Carbon and hydrogen isotopic compositions of n-alkanes as a tool in petroleum exploration

Compound-specific isotope analysis (CSIA) of individual organic compounds is a powerful but underutilized tool in petroleum exploration. When integrated with other organic geochemical methodologies it can provide evidence of fluid histories including source, maturity, charge history and reservoir processes that can support field development planning and exploration efforts. The purpose of this chapter is to provide a review of the methodologies used for generating carbon and hydrogen isotope data for mid- and high-molecular-weight n-alkanes. We discuss the factors that control stable carbon and hydrogen isotope compositions of n-alkanes and related compounds in sedimentary and petroleum systems and review current and future applications of this methodology for petroleum exploration. We discuss basin-specific case studies that demonstrate the usefulness of CSIA either when addressing particular aspects of petroleum exploration (e.g. charge evaluation, source rock–oil correlation, and investigation of maturity and in-reservoir processes) or when this technique is used to corroborate interpretations from integrated petroleum systems analysis, providing unique insights which may not be revealed when using other methods. CSIA of n-alkanes and related n-alkyl structures can provide independent data to strengthen petroleum systems concepts from generation and expulsion of fluids from source rock, to charge history, connectivity, and in-reservoir processes

Contrasting controls on the phosphorus concentration of suspended particulate matter under baseflow and storm event conditions in agricultural headwater streams

Whilst the processes involved in the cycling of dissolved phosphorus (P) in rivers have been extensively studied, less is known about the mechanisms controlling particulate P concentrations during small and large flows. This deficiency is addressed through an analysis of large numbers of suspended particulate matter (SPM) samples collected under baseflow (n = 222) and storm event (n = 721) conditions over a 23-month period across three agricultural headwater catchments of the River Wensum, UK. Relationships between clay mineral and metal oxyhydroxide associated elements were assessed and multiple linear regression models for the prediction of SPM P concentration under baseflow and storm event conditions were formulated. These models, which explained 71–96% of the variation in SPM P concentration, revealed a pronounced shift in P association from iron (Fe) dominated during baseflow conditions to particulate organic carbon (POC) dominated during storm events. It is hypothesised this pronounced transition in P control mechanism, which is consistent across the three study catchments, is driven by changes in SPM source area under differing hydrological conditions. In particular, changes in SPM Fe–P ratios between small and large flows suggest there are three distinct sources of SPM Fe; surface soils, subsurface sediments and streambed iron sulphide. Further examination of weekly baseflow data also revealed seasonality in the Fe–P and aluminium oxalate–dithionate (Alox–Aldi) ratios of SPM, indicating temporal variability in sediment P sorption capacity. The results presented here significantly enhance our understanding of SPM P associations with soil derived organic and inorganic fractions under different flow regimes and has implications for the mitigation of P originating from different sources in agricultural catchments

δ13C and δD values of n-alkanes from in-reservoir biodegraded oils: Implications for understanding the mechanisms of biodegradation and for petroleum exploration

This study investigates the magnitude and direction of stable C and H isotope shifts of n-C 15–30 alkanes from biodegraded oils sourced from Type II (Oil suite S) and Type II/III (Oil suite H) kerogens. Compound-specific isotope data show a 2.0‰ 13C-enrichment and no D-enrichment of n-alkanes in the most biodegraded oil from sample suite S. Similarly, there is a 1.5–2.5‰ 13C-enrichment and no D-enrichment in Oil suite H. Overall, there is a <2.5‰ δ 13C and <20‰ δD variability among individual n-alkanes in the whole sequence of biodegradation. N-alkanes from the least biodegraded Oil H samples are 2–4‰ 13C-enriched in comparison with the least biodegraded Oil S. However, there are no differences in the δD values of n-alkanes in these samples. Our indirect isotopic evidence suggests (1) a site-specific biodegradation process, most likely at position C-2 and/or C-3 or another site-specific process, and (2) a significant D/H exchange between organic compounds in the source rock and isotopically similar marine formation waters. We conclude that, unlike δD methodology, investigation of δ 13C composition of n-alkanes has strong potential as a supplementary tool for oil–oil and oil–source-rock correlation even in biodegraded oils when n-alkanes are present

Fire and ecosystem change in the Arctic across the Paleocene-Eocene Thermal Maximum

Fire has been an important component of ecosystems on a range of spatial and temporal scales. Fire can affect vegetation distribution, the carbon cycle, and climate. The relationship between climate and fire is complex, in large part because of a key role of vegetation type. Here, we evaluate regional scale fire–climate relationships during a past global warming event, the Paleocene–Eocene Thermal Maximum (PETM), in order to understand how vegetation influenced the links between climate and fire occurrence in the Arctic region. To document concurrent changes in climate, vegetation, and fire occurrence, we evaluated biomarkers, including polycyclic aromatic hydrocarbons (PAHs), terpenoids, and alkanes, from the PETM interval at a marine depositional site (IODP site 302, the Lomonosov Ridge) in the Arctic Ocean. Biomarker, fossil, and isotope evidence from site 302 indicates that terrestrial vegetation changed during the PETM. The abundance of the C29n-alkanes, pollen, and the ratio of leaf-wax n-alkanes relative to diterpenoids all indicate that proportional contributions from angiosperm vegetation increased relative to that from gymnosperms. These changes accompanied increased moisture transport to the Arctic and higher temperatures, as recorded by previously published proxy records. We find that PAH abundances were elevated relative to total plant biomarkers throughout the PETM, and suggest that fire occurrence increased relative to plant productivity. The fact that fire frequency or prevalence may have increased during wetter Arctic conditions suggests that changes in fire occurrence were not a simple function of aridity, as is commonly conceived. Instead, we suggest that the climate-driven ecological shift to angiosperm-dominated vegetation was what led to increased fire occurrence. Potential increases in terrestrial plant biomass that arose from warm, wet, and high CO2 conditions were possibly attenuated by biomass burning associated with compositional changes in the plant community

Impact of climate change on the ecology of the Kyambangunguru crater marsh in southwestern Tanzania during the Late Holocene

Instrumental records of temperature and hydrological regimes in East Africa evidence frequent droughts with dramatic effects on population and ecosystems. Sources of these climatic variations remain largely unconstrained, partly because of a paucity of Late Holocene records. Here, we present a multi-proxy analysis of a 4-m continuous sediment core collected in the Kyambangunguru crater marsh, in southwest Tanzania, covering the last 4000 yrs (cal. BP). We used microscopic (macro-remains, microfossils, palynofacies, pollen), elemental (carbon, nitrogen contents), molecular (br GDGTs, n-alkanes) and compound-specific isotopic (δ2H n-alkanes) investigations to reconstruct the environmental history of the marsh. The multi proxy record reveals that, 2500 years ago, the marsh underwent a major ecological transition from a lake to a peatland. Temperature and hydrological reconstructions evidence warmer and drier conditions between 2200 and 860 cal. BP, which probably triggered the establishment of a perennial peatland. This study is one of the first combined temperature and precipitation record of Late Holocene in the region and highlights changes in the spatial distribution of the East African climate regimes. Several cold periods are observed, between 3300 and 2000 cal. BP and since 630 cal. BP, the latter corresponding to the Little Ice Age. Moreover, wetter conditions are reported during the Medieval Climate Anomaly in contrast to other north-eastern African records suggesting that Tanzania is located at the transition between two hydro-climatic zones (north-eastern versus southern Africa) and has experienced variable contributions of these two zones over the last millennium

Apportioning sources of organic matter in streambed sediments: An integrated molecular and compound-specific stable isotope approach

We present a novel application for quantitatively apportioning sources of organic matter in streambed sediments via a coupled molecular and compound-specific isotope analysis (CSIA) of long-chain leaf wax n-alkane biomarkers using a Bayesian mixing model. Leaf wax extracts of 13 plant species were collected from across two environments (aquatic and terrestrial) and four plant functional types (trees, herbaceous perennials, and C3 and C4 graminoids) from the agricultural River Wensum catchment, UK. Seven isotopic (δ13C27, δ13C29, δ13C31, δ13C27–31, δ2H27, δ2H29, and δ2H27–29) and two n-alkane ratio (average chain length (ACL), carbon preference index (CPI)) fingerprints were derived, which successfully differentiated 93% of individual plant specimens by plant functional type. The δ2H values were the strongest discriminators of plants originating from different functional groups, with trees (δ2H27–29 = − 208‰ to − 164‰) and C3 graminoids (δ2H27–29 = − 259‰ to − 221‰) providing the largest contrasts. The δ13C values provided strong discrimination between C3 (δ13C27–31 = − 37.5‰ to − 33.8‰) and C4 (δ13C27–31 = − 23.5‰ to − 23.1‰) plants, but neither δ13C nor δ2H values could uniquely differentiate aquatic and terrestrial species, emphasizing a stronger plant physiological/biochemical rather than environmental control over isotopic differences. ACL and CPI complemented isotopic discrimination, with significantly longer chain lengths recorded for trees and terrestrial plants compared with herbaceous perennials and aquatic species, respectively. Application of a comprehensive Bayesian mixing model for 18 streambed sediments collected between September 2013 and March 2014 revealed considerable temporal variability in the apportionment of organic matter sources. Median organic matter contributions ranged from 22% to 52% for trees, 29% to 50% for herbaceous perennials, 17% to 34% for C3 graminoids and 3% to 7% for C4 graminoids. The results presented here clearly demonstrate the effectiveness of an integrated molecular and stable isotope analysis for quantitatively apportioning, with uncertainty, plant-specific organic matter contributions to streambed sediments via a Bayesian mixing model approach

Evaluation of branched GDGTs and leaf wax n-alkane δ2H as (paleo) environmental proxies in East Africa

The role of mountain evolution on local climate is poorly understood and potentially underestimated in climate models. One prominent example is East Africa, which underwent major geodynamic changes with the onset of the East African Rift System (EARS) more than 250 Myr ago. This study explores, at the regional East African scale, a molecular approach for terrestrially-based paleo-climatic reconstructions that takes into account both changes in temperature and in altitude, potentially leading to an improved concept in paleo-climatic reconstructions. Using surface soils collected along pronounced altitudinal gradients in Mt. Rungwe (n=40; Southwest Tanzania) and Mt. Kenya (n=20; Central Kenya), we investigate the combination of 2 terrestrial proxies, leaf wax n-alkane δ2H (δ2Hwax) and branched glycerol dialkyl glycerol tetraether (br GDGT) membrane lipids, as (paleo) elevation and (paleo) temperature proxies, respectively. At the mountain scale, a weak link between δ2Hwax and altitude (R2 = 0.33) is observed at Mt. Kenya, but no relationship is observed at Mt. Rungwe. It is likely that additional parameters, such as decreasing relative humidity (RH) or vegetation changes with altitude, are outcompeting the expected 2H-depletion trend along Mt. Rungwe. In contrast, br GDGT-derived absolute mean annual air temperature (MAAT) and temperature lapse rate (0.65 °C/100 m) for both mountains are in good agreement with direct field measurements, further supporting the robustness of this molecular proxy for (paleo) temperature reconstructions. At the regional scale, estimated and observed δ2H data in precipitation along 3 mountains in East Africa (Mts. Rungwe, Kenya and Kilimanjaro) highlight a strong spatial heterogeneity, preventing the establishment of a regional based calibration of δ2Hwax for paeloaltitudinal reconstructions. Different from that, an improved regional soil calibration is developed between br GDGT distribution and MAAT by combining the data from this study (Mts. Rungwe and Kenya) with previous results from East African surface soils along Mts. Kilimanjaro (Tanzania) and Rwenzori (Uganda). This new regional calibration, based on 105 samples, improves both the R2 (0.77) and RMSE (root mean square error; 2.4 °C) of br GDGT-derived MAAT over the global soil calibrations previously established (R2 = 0.56; RMSE = 4.2 °C) and leads to more accurate (paleo) temperature reconstructions in the region

Relationships between riverine and terrestrial dissolved organic carbon: Concentration, radiocarbon signature, specific UV absorbance

The transfer of dissolved organic carbon (DOC) from land to watercourses plays a major role in the carbon cycle, and in the transport and fate of associated organic and inorganic contaminants. We investigated, at global scale, how the concentrations and properties of riverine DOC depend upon combinations of terrestrial source solutions. For topsoil, subsoil, groundwater and river solutions in different Köppen-Geiger climatic zones, we compiled published and new values of DOC concentration ([DOC]), radiocarbon signature (DO14C), and specific UV absorbance (SUVA). The average value of each DOC variable decreased significantly in magnitude from topsoil to subsoil to groundwater, permitting the terrestrial sources to be distinguished. We used the terrestrial data to simulate the riverine distributions of each variable, and also relationships between pairs of variables. To achieve good matches between observed and simulated data, it was necessary to optimise the distributions of water fractions contributed by each of the three terrestrial sources, and also to reduce the mean input terrestrial [DOC] values, to about 60% of the measured ones. One possible explanation for the required lowering of the modelled terrestrial [DOC] values might be unrepresentative sampling of terrestrial DOC, including dilution effects; another is the loss of DOC during riverine transport. High variations in simulated riverine DOC variables, which match observed data, are due predominantly to variations in source solution values, with a lesser contribution from the different combinations of source waters. On average, most DOC in rivers draining catchments with forest and/or grass-shrub land cover comes in similar amounts from topsoil and subsoil, with about 10% from groundwater. In rivers draining croplands, subsoil and groundwater solutions are the likely dominant DOC sources, while in wetland rivers most DOC is from topsoil

A unique subseafloor microbiosphere in the Mariana Trench driven by episodic sedimentation

Hadal trenches are characterized by enhanced and infrequent high-rate episodic sedimentation events that likely introduce not only labile organic carbon and key nutrients but also new microbes that significantly alter the subseafloor microbiosphere. Currently, the role of high-rate episodic sedimentation in controlling the composition of the hadal subseafloor microbiosphere is unknown. Here, analyses of carbon isotope composition in a ~ 750 cm long sediment core from the Challenger Deep revealed noncontinuous deposition, with anomalous 14C ages likely caused by seismically driven mass transport and the funneling effect of trench geomorphology. Microbial community composition and diverse enzyme activities in the upper ~ 27 cm differed from those at lower depths, probably due to sudden sediment deposition and differences in redox condition and organic matter availability. At lower depths, microbial population numbers, and composition remained relatively constant, except at some discrete depths with altered enzyme activity and microbial phyla abundance, possibly due to additional sudden sedimentation events of different magnitude. Evidence is provided of a unique role for high-rate episodic sedimentation events in controlling the subsurface microbiosphere in Earth’s deepest ocean floor and highlight the need to perform thorough analysis over a large depth range to characterize hadal benthic populations. Such depositional processes are likely crucial in shaping deep-water geochemical environments and thereby the deep subseafloor biosphere