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

The biogeochemistry of carbon across a gradient of streams and rivers within the Congo Basin

Author Posting. © American Geophysical Union, 2014. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Biogeosciences 119 (2014): 687–702, doi:10.1002/2013JG002442.Dissolved organic carbon (DOC) and inorganic carbon (DIC, pCO2), lignin biomarkers, and theoptical properties of dissolved organic matter (DOM) were measured in a gradient of streams and rivers within the Congo Basin, with the aim of examining how vegetation cover and hydrology influences the composition and concentration of fluvial carbon (C). Three sampling campaigns (February 2010, November 2010, and August 2011) spanning 56 sites are compared by subbasin watershed land cover type (savannah, tropical forest, and swamp) and hydrologic regime (high, intermediate, and low). Land cover properties predominately controlled the amount and quality of DOC, chromophoric DOM (CDOM) and lignin phenol concentrations (∑8) exported in streams and rivers throughout the Congo Basin. Higher DIC concentrations and changing DOM composition (lower molecular weight, less aromatic C) during periods of low hydrologic flow indicated shifting rapid overland supply pathways in wet conditions to deeper groundwater inputs during drier periods. Lower DOC concentrations in forest and swamp subbasins were apparent with increasing catchment area, indicating enhanced DOC loss with extended water residence time. Surface water pCO2 in savannah and tropical forest catchments ranged between 2,600 and 11,922 µatm, with swamp regions exhibiting extremely high pCO2 (10,598–15,802 µatm), highlighting their potential as significant pathways for water-air efflux. Our data suggest that the quantity and quality of DOM exported to streams and rivers are largely driven by terrestrial ecosystem structure and that anthropogenic land use or climate change may impact fluvial C composition and reactivity, with ramifications for regional C budgets and future climate scenarios.This work was supported by the National Science Foundation as part of the ETBC Collaborative Research: Controls on the Flux, Age, and Composition of Terrestrial Organic Carbon Exported by Rivers to the Ocean (0851101 and 0851015).2014-10-3

Inorganic Carbon Speciation and Fluxes in the Congo River

Seasonal variations in inorganic carbon chemistry and associated fluxes from the Congo River were investigated at Brazzaville-Kinshasa. Small seasonal variation in dissolved inorganic carbon (DIC) was found in contrast with discharge-correlated changes in pH, total alkalinity (TA), carbonate species, and dissolved organic carbon (DOC). DIC was almost always greater than TA due to the importance of CO2*, the sum of dissolved CO2 and carbonic acid, as a result of low pH. Organic acids in DOC contributed 11–61% of TA and had a strong titration effect on water pH and carbonate speciation. The CO2* and bicarbonate fluxes accounted for ~57% and 43% of the DIC flux, respectively. Congo River surface water released CO2 at a rate of ~109 mol m−2 yr−1. The basin-wide DIC yield was ~8.84 × 104 mol km−2 yr−1. The discharge normalized DIC flux to the ocean amounted to 3.11 × 1011 mol yr−1. The DOC titration effect on the inorganic carbon system may also be important on a global scale for regulating carbon fluxes in rivers