Earthquake-enhanced dissolved carbon cycles in ultra-deep ocean sediments.

Hadal trenches are unique geological and ecological systems located along subduction zones. Earthquake-triggered turbidites act as efficient transport pathways of organic carbon (OC), yet remineralization and transformation of OC in these systems are not comprehensively understood. Here we measure concentrations and stable- and radiocarbon isotope signatures of dissolved organic and inorganic carbon (DOC, DIC) in the subsurface sediment interstitial water along the Japan Trench axis collected during the IODP Expedition 386. We find accumulation and aging of DOC and DIC in the subsurface sediments, which we interpret as enhanced production of labile dissolved carbon owing to earthquake-triggered turbidites, which supports intensive microbial methanogenesis in the trench sediments. The residual dissolved carbon accumulates in deep subsurface sediments and may continue to fuel the deep biosphere. Tectonic events can therefore enhance carbon accumulation and stimulate carbon transformation in plate convergent trench systems, which may accelerate carbon export into the subduction zones.

Bilateral nucleus basalis of Meynert deep brain stimulation for dementia with Lewy bodies: A randomised clinical trial.

BACKGROUND: Dementia with Lewy bodies (DLB) is the second most common form of dementia. Current symptomatic treatment with medications remains inadequate. Deep brain stimulation of the nucleus basalis of Meynert (NBM DBS) has been proposed as a potential new treatment option in dementias. OBJECTIVE: To assess the safety and tolerability of low frequency (20 Hz) NBM DBS in DLB patients and explore its potential effects on both clinical symptoms and functional connectivity in underlying cognitive networks. METHODS: We conducted an exploratory randomised, double-blind, crossover trial of NBM DBS in six DLB patients recruited from two UK neuroscience centres. Patients were aged between 50 and 80 years, had mild-moderate dementia symptoms and were living with a carer-informant. Patients underwent image guided stereotactic implantation of bilateral DBS electrodes with the deepest contacts positioned in the Ch4i subsector of NBM. Patients were subsequently assigned to receive either active or sham stimulation for six weeks, followed by a two week washout period, then the opposite condition for six weeks. Safety and tolerability of both the surgery and stimulation were systematically evaluated throughout. Exploratory outcomes included the difference in scores on standardised measurements of cognitive, psychiatric and motor symptoms between the active and sham stimulation conditions, as well as differences in functional connectivity in discrete cognitive networks on resting state fMRI. RESULTS: Surgery and stimulation were well tolerated by all six patients (five male, mean age 71.33 years). One serious adverse event occurred: one patient developed antibiotic-associated colitis, prolonging his hospital stay by two weeks. No consistent improvements were observed in exploratory clinical outcome measures, but the severity of neuropsychiatric symptoms reduced with NBM DBS in 3/5 patients. Active stimulation was associated with functional connectivity changes in both the default mode network and the frontoparietal network. CONCLUSION: Low frequency NBM DBS can be safely conducted in DLB patients. This should encourage further exploration of the possible effects of stimulation on neuropsychiatric symptoms and corresponding changes in functional connectivity in cognitive networks. TRIAL REGISTRATION NUMBER: NCT02263937.

Significance of Perylene for Source Allocation of Terrigenous Organic Matter in Aquatic Sediments.

Perylene is a frequently abundant, and sometimes the only polycyclic aromatic hydrocarbon (PAH) in aquatic sediments, but its origin has been subject of a longstanding debate in geochemical research and pollutant forensics because its historical record differs markedly from typical anthropogenic PAHs. Here we investigate whether perylene serves as a source-specific molecular marker of fungal activity in forest soils. We use a well-characterized sedimentary record (1735-1999) from the anoxic-bottom waters of the Pettaquamscutt River basin, RI to examine mass accumulation rates and isotope records of perylene, and compare them with total organic carbon and the anthropogenic PAH fluoranthene. We support our arguments with radiocarbon (14C) data of higher plant leaf-wax n-alkanoic acids. Isotope-mass balance-calculations of perylene and n-alkanoic acids indicate that ∼40% of sedimentary organic matter is of terrestrial origin. Further, both terrestrial markers are pre-aged on millennial time-scales prior to burial in sediments and are insensitive to elevated 14C concentrations following nuclear weapons testing in the mid-20th Century. Instead, changes coincide with enhanced erosional flux during urban sprawl. These findings suggest that perylene is definitely a product of soil-derived fungi, and a powerful chemical tracer to study the spatial and temporal connectivity between terrestrial and aquatic environments.

Petrocarbon evolution: Ramped pyrolysis/oxidation and isotopic studies of contaminated oil sediments from the Deepwater Horizon oil spill in the Gulf of Mexico.

Hydrocarbons released during the Deepwater Horizon (DWH) oil spill weathered due to exposure to oxygen, light, and microbes. During weathering, the hydrocarbons' reactivity and lability was altered, but it remained identifiable as "petrocarbon" due to its retention of the distinctive isotope signatures (14C and 13C) of petroleum. Relative to the initial estimates of the quantity of oil-residue deposited in Gulf sediments based on 2010-2011 data, the overall coverage and quantity of the fossil carbon on the seafloor has been attenuated. To analyze recovery of oil contaminated deep-sea sediments in the northern Gulf of Mexico we tracked the carbon isotopic composition (13C and 14C, radiocarbon) of bulk sedimentary organic carbon through time at 4 sites. Using ramped pyrolysis/oxidation, we determined the thermochemical stability of sediment organic matter at 5 sites, two of these in time series. There were clear differences between crude oil (which decomposed at a lower temperature during ramped oxidation), natural hydrocarbon seep sediment (decomposing at a higher temperature; Δ14C = -912‰) and our control site (decomposing at a moderate temperature; Δ14C = -189‰), in both the stability (ability to withstand ramped temperatures in oxic conditions) and carbon isotope signatures. We observed recovery toward our control site bulk Δ14C composition at sites further from the wellhead in ~4 years, whereas sites in closer proximity had longer recovery times. The thermographs also indicated temporal changes in the composition of contaminated sediment, with shifts towards higher temperature CO2 evolution over time at a site near the wellhead, and loss of higher temperature CO2 peaks at a more distant site.

Tectonically-triggered sediment and carbon export to the Hadal zone.

Sediments in deep ocean trenches may contain crucial information on past earthquake history and constitute important sites of carbon burial. Here we present 14C data on bulk organic carbon (OC) and its thermal decomposition fractions produced by ramped pyrolysis/oxidation for a core retrieved from the >7.5 km-deep Japan Trench. High-resolution 14C measurements, coupled with distinctive thermogram characteristics of OC, reveal hemipelagic sedimentation interrupted by episodic deposition of pre-aged OC in the trench. Low δ13C values and diverse 14C ages of thermal fractions imply that the latter material originates from the adjacent margin, and the co-occurrence of pre-aged OC with intervals corresponding to known earthquake events implies tectonically triggered, gravity-flow-driven supply. We show that 14C ages of thermal fractions can yield valuable chronological constraints on sedimentary sequences. Our findings shed new light on links between tectonically driven sedimentological processes and marine carbon cycling, with implications for carbon dynamics in hadal environments.

What on Earth Have We Been Burning? Deciphering Sedimentary Records of Pyrogenic Carbon.

Humans have interacted with fire for thousands of years, yet the utilization of fossil fuels marked the beginning of a new era. Ubiquitous in the environment, pyrogenic carbon (PyC) arises from incomplete combustion of biomass and fossil fuels, forming a continuum of condensed aromatic structures. Here, we develop and evaluate 14C records for two complementary PyC molecular markers, benzene polycarboxylic acids (BPCAs) and polycyclic aromatic hydrocarbons (PAHs), preserved in aquatic sediments from a suburban and a remote catchment in the United States (U.S.) from the mid-1700s to 1998. Results show that the majority of PyC stems from local sources and is transferred to aquatic sedimentary archives on subdecadal to millennial time scales. Whereas a small portion stems from near-contemporaneous production and sedimentation, the majority of PyC (∼90%) experiences delayed transmission due to "preaging" on millennial time scales in catchment soils prior to its ultimate deposition. BPCAs (soot) and PAHs (precursors of soot) trace fossil fuel-derived PyC. Both markers parallel historical records of the consumption of fossil fuels in the U.S., yet never account for more than 19% total PyC. This study demonstrates that isotopic characterization of multiple tracers is necessary to constrain histories and inventories of PyC and that sequestration of PyC can markedly lag its production.

A two-dimensional, heart-cutting preparative gas chromatograph facilitates highly resolved single-compound isolations with utility towards compound-specific natural abundance radiocarbon (14C) analyses.

Motivated by the need to develop clean, high purity preparative enrichments of individual compounds for micro-scale compound-specific natural abundance isotope and radiocarbon ((14)C) analyses, we describe a new, two-dimensional, heart-cutting, low-bleed, three-oven, single GC preparative system, demonstrate its resolving capabilities as applied to a typically complex environmental sample matrix, and investigate the robustness with which it preserves the authigenic (13)C/(12)C and (14)C/(12)C ratios of individual compounds it targets for preparative enrichment. The system is comprised of a programmable temperature vaporizing (PTV) inlet, a single GC oven, two modular, door-mounted, resistively heated low thermal mass (LTM) columns, a preparative fraction collector (PFC), and a Deans pneumatic switching device which facilitates heart-cutting between the system's 1° and 2° chromatographic dimensions. Further, the system's inlet and trapping parameters are optimized for the efficient preparative enrichment of the methyl ether and ester derivatives of the lignin phenol compound class. The lignin phenols include such compounds as the vanillyl and syringyl aldehydes, ethanones, and acids and are unrivaled biomarkers of terrestrial organic matter, some of which are also important components of fragrances and flavors. Using this suite of compounds, the suitability of this augmented preparative capillary GC (PCGC) system was investigated for micro-scale compound-specific (CS) stable isotope and natural abundance radiocarbon analyses (RA). Analysis of a >300 injection enrichment scheme reveals the instrument to fractionate (13)C in predictable ways and to preserve the authigenic Δ(14)C of compounds it targets for preparative enrichment to within 6.7±5.0‰, demonstrating the promising new utility of such systems towards micro-scale CSRA investigations for which clean and high resolution separation techniques are prerequisite.

Radiocarbon dating of individual lignin phenols: a new approach for establishing chronology of late quaternary lake sediments.

The reliability of chronology is a prerequisite for meaningful paleoclimate reconstructions from sedimentary archives. The conventional approach of radiocarbon dating bulk organic carbon in lake sediments is often hampered by the old carbon effect, i.e., the assimilation of ancient dissolved inorganic carbon (DIC) derived from carbonate bedrocks or other sources. Therefore, radiocarbon dating is ideally performed on organic compounds derived from land plants that use atmospheric CO(2) and rapidly delivered to sediments. We demonstrate that lignin phenols isolated from lake sediments using reversed phase high performance liquid chromatography (HPLC) can serve as effective (14)C dating materials for establishing chronology during the late Quaternary. We developed a procedure to purify lignin phenols, building upon a published method. By isolating lignin from standard wood reference substances, we show that our method yields pure lignin phenols and consistent ages as the consensus ages and that our procedure does not introduce radiocarbon contamination. We further demonstrate that lignin phenol ages are compatible with varve counted and macrofossil dated sediment horizons in Steel Lake and Fayetteville Green Lake. Applying the new method to lake sediment cores from Lake Qinghai demonstrates that lignin phenol ages in Lake Qinghai are consistently younger than bulk total organic carbon (TOC) ages which are contaminated by old carbon effect. We also show that the age offset between lignin and bulk organic carbon differs at different Lake Qinghai sedimentary horizons, suggesting a variable hard water effect at different times and that a uniform age correction throughout the core is inappropriate.

Evaluation of gas chromatographic isotope fractionation and process contamination by carbon in compound-specific radiocarbon analysis.

The relevance of both modern and fossil carbon contamination as well as isotope fractionation during preparative gas chromatography for compound-specific radiocarbon analysis (CSRA) was evaluated. Two independent laboratories investigated the influence of modern carbon contamination in the sample cleanup procedure and preparative capillary gas chromatography (pcGC) of a radiocarbon-dead 3,3',4,4',5,5'-hexachlorobiphenyl (PCB 169) reference. The isolated samples were analyzed for their 14C/12C ratio by accelerator mass spectrometry. Sample Delta14C values of -996 +/- 20 and -985 +/- 20 per thousand agreed with a Delta14C of -995 +/- 20 per thousand for the unprocessed PCB 169, suggesting that no significant contamination by nonfossil carbon was introduced during the sample preparation process at either laboratory. A reference compound containing a modern 14C/12C ratio (vanillin) was employed to evaluate process contamination from fossil C. No negative bias due to fossil C was observed (sample Delta14C value of 165 +/- 20 per thousand agreed with Delta14C of 155 +/- 12 per thousand for the unprocessed vanillin). The extent of isotopic fractionation that can be induced during pcGC was evaluated by partially collecting the vanillin model compound of modern 14C/12C abundance. A significant change in the delta13C and delta14C values was observed when only parts of the eluting peak were collected (delta13C values ranged from -15.75 to -49.91 per thousand and delta14C values from -82.4 to +4.71 per thousand). Delta14C values, which are normalized to a delta13C of -25 per thousand, did not deviate significantly (-58.9 to -5.8 per thousand, considering the uncertainty of approximately +/-20 per thousand). This means that normalization of radiocarbon results to a delta13C of -25 per thousand, normally performed to remove effects of environmental isotope fractionation on 14C-based age determinations, also cor-rects sufficiently for putative isotopic fractionation that may occur during pcGC isolation of individual compounds for CSRA.

Radiocarbon as a tool to apportion the sources of polycyclic aromatic hydrocarbons and black carbon in environmental samples.

To determine the relative inputs of polycyclic aromatic hydrocarbons (PAHs) and black carbon (BC) in environmental samples from the combustion of fossil fuels and biomass, we have developed two independent analytical methods for determining the 14C abundance of PAHs and BC. The 5730 yr half-life of 14C makes it an ideal tracer for identifying combustion products derived from fossil fuels (14C-free) versus those stemming from modern biomass (contemporary 14C). The 14C abundance of PAHs in several environmental Standard Reference Materials was measured by accelerator mass spectrometry after extraction and then purification by high-performance liquid chromatography and preparative capillary gas chromatography. This method yields pure compounds that allow for a high degree of confidence in the 14C results. The PAHs data were then used to compare and evaluate results from an operationally defined thermal oxidation method used to isolate a BC fraction. The 14C compositions of PAHs and BC were very similar and suggest that the thermal oxidation method employed for isolating BC is robust and free from interferences by non-BC components. In addition, these data indicate that both the PAHs and the BC species derive mostly from fossil fuels and/or their combustion products.