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

Technical note : an inverse method to relate organic carbon reactivity to isotope composition from serial oxidation

© The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 14 (2017): 5099-5114, doi:10.5194/bg-14-5099-2017.Serial oxidation coupled with stable carbon and radiocarbon analysis of sequentially evolved CO2 is a promising method to characterize the relationship between organic carbon (OC) chemical composition, source, and residence time in the environment. However, observed decay profiles depend on experimental conditions and oxidation pathway. It is therefore necessary to properly assess serial oxidation kinetics before utilizing decay profiles as a measure of OC reactivity. We present a regularized inverse method to estimate the distribution of OC activation energy (E), a proxy for bond strength, using serial oxidation. Here, we apply this method to ramped temperature pyrolysis or oxidation (RPO) analysis but note that this approach is broadly applicable to any serial oxidation technique. RPO analysis directly compares thermal reactivity to isotope composition by determining the E range for OC decaying within each temperature interval over which CO2 is collected. By analyzing a decarbonated test sample at multiple masses and oven ramp rates, we show that OC decay during RPO analysis follows a superposition of parallel first-order kinetics and that resulting E distributions are independent of experimental conditions. We therefore propose the E distribution as a novel proxy to describe OC thermal reactivity and suggest that E vs. isotope relationships can provide new insight into the compositional controls on OC source and residence time.This research was supported by the NSF Graduate Research Fellowship Program grant no. 2012126152 (Jordon D. Hemingway), NASA Astrobiology grant no. NNA13AA90A and NSF grant no. EAR-1338810 (Daniel H. Rothman), and the WHOI Independent Study Award (Valier V. Galy)

Polyparameter linear free energy relationship for wood char–water sorption coefficients of organic sorbates

Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of John Wiley & Sons for personal use, not for redistribution. The definitive version was published in Environmental Toxicology and Chemistry 34 (2015): 1464-1471, doi:10.1002/etc.2951.Black carbons (BCs), including soots, chars, activated carbons, and engineered nanocarbons, have different surface properties, but we do not know to what extent these affect their sorbent properties. To evaluate this for an environmentally ubiquitous form of BC, biomass char, we probed the surface of a well-studied wood char using 14 sorbates exhibiting diverse functional groups and then fit the data with a polyparameter linear free energy relationship (ppLFER) to assess the importance of the various possible sorbate-char surface interactions. Sorption from water to water-wet char evolved with the sorbate's degree of surface saturation and depended on only a few sorbate parameters: log Kd(L/kg) = [(4.03 ± 0.14) + (-0.15 ± 0.04) log ai)] V + [(-0.28 ± 0.04) log ai)] S + (-5.20 ± 0.21) B where ai is the aqueous saturation of the sorbate i, V is McGowan’s characteristic volume, S reflects polarity, and B represents the electron-donation basicity. As generally observed for activated carbon, the sorbate’s size encouraged sorption from water to the char, while its electron donation/proton acceptance discouraged sorption from water. However, the magnitude and saturation dependence differed significantly from what has been seen for activated carbons, presumably reflecting the unique surface chemistries of these two BC materials and suggesting BC-specific sorption coefficients will yield more accurate assessments of contaminant mobility and bioavailability and evaluation of a site's response to remediation.This material is based upon work supported by the U.S. Army Corps of Engineering, Humphreys Engineer Center Support Activity under Contract No. W912HQ-10-C-0005 awarded as part of the SERDP program.2016-05-1

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

Structure of Lambda(1405) and chiral dynamics

We report on a recent theoretical work on the structure of the Lambda(1405) resonance within a chiral unitary approach, in which the resonance is dynamically generated in meson-baryon scattering. Studying the analytic structure of the scattering amplitude, we have found that there are two poles lying around energies of Lambda(1405) with different widths and couplings to the meson-baryon states. We discuss reactions to conform the double pole structure in experiment and elastic K^- p scattering at low energies.Comment: 4 pages, LaTeX, 2 eps figures. Talk given at 10th International Conference on the Structure of Baryons (Baryon 2004) at Palaiseau (France), 25-29 October 200

Developing and validating a cardiovascular risk score for patients in the community with prior cardiovascular disease

OBJECTIVE: Patients with atherosclerotic cardiovascular disease (CVD) vary significantly in their risk of future CVD events; yet few clinical scores are available to aid assessment of risk. We sought to develop a score for use in primary care that estimates short-term CVD risk in these patients. METHODS: Adults aged <80 years with prior CVD were identified from a New Zealand primary care cohort study (PREDICT), and linked to national mortality, hospitalisation and dispensing databases. A Cox model with an outcome of myocardial infarction, stroke or CVD death within 2 years was developed. External validation was performed in a cohort from the UK. RESULTS: 24 927 patients, 63% men, 63% European, median age 65 years (IQR 58-72 years), experienced 1480 CVD events within 2 years after a CVD risk assessment. A risk score including ethnicity, comorbidities, body mass index, creatine creatinine and treatment, in addition to established risk factors used in primary prevention, predicted a median 2-year CVD risk of 5.0% (IQR 3.5%-8.3%). A plot of actual against predicted event rates showed very good calibration throughout the risk range. The score performed well in the UK cohort but overestimated risk for those at highest risk, who were predominantly patients defined as having heart failure. CONCLUSIONS: The PREDICT-CVD secondary prevention score uses routine measurements from clinical practice that enable it to be implemented in a primary care setting. The score will facilitate risk communication between primary care practitioners and patients with prior CVD, particularly as a resource to show the benefit of risk factor modification

Planning and Leveraging Event Portfolios: Towards a Holistic Theory

This conceptual paper seeks to advance the discourse on the leveraging and legacies of events by examining the planning, management, and leveraging of event portfolios. This examination shifts the common focus from analyzing single events towards multiple events and purposes that can enable cross-leveraging among different events in pursuit of attainment and magnification of specific ends. The following frameworks are proposed: (1) event portfolio planning and leveraging, and (2) analyzing events networks and inter-organizational linkages. These frameworks are intended to provide, at this infancy stage of event portfolios research, a solid ground for building theory on the management of different types and scales of events within the context of a portfolio aimed to obtain, optimize and sustain tourism, as well as broader community benefits

Comparison of random forest and parametric imputation models for imputing missing data using MICE: a CALIBER study.

Multivariate imputation by chained equations (MICE) is commonly used for imputing missing data in epidemiologic research. The "true" imputation model may contain nonlinearities which are not included in default imputation models. Random forest imputation is a machine learning technique which can accommodate nonlinearities and interactions and does not require a particular regression model to be specified. We compared parametric MICE with a random forest-based MICE algorithm in 2 simulation studies. The first study used 1,000 random samples of 2,000 persons drawn from the 10,128 stable angina patients in the CALIBER database (Cardiovascular Disease Research using Linked Bespoke Studies and Electronic Records; 2001-2010) with complete data on all covariates. Variables were artificially made "missing at random," and the bias and efficiency of parameter estimates obtained using different imputation methods were compared. Both MICE methods produced unbiased estimates of (log) hazard ratios, but random forest was more efficient and produced narrower confidence intervals. The second study used simulated data in which the partially observed variable depended on the fully observed variables in a nonlinear way. Parameter estimates were less biased using random forest MICE, and confidence interval coverage was better. This suggests that random forest imputation may be useful for imputing complex epidemiologic data sets in which some patients have missing data

Glacier meltwater and monsoon precipitation drive Upper Ganges Basin dissolved organic matter composition

Author Posting. © The Author(s), 2019. This is the author's version of the work. It is posted here by permission of Elsevier Ltd. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 244 (2019): 216-228, doi:10.1016/j.gca.2018.10.012.Mountain glaciers store dissolved organic carbon (DOC) that can be exported to river networks and subsequently respired to CO2. Despite this potential importance within the global carbon cycle, the seasonal variability and downstream transport of glacier-derived DOC in mountainous river basins remains largely unknown. To provide novel insight, here we present DOC concentrations and molecular-level dissolved organic matter (DOM) compositions from 22 nested, glaciated catchments (1.4 – 81.8 % glacier cover by area) in the Upper Ganges Basin, Western Himalaya over the course of the Indian summer monsoon (ISM) in 2014. Aliphatic and peptide-like compounds were abundant in glaciated headwaters but were overprinted by soil-derived phenolic, polyphenolic and condensed aromatic material as DOC concentrations increase moving downstream. Across the basin, DOC concentrations and soil-derived compound class contributions decreased sharply from pre- to post-ISM, implying increased relative contribution of glaciated headwater signals as the monsoon progresses. Incubation experiments further revealed a strong compositional control on the fraction of bioavailable DOC (BDOC), with glacier-derived DOC exhibiting the highest bioavailability. We hypothesize that short-term (i.e. in the coming decades) increases in glacier melt flux driven by climate change will further bias exported DOM toward an aliphatic-rich, bioavailable signal, especially during the ISM and post-ISM seasons. In contrast, eventual decreases in glacier melt flux due to mass loss will likely lead to more a soil-like DOM composition and lower bioavailability of exported DOC in the long term.We thank Britta Voss (WHOI) for assisting with sample collection; Travis Drake (FSU), and Ekaterina Bulygina (Woods Hole Research Center) for laboratory assistance; and the NHMFL ICR user program (NSF-DMR-1157490) for aiding in data acquisition and analysis. This study was partly supported by NSF-DEB-1145932 to R.G.M.S. J.D.H. was partially supported by the NSF Graduate Research Fellowship Program under grant number 2012126152, with additional support in the form of travel grants awarded by the MIT Houghten Fund and NHMFL. All data used in this study are available in the Supporting Information Tables S1 and S2