Petrogenic Carbon Research Articles

Net effect of chemical erosion in a tropical basin on carbon cycle: Constraints from elemental and sulfur isotopic composition of the Mahanadi river water

Chemical erosion in river basins influence the climate by both consuming (via silicate erosion and carbon burial) and releasing (via H2SO4-mediated carbonate weathering and organic oxidation) atmospheric CO2. Net erosional effect of a basin on carbon cycle, therefore, requires precise rate assessment of all these pathways; combined data for the four processes for a given basin are sparse. In this contribution, we have quantified these process intensities for a large tropical basin (Mahanadi river) from the eastern part of India using new time-series (weekly) data for dissolved major ions and sulfur isotopes, and compiled data for rhenium concentrations and particulate carbon isotopes for the basin. The discharge-weighted silica concentrations (∼215 μM) of these samples is higher than that reported as global average for rivers (∼145 μM), indicating intense silicate erosion in the basin. The δ34S of the riverine sulfates vary between 8.8 ‰ and 17 ‰, with a discharge-weighted average of 12 ± 4 ‰ (global riverine value ∼4.4 ± 4.5‰). Temporal changes in concentrations for most of the elements (and δ34S) show relatively higher (enriched) values during lean-flow stages. Mass balance calculations involving Ca, Mg and Si values confirm that these seasonal changes are mainly due to increase (by 18 ± 9%) of groundwater supply to the stream during non-monsoon seasons. The silicate-derived cations (Catsilicate) for the Mahanadi show minimal changes during monsoon (36 ± 5%) and non-monsoon (33 ± 8%) seasons. These data correspond to a CO2 consumption rate of 2.4 ± 1.6 tC/km2/yr, which is about two times higher than that reported for global rivers. Comparison of δ34S values of riverine sulfate with its possible sources computes the relative supply of sulfates from atmospheric deposition (38%), gypsum (46%), and sulfides (16% (a lower limit)) to the river. The minimal contribution via sulfide oxidation confirms low CO2 release (0.1 ± 0.1 tC/km2/yr) in this basin through sulfuric-acid mediated carbonate weathering. Average rhenium for this river is 5 ± 3 pmol/kg. The source apportionment using S/Re and Na/Re ratios indicates that 85 ± 10% of the Re is derived through organic oxidation. The rhenium data are used to estimate the CO2 release rate (0.50 ± 0.57 tC/km2/yr) by oxidation of petrogenic carbon, which is higher than the estimated organic burial rate (0.27 ± 0.12) for the basin. The estimated four erosion rates confirm a net negative (∼ − 2.1 ± 1.7 tC/km2/yr) effect of chemical erosion in the Mahanadi basin on the CO2 budget. Low sulfide-oxidation in this supply-limited regime is possibly linked to limited exposure of fresher minerals, whereas high silicate erosion in the basin is consistent with its silicate-dominated lithology and tropical climate.

Radio- and stable carbon isotope analysis reveals minimal assimilation of petrogenic carbon into an oligotrophic freshwater food web after experimental spills of diluted bitumen

Following an oil spill into water, bacteria can biodegrade petroleum hydrocarbons which could lead to petrogenic carbon assimilation by aquatic biota. We used changes in the isotope ratios of radio- (Δ14C) and stable (δ13C) carbon to examine the potential for assimilation of petrogenic carbon into a freshwater food web following experimental spills of diluted bitumen (dilbit) into a boreal lake in northwestern Ontario, Canada. Different volumes (1.5, 2.9, 5.5, 18, 42, 82, and 180 L) of Cold Lake Winter Blend (a heavy crude blend of bitumen and condensate) dilbit were applied to seven 10-m diameter littoral limnocorrals (approximate volume of 100 m3), and two additional limnocorrals had no added dilbit to serve as controls. Particulate organic matter (POM) and periphyton from oil-treated limnocorrals had lower δ13C (up to 3.2‰ and 2.1‰ for POM and periphyton, respectively) than the control at every sampled interval (3, 6 and 10 weeks for POM and 6, 8 and 10 weeks for periphyton). Dissolved organic and inorganic carbon (DOC and DIC, respectively) had lower Δ14C in the oil-treated limnocorrals relative to the control (up to 122‰ and 440‰ lower, respectively). Giant floater mussel (Pyganodon grandis) housed for 25 days in aquaria containing oil-contaminated water from the limnocorrals did not show significant changes in δ13C values of muscle tissue compared to mussels housed in control water. Overall, the changes in δ13C and Δ14C observed indicated small amounts (up to 11% in DIC) of oil carbon incorporation into the food web. The combined δ13C and Δ14C data provide evidence for minimal incorporation of dilbit into the food web of this oligotrophic lake, suggesting that microbial degradation and subsequent incorporation of oil C into the food web may play a relatively small role in the ultimate fate of oil in this type of ecosystem.

Deglacial release of petrogenic and permafrost carbon from the Canadian Arctic impacting the carbon cycle

The changes in atmospheric pCO2 provide evidence for the release of large amounts of ancient carbon during the last deglaciation. However, the sources and mechanisms that contributed to this process remain unresolved. Here, we present evidence for substantial ancient terrestrial carbon remobilization in the Canadian Arctic following the Laurentide Ice Sheet retreat. Glacial-retreat-induced physical erosion of bedrock has mobilized petrogenic carbon, as revealed by sedimentary records of radiocarbon dates and thermal maturity of organic carbon from the Canadian Beaufort Sea. Additionally, coastal erosion during the meltwater pulses 1a and 1b has remobilized pre-aged carbon from permafrost. Assuming extensive petrogenic organic carbon oxidation during the glacial retreat, a model-based assessment suggests that the combined processes have contributed 12 ppm to the deglacial CO2 rise. Our findings suggest potentially positive climate feedback of ice-sheet retreat by accelerating terrestrial organic carbon remobilization and subsequent oxidation during the glacial-interglacial transition.

Concentration-runoff relationships of contrasting small mountainous rivers in the Pacific Northwest, USA: Insights into the weathering of rhenium relative to other weathering products

This study examines dissolved rhenium (Re) concentrations as a function of water runoff using river samples from two contrasting mountainous watersheds, the Eel and Umpqua Rivers in the Pacific Northwest, USA. These watersheds share many key characteristics in terms of size, discharge, climate, and vegetation, but they have a 15-fold difference in sediment yield due to differences in their tectonic setting and uplift and erosion rates. We evaluate concentration-runoff (C-R) relationships and ratios of coefficients of variation (CVC/CVR) for major cations, anions, dissolved inorganic carbon, selected trace elements including Re, and 87Sr/86Sr ratios. Recent research outlines the potential of Re to serve as a tracer for the oxidation of ancient/fossil organic matter because of its close association with petrogenic carbon (OCpetro) in rocks. In both the Eel and Umpqua Rivers, our measurements show that Re behaves similarly to major weathering derived-solutes corrected for atmospheric input, such as Ca2+*, Mg2+*, and Na+* with modest dilution across all tributaries with increasing runoff. Rhenium behaves dissimilarly from other trace elements, such as Mo and U, and is also dissimilar to biologically-cycled nutrients, such as NO3–, PO43−, and K+*, suggesting differences in sources, solute generation mechanisms, and flowpaths. Rhenium behavior is also distinct from that of colloids, which have increasing concentrations with increasing runoff. We find that Re and sulfate corrected for atmospheric input (SO42−*) have distinct C-R relationships, in which SO42−* undergoes greater dilution with increasing runoff. This implies that Re is not dominantly sourced from sulfide weathering, which leaves primary bedrock minerals and OCpetro hosted in bedrock of these watersheds as the likely dominant sources of dissolved Re release. At mean discharge, Re concentration in the Eel river (3.5 pmol L-1) is more than two times greater than Re concentrations in the Umpqua River (1.5 pmol L-1). Furthermore, comparison of two tributary watersheds with similar bedrock but marked differences in erosion rates show higher Re concentrations in Bull Creek (erosion rate of 0.5 mm yr−1) relative to Elder Creek (erosion rate of 0.2 mm yr−1). The results of this study suggest that dissolved Re in the Eel and Umpqua River basins is likely derived from primary mineral dissolution or OCpetro oxidation, and Re fluxes are higher in areas with higher erosion rates, suggesting that tectonic setting is one factor that controls Re release and therefore OCpetro oxidation.

Bulk carbon and lignin fingerprinting of catchment sediments transported by mountain rivers in Nepal Himalayas

The Himalayan rivers yield the most significant flux of continental sediments into the ocean. Organic matter (OM) transported by these rivers provides a peek at the influence of diverse geological terrains, soil types, vegetation, and climate on carbon cycling within a narrow boundary. We analyzed suspended and bedload sediments from four Himalayan rivers to trace their sources, elucidate their fate during fluvial transport, and estimate the organic carbon (OC) flux. Hence, total OC (TOC), dissolved organic carbon (DOC), C:N ratios, and lignin phenols were measured. Consistent with the erosional intensity in the rivers, suspended sediment load input followed the order: Kaligandaki > Myagdikhola > Aadhikhola > Tinahukhola. C:N values in rivers from the Lesser Himalayas and Siwalik indicate sediments from mixed biogenic sources. In contrast, high TOC and C/N values in the trans-Himalaya rivers flowing through barren landscapes reflect the erosion of catchment sediments yielding petrogenic carbon. The suspended matter in rivers from the Lesser Himalayas and Siwalik has higher lignin phenol concentrations than the trans-Himalaya and Higher Himalaya rivers. The lignin phenol ratios indicate higher degradation in rivers from the trans and Higher Himalaya sections. This implies that only a small fraction of the terrestrial OM transported by these rivers deposits in the ocean sink. In contrast, rivers from the Lesser Himalayas and Siwaliks sequester a significant amount of OM bound to their bedload. As a result, these rivers transferred lower particulate OC (POC) but higher DOC than similar rivers worldwide. Rivers from Lesser Himalayas and Siwaliks transfer > 90 % of annual POC flux during monsoons. Finally, although Himalayan rivers transport less OC than other global rivers traversing densely vegetated landscapes, the sheer number of these rivers has significant implications on the fate and transport of total OC from catchments sediments.

Terrestrial organic carbon age and reactivity in the Yellow River fueling efficient preservation in marine sediments

The Yellow River is one of the largest suppliers of sediments and organic carbon (OC) to the ocean. Previous studies have revealed that OC transported by the Yellow River largely derives from the erosion of the Chinese Loess Plateau, which is dominated by pre-aged soil carbon and could be efficiently preserved in marine sediments. Here, we used ramped oxidation radiocarbon analysis (RPO-14C) to characterize the age and reactivity distribution of OC in two Yellow River suspended sediment samples and six Bohai Sea and Yellow Sea (BS–YS) surface sediments from a transect along the sediment transport pathway. RPO-14C independently characterizes the full spectrum of OC thermal stability and isotope compositions to reveal the source, age and reactivity structure of OC transported by the Yellow River and preserved in Chinese marginal sea sediments. We calculated the activation energy (E) distribution—a proxy for bonding environment and by extension reactivity—which, combined with 14C and stable carbon isotope (δ13C) compositions, reveals OC origin and stability. Our data suggest that 96% of OC in Yellow River suspended sediments is biospheric and weathered petrogenic, while unweathered petrogenic OC only accounts for 4% which is almost an order of magnitude lower than the fossil OC estimates (32%) based on compound specific 14C analysis. RPO data reveal the prevalence of aged biospheric loess OC in the Yellow River. We use δ13C, 14C and RPO-derived activation energy data to quantify the contribution of terrestrial OC to surface sediments in the BS–YS. The resulting estimates of terrestrial OC proto-burial efficiencies yield an average value of 89 ± 30%, revealing overall very high terrestrial OC preservation in the BS–YS. Additionally, and somewhat counter intuitively, we find that the preservation of terrestrial OC decreases with increasing E. This pattern may arise from an enhanced preservation of a pre-aged C4 plants derived fraction of the loess-derived OC associated with secondary clays characterized by smaller grain size and higher surface area. Alternatively, the high E component of the Yellow River OC might comprise partially weathered petrogenic carbon, undergoing further mineralization during transport from rivers to marginal sea sediments via marine organic matter priming.

Increased petrogenic and biospheric organic carbon burial in sub‐Antarctic fjord sediments in response to recent glacier retreat

AbstractFjords are recognized as hotspots of organic carbon (OC) burial in the coastal ocean. In fjords with glaciated catchments, glacier discharge carries large amounts of suspended matter. This sedimentary load includes OC from bedrock and terrigenous sources (modern vegetation, peat, soil deposits), which is either buried in the fjord or remineralized during export, acting as a potential source of CO2 to the atmosphere. In sub‐Antarctic South Georgia, fjord‐terminating glaciers have been retreating during the past decades, likely as a response to changing climate conditions. We determine sources of OC in surface sediments of Cumberland Bay, South Georgia, using lipid biomarkers and the bulk 14C isotopic composition, and quantify OC burial at present and for the time period of documented glacier retreat (between 1958 and 2017). Petrogenic OC is the dominant type of OC in proximity to the present‐day calving fronts (60.4 ± 1.4% to 73.8 ± 2.6%) and decreases to 14.0 ± 2.7% outside the fjord, indicating that petrogenic OC is effectively buried in the fjord. Beside of marine OC, terrigenous OC comprises 2.7 ± 0.5% to 7.9 ± 5.9% and is mostly derived from modern plants and Holocene peat and soil deposits that are eroded along the flanks of the fjord, rather than released by the retreating fjord glaciers. We estimate that the retreat of tidewater glaciers between 1958 and 2017 led to an increase in petrogenic carbon accumulation of 22% in Cumberland West Bay and 6.5% in Cumberland East Bay, suggesting that successive glacier retreat does not only release petrogenic OC into the fjord, but also increases the capacity of OC burial.

Preferential export of permafrost-derived organic matter as retrogressive thaw slumping intensifies

Enhanced warming of the Northern high latitudes has intensified thermokarst processes throughout the permafrost zone. Retrogressive thaw slumps (RTS), where thaw-driven erosion caused by ground ice melt creates terrain disturbances extending over tens of hectares, represent particularly dynamic thermokarst features. Biogeochemical transformation of the mobilized substrate may release CO2 to the atmosphere and impact downstream ecosystems, yet its fate remains unclear. The Peel Plateau in northwestern Canada hosts some of the largest RTS features in the Arctic. Here, thick deposits of Pleistocene-aged glacial tills are overlain by a thinner layer of relatively organic-rich Holocene-aged permafrost that aggraded upward following deeper thaw and soil development during the early Holocene warm period. In this study, we characterize exposed soil layers and the mobilized material by analysing sediment properties and organic matter composition in active layer, Holocene and Pleistocene permafrost, recently thawed debris deposits and fresh deposits of slump outflow from four separate RTS features. We found that organic matter content, radiocarbon age and biomarker concentrations in debris and outflow deposits from all four sites were most similar to permafrost soils, with a lesser influence of the organic-rich active layer. Lipid biomarkers suggested a significant contribution of petrogenic carbon especially in Pleistocene permafrost. Active layer samples contained abundant intrinsically labile macromolecular components (polysaccharides, lignin markers, phenolic and N-containing compounds). All other samples were dominated by degraded organic constituents. Active layer soils, although heterogeneous, also had the highest median grain sizes, whereas debris and runoff deposits consisted of finer mineral grains and were generally more homogeneous, similar to permafrost. We thus infer that both organic matter degradation and hydrodynamic sorting during transport affect the mobilized material. Determining the relative magnitude of these two processes will be crucial to better assess the role of intensifying RTS activity in CO2 release and ecosystem carbon fluxes.

Multi-proxy assessment of recent regional-scale events recorded in Southern Gulf of Mexico sediments

The Ixtoc-1 oil spill (1979–80) released 475 million liters of petroleum into the Southern Gulf of Mexico (sGoM) likely causing Marine Oil Snow Sedimentation and Flocculent Accumulation (MOSSFA) to occur. A multiproxy approach including short-lived radioisotopes (210Pbxs), benthic foraminifera stable isotopes (δ13CCaCO3), and volcanic sediment grains was used to investigate regional events (e.g. oil spills and volcanic eruptions) recorded in sedimentary records. Depleted δ13CCaCO3 from 1979 to 80 outside of natural variability most likely results from petrogenic carbon deposition 100–250 km west of Ixtoc-1, possibly associated with MOSSFA. An event, characterized by increased volcanic input, depleted δ13CCaCO3, and increased mass accumulation rates was consistent with the El Chichón eruption (1982) 80–100 km north of Ixtoc-1. Many factors confound the uniform distribution and preservation of these events in the sGoM. However, a multiproxy approach may aid to distinguish multiple events in the sGoM sedimentary record.

Compound‐Specific Radiocarbon Analysis of (Sub‐)Antarctic Coastal Marine Sediments—Potential and Challenges for Chronologies

AbstractIn Antarctic and Subantarctic environments, 14C‐based age determination is often challenging due to unknown reservoir effects, low organic carbon contents of sediments, and high contributions of petrogenic (14C‐free) carbon in ice marginal settings. In this study, we evaluate possible benefits and challenges of compound‐specific radiocarbon analysis (CSRA) as a tool for age determination of marine Antarctic and Subantarctic sediment sequences. We present a comprehensive data set of 14C ages obtained on bulk organic carbon, carbonates, and on fatty acids (FA) from three coastal marine sediment cores from Subantarctic South Georgia and East Antarctica. Low molecular weight (LMW) FA represent the least 14C‐depleted fraction, indicating that the phytoplankton‐derived compounds can be a means of dating sediments. In contrast, vascular plant‐derived high molecular weight FA are systematically depleted in 14C relative to the low molecular weight homologues, reflecting processes such as soil formation/erosion in the catchment. Comparative age‐depth models show significant differences, depending on the material used for the respective models. While the land plant‐derived FA may lead to an overestimation of the actual sediment age, LMW FA reveal complex aquatic reservoir effects. Bulk sedimentary organic carbon 14C ages likely provide appropriate age estimates in settings with low petrogenic carbon input in the Antarctic, whereas CSRA has the potential to produce improved age control in settings with high contributions of petrogenic carbon.

Urban soils impacted by tailings from coal mining: PAH source identification by 59 PAHs, BPCA and alkylated PAHs

Urban soils in mining and industrial regions like the Ruhr Area are characterized by admixtures of anthropogenic substrates, e. g. tailings, coals, ashes, debris or scoria. These soils often show elevated concentrations of polycyclic aromatic hydrocarbons (PAHs) which are commonly attributed to non-point pyrogenic carbon sources like soot and particulate matter. An emission source of PAHs into urban soils in these regions, that surprisingly is still largely neglected, are the millions of tons of tailings from underground coal mining that have been used as material for road construction, terrain leveling, river channeling and support of embankments.Here we classify the PAH sources of 13 urban soils as either petrogenic or pyrogenic. The soils contained (1) tailings, (2) ashes and (3) different anthropogenic substrates. The classification is based on a comprehensive analysis of 59 PAHs and alkylated PAH distributions by GC-MS and BPCA analyses by LC-TOF-MS.PAH concentrations (∑59 PAHs) of all soils ranged from 60 to 140 mg/kg, except one soil showing 559 mg/kg. The PAH source in the urban soils containing tailings was identified as petrogenic carbon due to (1) the dominance of low molecular weight PAHs, (2) bell shape distribution patterns of the alkylated PAHs, and (3) comparable BPCA distribution patterns to bituminous coals. In contrast, the PAH source of the ash-containing soil was identified as pyrogenic carbon by high molecular weight PAH percentages >80%, slope shape distribution patterns of the alkylated PAHs and a higher degree of aromatic condensation (B6CA/BPCA) than bituminous coals, coal ashes or charcoal. The urban soils containing different anthropogenic substrates revealed the occurrence of both a petrogenic and a pyrogenic PAH source. Surprisingly, the separate analyses of isolated coal ash particles revealed typical petrogenic indicators showing that by visual approach coal ashes cannot generally be classified as being of a pyrogenic PAH source.

Accelerated benzene polycarboxylic acid analysis by liquid chromatography–time-of-flight–mass spectrometry for the determination of petrogenic and pyrogenic carbon

Pyrogenic carbon species are of particular interest due to their ubiquitous occurrence in the environment and their high sorption capacities for nonpolar organic compounds. It has recently been shown that the analysis of the molecular markers for complex aromatic carbon structures, benzene polycarboxylic acids (BPCA), has a high potential for aid in the identification of different carbon sources.In this study, the first LC method using mass spectrometry (MS) for reliable and accelerated (<24h) quantification of pyrogenic and petrogenic carbon by BPCA analysis has been developed. The main advantage of LC–MS compared to previous methods is the higher sensitivity, which is important if only small sample amounts are available. Sample pre-treatment could be reduced to a minimum. Deuterated phthalic acid was introduced as internal standard due to its structural similarity to BPCA and its lack of occurrence in the environment. Linear quantification with r2≥0997 was accomplished for all BPCA. Method validation showed an excellent quantification reproducibility (mean CV<5%) which is comparable to LC-DAD methods and more reliable than GC-FID measurements (CV 16–23%). In summary, the presented BPCA method is more economic, efficient and presumably attractive to use.Besides reference materials, various pyrogenic and petrogenic samples were analyzed to test if the sources were indicated by BPCA analysis. In addition to pyrogenic carbon, large amounts of petrogenic carbon species can also be present in urban soils and river sediments, especially in mining regions. They also to a large degree consist of aromatic carbon structures and therefore have an impact on source identification by BPCA analysis. Comparison of petrogenic and pyrogenic carbon samples shows similarities in the BPCA concentrations and patterns, in their aromaticity and degree of aromatic condensation. Thus, a differentiation between petrogenic and pyrogenic carbon only by BPCA analysis of samples with unknown carbon sources is not possible. For reliable source identification of the carbon species, the combination with other methods, such as e. g. analysis of polycyclic aromatic hydrocarbons may be successful.

Stable isotope analysis of a newly established macrofaunal food web 1.5 years after the Hebei Spirit oil spill

We examined trophic relationships in a newly established community 1.5years after the Hebei Spirit oil spill on the west coast of Korea. Carbon and nitrogen stable isotope ratios in consumers and their potential food sources were compared between the oil-spill site and reference site, located 13.5km from the oil-spill spot. The isotopic mixing model and a novel circular statistics rejected the influx of petrogenic carbon into the community and identified spatial consistencies such as the high contributions of microphytobenthos, food-chain length, and the isotopic niche of each feeding guild between sites. We suggested that high level of trophic plasticity and the prevalence of omnivory of consumers may promote the robustness of food web against the oil contamination. Furthermore, we highlighted the need of holistic approaches including different functional groups to quantify changes in the food web structure and assess the influence of different perturbations including oil spill.

River discharge influences on particulate organic carbon age structure in the Mississippi/Atchafalaya River System

Applying ramped pyrolysis radiocarbon analysis to suspended river sediments, we generate radiocarbon (14C) age spectra for particulate organic carbon (POC) from the lower Mississippi‐Atchafalaya River system (MARS) to better understand a major river system's role in carbon transport. Ramped pyrolysis 14C analysis generates age distributions of bulk carbon based on thermochemical stability of different organic components. Our results indicate higher proportions of older material in the POC during higher discharge. Ages increase throughout the high‐discharge age spectra, indicating that no single component of the POC is responsible for the overall age increases observed. Instead, older material is contributed across the POC age spectrum and unrelated to increased bedload suspension. In this comparison of 2 spring discharges, less than half of the POC transported during higher discharge is less than 1000 14C years in age, constraining of the role of the MARS as a flux of atmospheric CO2 toward longer‐term sedimentary sinks in the Mississippi delta and the Gulf of Mexico. The results suggest that delta‐building processes benefit disproportionately from high discharge events carrying larger amounts of sediment because these events involve both a higher proportion of millennially‐aged carbon from floodplain exchange of POC and a potentially higher proportion of petrogenic carbon (30‐530% increase). Overall, an internally consistent picture of PO14C age distributions from a major river system emerges, as differences in space and time are small compared to the range of ages of POC sources in such a large basin.