reduction of summer precipitation, triggered by a positive phase of the Arctic Oscillation in May.

High-frequency stable isotope signals in uneven-aged forests as proxy for physiological responses to climate in Central Europe.

Picea abies (L.) Karst. and Fagus sylvatica (L.) are important tree species in Europe, and the foreseen increase in temperature and vapour pressure deficit (VPD) could increase the vulnerability of these species. However, their physiological performance under climate change at temperate and productive sites is not yet fully understood, especially in uneven-aged stands. Therefore, we investigated tree-ring width and stable isotope chronologies (δ13C/δ18O) of these two species at 10 sites along a climate gradient in Central Europe. In these uneven-aged stands, we compared the year-to-year variability of dominant and suppressed trees for the last 80 years in relation to the sites' spatial distribution and climate. δ18O and δ13C were generally consistent across sites and species, showing high sensitivity to summer VPD, whereas climate correlations with radial growth varied much more and depended on mean local climate. We found no significant differences between dominant and suppressed trees in the response of stable isotope ratios to climate variability, especially within the annual high-frequency signals. In addition, we observed a strikingly high coherence of the high-frequency δ18O variations across long distances with significant correlations above 1500 km, whereas the spatial agreement of δ13C variations was weaker (~700 km). We applied a dual-isotope approach that is based on known theoretical understanding of isotope fractionations to translate the observed changes into physiological components, mainly photosynthetic assimilation rate and stomatal conductance. When separating the chronologies in two time windows and investigating the shifts in isotopes ratios, a significant enrichment of either or both isotope ratios over the last decades can be observed. These results, translated by the dual-isotope approach, indicate a general climate-driven decrease in stomatal conductance. This improved understanding of the physiological mechanisms controlling the short-term variation of the isotopic signature will help to define the performance of these tree species under future climate.

Effects of soil moisture, needle age and leaf morphology on carbon and oxygen uptake, incorporation and allocation: a dual labeling approach with 13CO2 and H218O in foliage of a coniferous forest.

The carbon and oxygen isotopic composition of water and assimilates in plants reveals valuable information on plant responses to climatic conditions. Yet, the carbon and oxygen uptake, incorporation and allocation processes determining isotopic compositions are not fully understood. We carried out a dual-isotope labeling experiment at high humidity with 18O-enriched water (H218O) and 13C-enriched CO2 (13CO2) with attached Scots pine (Pinus sylvestris L.) branches and detached twigs of hemiparasitic mistletoes (Viscum album ssp. austriacum) in a naturally dry coniferous forest, where also a long-term irrigation takes place. After 4 h of label exposure, we sampled previous- and recent-year leaves, twig phloem and twig xylem over 192 h for the analysis of isotope ratios in water and assimilates. For both species, the uptake into leaf water and the incorporation of the 18O-label into leaf assimilates was not influenced by soil moisture, while the 13C-label incorporation into assimilates was significantly higher under irrigation compared with control dry conditions. Species-specific differences in leaf morphology or needle age did not affect 18O-label uptake into leaf water, but the incorporation of both tracers into assimilates was two times lower in mistletoe than in pine. The 18O-label allocation in water from pine needles to twig tissues was two times higher for phloem than for xylem under both soil moisture conditions. In contrast, the allocation of both tracers in pine assimilates were similar and not affected by soil moisture, twig tissue or needle age. Soil moisture effects on 13C-label but not on 18O-label incorporation into assimilates can be explained by the stomatal responses at high humidity, non-stomatal pathways for water and isotope exchange reactions. Our results suggest that non-photosynthetic 18O-incorporation processes may have masked prevalent photosynthetic processes. Thus, isotopic variation in leaf water could also be imprinted on assimilates when photosynthetic assimilation rates are low.

Nitrate and ammonium differ in their impact on δ13C of plant metabolites and respired CO2 from tobacco leaves.

The carbon isotopic composition (δ13C) of foliage is often used as proxy for plant performance. However, the effect of N O 3 - vs. N H 4 + supply on δ13C of leaf metabolites and respired CO2 is largely unknown. We supplied tobacco plants with a gradient of N O 3 - to N H 4 + concentration ratios and determined gas exchange variables, concentrations and δ13C of tricarboxylic acid (TCA) cycle intermediates, δ13C of dark-respired CO2, and activities of key enzymes nitrate reductase, malic enzyme and phosphoenolpyruvate carboxylase. Net assimilation rate, dry biomass and concentrations of organic acids and starch decreased along the gradient. In contrast, respiration rates, concentrations of intercellular CO2, soluble sugars and amino acids increased. As N O 3 - decreased, activities of all measured enzymes decreased. δ13C of CO2 and organic acids closely co-varied and were more positive under N O 3 - supply, suggesting organic acids as potential substrates for respiration. Together with estimates of intra-molecular 13C enrichment in malate, we conclude that a change in the anaplerotic reaction of the TCA cycle possibly contributes to 13C enrichment in organic acids and respired CO2 under N O 3 - supply. Thus, the effect of N O 3 - vs. N H 4 + on δ13C is highly relevant, particularly if δ13C of leaf metabolites or respiration is used as proxy for plant performance.

Plant responses to rising vapor pressure deficit.

Recent decades have been characterized by increasing temperatures worldwide, resulting in an exponential climb in vapor pressure deficit (VPD). VPD has been identified as an increasingly important driver of plant functioning in terrestrial biomes and has been established as a major contributor in recent drought-induced plant mortality independent of other drivers associated with climate change. Despite this, few studies have isolated the physiological response of plant functioning to high VPD, thus limiting our understanding and ability to predict future impacts on terrestrial ecosystems. An abundance of evidence suggests that stomatal conductance declines under high VPD and transpiration increases in most species up until a given VPD threshold, leading to a cascade of subsequent impacts including reduced photosynthesis and growth, and higher risks of carbon starvation and hydraulic failure. Incorporation of photosynthetic and hydraulic traits in 'next-generation' land-surface models has the greatest potential for improved prediction of VPD responses at the plant- and global-scale, and will yield more mechanistic simulations of plant responses to a changing climate. By providing a fully integrated framework and evaluation of the impacts of high VPD on plant function, improvements in forecasting and long-term projections of climate impacts can be made.

The 18 O-signal transfer from water vapour to leaf water and assimilates varies among plant species and growth forms.

The 18 O signature of atmospheric water vapour (δ18 OV ) is known to be transferred via leaf water to assimilates. It remains, however, unclear how the 18 O-signal transfer differs among plant species and growth forms. We performed a 9-hr greenhouse fog experiment (relative humidity ≥ 98%) with 18 O-depleted water vapour (-106.7‰) on 140 plant species of eight different growth forms during daytime. We quantified the 18 O-signal transfer by calculating the mean residence time of O in leaf water (MRTLW ) and sugars (MRTSugars ) and related it to leaf traits and physiological drivers. MRTLW increased with leaf succulence and thickness, varying between 1.4 and 10.8 hr. MRTSugars was shorter in C3 and C4 plants than in crassulacean acid metabolism (CAM) plants and highly variable among species and growth forms; MRTSugars was shortest for grasses and aquatic plants, intermediate for broadleaf trees, shrubs, and herbs, and longest for conifers, epiphytes, and succulents. Sucrose was more sensitive to δ18 OV variations than other assimilates. Our comprehensive study shows that plant species and growth forms vary strongly in their sensitivity to δ18 OV variations, which is important for the interpretation of δ18 O values in plant organic material and compounds and thus for the reconstruction of climatic conditions and plant functional responses.

Effect of Vapor Pressure Deficit on Gas Exchange in Wild-Type and Abscisic Acid-Insensitive Plants.

Stomata control the gas exchange of terrestrial plant leaves, and are therefore essential to plant growth and survival. We investigated gas exchange responses to vapor pressure deficit (VPD) in two gray poplar (Populus × canescens) lines: wild type and abscisic acid-insensitive (abi1) with functionally impaired stomata. Transpiration rate in abi1 increased linearly with VPD, up to about 2 kPa. Above this, sharply declining transpiration was followed by leaf death. In contrast, wild type showed a steady or slightly declining transpiration rate up to VPD of nearly 7 kPa, and fully recovered photosynthetic function afterward. There were marked differences in discrimination against 13CO2 (Δ13C) and C18OO (Δ18O) between abi1 and wild-type plants. The Δ13C indicated that intercellular CO2 concentrations decreased with VPD in wild-type plants, but not in abi1 plants. The Δ18O reflected progressive stomatal closure in wild type in response to increasing VPD; however, in abi1, stomata remained open and oxygen atoms of CO2 continued to exchange with 18O enriched leaf water. Coupled measurements of Δ18O and gas exchange were used to estimate intercellular vapor pressure, e i In wild-type leaves, there was no evidence of unsaturation of e i, even at VPD above 6 kPa. In abi1 leaves, e i approached 0.6 times saturation vapor pressure before the precipitous decline in transpiration rate. For wild type, a sensitive stomatal response to increasing VPD was pivotal in preventing unsaturation of e i In abi1, after taking unsaturation into account, stomatal conductance increased with increasing VPD, consistent with a disabled active response of guard cell osmotic pressure.

Compound-specific carbon isotope patterns in needles of conifer tree species from the Swiss National Park under recent climate change.

Elevated CO2 along with rising temperature and water deficits can lead to changes in tree physiology and leaf biochemistry. These changes can increase heat- and drought-induced tree mortality. We aim to reveal the impacts of climatic drivers on individual compounds at the leaf level among European larch (Larix decidua) and mountain pine (Pinus mugo) trees, which are widely distributed at high elevations. We investigated seasonal carbon isotope composition (δ13C) and concentration patterns of carbohydrates and organic acids in needles of these two different species from a case study in the Swiss National Park (SNP). We found that average and minimum air temperatures were the main climatic drivers of seasonal variation of δ13C in sucrose and glucose as well as in concentrations of carbohydrates and citric acid/citrate in needles of both tree species. The impact of seasonal climatic drivers on larch and mountain pine trees at the needle level is in line with our earlier study in this region for long-term changes at the tree-ring level. We conclude that the species-specific changes in δ13C and concentrations of carbohydrates and organic acids are sensitive indicators of changes in the metabolic pathways occurring as a result of climatic changes.

Source partitioning of atmospheric methane using stable carbon isotope measurements in the Reuss Valley, Switzerland.

Measurements of methane ( CH4 ) mole fractions and δ13 C-CH4 that resolve the diel cycle in the agriculturally dominated Reuss Valley, Switzerland, were used to quantify the contributions of different CH4 sources to the atmospheric CH4 source mix. Both a nocturnal (NBL) and a diurnal convective boundary layer (CBL) approach were employed. A diel course of CH4 mole fractions was found with a daytime minimum (background around 1900 ppb) and a nocturnal maximum (up to 3500 ppb). The δ13 C value in CH4 only showed small variations during the day (9-21 hours CET, -45.0±0.2 ‰ mean±SE ) when the atmosphere was well mixed, but decreased by -4.8±0.1 ‰ during the night. Biogenic emissions dominated in both approaches (ranging from 60 to 94%), but non-biogenic sources were rather important (42.2% and 46.0% with CBL, 5.8% and 40% with NBL approach in 2011 and 2012, respectively, of total emissions). The CH4 sink, dominated by tropospheric OH oxidation and only to a minor extend by soil surface uptake, was quantified at roughly 4% of local emissions.

Surrounding species diversity improves subtropical seedlings' carbon dynamics.

Increasing biodiversity has been linked to higher primary productivity in terrestrial ecosystems. However, the underlying ecophysiological mechanisms remain poorly understood. We investigated the effects of surrounding species richness (monoculture, two- and four-species mixtures) on the ecophysiology of Lithocarpus glaber seedlings in experimental plots in subtropical China. A natural rain event isotopically labelled both the water uptaken by the L. glaber seedlings and the carbon in new photoassimilates through changes of photosynthetic discrimination. We followed the labelled carbon (C) and oxygen (O) in the plant-soil-atmosphere continuum. We measured gas-exchange variables (C assimilation, transpiration and above- and belowground respiration) and δ13C in leaf biomass, phloem, soil microbial biomass, leaf- and soil-respired CO 2 as well as δ18O in leaf and xylem water. The 13C signal in phloem and respired CO 2 in L. glaber in monoculture lagged behind those in species mixture, showing a slower transport of new photoassimilates to and through the phloem in monoculture. Furthermore, leaf-water 18O enrichment above the xylem water in L. glaber increased after the rain in lower diversity plots suggesting a lower ability to compensate for increased transpiration. Lithocarpus glaber in monoculture showed higher C assimilation rate and water-use efficiency. However, these increased C resources did not translate in higher growth of L. glaber in monoculture suggesting the existence of larger nongrowth-related C sinks in monoculture. These ecophysiological responses of L. glaber, in agreement with current understanding of phloem transport are consistent with a stronger competition for water resources in monoculture than in species mixtures. Therefore, increasing species diversity in the close vicinity of the studied plants appears to alleviate physiological stress induced by water competition and to counterbalance the negative effects of interspecific competition on assimilation rates for L. glaber by allowing a higher fraction of the C assimilated to be allocated to growth in species mixture than in monoculture.

Oxygen isotopes in tree rings are less sensitive to changes in tree size and relative canopy position than carbon isotopes.

Stable isotope ratios in tree rings have become an important proxy for palaeoclimatology, particularly in temperate regions. Yet temperate forests are often characterized by heterogeneous stand structures, and the effects of stand dynamics on carbon (δ13 C) and oxygen isotope ratios (δ18 O) in tree rings are not well explored. In this study, we investigated long-term trends and offsets in δ18 O and δ13 C of Picea abies and Fagus sylvatica in relation to tree age, size, and distance to the upper canopy at seven temperate sites across Europe. We observed strong positive trends in δ13 C that are best explained by the reconstructed dynamics of individual trees below the upper canopy, highlighting the influence of light attenuation on δ13 C in shade-tolerant species. We also detected positive trends in δ18 O with increasing tree size. However, the observed slopes are less steep and consistent between trees of different ages and thus can be more easily addressed. We recommend restricting the use of δ13 C to years when trees are in a dominant canopy position to infer long-term climate signals in δ13 C when relying on material from shade-tolerant species, such as beech and spruce. For such species, δ18 O should be in principle the superior proxy for climate reconstructions.

Resilient Leaf Physiological Response of European Beech (Fagus sylvatica L.) to Summer Drought and Drought Release.

Drought is a major environmental constraint to trees, causing severe stress and thus adversely affecting their functional integrity. European beech (Fagus sylvatica L.) is a key species in mesic forests that is commonly expected to suffer in a future climate with more intense and frequent droughts. Here, we assessed the seasonal response of leaf physiological characteristics of beech saplings to drought and drought release to investigate their potential to recover from the imposed stress and overcome previous limitations. Saplings were transplanted to model ecosystems and exposed to a simulated summer drought. Pre-dawn water potentials (ψpd), stomatal conductance (gS), intercellular CO2 concentration (ci), net-photosynthesis (AN), PSII chlorophyll fluorescence (PItot), non-structural carbohydrate concentrations (NSC; soluble sugars, starch) and carbon isotope signatures were measured in leaves throughout the growing season. Pre-dawn water potentials (ψpd), gS, ci, AN, and PItot decreased as drought progressed, and the concentration of soluble sugars increased at the expense of starch. Carbon isotopes in soluble sugars (δ13CS) showed a distinct increase under drought, suggesting, together with decreased ci, stomatal limitation of AN. Drought effects on ψpd, ci, and NSC disappeared shortly after re-watering, while full recovery of gS, AN, and PItot was delayed by 1 week. The fast recovery of NSC was reflected by a rapid decay of the drought signal in δ13C values, indicating a rapid turnover of assimilates and a reactivation of carbon metabolism. After recovery, the previously drought-exposed saplings showed a stimulation of AN and a trend toward elevated starch concentrations, which counteracted the previous drought limitations. Overall, our results suggest that the internal water relations of beech saplings and the physiological activity of leaves are restored rapidly after drought release. In the case of AN, stimulation after drought may partially compensate for limitations on photosynthetic activity during drought. Our observations suggest high resilience of beech to drought, contradicting the general belief that beech is particularly sensitive to environmental stressors.

The effect of 18 O-labelled water vapour on the oxygen isotope ratio of water and assimilates in plants at high humidity.

Our understanding of how temporal variations of atmospheric water vapour and its isotopic composition (δ18 OV ) influence water and assimilates in plants remains limited, restricting our ability to use δ18 O as a tracer of ecophysiological processes. We exposed oak (Quercus robur) saplings under wet and dry soil moisture conditions to 18 O-depleted water vapour (c. - 200‰) at high relative humidity (c. 93%) for 5 h, simulating a fog event. We then traced the step change in δ18 OV into water and assimilates (e.g. sucrose, hexoses, quercitol and starch) in the leaf lamina, main veins and twigs over 24 h. The immediate δ18 OV effect was highest for δ18 O of leaf lamina water, but 40% lower on δ18 O of main vein water. To a smaller extent, we also observed changes in δ18 O of twig xylem water. Depending on the individual assimilation rate of each plant, the 18 O-label was partitioned among different assimilates, with highest changes in δ18 O of starch/sucrose and lowest in δ18 O of quercitol. Additionally, 18 O-label partitioning and allocation towards leaf starch and twig phloem sugars was influenced by the plant water status. Our results have important implications for water isotope heterogeneity in plants and for our understanding of how the δ18 O signal is incorporated into biomarkers.

The influence of increasing temperature and CO2 concentration on recent growth of old-growth larch: contrasting responses at leaf and stem processes derived from tree-ring width and stable isotopes.

Time series of tree-ring growth show significant increases since the early 1970s at the alpine tree line, with simultaneously increasing temperatures and atmospheric CO2 concentration. For a comprehensive understanding of this growth change, the physiological response patterns at both the leaf and stem level need to be separately analyzed and identified, and can be retrieved from tree-ring growth and isotope (δ13C, δ18O) series. In this study, we assessed the relative contribution of environmental factors to interannual tree-ring variability by multivariate linear mixed-effects models and the dual isotope approach on a dataset of tree-ring records of ~400-year-old larch (Larix decidua Mill.) from a non-water-limited high-elevation site in the Swiss Alps. The models suggest that summer temperatures and the recent lack of larch budmoth outbreaks were most important for explaining growth variations and trends, while a significant direct effect of the continuously increasing CO2 concentration could not be confirmed. In contrast, δ13C and δ18O, which are strongly influenced by fractionation changes in the leaf, clearly reflected the impact of air humidity (precipitation and vapor pressure deficit) and CO2 concentration: the increase in (δ13C-derived) intrinsic water-use efficiency over the second half of the 20th century suggests an increase in carbon assimilation as a result of enhanced CO2 concentration. The tree-ring δ18O largely reflected recent precipitation as source water, thus indicating a low variability in stomatal conductance, which was confirmed by the dual isotope approach. These leaf-level effects were not reflected in stem growth as they may have been masked by the temperature-caused growth limitation controlling the allocation of increased amounts of photosynthates into wood growth. Our approach demonstrates that the identification of different roles of environmental factors on leaf and stem processes helps to improve the assessment of site-specific changes of carbon fluxes and growth performance under future environmental conditions.

Oxygen isotope analysis of levoglucosan, a tracer of wood burning, in experimental and ambient aerosol samples.

RATIONALE: Levoglucosan is formed from cellulose during biomass burning. It is therefore often used as a specific tracer to quantify the contribution of wood burning to the aerosol loading. The stable oxygen isotope composition (δ18 O value) of biomass is determined by the water cycle and varies regionally, and hence the δ18 O value of levoglucosan could help to identify source regions of organic aerosols. METHODS: After solvent extraction of the organic fraction and concentration steps, a recently developed methylation derivatisation technique was applied on experimental (i.e. controlled wood-burning experiments) and on ambient aerosol samples from Switzerland and Lithuania. The method achieves sufficient compound separation for isotope analysis in atmospheric particulate matter, enabling δ18 O analysis of levoglucosan by gas chromatography/pyrolysis-isotope ratio mass spectrometry (GC/Pyr-IRMS), with a precision better than 1.0 ‰ and an accuracy of 0.3 ‰. RESULTS: The δ18 O value of the levoglucosan released during controlled wood-burning experiments was not significantly different from the cellulose δ18 O values, which implies very little or no isotope fractionation during wood burning under the given conditions. While the δ18 O values of levoglucosan in Swiss samples were as expected for the source region, those in Lithuania were 1-4 ‰ lower than expected. This may be due to differences in vegetation (grass vs wood) or burning conditions (high vs low temperatures). CONCLUSIONS: Low oxygen isotope fractionation between cellulose and levoglucosan and clear differences in levoglucosan δ18 O values between the Swiss and Lithuanian ambient samples demonstrate that our new method is useful for source appointment studies on wood-burning-derived aerosols.