Hydrologic controls on seasonal and inter-annual variability of Congo River particulate organic matter source and reservoir age

We present dissolved organic carbon (DOC) concentrations, particulate organic matter (POM) composition (δ13C, δ15N, ∆14C, N/C), and particulate glycerol dialkyl glycerol tetraether (GDGT) distributions from a 34-month time-series near the mouth of the Congo River. An end-member mixing model using δ13C and N/C indicates that exported POM is consistently dominated by C3 rainforest soil sources, with increasing contribution from C3 vegetation and decreasing contribution from phytoplankton at high discharge. Large C4 inputs are never observed despite covering ≈ 13% of the catchment. Low and variable ∆14C values during 2011 [annual mean = (− 148 ± 82) ‰], when discharge from left-bank tributaries located in the southern hemisphere reached record lows, likely reflect a bias toward pre-aged POM derived from the Cuvette Congolaise swamp forest. In contrast, ∆14C values were stable near − 50‰ between January and June 2013, when left-bank discharge was highest. We suggest that headwater POM is replaced and/or diluted by C3 vegetation and pre-aged soils during transit through the Cuvette Congolaise, whereas left-bank tributaries export significantly less pre-aged material. GDGT distributions provide further evidence for seasonal and inter-annual variability in soil provenance. The cyclization of branched tetraethers and the GDGT-0 to crenarchaeol ratio are positively correlated with discharge (r ≥ 0.70; p-value ≤ 4.3 × 10− 5) due to the incorporation of swamp-forest soils when discharge from right-bank tributaries located in the northern hemisphere is high. Both metrics reach record lows during 2013, supporting our interpretation of increased left-bank contribution at this time. We conclude that hydrologic variability is a major control of POM provenance in the Congo River Basin and that tropical wetlands can be a significant POM source despite their small geographic coverage

Constraints on the sources of branched tetraether membrane lipids in distal marine sediments

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids produced by soil bacteria and occur in near coastal marine sediments as a result of soil organic matter input. Their abundance relative to marine-derived crenarchaeol, quantified in the BIT index, generally decreases offshore. However, in distal marine sediments, low relative amounts of brGDGTs can often still be observed. Sedimentary in situ production as well as dust input have been suggested as potential, though as yet not well constrained, sources. In this study brGDGT distributions in dust were examined and compared with those in distal marine sediments. Dust was sampled along the equatorial West African coast and brGDGTs were detected in most of the samples, albeit in low abundance. Their degree of methylation and cyclisation, expressed in the MBT' (methylation index of branched tetraethers) and DC (degree of cyclisation) indices, respectively, were comparable with those for African soils, their presumed source. Comparison of DC index values for brGDGTS in global soils, Congo deep-sea river fan sediments and dust with those of distal marine sediments clearly showed, however, that distal marine sediments had significantly higher values. This distinctive distribution is suggestive of sedimentary in situ production as a source of brGDGTs in marine sediments, rather than dust input. The presence of in situ produced brGDGTs in marine sediments means that caution should be exercised when applying the MBT'–CBT palaeothermometer to sediments with low BIT index values, i.e. < 0.1, based on our dataset

Multiple plant-wax compounds record differential sources and ecosystem structure in large river catchments

© The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Geochimica et Cosmochimica Acta 184 (2016): 20-40, doi:10.1016/j.gca.2016.04.003.The concentrations, distributions, and stable carbon isotopes (δ13C) 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 δ13C 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‰ (±1σ standard deviation) spread in δ13C 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 δ13C values (individual homologues average ≤ -31.3‰ and -30.8‰, respectively), with lower δ13C variability across chain-lengths (2.6 ± 0.6‰ and 2.0 ± 1.1‰, respectively). All individual plant-wax lipids show little temporal δ13C variability throughout the time-series (1σ ≤ 0.9‰), 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.J.D.H. was supported by the National Science Foundation Graduate Research Fellowship under Grant No. 2012126152. V.V.G. was partly supported by the US National Science Foundation, grants OCE-0851015 and OCE-0928582. Parts of this work were supported by the DFG Research Center/Cluster of Excellence “The Ocean in the Earth System” at MARUM - Center for Marine Environmental Science, University of Bremen.2017-04-0

Wetland expansion on the continental shelf of the northern South China Sea during deglacial sea level rise

To identify environmental causes for past changes in vegetation in subtropical East Asia, we present carbon isotope compositions of plant-wax n-alkanes and provide estimates of the C4-plant contribution across the past four glacial terminations and interglacials, based on cores recovered from the northern South China Sea. Our results show a comparable C4-plant contribution between the Last Glacial Maximum (LGM) and the Holocene. An increase of the C4-plant contribution by 15–20% is found for Terminations IV, II and I relative to subsequent interglacial peaks, coeval with an expansion of Cyperaceae and Poaceae. In contrast, Termination V reveals a lower C4-plant contribution than Marine Isotope Stage (MIS) 11c. The data exhibit a long-term trend, with a stepwise increase of the C4-plant contribution across interglacials MIS 11c, 9e, 7e and 1. We suggest that no substantial changes in humidity levels over glacial-interglacial cycles occurred facilitating a similar C3/C4-plant ratio for the LGM and the Holocene. Instead, deglacial sea-level rises caused an extensive development of floodplains and wetlands on the exposed continental shelf, providing habitats for the spread of C4 sedges and grasses. The progressive subsidence of Chinese coastal areas and the broadening of the continental shelf over the late Quaternary explains the nearly absence of C4 plant occurrence during Termination V and a gradual increase of the C4-plant contribution across interglacial peaks. Taken together, changes in coastal environments should be considered when interpreting marine-based vegetation reconstructions from subtropical Asia

Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 5 (2004): Q10004, doi:10.1029/2004GC000772.Long-chain, odd-carbon-numbered C25 to C35 n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (<C25) are removed by evaporation on the moving wire. Test samples processed using this procedure yielded n-alkane fractions essentially free of interfering components. The δ13C values obtained by MW-irMS did not differ significantly from weighted averages of individual n-alkane δ13C values obtained by irmGC-MS. Isotopic variations in compound-class n-alkane fractions from a latitudinal transect of core-top sediments from the Southwest African margin (3°N–28°S) were congruent with those measured by compound-specific isotopic analyses of plant-wax n-alkanes. The amplitude of the variations was smaller, indicating contributions from non-plant-wax hydrocarbons, but the measurements revealed variations in carbon isotopic composition that are consistent with vegetation zones on the adjacent continent.We thank the WHOI Summer Student Fellow program and NSF (BCS-0218511) for funding

Late Holocene slowdown of the Indian Ocean Walker circulation

Changes in tropical zonal atmospheric (Walker) circulation induce shifts in rainfall patterns along with devastating floods and severe droughts that dramatically impact the lives of millions of people. Historical records and observations of the Walker circulation over the 20th century disagree on the sign of change and therefore, longer climate records are necessary to better project tropical circulation changes in response to global warming. Here we examine proxies for thermocline depth and rainfall in the eastern tropical Indian Ocean during the globally colder Last Glacial Maximum (19–23 thousand years ago) and for the past 3000 years. We show that increased thermocline depth and rainfall indicate a stronger-than-today Walker circulation during the Last Glacial Maximum, which is supported by an ensemble of climate simulations. Our findings underscore the sensitivity of tropical circulation to temperature change and provide evidence for a further weakening of the Walker circulation in response to greenhouse warming

The Provenance of Terrigenous Components in Marine Sediments Along the East Coast of Southern Africa

AbstractTerrestrial signals in marine sediment archives are often used for paleoclimatic reconstructions. It is therefore important to know the origin of the different terrestrial sedimentary components. The proximity to a river mouth is often the key location to determine the source. Especially in regions with strong ocean currents, such an assumption might, however, lead to considerable misinterpretations. To investigate the source of various terrigenous sediment fractions in southeastern Africa, a region with strong sediment redistribution, we have performed an extensive comparison between terrestrial material (pollen, plant lipids, detrital modes, and heavy minerals as well as bulk inorganic geochemical composition) from potential source regions and the same components in the adjacent coastal and continental shelf sediments. Onshore the proxy‐indicators reflect small‐scale diversity in sampling locations and associated environments (riverbank sediments, flood deposits, suspension loads, and soils). Nevertheless, the overall trends reflect significant environmental gradients along a SW to NE transect. We note a general comparability of the studied parameters between the continental and marine sediments regardless of their specific differences in transport and depositional characteristics. We propose that the influence of the Agulhas Current affects sediment deposition and distribution only seaward of the midshelf and that pockets of sediment remain preserved in the lee of coastal protrusions where they are protected from erosion. This study provides the essential prerequisite to allow the attribution of temporal variations of compositional changes in marine sediment cores to environmental changes in southeastern Africa

Variability in aerobic methane oxidation over the past 1.2 Myrs recorded in microbial biomarker signatures from Congo fan sediments

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of −30‰ to −40‰ for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources

Evaluation of long chain 1,14-alkyl diols in marine sediments as indicators for upwelling and temperature

Long chain alkyl diols form a group of lipids occurring widely in marine environments. Recent studies have suggested several palaeoclimatological applications for proxies based on their distributions, but have also revealed uncertainty about their applicability. Here we evaluate the use of long chain 1,14-alkyl diol indices for reconstruction of temperature and upwelling conditions by comparing index values, obtained from a comprehensive set of marine surface sediments, with environmental factors such as sea surface temperature (SST), salinity and nutrient concentration. Previous studies of cultures indicated a strong effect of temperature on the degree of saturation and the chain length distribution of long chain 1,14-alkyl diols in Proboscia spp., quantified as the diol saturation index (DSI) and diol chain length index (DCI), respectively. However, values of these indices for surface sediments showed no relationship with annual mean SST of the overlying water. It remains unknown as to what determines the DSI, although our data suggest that it may be affected by diagenesis, while the relationship between temperature and DCI may be different for different Proboscia species. In addition, contributions from algae other than Proboscia diatoms may affect both indices, although our data provide no direct evidence for additional long chain 1,14-alkyl diol sources. Two other indices using the abundance of 1,14-diols vs. 1,13-diols and C30 1,15-diols have been applied previously as indicators for upwelling intensity at different locations. The geographical distribution of their values supports the use of 1,14 diols vs. 1,13 diols [C28 + C30 1,14-diols]/[(C28 + C30 1,13-diols) + (C28 + C30 1,14-diols)] as a general indicator for high nutrient or upwelling conditions