Sedimentology of a profile from Etoliko Lagoon, Western Greece

A key feature of Greece is the large amount of historical and archaeological records. The sedimentary record of the Etoliko Lagoon, Aetolia, Western Greece, offers an ideal opportunity to study human-environment interaction and to disentangle natural and anthropogenic imprints in the sedimentary record. By applying an interdisciplinary approach of combining geoscientific methods (XRF, LOI, grain size analysis) with archaeological and historical records, the 8.8 m long sedimentary sequence ETO1C reveals the palaeoenvironmental history of the lagoon and its catchment since 11,670 cal BP. With a thorough chronology based on 14C age-depth-modelling including varve counting, different evolutionary stages were put in a chronological context. These stages include a lake period (11,670-8310 cal BP) followed by a period of sporadic saltwater intrusion (8310-1350 cal BP) as a result of continuing transgression. Phases of limnic predominance associated with freshwater inflow of episodically activated distributaries (around 5230 cal BP) still occurred. By 1350 cal BP, ongoing sea level rise had connected the lagoons of Etoliko and Messolonghi and freshwater influence had ceased. With the onset of settlement activity in the Late Helladic (1700-1100 cal BC) humans took advantage of the prevailing environmental landscape. A sudden increase in coarse sedimentation correlates with the history of human occupation with its peak of prosperity from the Late Helladic until the end of the Hellenistic Period (30 cal BC).

Hydrological and meteorological investigations in a lake near Kangerlussuaq, west Greenland

Few hydrological studies have been made in Greenland, other than on glacial hydrology associated with the ice sheet. Understanding permafrost hydrology and hydroclimatic change and variability, however, provides key information for understanding climate change effects and feedbacks in the Arctic landscape. This paper presents a new extensive and detailed hydrological and meteorological open access dataset, with high temporal resolution from a 1.56 km**2 permafrost catchment with a lake underlain by a through talik close to the ice sheet in the Kangerlussuaq region, western Greenland. The paper describes the hydrological site investigations and utilized equipment, as well as the data collection and processing. The investigations were performed between 2010 and 2013. The high spatial resolution, within the investigated area, of the dataset makes it highly suitable for various detailed hydrological and ecological studies on catchment scale.

Long chain diols and diol indices of surface sediments of the Iberian Atlantic margin

Long chain diols are lipids that have gained interest over the last years due to their high potential to serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea surface temperature (SST). However, little is known about the sources of the diols and the mechanisms impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13- and 1,15-diols) were observed in surface sediments in front of major river mouths and this abundance correlates strongly with the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic difference of 1.3? with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface sediments directly along the northern part of the coast, close to the upwelling zone, suggesting that Diol Indices based on 1,14-diols would work well as upwelling tracers in this region. Strikingly, we observed a significant difference in stable carbon isotopic composition between the monounsaturated C30:1 1,14- and the saturated C28 1,14-diol (3.8±0.7 per mil), suggesting different sources, in accordance with their different distributions. In addition, the Long chain Diol Index (LDI), a proxy for sea surface temperature, was applied for the surface sediments. The results correlate well with satellite SSTs offshore but reveal a significant discrepancy with satellite-derived SSTs in front of the Tagus and Sado rivers. This suggests that river outflow might compromise the applicability of this proxy.

(Table 2) Age determination of sediment cores from the Portuguese Margin

We demonstrate that changes in the behavior of the Mediterranean Outflow Water (MOW) prior to and through the last deglaciation played an important role in promoting Meridional Overturning Circulation (MOC). Estimation of past MOW salt and heat fluxes indicates that they gradually increased through the last deglaciation. Between 17.5 and 14.6 thousand years ago (ka B.P., where B.P. references year 1950), net evaporation from the Mediterranean exported sufficient fresh water from the North Atlantic catchment to cause an average salinity increase of 0.5 psu throughout the upper 2000 m of the entire North Atlantic to the north of 25°N. Combined with rapid intensification and shoaling of the MOW plume, which we identify around 15-14.5 ka B.P., this deglacial MOW-related salt accumulation preconditioned the North Atlantic for abrupt resumption of the MOC at 14.6 ka B.P.

n-Alkane content and compound-specific d13C values of soil samples, river samples, and marine surface samples

Southwestern Africa's coastal marine mudbelt, a prominent Holocene sediment package, provides a valuable archive for reconstructing terrestrial palaeoclimates on the adjacent continent. While the origin of terrestrial inorganic material has been intensively studied, the sources of terrigenous organic material deposited in the mudbelt are yet unclear. In this study, plant wax derived n-alkanes and their compound-specific d13C in soils, flood deposits and suspension loads from regional fluvial systems and marine sediments are analysed to characterize the origin of terrestrial organic material in the southwest African mudbelt. Soils from different biomes in the catchments of the Orange River and small west coast rivers show on average distinct n-alkane distributions and compound-specific d13C values reflecting biome-specific vegetation types, most notably the winter rainfall associated Fynbos Biome of the southwestern Cape. In the fluvial sediment samples from the Orange River, changes in the n-alkane distributions and compound-specific d13C compositions reveal an overprint by local vegetation along the river's course. The smaller west coast rivers show distinct signals, reflecting their small catchment areas and particular vegetation communities. Marine surface sediments spanning a transect from the northern mudbelt (29°S) to St. Helena Bay (33°S) reveal subtle, but spatially coherent, changes in n-alkane distributions and compound-specific d13C, indicating the influence of Orange River sediments in the northern mudbelt, the increasing importance of terrigenous input from the adjacent western coastal biomes in the central mudbelt, and contributions from the Fynbos Biome to the southern mudbelt. These findings indicate the different sources of terrestrial organic material deposited in the mudbelt, and highlight the potential the mudbelt has to preserve evidence of environmental change from the adjacent continent.

Late Pleistocene sedimentation in the Western Mediterranean Sea

Sediment cores from the Western Mediterranean Sea (WMS) have been analyzed for their bulk element composition, delta18O values of planktic foraminiferal tests, and 87Sr/86Sr and 143Nd/144Nd ratios of their bulk lithogenic components. The investigated time interval comprises the last 215 kyr. Si/Al and Ti/Al ratios as well as radiogenic isotope compositions indicate changes in the provenance of the lithogenic components between glacial intervals and interglacial phases. Comparison with modern data indicates that detrital input from the northwestern and northeastern Sahara may have dominated during interglacial phases. In contrast, during glacial periods the accumulation rate of terrigenous sediment is high and changes in the sediment source areas are evident that may be related to changes in the prevailing atmospheric circulation over the basin and its source areas. A productivity reconstruction based on bio-mediated barium accumulation rates reveals increased surface productivity during glacial phases. Intervals time-equivalent to sapropel formation in the Eastern Mediterranean Sea (EMS) show no changes in surface productivity compared to the intervening intervals. Comparison of the productivity patterns between the WMS and EMS suggests a decoupling during Late Pleistocene sapropel formation and highlights the importance of more localized factors such as the freshwater drainage basin.

Nitrite consumption and associated isotope changes during a river flood event in the Elbe river

In oceans, estuaries, and rivers, nitrification is an important nitrate source, and stable isotopes of nitrate are often used to investigate recycling processes (e.g. remineralisation, nitrification) in the water column. Nitrification is a two-step process, where ammonia is oxidised via nitrite to nitrate. Nitrite usually does not accumulate in natural environments, which makes it difficult to study the single isotope effect of ammonia oxidation or nitrite oxidation in natural systems. However, during an exceptional flood in the Elbe River in June 2013, we found a unique co-occurrence of ammonium, nitrite, and nitrate in the water column, returning towards normal summer conditions within 1 week. Over the course of the flood, we analysed the evolution of d15N-[NH4]+ and d15N-[NO2]- in the Elbe River. In concert with changes in suspended particulate matter (SPM) and d15N SPM, as well as nitrate concentration, d15N-NO3 - and d18O-[NO3] -, we calculated apparent isotope effects during net nitrite and nitrate consumption. During the flood event, > 97 % of total reactive nitrogen was nitrate, which was leached from the catchment area and appeared to be subject to assimilation. Ammonium and nitrite concentrations increased to 3.4 and 4.4 µmol/l, respectively, likely due to remineralisation, nitrification, and denitrification in the water column. d15N-[NH4]+ values increased up to 12 per mil, and d15N-[NO2]- ranged from -8.0 to -14.2 per mil. Based on this, we calculated an apparent isotope effect 15-epsilon of -10.0 ± 0.1 per mil during net nitrite consumption, as well as an isotope effect 15-epsilon of -4.0 ± 0.1 per mil and 18-epsilon of -5.3 ± 0.1 per mil during net nitrate consumption. On the basis of the observed nitrite isotope changes, we evaluated different nitrite uptake processes in a simple box model. We found that a regime of combined riparian denitrification and 22 to 36 % nitrification fits best with measured data for the nitrite concentration decrease and isotope increase.

n-alkane carbon isotope ratios in plants and recent lake sediments from Cameroon

Trees and shrubs in tropical Africa use the C3 cycle as a carbon fixation pathway during photosynthesis, while grasses and sedges mostly use the C4 cycle. Leaf-wax lipids from sedimentary archives such as the long-chain n-alkanes (e.g., n-C27 to n-C33) inherit carbon isotope ratios that are representative of the carbon fixation pathway. Therefore, n-alkane d13C values are often used to reconstruct past C3/C4 composition of vegetation, assuming that the relative proportions of C3 and C4 leaf waxes reflect the relative proportions of C3 and C4 plants. We have compared the d13C values of n-alkanes from modern C3 and C4 plants with previously published values from recent lake sediments and provide a framework for estimating the fractional contribution (areal-based) of C3 vegetation cover (fC3) represented by these sedimentary archives. Samples were collected in Cameroon, across a latitudinal transect that accommodates a wide range of climate zones and vegetation types, as reflected in the progressive northward replacement of C3-dominated rain forest by C4-dominated savanna. The C3 plants analysed were characterised by substantially higher abundances of n-C29 alkanes and by substantially lower abundances of n-C33 alkanes than the C4 plants. Furthermore, the sedimentary d13C values of n-C29 and n-C31 alkanes from recent lake sediments in Cameroon (-37.4 per mil to -26.5 per mil) were generally within the range of d13C values for C3 plants, even when from sites where C4 plants dominated the catchment vegetation. In such cases simple linear mixing models fail to accurately reconstruct the relative proportions of C3 and C4 vegetation cover when using the d13C values of sedimentary n-alkanes, overestimating the proportion of C3 vegetation, likely as a consequence of the differences in plant wax production, preservation, transport, and/or deposition between C3 and C4 plants. We therefore tested a set of non-linear binary mixing models using d13C values from both C3 and C4 vegetation as end-members. The non-linear models included a sigmoid function (sine-squared) that describes small variations in the fC3 values as the minimum and maximum d13C values are approached, and a hyperbolic function that takes into account the differences between C3 and C4 plants discussed above. Model fitting and the estimation of uncertainties were completed using the Monte Carlo algorithm and can be improved by future data addition. Models that provided the best fit with the observed d13C values of sedimentary n-alkanes were either hyperbolic functions or a combination of hyperbolic and sine-squared functions. Such non-linear models may be used to convert d13C measurements on sedimentary n-alkanes directly into reconstructions of C3 vegetation cover.

Younger Dryas-Holocene sedimentary plant-wax hydrogen isotopes from the southern European Alps

We present a Younger Dryas-Holocene record of the hydrogen isotopic composition of sedimentary plant waxes (dDwax) from the southern European Alps (Lake Ghirla, N-Italy) to investigate its sensitivity to climatic forcing variations in this mid-latitude region (45°N). A modern altitudinal transect of dD values of river water and leaf waxes in the Lake Ghirla catchment is used to test present-day climate sensitivity of dDwax. While we find that altitudinal effects on dDwax are minor at our study site, temperature, precipitation amount, and evapotranspiration all appear to influence dDwax to varying extents. In the lake-sediment record, dDwax values vary between -134 and -180 per mil over the past 13 kyr. The long-term Holocene pattern of dDwax parallels the trend of decreasing temperature and is thus likely forced by the decline of northern hemisphere summer insolation. Shorter-term fluctuations, in contrast, may reflect both temperature and moisture-source changes. During the cool Younger Dryas and Little Ice Age (LIA) periods we observe unexpectedly high dDwax values relative to those before and after. We suggest that a change towards a more D-enriched moisture source is required during these intervals. In fact, a shift from northern N-Atlantic to southern N-Atlantic/western Mediterranean Sea sources would be consistent with a southward migration of the Westerlies with climate cooling. Prominent dDwax fluctuations in the early and middle Holocene are negative and potentially associated with temperature declines. In the late Holocene (<4 kyr BP), excursions are partly positive (as for the LIA) suggesting a stronger influence of moisture-source changes on dDwax variation. In addition to isotopic fractionations of the hydrological cycle, changes in vegetation composition, in the length of the growing season, and in snowfall amount provide additional potential sources of variability, although we cannot yet quantitatively assess these in the paleo-record. We conclude that while our dDwax record from the Alps does contain climatic information, it is a complicated record that would require additional constraints to be robustly interpreted. This also has important implications for other water-isotope-based proxy records of precipitation and hydro-climate from this region, such as cave speleothems.

Modern major element concentrations and ratios measured in Atlantic surface sediments (36°N-49°S)

Numerous studies use major element concentrations measured on continental margin sediments to reconstruct terrestrial climate variations. The choice and interpretation of climate proxies however differ from site to site. Here we map the concentrations of major elements (Ca, Fe, Al, Si, Ti, K) in Atlantic surface sediments (36°N-49°S) to assess the factors influencing the geochemistry of Atlantic hemipelagic sediments and the potential of elemental ratios to reconstruct different terrestrial climate regimes. High concentrations of terrigenous elements and low Ca concentrations along the African and South American margins reflect the dominance of terrigenous input in these regions. Single element concentrations and elemental ratios including Ca (e.g., Fe/Ca) are too sensitive to dilution effects (enhanced biological productivity, carbonate dissolution) to allow reliable reconstructions of terrestrial climate. Other elemental ratios reflect the composition of terrigenous material and mirror the climatic conditions within the continental catchment areas. The Atlantic distribution of Ti/Al supports its use as a proxy for eolian versus fluvial input in regions of dust deposition that are not affected by the input of mafic rock material. The spatial distributions of Al/Si and Fe/K reflect the relative input of intensively weathered material from humid regions versus slightly weathered particles from drier areas. High biogenic opal input however influences the Al/Si ratio. Fe/K is sensitive to the input of mafic material and the topography of Andean river drainage basins. Both ratios are suitable to reconstruct African and South American climatic zones characterized by different intensities of chemical weathering in well-understood environmental settings.

Soil and sediment analyses of Lake La Thuile (Bauges, France)

Data used in the study of the evolution of soils of Lake La Thuile catchment, in relation with the long sediment sequence of the lake. Data of pH, Loss On Ignition, Oxygen and Hydrogen Index (Rock-eval analyses) and mineral geochemistry (Portative XRF, Al2O3/TiO2 and K2O/TiO2 ratios) are available for each soil horizons that have been studied in the catchment. For sediments, data of Oxygen and Hydrogen Index (Rock-eval analyses), mineral geochemistry (Portative XRF, Al2O3/TiO2 and K2O/TiO2 ratios), erosion, soil evolution modelization and the ages are available according to depth.

Interannual and (multi-)decadal variability in the sedimentary BIT index of Lake Challa, East Africa, over the past 2200 years: assessment of the precipitation proxy

The branched vs. isoprenoid tetraether (BIT) index is based on the relative abundance of branched tetraether lipids (brGDGTs) and the isoprenoidal GDGT crenarchaeol. In Lake Challa sediments the BIT index has been applied as a proxy for local monsoon precipitation on the assumption that the primary source of brGDGTs is soil washed in from the lake's catchment. Since then, microbial production within the water column has been identified as the primary source of brGDGTs in Lake Challa sediments, meaning that either an alternative mechanism links BIT index variation with rainfall or that the proxy's application must be reconsidered. We investigated GDGT concentrations and BIT index variation in Lake Challa sediments at a decadal resolution over the past 2200 years, in combination with GDGT time-series data from 45 monthly sediment-trap samples and a chronosequence of profundal surface sediments.

Our 2200-year geochemical record reveals high-frequency variability in GDGT concentrations, and therefore in the BIT index, superimposed on distinct lower-frequency fluctuations at multi-decadal to century timescales. These changes in BIT index are correlated with changes in the concentration of crenarchaeol but not with those of the brGDGTs. A clue for understanding the indirect link between rainfall and crenarchaeol concentration (and thus thaumarchaeotal abundance) was provided by the observation that surface sediments collected in January 2010 show a distinct shift in GDGT composition relative to sediments collected in August 2007. This shift is associated with increased bulk flux of settling mineral particles with high Ti / Al ratios during March–April 2008, reflecting an event of unusually high detrital input to Lake Challa concurrent with intense precipitation at the onset of the principal rain season that year. Although brGDGT distributions in the settling material are initially unaffected, this soil-erosion event is succeeded by a massive dry-season diatom bloom in July–September 2008 and a concurrent increase in the flux of GDGT-0. Complete absence of crenarchaeol in settling particles during the austral summer following this bloom indicates that no Thaumarchaeota bloom developed at that time. We suggest that increased nutrient availability, derived from the eroded soil washed into the lake, caused the massive bloom of diatoms and that the higher concentrations of ammonium (formed from breakdown of this algal matter) resulted in a replacement of nitrifying Thaumarchaeota, which in typical years prosper during the austral summer, by nitrifying bacteria. The decomposing dead diatoms passing through the suboxic zone of the water column probably also formed a substrate for GDGT-0-producing archaea. Hence, through a cascade of events, intensive rainfall affects thaumarchaeotal abundance, resulting in high BIT index values.

Decade-scale BIT index fluctuations in Lake Challa sediments exactly match the timing of three known episodes of prolonged regional drought within the past 250 years. Additionally, the principal trends of inferred rainfall variability over the past two millennia are consistent with the hydroclimatic history of equatorial East Africa, as has been documented from other (but less well dated) regional lake records. We therefore propose that variation in GDGT production originating from the episodic recurrence of strong soil-erosion events, when integrated over (multi-)decadal and longer timescales, generates a stable positive relationship between the sedimentary BIT index and monsoon rainfall at Lake Challa. Application of this paleoprecipitation proxy at other sites requires ascertaining the local processes which affect the productivity of crenarchaeol by Thaumarchaeota and brGDGTs.