Raw X-ray fluorescence (XRF) scannings and radiocarbon age of sediment cores GeoB8331-4, and GeoB8322-2

Variations in the sediment input to the Namaqualand mudbelt during the Holocene are assessed using an integrative terrestrial to marine, source to sink approach. Geochemical and Sr and Nd isotopic signatures are used to distinguish fluvial sediment source areas. Relative to the sediments of the Olifants River, craton outcrops in the northern Orange River catchment have a more radiogenic Sr and a more unradiogenic Nd isotopic signature. Furthermore, upper Orange River sediments are rich in heavier elements such as Ti and Fe derived from the chemical weathering of Drakensberg flood basalt. Suspension load signatures change along the Orange River's westward transit as northern catchments contribute physical weathering products from the Fish and Molopo River catchment area. Marine cores offshore of the Olifants (GeoB8323-2) and Orange (GeoB8331-4) River mouths show pulses of increased contribution of Olifants River and upper Orange River input, respectively. These pulses coincide with intervals of increased terrestrial organic matter flux and increased paleo-production at the respective core sites. We attribute this to an increase in fluvial activity and vegetation cover in the adjacent catchments during more humid climate conditions. The contrast in the timing of these wet phases in the catchment areas reflects the bipolar behavior of the South African summer and winter rainfall zones. While rainfall in the Orange River catchment is related to southward shifts in the ICTZ, rainfall in the Olifants catchment is linked to northward shifts in Southern Hemisphere Westerly storm tracks. The later may also have increased southern Benguela upwelling in the past by reducing the shedding of Agulhas eddies into the Atlantic. The high-resolution records of latitudinal shifts in these atmospheric circulation systems correspond to late Holocene centennial-millennial scale climate variability evident in Antarctic ice core records. The mudbelt cores indicate that phases of high summer rainfall zone and low winter rainfall zone humidity (at ca. 2.8 and 1 ka BP) may be synchronous with Antarctic warming events. On the other hand, dry conditions in the summer rainfall zone along with wet conditions in the winter rainfall zone (at ca 3.3, 2 and 0.5 ka BP) may be associated with Antarctic cooling events.

Concentrations and d13C compositions of n-alkanes, n-alcohols, n-alkanoic acids in a 34-month time series of suspended sediments from the outflow of the Congo River

The concentrations, distributions, and stable carbon isotopes (d13C) of plant waxes carried by fluvial suspended sediments contain valuable information about terrestrial ecosystem characteristics. To properly interpret past changes recorded in sedimentary archives it is crucial to understand the sources and variability of exported plant waxes in modern systems on seasonal to inter-annual timescales. To determine such variability, we present concentrations and d13C compositions of three compound classes (n-alkanes, n-alcohols, n-alkanoic acids) in a 34-month time series of suspended sediments from the outflow of the Congo River. We show that exported plant-dominated n-alkanes (C25-C35) represent a mixture of C3 and C4 end members, each with distinct molecular distributions, as evidenced by an 8.1 ± 0.7 per mil (±1Sigma standard deviation) spread in d13C values across chain-lengths, and weak correlations between individual homologue concentrations (r = 0.52-0.94). In contrast, plant-dominated n-alcohols (C26-C36) and n-alkanoic acids (C26-C36) exhibit stronger positive correlations (r = 0.70-0.99) between homologue concentrations and depleted d13C values (individual homologues average <= -31.3 per mil and -30.8 per mil, respectively), with lower d13C variability across chain-lengths (2.6 ± 0.6 per mil and 2.0 ± 1.1 per mil, respectively). All individual plant-wax lipids show little temporal d13C variability throughout the time-series (1 Sigma <= 0.9 per mil), indicating that their stable carbon isotopes are not a sensitive tracer for temporal changes in plant-wax source in the Congo basin on seasonal to inter-annual timescales. Carbon-normalized concentrations and relative abundances of n-alcohols (19-58% of total plant-wax lipids) and n-alkanoic acids (26-76%) respond rapidly to seasonal changes in runoff, indicating that they are mostly derived from a recently entrained local source. In contrast, a lack of correlation with discharge and low, stable relative abundances (5-16%) indicate that n-alkanes better represent a catchment-integrated signal with minimal response to discharge seasonality. Comparison to published data on other large watersheds indicates that this phenomenon is not limited to the Congo River, and that analysis of multiple plant-wax lipid classes and chain lengths can be used to better resolve local vs. distal ecosystem structure in river catchments.

Desempenho de uma lagoa de infiltração na absorção de cheias e na recarga de aquífero

A type of macro drainage solution widely used in urban areas with predomi-nance of closed catchments (basins without outlet) is the implementation of detention and infiltration reservoirs (DIR). This type of solution has the main function of storing surface runoff and to promote soil infiltration and, consequently, aquifer recharge. The practice is to avoid floods in the drainage basin low-lying areas. The catchment waterproofing reduces the distributed groundwater recharge in urban areas, as is the case of Natal city, RN. However, the advantage of DIR is to concentrate the runoff and to promote aquifer recharge to an amount that can surpass the distributed natu-ral recharge. In this paper, we proposed studying a small urban drainage catchment, named Experimental Mirassol Watershed (EMW) in Natal, RN, whose outlet is a DIR. The rainfall-runoff transformation processes, water accumulation in DIR and the pro-cess of infiltration and percolation in the soil profile until the free aquifer were mod-eled and, from rainfall event observations, water levels in DIR and free aquifer water level measurements, and also, parameter values determination, it is was enabled to calibrate and modeling these combined processes. The mathematical modeling was carried out from two numerical models. We used the rainfall-runoff model developed by RIGHETTO (2014), and besides, we developed a one-dimensional model to simu-late the soil infiltration, percolation, redistribution soil water and groundwater in a combined system to the reservoir water balance. Continuous simulation was run over a period of eighteen months in time intervals of one minute. The drainage basin was discretized in blocks units as well as street reaches and the soil profile in vertical cells of 2 cm deep to a total depth of 30 m. The generated hydrographs were transformed into inlet volumes to the DIR and then, it was carried out water balance in these time intervals, considering infiltration and percolation of water in the soil profile. As a re-sult, we get to evaluate the storage water process in DIR as well as the infiltration of water, redistribution into the soil and the groundwater aquifer recharge, in continuous temporal simulation. We found that the DIR has good performance to storage excess water drainage and to contribute to the local aquifer recharge process (Aquifer Dunas / Barreiras).

Investigations on sediment core Co1010 from Rauer Group, Antarctica

The Rauer Group is an archipelago in Prydz Bay, East Antarctica. The ice-free islands and the surrounding shallow marine areas provide valuable archives for the reconstruction of the late Pleistocene and Holocene environmental and climatic history of the region. Two sediment records from two marine inlets of Rauer Group have been studied for their sedimentological, geochemical, and biological characteristics. Radiocarbon ages from one of the inlets indicate ice-free conditions within the last glacial cycle, probably during the second half of Marine Isotope Stage 3. Subsequent ice sheet coverage of Rauer Group during the Last Glacial Maxiumum (LGM) can be inferred from a till layer recovered in one of the basins. The inlets became ice-free prior to 11,200 cal yr BP, when biogenic sedimentation started. Deglacial processes in the catchments, however, influenced the inlets until ~9200 cal. yr BP as evidenced by the input of minerogenic material. Marine productivity under relatively open water conditions indicates an early Holocene climate optimum until 8200 cal. yr BP, which is followed by a cooler period with increased sea ice. Warmer conditions are inferred for the mid Holocene, when both basins experienced an input of freshwater between ~5700-3500 cal. yr BP, probably due to ice-sheet melting and increased precipitation on the islands. Neoglacial cooling in the late Holocene since c. 3500 cal yr BP is reflected by an increase in sea ice in both inlets.

Radiocarbon ages, grain sizes, paleomagentic properties and XRF data of Lake Nam Co sediments, Tibetan Plateau

In September 2008 several cores (68 cm-115 cm length) (water depth: 93 m) were retrieved from Lake Nam Co (southern-central Tibetan Plateau; 4718 m a.s.l.). This study focuses on the interpretation of high-resolution (partly 0.2 cm) data from three gravity cores and the upper part of a 10.4 m long piston core, i.e., the past 4000 cal BP in terms of lake level changes, hydrological variations in the catchment area and consequently variations in monsoon strength. A wide spectrum of sedimentological, geochemical and mineralogical investigations was carried out. Results are presented for XRF core-scans, grain size distribution, XRD-measurements and SEM-image analyses. These data are complemented by an age-depth model using 210Pb and 137Cs analyses as well as eleven AMS-14C-ages. This model is supported by excellent agreement between secular variations determined on one of the gravity cores to geomagnetic field models. This is a significant improvement of the chronology as most catchments of lacustrine systems on the Tibetan Plateau contain carbonates resulting in an unknown reservoir effect for radiocarbon dates. The good correlation of our record to the geomagnetic field models confirms our age-depth model and indicates only insignificant changes in the reservoir effect throughout the last 4 ka. High (summer-) monsoonal activity, i.e. moist environmental conditions, was detected in our record between approximately 4000 and 1950 cal BP as well as between 1480 and 1200 cal BP. Accordingly, lower monsoon activity prevails in periods between the two intervals and thereafter. This pattern shows a good correlation to the variability of the Indian Ocean Summer Monsoon (IOSM) as recorded in a peat bog ~1000 km in NE direction from Lake Nam Co. This is the first time that such a supra regional homogenous monsoon activity is shown on the Tibetan Plateau and beyond. Finally our data show a significant lake level rise after the Little Ice Age (LIA) in Lake Nam Co which is suggested to be linked to glacier melting in consequence of rising temperatures occurring on the whole Tibetan Plateau during this time.

14C specific radiocarbon ages and bulk ages accompanied by geochemical proxys from surface sediment samples in the Black Sea

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.

Geochemical analysis of surface sediments from the ocean floor and from sea ice in the northern Atlantic and Arctic Oceans

Barium in marine terrigenous surface sediments of the European Nordic Seas is analysed to evaluate its potential as palaeoproductivity proxy. Biogenic Ba is calculated from Ba and Al data using a conventional approach. For the determination of appropriate detrital Ba/Al ratios a compilation of Ba and Al analyses in rocks and soils of the catchments surrounding the Nordic Seas is presented. The resulting average detrital Ba/Al ratio of 0.0070 is similar to global crustal average values. In the southern Nordic Seas the high input of basaltic material with a low Ba/Al ratio is evident from high values of magnetic susceptibility and low Al/Ti ratios. Most of the Ba in the marine surface sediments is of terrigenous and not of biogenic origin. Variability in the lithogenic composition has been considered by the application of regionally varying Ba/Al ratios. The biogenic Ba values are comparable with those observed in the central Arctic Ocean, they are lower than in other oceanic regions. Biogenic Ba values are correlated with other productivity proxies and with oceanographic data for a validation of the applicability in paleoceanography. In the Iceland Sea and partly in the marginal sea-ice zone of the Greenland Sea elevated values of biogenic Ba indicate seasonal phytoplankton blooms. In both areas paleoproductivities may be reconstructed based on Ba and Al data of sediment cores.

(Supplement 1) Selected chemical composition of Icelandic river waters and bedrock age

In this study we map the spatial distribution of selected dissolved constituents in Icelandic river waters using GIS methods to study and interpret the connection between river chemistry, bedrock, hydrology, vegetation and aquatic ecology. Five parameters were selected: alkalinity, SiO2, Mo, F and the dissolved inorganic nitrogen and dissolved inorganic phosphorus mole ratio (DIN/DIP). The highest concentrations were found in rivers draining young rocks within the volcanic rift zone and especially those draining active central volcanoes. However, several catchments on the margins of the rift zone also had high values for these parameters, due to geothermal influence or wetlands within their catchment area. The DIN/DIP mole ratio was higher than 16 in rivers draining old rocks, but lowest in rivers within the volcanic rift zone. Thus primary production in the rivers is limited by fixed dissolved nitrogen within the rift zone, but dissolved phosphorus in the old Tertiary catchments. Nitrogen fixation within the rift zone can be enhanced by high dissolved molybdenum concentrations in the vicinity of volcanoes. The river catchments in this study were subdivided into several hydrological categories. Importantly, the variation in the hydrology of the catchments cannot alone explain the variation in dissolved constituents. The presence or absence of central volcanoes, young reactive rocks, geothermal systems and wetlands is important for the chemistry of the river waters. We used too many categories within several of the river catchments to be able to determine a statistically significant connection between the chem¬istry of the river waters and the hydrological categories. More data are needed from rivers draining one single hydrological category. The spatial dissolved constituent distribution clearly revealed the difference between the two extremes, the young rocks of the volcanic rift zone and the old Tertiary terrain.

Table 2: Water stable isotope results and sampling site information of samples taken between 2003 and 2009 on the island of Corsica (western Mediterranean)

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (dP) with values of -8.6(±0.2) per mil for d18O and -58(±2) per mil for d2H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of -0.17(±0.02) per mil per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

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.

Modeling long-term variability and change of soil moisture and groundwater level - from catchment to global scale

The water stored in and flowing through the subsurface is fundamental for sustaining human activities and needs, feeding water and its constituents to surface water bodies and supporting the functioning of their ecosystems. Quantifying the changes that affect the subsurface water is crucial for our understanding of its dynamics and changes driven by climate change and other changes in the landscape, such as in land-use and water-use. It is inherently difficult to directly measure soil moisture and groundwater levels over large spatial scales and long times. Models are therefore needed to capture the soil moisture and groundwater level dynamics over such large spatiotemporal scales. This thesis develops a modeling framework that allows for long-term catchment-scale screening of soil moisture and groundwater level changes. The novelty in this development resides in an explicit link drawn between catchment-scale hydroclimatic and soil hydraulics conditions, using observed runoff data as an approximation of soil water flux and accounting for the effects of snow storage-melting dynamics on that flux. Both past and future relative changes can be assessed by use of this modeling framework, with future change projections based on common climate model outputs. By direct model-observation comparison, the thesis shows that the developed modeling framework can reproduce the temporal variability of large-scale changes in soil water storage, as obtained from the GRACE satellite product, for most of 25 large study catchments around the world. Also compared with locally measured soil water content and groundwater level in 10 U.S. catchments, the modeling approach can reasonably well reproduce relative seasonal fluctuations around long-term average values. The developed modeling framework is further used to project soil moisture changes due to expected future climate change for 81 catchments around the world. The future soil moisture changes depend on the considered radiative forcing scenario (RCP) but are overall large for the occurrence frequency of dry and wet events and the inter-annual variability of seasonal soil moisture. These changes tend to be higher for the dry events and the dry season, respectively, than for the corresponding wet quantities, indicating increased drought risk for some parts of the world.