Stand scale variability of topsoil organic matter composition in a high-elevation Norway spruce forest ecosystem

Our knowledge about the effect of single-tree influence areas on the physicochemical properties of the underlying mineral soil in forest ecosystems is still limited. This restricts our ability to adequately estimate future changes in soil functioning due to forest management practices. We studied the stand scale spatial variation of different soil organic matter species investigated by 13C NMR spectroscopy, lignin phenol and neutral sugar analysis under an unmanaged mountainous high-elevation Norway spruce (Picea abies L.) forest in central Europe. Multivariate geostatistical approaches were applied to relate the spatial patterns of the different soil organic matter species to topographic parameters, bulk density, oxalate- and dithionite-extractable iron, pH, and the impact of tree distribution. Soil samples were taken from the mineral top soil. Generally, the stand scale distribution patterns of different soil organic matter compounds could be divided into two groups: Those compounds, which were significantly spatially correlated with topography/altitude and those with small scale spatial pattern (range ≤ 10 m) that was closely related to tree distribution. The concentration of plant-derived soil organic matter components, such as lignin, at a given sampling point was significantly spatially related to the distance of the nearest tree (p ≤ 0.05). In contrast, the spatial distribution of mainly microbial-derived compounds (e.g. galactose and mannose) could be attributed to the dominating impact of small-scale topography and the contribution of poorly crystalline iron oxides that were significantly larger in the central depression of the study site compared to crest and slope positions. Our results demonstrate that topographic parameters dominate the distribution of overall topsoil organic carbon (OC) stocks at temperate high-elevation forest ecosystems, particularly in sloped terrain. However, trees superimpose topography-controlled OC biogeochemistry beneath their crown by releasing litter and changing soil conditions in comparison to open areas. This may lead to distinct zones with different mechanisms of soil organic matter degradation and also stabilization in forest stands.

COSIMA calibration for the detection and characterization of the cometary solid organic matter

On the orbiter of the Rosetta spacecraft, the Cometary Secondary Ion Mass Analyser (COSIMA) will provide new in situ insights about the chemical composition of cometary grains all along 67P/Churyumov–Gerasimenko (67P/CG) journey until the end of December 2015 nominally. The aim of this paper is to present the pre-calibration which has already been performed as well as the different methods which have been developed in order to facilitate the interpretation of the COSIMA mass spectra and more especially of their organic content. The first step was to establish a mass spectra library in positive and negative ion mode of targeted molecules and to determine the specific features of each compound and chemical family analyzed. As the exact nature of the refractory cometary organic matter is nowadays unknown, this library is obviously not exhaustive. Therefore this library has also been the starting point for the research of indicators, which enable to highlight the presence of compounds containing specific atom or structure. These indicators correspond to the intensity ratio of specific peaks in the mass spectrum. They have allowed us to identify sample containing nitrogen atom, aliphatic chains or those containing polyaromatic hydrocarbons. From these indicators, a preliminary calibration line, from which the N/C ratio could be derived, has also been established. The research of specific mass difference could also be helpful to identify peaks related to quasi-molecular ions in an unknown mass spectrum. The Bayesian Positive Source Separation (BPSS) technique will also be very helpful for data analysis. This work is the starting point for the analysis of the cometary refractory organic matter. Nevertheless, calibration work will continue in order to reach the best possible interpretation of the COSIMA observations.

Oxygen isotope ratios (18O/16O) of hemicellulose-derived sugar biomarkers in plants, soils and sediments as paleoclimate proxy II: insight from a climate transect study

The oxygen isotopic composition of precipitation (δ18Oprec) is well known to be a valuable (paleo-)climate proxy. Paleosols and sediments and hemicelluloses therein have the potential to serve as archives recording the isotopic composition of paleoprecipitation. In a companion paper (Zech et al., 2014) we investigated δ18Ohemicellulose values of plants grown under different climatic conditions in a climate chamber experiment. Here we present results of compound-specific δ18O analyses of arabinose, fucose and xylose extracted from modern topsoils (n = 56) along a large humid-arid climate transect in Argentina in order to answer the question whether hemicellulose biomarkers in soils reflect δ18Oprec. The results from the field replications indicate that the homogeneity of topsoils with regard to δ18Ohemicellulose is very high for most of the 20 sampling sites. Standard deviations for the field replications are 1.5‰, 2.2‰ and 1.7‰, for arabinose, fucose and xylose, respectively. Furthermore, all three hemicellulose biomarkers reveal systematic and similar trends along the climate gradient. However, the δ18Ohemicellulose values (mean of the three sugars) do not correlate positively with δ18Oprec (r = −0.54, p < 0.014, n = 20). By using a Péclet-modified Craig-Gordon (PMCG) model it can be shown that the δ18Ohemicellulose values correlate highly significantly with modeled δ18Oleaf water values (r = 0.81, p < 0.001, n = 20). This finding suggests that hemicellulose biomarkers in (paleo-)soils do not simply reflect δ18Oprec but rather δ18Oprec altered by evaporative 18O enrichment of leaf water due to evapotranspiration. According to the modeling results, evaporative 18O enrichment of leaf water is relatively low (∼10‰) in the humid northern part of the Argentinian transect and much higher (up to 19‰) in the arid middle and southern part of the transect. Model sensitivity tests corroborate that changes in relative air humidity exert a dominant control on evaporative 18O enrichment of leaf water and thus δ18Ohemicellulose, whereas the effect of temperature changes is of minor importance. While oxygen exchange and degradation effects seem to be negligible, further factors needing consideration when interpreting δ18Ohemicellulose values obtained from (paleo-)soils are evaporative 18O enrichment of soil water, seasonality effects, wind effects and in case of abundant stem/root-derived organic matter input a partial loss of the evaporative 18O enrichment of leaf water. Overall, our results prove that compound-specific δ18O analyses of hemicellulose biomarkers in soils and sediments are a promising tool for paleoclimate research. However, disentangling the two major factors influencing δ18Ohemicellulose, namely δ18Oprec and relative air humidity controlled evaporative 18O enrichment of leaf water, is challenging based on δ18O analyses alone.

Lipid biomarkers in Holocene and glacial sediments from ancient Lake Ohrid (Macedonia, Albania)

Abstract. Organic matter preserved in Lake Ohrid sediments originates from aquatic and terrestrial sources. Its variable composition reflects climate-controlled changes in the lake basin’s hydrology and related organic matter export, i.e. changes in primary productivity, terrestrial plant matter input and soil erosion. Here, we present first results from lipid biomarker investigations of Lake Ohrid sediments from two near-shore settings: site Lz1120 near the southern shore, with low-lying lands nearby and probably influenced by river discharge, and site Co1202 which is close to the steep eastern slopes. Variable proportions of terrestrial n-alkanoic acids and n-alkanols as well as compositional changes of !- hydroxy acids document differences in soil organic matter supply between the sites and during different climate stages (glacial, Holocene, 8.2 ka cooling event). Changes in the vegetation cover are suggested by changes in the dominant chain length of terrestrial n-alkanols. Effective microbial degradation of labile organic matter and in situ contribution of organic matter derived from the microbes themselves are both evident in the sediments. We found evidence for anoxic conditions within the photic zone by detecting epicholestanol and tetrahymanol from sulphur-oxidising phototrophic bacteria and bacterivorous ciliates and for the influence of a settled human community from the occurrence of coprostanol, a biomarker for human and animal faeces (pigs, sheep, goats), in an early Holocene sample. This study illustrates the potential of lipid biomarkers for future environmental reconstructions using one of Europe’s oldest continental climate archives, Lake Ohrid.

Radiocarbon Analysis of Elemental and Organic Carbon in Switzerland during Winter-Smog Episodes from 2008 to 2012 – Part I: Source Apportionment and Spatial Variability

While several studies have investigated winter-time air pollution with a wide range of concentration levels, hardly any results are available for longer time periods covering several winter-smog episodes at various locations; e.g., often only a few weeks from a single winter are investigated. Here, we present source apportionment results of winter-smog episodes from 16 air pollution monitoring stations across Switzerland from five consecutive winters. Radiocarbon (14C) analyses of the elemental (EC) and organic (OC) carbon fractions, as well as levoglucosan, major water-soluble ionic species and gas-phase pollutant measurements were used to characterize the different sources of PM10. The most important contributions to PM10 during winter-smog episodes in Switzerland were on average the secondary inorganic constituents (sum of nitrate, sulfate and ammonium = 41 ± 15%) followed by organic matter (OM) (34 ± 13%) and EC (5 ± 2%). The non-fossil fractions of OC (fNF,OC) ranged on average from 69 to 85 and 80 to 95% for stations north and south of the Alps, respectively, showing that traffic contributes on average only up to ~ 30% to OC. The non-fossil fraction of EC (fNF,EC), entirely attributable to primary wood burning, was on average 42 ± 13 and 49 ± 15% for north and south of the Alps, respectively. While a high correlation was observed between fossil EC and nitrogen oxides, both primarily emitted by traffic, these species did not significantly correlate with fossil OC (OCF), which seems to suggest that a considerable amount of OCF is secondary, from fossil precursors. Elevated fNF,EC and fNF,OC values and the high correlation of the latter with other wood burning markers, including levoglucosan and water soluble potassium (K+) indicate that residential wood burning is the major source of carbonaceous aerosols during winter-smog episodes in Switzerland. The inspection of the non-fossil OC and EC levels and the relation with levoglucosan and water-soluble K+ shows different ratios for stations north and south of the Alps (most likely because of differences in burning technologies) for these two regions in Switzerland.

Grazing behaviour, physical activity and metabolic profile of two Holstein strains in an organic grazing system

The challenge for sustainable organic dairy farming is identification of cows that are well adapted to forage-based production systems. Therefore, the aim of this study was to compare the grazing behaviour, physical activity and metabolic profile of two different Holstein strains kept in an organic grazing system without concentrate supplementation. Twelve Swiss (HCH ; 566 kg body weight (BW) and 12 New Zealand Holstein-Friesian (HNZ ; 530 kg BW) cows in mid-lactation were kept in a rotational grazing system. After an adaptation period, the milk yield, nutrient intake, physical activity and grazing behaviour were recorded for each cow for 7 days. On three consecutive days, blood was sampled at 07:00, 12:00 and 17:00 h from each cow by jugular vein puncture. Data were analysed using linear mixed models. No differences were found in milk yield, but milk fat (3.69 vs. 4.05%, P = 0.05) and milk protein percentage (2.92 vs. 3.20%, P < 0.01) were lower in HCH than in HNZ cows. Herbage intake did not differ between strains, but organic matter digestibility was greater (P = 0.01) in HCH compared to HNZ cows. The HCH cows spent less (P = 0.04) time ruminating (439 vs. 469 min/day) and had a lower (P = 0.02) number of ruminating boli when compared to the HNZ cows. The time spent eating and physical activity did not differ between strains. Concentrations of IGF-1 and T3 were lower (P ≤ 0.05) in HCH than HNZ cows. In conclusion, HCH cows were not able to increase dry matter intake in order to express their full genetic potential for milk production when kept in an organic grazing system without concentrate supplementation. On the other hand, HNZ cows seem to compensate for the reduced nutrient availability better than HCH cows but could not use that advantage for increased production efficiency

Distribution of cutin and suberin biomarkers under forest trees with different root systems

Background and aims Differences in chemical composition of root compounds and root systems among tree species may affect organic matter (OM) distribution, source and composition in forest soils. The objective of this study was to elucidate the contribution of species specific cutin and suberin biomarkers as proxies for shoot- and root-derived organic carbon (OC) to soil OM at different depths with increasing distance to the stems of four different tree species. Methods The contribution of cutin- and suberin-derived lipids to OM in a Cutanic Alisol was analyzed with increasing soil depth and distance to the stems of Fagus sylvatica L., Picea abies (L.) Karst., Quercus robur L. and Pseudotsuga menziesii (Mirb.) Franco. Cutin and suberin monomers of plants and soils were analyzed by alkaline hydrolysis and subsequent gas chromatography–mass spectrometry. Results The amount and distribution of suberin-derived lipids in soil clearly reflected the specific root system of the different tree species. The amount of cutin-derived lipids decreased strongly with soil depth, indicating that the input of leaf/needle material is restricted to the topsoil. In contrast to the suberin-derived lipids, the spatial pattern of cutin monomer contribution to soil OM did not depend on tree species. Conclusions Our results document the importance of tree species as a main factor controlling the composition and distribution of OM in forest soils. They reveal the impact of tree species on root-derived OM distribution and the necessity to distinguish among different zones when studying soil OM storage in forests.

Loss on ignition as a method for estimating organic and carbonate content in sediments: reproducibility and comparability of results

Five test runs were performed to assess possible bias when performing the loss on ignition (LOI) method to estimate organic matter and carbonate content of lake sediments. An accurate and stable weight loss was achieved after 2 h of burning pure CaCO3 at 950 °C, whereas LOI of pure graphite at 530 °C showed a direct relation to sample size and exposure time, with only 40-70% of the possible weight loss reached after 2 h of exposure and smaller samples losing weight faster than larger ones. Experiments with a standardised lake sediment revealed a strong initial weight loss at 550 °C, but samples continued to lose weight at a slow rate at exposure of up to 64 h, which was likely the effect of loss of volatile salts, structural water of clay minerals or metal oxides, or of inorganic carbon after the initial burning of organic matter. A further test-run revealed that at 550 °C samples in the centre of the furnace lost more weight than marginal samples. At 950 °C this pattern was still apparent but the differences became negligible. Again, LOI was dependent on sample size. An analytical LOI quality control experiment including ten different laboratories was carried out using each laboratory's own LOI procedure as well as a standardised LOI procedure to analyse three different sediments. The range of LOI values between laboratories measured at 550 °C was generally larger when each laboratory used its own method than when using the standard method. This was similar for 950 °C, although the range of values tended to be smaller. The within-laboratory range of LOI measurements for a given sediment was generally small. Comparisons of the results of the individual and the standardised method suggest that there is a laboratory-specific pattern in the results, probably due to differences in laboratory equipment and/or handling that could not be eliminated by standardising the LOI procedure. Factors such as sample size, exposure time, position of samples in the furnace and the laboratory measuring affected LOI results, with LOI at 550 °C being more susceptible to these factors than LOI at 950 °C. We, therefore, recommend analysts to be consistent in the LOI method used in relation to the ignition temperatures, exposure times, and the sample size and to include information on these three parameters when referring to the method.

Drivers of nitrogen leaching from organic layers in Central European beech forests

Background and Aims: The response of forest ecosystems to continuous nitrogen (N) deposition is still uncertain. We investigated imports and exports of dissolved N from mull-type organic layers to identify the controls of N leaching in Central European beech forests under continuous N deposition. Methods: Dissolved N fluxes with throughfall and through mull-type organic layers (litter leachate) were measured continuously in 12 beech forests on calcareous soil in two regions in Germany over three consecutive growing seasons. Results Mean growing season net (i.e. litter leachate – throughfall flux) fluxes of total dissolved N (TDN) from the organic layer were low (2.3 ± 5.6 kg ha −1 ) but varied widely from 12.9 kg ha −1 to –8.3 kg ha −1 . The small increase of dissolved N fluxes during the water passage through mull-type organic layers suggested that high turnover rates coincided with high microbial N assimilation and plant N uptake. Stand basal area had a positive feedback on N fluxes by providing litter for soil organic matter forma- tion. Plant diversity, especially herb diversity, reduced dissolved N fluxes. Soil fauna biomass increased NO3−-N fluxes with litter leachate by stimulating mineralization. Microbial biomass measures were not related to dissolved N fluxes. Conclusions Our results show that dissolved N exports from organic layers contain significant amounts of throughfall-derived N (mainly NO3−-N) that flushes through the organic layer but also highlight that N leaching from organic layers is driven by the complex interplay of plants, animals and microbes. Furthermore, diverse understories reduce N leaching from Central European beech forests.

Global pulses of organic carbon burial in deep-sea sediments during glacial maxima

The burial of organic carbon in marine sediments removes carbon dioxide from the ocean–atmosphere pool, provides energy to the deep biosphere, and on geological timescales drives the oxygenation of the atmosphere. Here we quantify natural variations in the burial of organic carbon in deep-sea sediments over the last glacial cycle. Using a new data compilation of hundreds of sediment cores, we show that the accumulation rate of organic carbon in the deep sea was consistently higher (50%) during glacial maxima than during interglacials. The spatial pattern and temporal progression of the changes suggest that enhanced nutrient supply to parts of the surface ocean contributed to the glacial burial pulses, with likely additional contributions from more efficient transfer of organic matter to the deep sea and better preservation of organic matter due to reduced oxygen exposure. These results demonstrate a pronounced climate sensitivity for this global carbon cycle sink.

Source apportionment and dynamic changes of carbonaceous aerosols during the haze bloom-decay process in China based on radiocarbon and organic molecular tracers

Fine carbonaceous aerosols (CAs) is the key factor influencing the currently filthy air in megacities in China, yet few studies simultaneously focus on the origins of different CAs species using specific and powerful source tracers. Here, we present a detailed source apportionment for various CAs fractions, including organic carbon (OC), water-soluble OC (WSOC), water-insoluble OC (WIOC), elemental carbon (EC) and secondary OC (SOC) in the largest cities of North (Beijing, BJ) and South China (Guangzhou, GZ), using the measurements of radiocarbon and anhydrosugars. Results show that non-fossil fuel sources such as biomass burning and biogenic emission make a significant contribution to the total CAs in Chinese megacities: 56±4 in BJ and 46±5% in GZ, respectively. The relative contributions of primary fossil carbon from coal and liquid petroleum combustions, primary non-fossil carbon and secondary organic carbon (SOC) to total carbon are 19, 28 and 54% in BJ, and 40, 15 and 46% in GZ, respectively. Non-fossil fuel sources account for 52 in BJ and 71% in GZ of SOC, respectively. These results suggest that biomass burning has a greater influence on regional particulate air pollution in North China than in South China. We observed an unabridged haze bloom-decay process in South China, which illustrates that both primary and secondary matter from fossil sources played a key role in the blooming phase of the pollution episode, while haze phase is predominantly driven by fossil-derived secondary organic matter and nitrate.

Human–climate interactions in the central Mediterranean region during the last millennia: The laminated record of Lake Butrint (Albania)

Lake Butrint (39°47 N, 20°1 E) is a ca. 21 m deep, coastal lagoon located in SW Albania where finely-laminated sediments have been continuously deposited during the last millennia. The multi-proxy analysis (sedimentology, high-resolution elemental geochemistry and pollen) of a 12 m long sediment core, supported by seven AMS radiocarbon dates and 137Cs dating, enable a precise reconstruction of the environmental change that occurred in the central Mediterranean region during the last ∼4.5 cal kyrs BP. Sediments consist of triplets of authigenic carbonates, organic matter and clayey laminae. Fluctuations in the thickness and/or presence of these different types of seasonal laminae indicate variations in water salinity, organic productivity and runoff in the lake's catchment, as a result of the complex interplay of tectonics, anthropogenic forcing and climate variability. The progradation of the Pavllo river delta, favoured by variable human activity from the nearby ancient city of Butrint, led to the progressive isolation of this hydrological system from the Ionian Sea. The system evolved from an open bay to a restricted lagoon, which is consistent with archaeological data. An abrupt increase in mass-wasting activity between 1515 and 1450 BC, likely caused by nearby seismic activity, led to the accumulation of 24 homogenites, up to 17 cm thick. They have been deposited during the onset of finely laminated sedimentation, which indicates restricted, anoxic bottom water conditions and higher salinity. Periods of maximum water salinity, biological productivity, and carbonate precipitation coincide with warmer intervals, such as the early Roman Warm Period (RWP) (500 BC–0 AD), the Medieval Climate Anomaly (MCA) (800–1400 AD) and recent times (after 1800 AD). Conversely, lower salinity and more oxic conditions, with higher clastic input were recorded during 1400–500 BC, the Late Roman and the Early Medieval periods (0–800 AD) and during the Little Ice Age (1400–1800 AD). Hydrological fluctuations recorded in Butrint are in phase with most central and western Mediterranean records and correlate with NAO variability. In contrast, opposite hydrological patterns have been recorded in the Eastern Balkans and the Levant during the last millennium, emphasizing a complex spatial variability in the region. Phases of maximum settlement intensity in Butrint (Roman-Late Antique) coincide with warmer and/or stable climate periods (0–800 AD and MCA, respectively), indicating a long-term influence of climatic conditions on human activities. The Late Holocene sedimentary record of Lake Butrint demonstrates the complex interplay of climate variability, tectonics and human impact in the recent evolution of coastal Mediterranean regions.

A first chironomid-based summer temperature reconstruction (13–5 ka BP) around 49°N in inland Europe compared with local lake development

Temperature reconstructions for the end of the Pleistocene and the first half of the Holocene based on biotic proxies are rare for inland Europe around 49°N. We analysed a 7 m long sequence of lake deposits in the Vihorlat Mts in eastern Slovakia (820 m a.s.l.). Chironomid head capsules were used to reconstruct mean July temperature (TJuly), other proxies (diatoms, green algae, pollen, geochemistry) were used to reconstruct local environmental changes that might have affected the climate reconstruction, such as epilimnetic total phosphorus concentrations (TP), lake level changes and development of surrounding vegetation. During the Younger Dryas (YD), temperature fluctuated between 7 and 11 °C, with distinct, decadal to centennial scale variations, that agree with other palaeoclimate records in Europe such as δ18O content in stalagmites or Greenland ice cores. The results indicate that the site was somewhat colder than expected from the general south-to-north YD temperature gradient within Europe, possibly because of north-facing exposition. The warmer phases of the YD were characterised by low water level or even complete desiccation of the lake (12,200-12,400 cal yr BP). At the Late-Glacial/Holocene transition TJuly steeply increased from from 11 to 15.5 °C (11,700-11,400 cal yr BP) - the highest TJuly for entire sequence. This rapid climate change was reflected by all proxies as a compositional change and increasing species diversity. The open woodlands of Pinus, Betula, Larix and Picea were replaced by broad-leaved temperate forests dominated by Betula, later by Ulmus and finally by Corylus (ca 9700 cal yr BP). At the same time, input of eroded coarse-grained material into the lake decreased and organic matter (LOI) and biogenic silica increased. The Early-Holocene climate was rather stable till 8700 cal yr BP, with temporary decrease in TJuly around 11,200 cal yr BP. The lake was productive with a well-developed littoral, as indicated by both diatoms and chironomids. A distinct decline of TJuly to 10 °C between 8700 and 8000 cal yr BP was associated with decreasing chironomid diversity and increasing climate moistening indicated by pollen. Tychoplanktonic and phosphorus-demanding diatoms increased which might be explained by hydrological and land-cover changes. Later, a gradual warming started after 7000 cal yr BP and representation of macrophytes, periphytic diatoms and littoral chironomids increased. Our results suggest that the Holocene thermal maximum was taking place unusually early in the Holocene at our study site, but its timing might be affected by topography and mesoclimate. We further demonstrated that temperature changes had coincided with variations in local hydrology