Fluorescence spectroscopy applied to the optimisation of a desalting step by electrodialysis for the characterisation of marine organic matter

The isolation and characterisation of marine dissolved organic matter (DOM) are still not readily achieved today. The study of this chemically complex material is particularly difficult, especially as it is hindered by the high salinity of seawater. It is therefore essential to develop a method in which a sufficient quantity of marine organic matter can be collected for structural analyses. Reverse osmosis (RO) is often used for the concentration of DOM from freshwaters, due to the fact that DOM is not modified during RO and that DOC recoveries are high (about 80%). Unfortunately, RO cannot be used directly to isolate marine DOM,since both salts and organic matter are concentrated during the process. Therefore, marine samples have to be desalted before their concentration by RO. Our aim was to develop a desalting step of seawater by electrodialysis (ED), whilst minimising DOM modifications and losses. The process was first developed with small volumes (2 L) of artificial and Mediterranean seawater and was then applied to larger volumes.We showed that 20 L of Mediterranean seawater could be rapidly desalted (in less than 7 h) and, by monitoring the quality of DOM in desalted subsamples collected during ED using spectrofluorometry, that the quality of DOM was not significantly modified. It was concluded that desalted samples were still representative of the initial seawater samples. It should be noted, however, that care has to be taken in choosing the ratio of the volume of water to be desalted over the membrane surface area in order to limit DOM modifications and losses. Electrodialysis efficiently removed up to 75% of the salts present in the seawater samples whilst recovering most of unaltered DOM. ED and RO could then be combined in order to isolate, concentrate and characterise marine organic matter

Archaeal and bacterial tetraether lipids in tropical ponds with contrasted salinity (Guadeloupe, French West Indies): Implications for tetraether-based environmental proxies

International audienceThe occurrence and distribution of archaeal and bacterial glycerol dialkyl glycerol tetraether lipids (GDGTs) in continental saline environments have been rarely investigated. Here, the abundance and distribution of archaeal isoprenoid GDGTs (iGDGTs) and archaeol, and of bacterial branched GDGTs (brGDGTs) in four tropical water ponds of contrasting salinity in two islands from the French Western Indies, Grande-Terre and La Désirade, have been determined. The sedimentary distribution of the GDGTs strongly differed between the two islands. Caldarchaeol was largely predominant among iGDGTs in the (hyper)saline ponds from Grande-Terre, suggesting a substantial contribution of iGDGTs derived from methanogenic Archaea. In contrast, both caldarchaeol and crenarchaeol were present in high relative abundance in the low salinity ponds from La Désirade, suggesting that iGDGTs were derived from mixed archaeal communities. In addition, the relative proportion of the most methylated brGDGTs was much higher in Grande-Terre ponds than in La Désirade ponds. The applicability of different proxies based on GDGTs and archaeol was tested for these specific environments. The relative abundance of archaeol vs. caldarchaeol (ACE index) was comparable for the four ponds, independent of salinity, showing that the ACE might not necessarily track salinity change. Moreover, the relative proportion of caldarchaeol vs. total iGDGTs was unexpectedly observed to increase with salinity, suggesting production of this compound by halophilic Archaea. The supposed high abundance of methanogenic Archaea in Grande-Terre ponds prevented the application of TEX86 as a temperature proxy, whereas the TEX86 could be successfully used for local temperature reconstruction in La Désirade ponds. BrGDGTs seem to be produced predominantly in situ (water column and/or sediment) in hypersaline ponds from Grande-Terre, but in La Désirade ponds likely result from a mixture of soil and aquatic sources. In Grande-Terre ponds, brGDGT-derived temperature estimates generated using either soil or lacustrine calibrations were much lower than expected. The mismatch between expected and estimated temperature might be explained by the presence of halophilic microbial communities producing specific brGDGT distributions in the saline ponds from Grande-Terre. The study shows that the sources of brGDGTs, iGDGTs and archaeol (i) may strongly differ in aquatic environments of varying salinity, even at a regional scale, and (ii) have to be constrained before tetraether-derived proxies in such settings can be confidently applied

Effects of a short-term experimental microclimate warming on the abundance and distribution of branched GDGTs in a French peatland

International audienceBranched glycerol dialkyl glycerol tetraethers (GDGTs) are complex lipids of high molecular weight, recently discovered in soils and increasingly used as palaeoclimate proxies. Their degree of methylation, expressed in the MBT, was shown to depend on mean annual air temperature (MAAT) and to a lesser extent on soil pH, whereas the relative abundance of cyclopentyl rings of branched GDGTs, expressed in the CBT, was related to soil pH. To date, only a few studies were interested in the application of the MBT and CBT proxies in peatlands. In order to validate the applicability of branched GDGTs as temperature proxies in these environments, it is essential to investigate the effect of temperature on branched GDGT-producing bacteria and especially on the speed of adaptation of these microorganisms to temperature changes. The aim of this work was to study the effects of in situ experimental climate warming on the abundance and distribution of branched GDGTs in a Sphagnum-dominated peatland (Jura Mountains, France). Branched GDGTs either present as core lipids (CLs; presumed of fossil origin) or derived from intact polar lipids (IPLs, markers for living cells) were analysed. Air temperature was experimentally increased using a passive warming system consisting of open mini-greenhouses (Open-Top Chamber - OTC). The effect of the OTCs was especially apparent in spring and summer, with (i) an increase in maximal air temperature of ca. 3°C during these two seasons and (ii) an increase in average air temperature of ca. 1°C in summer. Despite the short duration of the climate experiment (26 months), branched GDGT distribution was significantly affected by this temperature rise, with higher MBT values in the OTCs than in the control plots, supporting the empirical relationship between MBT and MAAT established from a large range of soils. The difference in branched GDGT-derived temperatures between control and OTC plots (2-3 °C) was in the same range as the increase in maximal (daytime) temperature induced by the OTCs in spring and summer, suggesting that branched GDGT-producing bacteria might be more active during the warmest months of the year. The OTC treatment had no significant effect on the abundance of branched GDGTs, which were mainly present as "fossil" CLs (70 to 85% of the total branched GDGT pool). Furthermore, no significant differences in branched GDGT distribution were observed between the CLs and IPLs, which both provided higher MBT and MAAT values for the OTCs. This suggests that the fossil pool of branched GDGTs has a very fast turnover (less than the 2 year duration of the experiment) at the peat surface and that branched GDGT distribution may rapidly reflect changes in environmental conditions (at least air temperature) occurring in peat environments

Occurrence and distribution of glycerol dialkyl glycerol tetraethers in a French peat bog

International audienceThe present study was aimed at examining the distribution and abundance of glycerol dialkyl glycerol tetraethers (GDGTs) of archaeal and bacterial origin in peat samples from surface and deep (ca. 50 cm) horizons of a peat bog in the Jura Mountains (northeastern France). Two principal types of GDGTs are present: extractable GDGTs, recoverable by solvent extraction, and non-extractable GDGTs, linked to the soil matrix. Within the extractable pool, “free” (i.e. core lipids) and “bound” (i.e. intact polar and/or ester-bound lipids) GDGTs can be distinguished. Extractable “free” and “bound” GDGTs were extracted using both accelerated solvent extraction (ASE) and a modified Bligh and Dyer technique. Both methods were shown to allow adequate extraction of “free” archaeal and bacterial GDGTs from soil samples. Both extraction protocols afforded similar relative distributions of archaeal and bacterial GDGTs, although poorer extraction of “bound” GDGTs was observed for ASE relative to Bligh and Dyer. Even though only low amounts of bacterial GDGTs were released after acid hydrolysis of solvent-extracted samples, non-extractable and total extractable GDGTs showed different distribution patterns in some samples. Consequently, these two lipid pools potentially reflect different proxy records of mean annual air temperature (MAAT) and pH. Last, the distribution of bacterial GDGTs differed between the different samples. Samples from deep horizons gave lower GDGT-derived MAAT values than those from surficial horizons, in agreement with measured soil temperatures at 7 cm and 50 cm depths from April to September. MAAT estimates more closely resemble spring and summer temperatures rather than annual soil temperature. The variability in bacterial GDGT distribution and resulting MAAT estimates probably also reflects the heterogeneity of peat samples and the variation in several environmental factors such as peat moisture level and oxygen availability

Genesis and soil environmental implications of intact in-situ rhizoliths in dunes of the Badain Jaran Desert, northwestern China

Desert rhizoliths are generally found as weathered, broken and scattered samples on dune field surface, but rarely in-situ in their initial states buried under the soil of desert in the Badain Jaran Desert, northwest China. This study offers an assessment of the morphological, mineralogical, and chemical properties of intact and in-situ rhizoliths found in soils of swales and depressions among dune chains. The characteristics of these rare and precious objects were assessed using optical polarizing microscopy, cathodoluminescence, scanning electronic microscopy, radiocarbon dating, and stable isotopic analyses, providing the opportunity for discussion of the rhizolith formation mechanisms and associated environmental conditions. Field and laboratory investigations showed that the in-situ intact rhizoliths were formed only in the places where Artemisia shrubs are living, and the remaining root relicts within rhizoliths belong to this species. The spatial distribution of rhizoliths also suggested that low topographic positions on a landscape provided soil moisture, and redox environments favored rhizolith formation. A semi-closed redox environment in the subsoil at swales and depressions, where water is always present, along with the sandy soil texture, facilitated fast water percolation to deeper depths and condensation. Such a soil environment not only provides water for Artemisia growth, but also for the weathering of minerals such as felspars and calcite from primary carbonates, and for the decomposition of root relicts. Furthermore, harsh climatic conditions, such as strong winds and solar radiation, led to water evaporation through dead root channels and triggered the calcification along the root relicts. The entrapped lithogenic carbonates and to a lesser extent the decomposition of Artemisia roots provided the carbon sources for the rhizoliths formation, while the weathering of soil minerals, particularly feldspars and carbonates, was the main source of Ca. Rhizoliths in the Badain Jaran desert formed relatively quickly, probably over a few soil drying episodes. This led to the entrapment of a large quantity of lithogenic carbonates (more than 90% of carbon) within rhizolith cement. The re-dissolution of the entrapped lithogenic carbonates in rhizolith tubes should be taken into account in the paleoenvironmental interpretation of 14C ages, the latter suggesting that rhizoliths formed during the Holocene (~ 2053 years cal BP, based on root organic relicts)

Genesis and soil environmental implications of intact in-situ rhizoliths in dunes of the Badain Jaran Desert, northwestern China

Desert rhizoliths are generally found as weathered, broken and scattered samples on dune field surface, but rarely in-situ in their initial states buried under the soil of desert in the Badain Jaran Desert, northwest China. This study offers an assessment of the morphological, mineralogical, and chemical properties of intact and in-situ rhizoliths found in soils of swales and depressions among dune chains. The characteristics of these rare and precious objects were assessed using optical polarizing microscopy, cathodoluminescence, scanning electronic microscopy, radiocarbon dating, and stable isotopic analyses, providing the opportunity for discussion of the rhizolith formation mechanisms and associated environmental conditions. Field and laboratory investigations showed that the in-situ intact rhizoliths were formed only in the places where Artemisia shrubs are living, and the remaining root relicts within rhizoliths belong to this species. The spatial distribution of rhizoliths also suggested that low topographic positions on a landscape provided soil moisture, and redox environments favored rhizolith formation. A semi-closed redox environment in the subsoil at swales and depressions, where water is always present, along with the sandy soil texture, facilitated fast water percolation to deeper depths and condensation. Such a soil environment not only provides water for Artemisia growth, but also for the weathering of minerals such as felspars and calcite from primary carbonates, and for the decomposition of root relicts. Furthermore, harsh climatic conditions, such as strong winds and solar radiation, led to water evaporation through dead root channels and triggered the calcification along the root relicts. The entrapped lithogenic carbonates and to a lesser extent the decomposition of Artemisia roots provided the carbon sources for the rhizoliths formation, while the weathering of soil minerals, particularly feldspars and carbonates, was the main source of Ca. Rhizoliths in the Badain Jaran desert formed relatively quickly, probably over a few soil drying episodes. This led to the entrapment of a large quantity of lithogenic carbonates (more than 90% of carbon) within rhizolith cement. The re-dissolution of the entrapped lithogenic carbonates in rhizolith tubes should be taken into account in the paleoenvironmental interpretation of 14C ages, the latter suggesting that rhizoliths formed during the Holocene (~ 2053 years cal BP, based on root organic relicts). © 2022, The Author(s)

Whole-soil warming decreases abundance and modifies the community structure of microorganisms in the subsoil but not in surface soil

The microbial community composition in subsoils remains understudied, and it is largely unknown whether subsoil microorganisms show a similar response to global warming as microorganisms at the soil surface do. Since microorganisms are the key drivers of soil organic carbon decomposition, this knowledge gap causes uncertainty in the predictions of future carbon cycling in the subsoil carbon pool (> 50 % of the soil organic carbon stocks are below 30 cm soil depth). In the Blodgett Forest field warming experiment (California, USA) we investigated how +4 ∘C warming in the whole-soil profile to 100 cm soil depth for 4.5 years has affected the abundance and community structure of microorganisms. We used proxies for bulk microbial biomass carbon (MBC) and functional microbial groups based on lipid biomarkers, such as phospholipid fatty acids (PLFAs) and branched glycerol dialkyl glycerol tetraethers (brGDGTs). With depth, the microbial biomass decreased and the community composition changed. Our results show that the concentration of PLFAs decreased with warming in the subsoil (below 30 cm) by 28 % but was not affected in the topsoil. Phospholipid fatty acid concentrations changed in concert with soil organic carbon. The microbial community response to warming was depth dependent. The relative abundance of Actinobacteria increased in warmed subsoil, and Gram+ bacteria in subsoils adapted their cell membrane structure to warming-induced stress, as indicated by the ratio of anteiso to iso branched PLFAs. Our results show for the first time that subsoil microorganisms can be more affected by warming compared to topsoil microorganisms. These microbial responses could be explained by the observed decrease in subsoil organic carbon concentrations in the warmed plots. A decrease in microbial abundance in warmed subsoils might reduce the magnitude of the respiration response over time. The shift in the subsoil microbial community towards more Actinobacteria might disproportionately enhance the degradation of previously stable subsoil carbon, as this group is able to metabolize complex carbon sources

Impact of climate change on the ecology of the Kyambangunguru crater marsh in southwestern Tanzania during the Late Holocene

Instrumental records of temperature and hydrological regimes in East Africa evidence frequent droughts with dramatic effects on population and ecosystems. Sources of these climatic variations remain largely unconstrained, partly because of a paucity of Late Holocene records. Here, we present a multi-proxy analysis of a 4-m continuous sediment core collected in the Kyambangunguru crater marsh, in southwest Tanzania, covering the last 4000 yrs (cal. BP). We used microscopic (macro-remains, microfossils, palynofacies, pollen), elemental (carbon, nitrogen contents), molecular (br GDGTs, n-alkanes) and compound-specific isotopic (δ2H n-alkanes) investigations to reconstruct the environmental history of the marsh. The multi proxy record reveals that, 2500 years ago, the marsh underwent a major ecological transition from a lake to a peatland. Temperature and hydrological reconstructions evidence warmer and drier conditions between 2200 and 860 cal. BP, which probably triggered the establishment of a perennial peatland. This study is one of the first combined temperature and precipitation record of Late Holocene in the region and highlights changes in the spatial distribution of the East African climate regimes. Several cold periods are observed, between 3300 and 2000 cal. BP and since 630 cal. BP, the latter corresponding to the Little Ice Age. Moreover, wetter conditions are reported during the Medieval Climate Anomaly in contrast to other north-eastern African records suggesting that Tanzania is located at the transition between two hydro-climatic zones (north-eastern versus southern Africa) and has experienced variable contributions of these two zones over the last millennium

Correction to: Human behavior and Homo-mammal interactions at the first European peopling: new evidence from the Pirro Nord site (Apricena, Southern Italy)

In the original publication of this article, one of the author names was incorrectly captured. The first name should be Razika, then family name should be Chelli–Cheheb

Evaluation of branched GDGTs and leaf wax n-alkane δ2H as (paleo) environmental proxies in East Africa

The role of mountain evolution on local climate is poorly understood and potentially underestimated in climate models. One prominent example is East Africa, which underwent major geodynamic changes with the onset of the East African Rift System (EARS) more than 250 Myr ago. This study explores, at the regional East African scale, a molecular approach for terrestrially-based paleo-climatic reconstructions that takes into account both changes in temperature and in altitude, potentially leading to an improved concept in paleo-climatic reconstructions. Using surface soils collected along pronounced altitudinal gradients in Mt. Rungwe (n=40; Southwest Tanzania) and Mt. Kenya (n=20; Central Kenya), we investigate the combination of 2 terrestrial proxies, leaf wax n-alkane δ2H (δ2Hwax) and branched glycerol dialkyl glycerol tetraether (br GDGT) membrane lipids, as (paleo) elevation and (paleo) temperature proxies, respectively. At the mountain scale, a weak link between δ2Hwax and altitude (R2 = 0.33) is observed at Mt. Kenya, but no relationship is observed at Mt. Rungwe. It is likely that additional parameters, such as decreasing relative humidity (RH) or vegetation changes with altitude, are outcompeting the expected 2H-depletion trend along Mt. Rungwe. In contrast, br GDGT-derived absolute mean annual air temperature (MAAT) and temperature lapse rate (0.65 °C/100 m) for both mountains are in good agreement with direct field measurements, further supporting the robustness of this molecular proxy for (paleo) temperature reconstructions. At the regional scale, estimated and observed δ2H data in precipitation along 3 mountains in East Africa (Mts. Rungwe, Kenya and Kilimanjaro) highlight a strong spatial heterogeneity, preventing the establishment of a regional based calibration of δ2Hwax for paeloaltitudinal reconstructions. Different from that, an improved regional soil calibration is developed between br GDGT distribution and MAAT by combining the data from this study (Mts. Rungwe and Kenya) with previous results from East African surface soils along Mts. Kilimanjaro (Tanzania) and Rwenzori (Uganda). This new regional calibration, based on 105 samples, improves both the R2 (0.77) and RMSE (root mean square error; 2.4 °C) of br GDGT-derived MAAT over the global soil calibrations previously established (R2 = 0.56; RMSE = 4.2 °C) and leads to more accurate (paleo) temperature reconstructions in the region