Modelling Fagus sylvatica stem growth along a wide thermal gradient in Italy by incorporating dendroclimatic classification and land surface phenology metrics.

Calibrating land surface phenology (LSP) with tree rings is important to model spatio-temporal variations in forest productivity. We used MODIS (resolution: 250 m) NDVI, WDRVI and EVI series 2000-2014 to derive LSP metrics quantifying phenophase timing and canopy photosynthetic rates of 26 European beech forests covering a large thermal gradient (5-16 °C) in Italy. Average phenophase timing changed greatly with site temperature (e.g. growing season 70 days longer at low- than high-elevation); average VI values were affected by precipitation. An annual temperature about 12 °C (c. 1100 m asl) represented a bioclimatic threshold dividing warm from cold beech forests, distinguished by different phenology-BAI (basal area increment) relationships and LSP trends. Cold forests showed decreasing VI values (browning) and delayed phenophases and had negative BAI slopes. Warmer forests tended to increase VI (greening), and positive BAI slopes. NDVI peak, commonly used in global trend assessments, changed with elevation in agreement with changes in wood production. A cross-validation modelling approach demonstrated the ability of LSP to predict average BAI and its interannual variability. Merging sites into bioclimatic groups improved models by amplifying the signal in growth or LSP. NDVI had highest performances when informing on BAI trends; WDRVI and EVI were mostly selected for modelling mean and interannual BAI. WDRVI association with tree rings, tested in this study for the first time, showed that this VI is highly promising for studying forest dynamics. MODIS LSP can quantify forest functioning changes across landscapes and model interannual spatial variations and trends in productivity dynamics under climate change.

Addressing the need for interactive, efficient, and reproducible data processing in ecology with the datacleanr R package.

Ecological research, just as all Earth System Sciences, is becoming increasingly data-rich. Tools for processing of "big data" are continuously developed to meet corresponding technical and logistical challenges. However, even at smaller scales, data sets may be challenging when best practices in data exploration, quality control and reproducibility are to be met. This can occur when conventional methods, such as generating and assessing diagnostic visualizations or tables, become unfeasible due to time and practicality constraints. Interactive processing can alleviate this issue, and is increasingly utilized to ensure that large data sets are diligently handled. However, recent interactive tools rarely enable data manipulation, may not generate reproducible outputs, or are typically data/domain-specific. We developed datacleanr, an interactive tool that facilitates best practices in data exploration, quality control (e.g., outlier assessment) and flexible processing for multiple tabular data types, including time series and georeferenced data. The package is open-source, and based on the R programming language. A key functionality of datacleanr is the "reproducible recipe"-a translation of all interactive actions into R code, which can be integrated into existing analyses pipelines. This enables researchers experienced with script-based workflows to utilize the strengths of interactive processing without sacrificing their usual work style or functionalities from other (R) packages. We demonstrate the package's utility by addressing two common issues during data analyses, namely 1) identifying problematic structures and artefacts in hierarchically nested data, and 2) preventing excessive loss of data from 'coarse,' code-based filtering of time series. Ultimately, with datacleanr we aim to improve researchers' workflows and increase confidence in and reproducibility of their results.

The 2018 European heatwave led to stem dehydration but not to consistent growth reductions in forests.

Heatwaves exert disproportionately strong and sometimes irreversible impacts on forest ecosystems. These impacts remain poorly understood at the tree and species level and across large spatial scales. Here, we investigate the effects of the record-breaking 2018 European heatwave on tree growth and tree water status using a collection of high-temporal resolution dendrometer data from 21 species across 53 sites. Relative to the two preceding years, annual stem growth was not consistently reduced by the 2018 heatwave but stems experienced twice the temporary shrinkage due to depletion of water reserves. Conifer species were less capable of rehydrating overnight than broadleaves across gradients of soil and atmospheric drought, suggesting less resilience toward transient stress. In particular, Norway spruce and Scots pine experienced extensive stem dehydration. Our high-resolution dendrometer network was suitable to disentangle the effects of a severe heatwave on tree growth and desiccation at large-spatial scales in situ, and provided insights on which species may be more vulnerable to climate extremes.

Wood Anatomy of Douglas-Fir in Eastern Arizona and Its Relationship With Pacific Basin Climate.

Dendroclimatic reconstructions, which are a well-known tool for extending records of climatic variability, have recently been expanded by using wood anatomical parameters. However, the relationships between wood cellular structures and large-scale climatic patterns, such as El Niño-Southern Oscillation (ENSO) and the Pacific Decadal Oscillation (PDO), are still not completely understood, hindering the potential for wood anatomy as a paleoclimatic proxy. To better understand the teleconnection between regional and local climate processes in the western United States, our main objective was to assess the value of these emerging tree-ring parameters for reconstructing climate dynamics. Using Confocal Laser Scanning Microscopy, we measured cell lumen diameter and cell wall thickness (CWT) for the period 1966 to 2015 in five Douglas-firs [Pseudotsuga menziesii (Mirb.) Franco] from two sites in eastern Arizona (United States). Dendroclimatic analysis was performed using chronologies developed for 10 equally distributed sectors of the ring and daily climatic records to identify the strongest climatic signal for each sector. We found that lumen diameter in the first ring sector was sensitive to previous fall-winter temperature (September 25th to January 23rd), while a precipitation signal (October 27th to February 13th) persisted for the entire first half of the ring. The lack of synchronous patterns between trees for CWT prevented conducting meaningful climate-response analysis for that anatomical parameter. Time series of lumen diameter showed an anti-phase relationship with the Southern Oscillation Index (a proxy for ENSO) at 10 to 14year periodicity and particularly in 1980-2005, suggesting that chronologies of wood anatomical parameters respond to multidecadal variability of regional climatic modes. Our findings demonstrate the potential of cell structural characteristics of southwestern United States conifers for reconstructing past climatic variability, while also improving our understanding of how large-scale ocean-atmosphere interactions impact local hydroclimatic patterns.

Recent CO2 rise has modified the sensitivity of tropical tree growth to rainfall and temperature.

Atmospheric CO2 (ca ) rise changes the physiology and possibly growth of tropical trees, but these effects are likely modified by climate. Such ca  × climate interactions importantly drive CO2 fertilization effects of tropical forests predicted by global vegetation models, but have not been tested empirically. Here we use tree-ring analyses to quantify how ca rise has shifted the sensitivity of tree stem growth to annual fluctuations in rainfall and temperature. We hypothesized that ca rise reduces drought sensitivity and increases temperature sensitivity of growth, by reducing transpiration and increasing leaf temperature. These responses were expected for cooler sites. At warmer sites, ca rise may cause leaf temperatures to frequently exceed the optimum for photosynthesis, and thus induce increased drought sensitivity and stronger negative effects of temperature. We tested these hypotheses using measurements of 5,318 annual rings from 129 trees of the widely distributed (sub-)tropical tree species, Toona ciliata. We studied growth responses during 1950-2014, a period during which ca rose by 28%. Tree-ring data were obtained from two cooler (mean annual temperature: 20.5-20.7°C) and two warmer (23.5-24.8°C) sites. We tested ca  × climate interactions, using mixed-effect models of ring-width measurements. Our statistical models revealed several significant and robust ca  × climate interactions. At cooler sites (and seasons), ca  × climate interactions showed good agreement with hypothesized growth responses of reduced drought sensitivity and increased temperature sensitivity. At warmer sites, drought sensitivity increased with increasing ca , as predicted, and hot years caused stronger growth reduction at high ca . Overall, ca rise has significantly modified sensitivity of Toona stem growth to climatic variation, but these changes depended on mean climate. Our study suggests that effects of ca rise on tropical tree growth may be more complex and less stimulatory than commonly assumed and require a better representation in global vegetation models.

Removing the no-analogue bias in modern accelerated tree growth leads to stronger medieval drought.

In many parts of the world, especially in the temperate regions of Europe and North-America, accelerated tree growth rates have been observed over the last decades. This widespread phenomenon is presumably caused by a combination of factors like atmospheric fertilization or changes in forest structure and/or management. If not properly acknowledged in the calibration of tree-ring based climate reconstructions, considerable bias concerning amplitudes and trends of reconstructed climatic parameters might emerge or low frequency information is lost. Here we present a simple but effective, data-driven approach to remove the recent non-climatic growth increase in tree-ring data. Accounting for the no-analogue calibration problem, a new hydroclimatic reconstruction for northern-central Europe revealed considerably drier conditions during the medieval climate anomaly (MCA) compared with standard reconstruction methods and other existing reconstructions. This demonstrates the necessity to account for fertilization effects in modern tree-ring data from affected regions before calibrating reconstruction models, to avoid biased results.

Subfossil trees suggest enhanced Mediterranean hydroclimate variability at the onset of the Younger Dryas.

Nearly 13,000 years ago, the warming trend into the Holocene was sharply interrupted by a reversal to near glacial conditions. Climatic causes and ecological consequences of the Younger Dryas (YD) have been extensively studied, however proxy archives from the Mediterranean basin capturing this period are scarce and do not provide annual resolution. Here, we report a hydroclimatic reconstruction from stable isotopes (δ18O, δ13C) in subfossil pines from southern France. Growing before and during the transition period into the YD (12 900-12 600 cal BP), the trees provide an annually resolved, continuous sequence of atmospheric change. Isotopic signature of tree sourcewater (δ18Osw) and estimates of relative air humidity were reconstructed as a proxy for variations in air mass origin and precipitation regime. We find a distinct increase in inter-annual variability of sourcewater isotopes (δ18Osw), with three major downturn phases of increasing magnitude beginning at 12 740 cal BP. The observed variation most likely results from an amplified intensity of North Atlantic (low δ18Osw) versus Mediterranean (high δ18Osw) precipitation. This marked pattern of climate variability is not seen in records from higher latitudes and is likely a consequence of atmospheric circulation oscillations at the margin of the southward moving polar front.

Quantification of uncertainties in conifer sap flow measured with the thermal dissipation method.

Trees play a key role in the global hydrological cycle and measurements performed with the thermal dissipation method (TDM) have been crucial in providing whole-tree water-use estimates. Yet, different data processing to calculate whole-tree water use encapsulates uncertainties that have not been systematically assessed. We quantified uncertainties in conifer sap flux density (Fd ) and stand water use caused by commonly applied methods for deriving zero-flow conditions, dampening and sensor calibration. Their contribution has been assessed using a stem segment calibration experiment and 4 yr of TDM measurements in Picea abies and Larix decidua growing in contrasting environments. Uncertainties were then projected on TDM data from different conifers across the northern hemisphere. Commonly applied methods mostly underestimated absolute Fd . Lacking a site- and species-specific calibrations reduced our stand water-use measurements by 37% and induced uncertainty in northern hemisphere Fd . Additionally, although the interdaily variability was maintained, disregarding dampening and/or applying zero-flow conditions that ignored night-time water use reduced the correlation between environment and Fd . The presented ensemble of calibration curves and proposed dampening correction, together with the systematic quantification of data-processing uncertainties, provide crucial steps in improving whole-tree water-use estimates across spatial and temporal scales.

Increased water-use efficiency translates into contrasting growth patterns of Scots pine and sessile oak at their southern distribution limits.

In forests, the increase in atmospheric CO2 concentrations (Ca ) has been related to enhanced tree growth and intrinsic water-use efficiency (iWUE). However, in drought-prone areas such as the Mediterranean Basin, it is not yet clear to what extent this "fertilizing" effect may compensate for drought-induced growth reduction. We investigated tree growth and physiological responses at five Scots pine (Pinus sylvestris L.) and five sessile oak (Quercus petraea (Matt.) Liebl.) sites located at their southernmost distribution limits in Europe for the period 1960-2012 using annually resolved tree-ring width and δ13 C data to track ecophysiological processes. Results indicated that all 10 natural stands significantly increased their leaf intercellular CO2 concentration (Ci ), and consequently iWUE. Different trends in the theoretical gas-exchange scenarios as a response to increasing Ca were found: generally, Ci tended to increase proportionally to Ca , except for trees at the driest sites in which Ci remained constant. Ci from the oak sites displaying higher water availability tended to increase at a comparable rate to Ca . Multiple linear models fitted at site level to predict basal area increment (BAI) using iWUE and climatic variables better explained tree growth in pines (31.9%-71.4%) than in oak stands (15.8%-46.8%). iWUE was negatively linked to pine growth, whereas its effect on growth of oak differed across sites. Tree growth in the western and central oak stands was negatively related to iWUE, whereas BAI from the easternmost stand was positively associated with iWUE. Thus, some Q. petraea stands might have partially benefited from the "fertilizing" effect of rising Ca , whereas P. sylvestris stands due to their strict closure of stomata did not profit from increased iWUE and consequently showed in general growth reductions across sites. Additionally, the inter-annual variability of BAI and iWUE displayed a geographical polarity in the Mediterranean.

Dissimilar responses of larch stands in northern Siberia to increasing temperatures-a field and simulation based study.

Arctic and alpine treelines worldwide differ in their reactions to climate change. A northward advance of or densification within the treeline ecotone will likely influence climate-vegetation feedback mechanisms. In our study, which was conducted in the Taimyr Depression in the North Siberian Lowlands, w present a combined field- and model-based approach helping us to better understand the population processes involved in the responses of the whole treeline ecotone, spanning from closed forest to single-tree tundra, to climate warming. Using information on stand structure, tree age, and seed quality and quantity from seven sites, we investigate effects of intra-specific competition and seed availability on the specific impact of recent climate warming on larch stands. Field data show that tree density is highest in the forest-tundra, and average tree size decreases from closed forest to single-tree tundra. Age-structure analyses indicate that the trees in the closed forest and forest-tundra have been present for at least ~240 yr. At all sites except the most southerly ones, past establishment is positively correlated with regional temperature increase. In the single-tree tundra, however, a change in growth form from krummholz to erect trees, beginning ~130 yr ago, rather than establishment date has been recorded. Seed mass decreases from south to north, while seed quantity increases. Simulations with LAVESI (Larix Vegetation Simulator) further suggest that relative density changes strongly in response to a warming signal in the forest-tundra while intra-specific competition limits densification in the closed forest and seed limitation hinders densification in the single-tree tundra. We find striking differences in strength and timing of responses to recent climate warming. While forest-tundra stands recently densified, recruitment is almost non-existent at the southern and northern end of the ecotone due to autecological processes. Palaeo-treelines may therefore be inappropriate to infer past temperature changes at a fine scale. Moreover, a lagged treeline response to past warming will, via feedback mechanisms, influence climate change in the future.

Xylem adjustment of sessile oak at its southern distribution limits.

Drought is a key limiting factor for tree growth in the Mediterranean Basin. However, the variability in acclimation via xylem traits is largely unknown. We studied tree growth and vessel features of Quercus petraea (Matt.) Lieb. in five marginal stands across southern Europe. Tree-ring width (TRW), mean earlywood vessel area (MVA) and number of earlywood vessels (NV) as well as theoretical hydraulic conductivity (Kh) chronologies were developed for the period 1963-2012. Summer drought signals were consistent among TRW chronologies; however, climatic responses of vessel features differed considerably among sites. At the three xeric sites, previous year's summer drought had a negative effect on MVA and a positive effect on NV. In contrast, at the two mesic sites, current year's spring drought negatively affected NV, while exerting a positive influence on MVA. In both cases, Kh was not altered by this xylem adjustment. All variables revealed identical east-west geographical patterns in growth and anatomical features. Sessile oak copes with drought in different ways: at xeric sites and after unfavourable previous summer conditions more but smaller vessels are built, lowering vulnerability to cavitation, whereas at mesic sites, dry springs partly lead to tree-rings with wider but fewer vessels. The variability of vessel-related features displays a similar geographical dipole in the Mediterranean Basin previously described for tree growth by other studies.

Wood Cellular Dendroclimatology: Testing New Proxies in Great Basin Bristlecone Pine.

Dendroclimatic proxies can be generated from the analysis of wood cellular structures, allowing for a more complete understanding of the physiological mechanisms that control the climatic response of tree species. Century-long (1870-2013) time series of anatomical parameters were developed for Great Basin bristlecone pine (Pinus longaeva D.K. Bailey) by capturing strongly contrasted microscopic images through a Confocal Laser Scanning Microscope. Environmental information embedded in wood anatomical series was analyzed in comparison with ring-width series using measures of empirical signal strength. Response functions were calculated against monthly climatic variables to evaluate climate sensitivity of cellular features (e.g., lumen area; lumen diameter) for the period 1950-2013. Calibration-verification tests were used to determine the potential to generate long climate reconstructions from these anatomical proxies. A total of eight tree-ring parameters (two ring-width and six chronologies of xylem anatomical parameters) were analyzed. Synchronous variability among samples varied among tree-ring parameters, usually decreasing from ring-width to anatomical features. Cellular parameters linked to plant hydraulic performance (e.g., tracheid lumen area and radial lumen diameter) showed empirical signal strength similar to ring-width series, while noise was predominant in chronologies of lumen tangential width and cell wall thickness. Climatic signals were different between anatomical and ring-width chronologies, revealing a positive and temporally stable correlation of tracheid size (i.e., lumen and cell diameter) with monthly (i.e., March) and seasonal precipitation. In particular, tracheid lumen diameter emerged as a reliable moisture indicator and was then used to reconstruct total March-August precipitation from 1870 to 2013. Wood anatomy holds great potential to refine and expand dendroclimatic records by allowing estimates of plant physiological adaptations to external stressors. Integrating xylem cellular features with ring-width chronologies can widen our understanding of past climatic variability (including annual extreme events) and improve the evaluation of long-term plant response to drought, especially in connection with future warming scenarios.

Meteorological Drivers of Extremes in Daily Stem Radius Variations of Beech, Oak, and Pine in Northeastern Germany: An Event Coincidence Analysis.

Observed recent and expected future increases in frequency and intensity of climatic extremes in central Europe may pose critical challenges for domestic tree species. Continuous dendrometer recordings provide a valuable source of information on tree stem radius variations, offering the possibility to study a tree's response to environmental influences at a high temporal resolution. In this study, we analyze stem radius variations (SRV) of three domestic tree species (beech, oak, and pine) from 2012 to 2014. We use the novel statistical approach of event coincidence analysis (ECA) to investigate the simultaneous occurrence of extreme daily weather conditions and extreme SRVs, where extremes are defined with respect to the common values at a given phase of the annual growth period. Besides defining extreme events based on individual meteorological variables, we additionally introduce conditional and joint ECA as new multivariate extensions of the original methodology and apply them for testing 105 different combinations of variables regarding their impact on SRV extremes. Our results reveal a strong susceptibility of all three species to the extremes of several meteorological variables. Yet, the inter-species differences regarding their response to the meteorological extremes are comparatively low. The obtained results provide a thorough extension of previous correlation-based studies by emphasizing on the timings of climatic extremes only. We suggest that the employed methodological approach should be further promoted in forest research regarding the investigation of tree responses to changing environmental conditions.

Tuning the Voices of a Choir: Detecting Ecological Gradients in Time-Series Populations.

This paper introduces a new approach-the Principal Component Gradient Analysis (PCGA)-to detect ecological gradients in time-series populations, i.e. several time-series originating from different individuals of a population. Detection of ecological gradients is of particular importance when dealing with time-series from heterogeneous populations which express differing trends. PCGA makes use of polar coordinates of loadings from the first two axes obtained by principal component analysis (PCA) to define groups of similar trends. Based on the mean inter-series correlation (rbar) the gain of increasing a common underlying signal by PCGA groups is quantified using Monte Carlo Simulations. In terms of validation PCGA is compared to three other existing approaches. Focusing on dendrochronological examples, PCGA is shown to correctly determine population gradients and in particular cases to be advantageous over other considered methods. Furthermore, PCGA groups in each example allowed for enhancing the strength of a common underlying signal and comparably well as hierarchical cluster analysis. Our results indicate that PCGA potentially allows for a better understanding of mechanisms causing time-series population gradients as well as objectively enhancing the performance of climate transfer functions in dendroclimatology. While our examples highlight the relevance of PCGA to the field of dendrochronology, we believe that also other disciplines working with data of comparable structure may benefit from PCGA.

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.

UV-laser-based microscopic dissection of tree rings - a novel sampling tool for δ(13) C and δ(18) O studies.

UV-laser-based microscopic systems were utilized to dissect and sample organic tissue for stable isotope measurements from thin wood cross-sections. We tested UV-laser-based microscopic tissue dissection in practice for high-resolution isotopic analyses (δ(13) C/δ(18) O) on thin cross-sections from different tree species. The method allows serial isolation of tissue of any shape and from millimetre down to micrometre scales. On-screen pre-defined areas of interest were automatically dissected and collected for mass spectrometric analysis. Three examples of high-resolution isotopic analyses revealed that: in comparison to δ(13) C of xylem cells, woody ray parenchyma of deciduous trees have the same year-to-year variability, but reveal offsets that are opposite in sign depending on whether wholewood or cellulose is considered; high-resolution tree-ring δ(18) O profiles of Indonesian teak reflect monsoonal rainfall patterns and are sensitive to rainfall extremes caused by ENSO; and seasonal moisture signals in intra-tree-ring δ(18) O of white pine are weighted by nonlinear intra-annual growth dynamics. The applications demonstrate that the use of UV-laser-based microscopic dissection allows for sampling plant tissue at ultrahigh resolution and unprecedented precision. This new technique facilitates sampling for stable isotope analysis of anatomical plant traits like combined tree eco-physiological, wood anatomical and dendroclimatological studies.

Climate signals derived from cell anatomy of Scots pine in NE Germany.

Tree-ring chronologies of Pinus sylvestris L. from latitudinal and altitudinal limits of the species distribution have been widely used for climate reconstructions, but there are many sites within the temperate climate zone, as is the case in northeastern Germany, at which there is little evidence of a clear climate signal in the chronologies. In this study, we developed long chronologies of several cell structure variables (e.g., average lumen area and cell wall thickness) from P. sylvestris growing in northeastern Germany and investigated the influence of climate on ring widths and cell structure variables. We found significant correlations between cell structure variables and temperature, and between tree-ring width and relative humidity and vapor pressure, respectively, enabling the development of robust reconstructions from temperate sites that have not yet been realized. Moreover, it has been shown that it may not be necessary to detrend chronologies of cell structure variables and thus low-frequency climate signals may be retrieved from longer cell structure chronologies. The relatively extensive resource of archaeological material of P. sylvestris covering approximately the last millennium may now be useful for climate reconstructions in northeastern Germany and other sites in the temperate climate zone.

Pooled versus separate measurements of tree-ring stable isotopes.

δ(13)C and δ(18)O of tree rings contain time integrated information about the environmental conditions weighted by seasonal growth dynamics and are well established as sources of palaeoclimatic and ecophysiological data. Annually resolved isotope chronologies are frequently produced by pooling dated growth rings from several trees prior to the isotopic analyses. This procedure has the advantage of saving time and resources, but precludes from defining the isotopic error or statistical uncertainty related to the inter-tree variability. Up to now only a few studies have compared isotope series from pooled tree rings with isotopic measurements from individual trees. We tested whether or not the δ(13)C and the δ(18)O chronologies derived from pooled and from individual tree rings display significant differences at two locations from the Iberian Peninsula to assess advantages and constraints of both methodologies. The comparisons along the period 1900-2003 reveal a good agreement between pooled chronologies and the two mean master series which were created by averaging raw individual values (Mean) or by generating a mass calibrated mean (MassC). In most of the cases, pooled chronologies show high synchronicity with averaged individual samples at interannual scale but some differences also show up especially when comparing δ(18)O decadal to multi-decadal variations. Moreover, differences in the first order autocorrelation among individuals may be obscured by pooling strategies. The lack of replication of pooled chronologies prevents detection of a bias due to a higher mass contribution of one sample but uncertainties associated with the analytical process itself, as sample inhomogeneity, seems to account for the observed differences.