Ecosystem state shifts during long-term development of an Amazonian peatland.

The most carbon (C)-dense ecosystems of Amazonia are areas characterized by the presence of peatlands. However, Amazonian peatland ecosystems are poorly understood and are threatened by human activities. Here, we present an investigation into long-term ecohydrological controls on C accumulation in an Amazonian peat dome. This site is the oldest peatland yet discovered in Amazonia (peat initiation ca. 8.9 ka BP), and developed in three stages: (i) peat initiated in an abandoned river channel with open water and aquatic plants; (ii) inundated forest swamp; and (iii) raised peat dome (since ca. 3.9 ka BP). Local burning occurred at least three times in the past 4,500 years. Two phases of particularly rapid C accumulation (ca. 6.6-6.1 and ca. 4.9-3.9 ka BP), potentially resulting from increased net primary productivity, were seemingly driven by drier conditions associated with widespread drought events. The association of drought phases with major ecosystem state shifts (open water wetland-forest swamp-peat dome) suggests a potential climatic control on the developmental trajectory of this tropical peatland. A third drought phase centred on ca. 1.8-1.1 ka BP led to markedly reduced C accumulation and potentially a hiatus during the peat dome stage. Our results suggest that future droughts may lead to phases of rapid C accumulation in some inundated tropical peat swamps, although this can lead ultimately to a shift to ombrotrophy and a subsequent return to slower C accumulation. Conversely, in ombrotrophic peat domes, droughts may lead to reduced C accumulation or even net loss of peat. Increased surface wetness at our site in recent decades may reflect a shift towards a wetter climate in western Amazonia. Amazonian peatlands represent important carbon stores and habitats, and are important archives of past climatic and ecological information. They should form key foci for conservation efforts.

Lacustrine Arcellinina (Testate Amoebae) as Bioindicators of Arsenic Contamination.

Arcellininids (testate amoebae) were examined from 61 surface sediment samples collected from 59 lakes in the vicinity of former gold mines, notably Giant Mine, near Yellowknife, Northwest Territories, Canada to determine their utility as bioindicators of arsenic (As), which occurs both as a byproduct of gold extraction at mines in the area and ore-bearing outcrops. Cluster analysis (Q-R-mode) and detrended correspondence analysis (DCA) reveal five arcellininid assemblages, three of which are related to varying As concentrations in the sediment samples. Redundancy analysis (RDA) showed that 14 statistically significant environmental parameters explained 57 % of the variation in faunal distribution, while partial RDA indicated that As had the greatest influence on assemblage variance (10.7 %; p < 0.10). Stress-indicating species (primarily centropyxids) characterized the faunas of samples with high As concentrations (median = 121.7 ppm, max > 10000 ppm, min = 16.1 ppm, n = 32), while difflugiid dominated assemblages were prevalent in substrates with relatively low As concentrations (median = 30.2 ppm, max = 905.2 ppm, min = 6.3 ppm, n = 20). Most of the lakes with very high As levels are located downwind (N and W) of the former Giant Mine roaster stack where refractory ore was roasted and substantial quantities of As were released (as As2O3) to the atmosphere in the first decade of mining. This spatial pattern suggests that a significant proportion of the observed As, in at least these lakes, are industrially derived. The results of this study highlight the sensitivity of Arcellinina to As and confirm that the group has considerable potential for assessing the impact of As contamination on lakes.

Organic matter is a predominant control on total mercury concentration of near-surface lake sediments across a boreal to low Arctic tundra transect in northern Canada.

Mercury (Hg) is a bioavailable and toxic element with concentrations that are persistently high or rising in some Arctic and subarctic lakes despite reduced atmospheric emissions in North America. This is due to rising Hg emissions to the atmosphere outside of North America, enhanced sequestration of Hg to sediments by climate-mediated increases in primary production, and ongoing release of Hg from terrestrial reservoirs. To evaluate the influence of organic matter and other parameters on Hg accumulation in northern lakes, near-surface sediments were sampled from 60 lakes across a boreal to shrub tundra gradient in the central Northwest Territories, Canada. The organic matter of the lake sediments, assessed using programmed pyrolysis and petrology, is composed of a mixture of terrestrial, aquatic, and inert organic matter. The proportion of algal-derived organic matter is higher in sediments of lakes below treeline relative to shrub tundra sites. Total sedimentary Hg concentration is correlated to all organic matter constituents but is unrelated to latitude or lake position below or above treeline. The concentrations of Ag, Ca, P, S, U, Ti, Y, S, Cd, and Zn are also strong predictors of total sedimentary Hg concentration, indicating input from a common geogenic source and/or common sequestration pathways associated with organic matter. Catchment area is a strong negative predictor of total sedimentary Hg concentration, particularly in lakes above treeline, possibly due to retention capacity of Hg and other elements in local sinks. This research highlights the complexity of controls on Hg sequestration in sediment and shows that while organic matter is a strong predictor of total sedimentary Hg concentration on a landscape scale and across extreme gradients in climate and associated vegetation and permafrost, other factors such as catchment area and sources from mineralized bedrock are also important.

Climate-forced Hg-remobilization associated with fern mutagenesis in the aftermath of the end-Triassic extinction.

The long-term effects of the Central Atlantic Magmatic Province, a large igneous province connected to the end-Triassic mass-extinction (201.5 Ma), remain largely elusive. Here, we document the persistence of volcanic-induced mercury (Hg) pollution and its effects on the biosphere for ~1.3 million years after the extinction event. In sediments recovered in Germany (Schandelah-1 core), we record not only high abundances of malformed fern spores at the Triassic-Jurassic boundary, but also during the lower Jurassic Hettangian, indicating repeated vegetation disturbance and stress that was eccentricity-forced. Crucially, these abundances correspond to increases in sedimentary Hg-concentrations. Hg-isotope ratios (δ202Hg, Δ199Hg) suggest a volcanic source of Hg-enrichment at the Triassic-Jurassic boundary but a terrestrial source for the early Jurassic peaks. We conclude that volcanically injected Hg across the extinction was repeatedly remobilized from coastal wetlands and hinterland areas during eccentricity-forced phases of severe hydrological upheaval and erosion, focusing Hg-pollution in the Central European Basin.

Organic matter degradation causes enrichment of organic pollutants in hadal sediments.

Burial of persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) in deep-sea sediments contributes to 60% of their historical emissions. Yet, empirical data on their occurrence in the deep-ocean is scarce. Estimates of the deep-ocean POP sink are therefore uncertain. Hadal trenches, representing the deepest part of the ocean, are hotspots for organic carbon burial and decomposition. POPs favorably partition to organic carbon, making trenches likely significant sinks for contaminants. Here we show that PCBs occur in both hadal (7720-8085 m) and non-hadal (2560-4050 m) sediment in the Atacama Trench. PCB concentrations normalized to sediment dry weight were similar across sites while those normalized to sediment organic carbon increased exponentially as the inert organic carbon fraction of the sediment increased in degraded hadal sediments. We suggest that the unique deposition dynamics and elevated turnover of organic carbon in hadal trenches increase POP concentrations in the deepest places on Earth.

Spatial and temporal assessment of mercury and organic matter in thermokarst affected lakes of the Mackenzie Delta uplands, NT, Canada.

We examined dated sediment cores from 14 thermokarst affected lakes in the Mackenzie Delta uplands, NT, Arctic Canada, using a case-control analysis to determine how retrogressive thaw slump development from degrading permafrost affected the delivery of mercury (Hg) and organic carbon (OC) to lakes. We show that sediments from the lakes with retrogressive thaw slump development on their shorelines (slump-affected lakes) had higher sedimentation rates and lower total Hg (THg), methyl mercury (MeHg), and lower organic carbon concentrations compared to lakes where thaw slumps were absent (reference lakes). There was no difference in focus-corrected Hg flux to sediments between reference lakes and slump-affected lakes, indicating that the lower sediment Hg concentration in slump-affected lakes was due to dilution by rapid inorganic sedimentation in the slump-affected lakes. Sedimentation rates were inversely correlated with THg concentrations in sediments among the 14 lakes considered, and explained 68% of the variance in THg concentration in surface sediment, further supporting the dilution hypothesis. We observed higher S2 (algal-derived carbon) and particulate organic carbon (POC) concentrations in sediment profiles from reference lakes than in slump lakes, likely because of dilution by inorganic siliciclastic matter in cores from slump-affected lakes. We conclude that retrogressive thaw slump development increases inorganic sedimentation in lakes, and decreases concentrations of organic carbon and associated Hg and MeHg in sediments.

Geochemical evidence for the internal migration of gas condensate in a major unconventional tight petroleum system.

Unconventional petroleum systems go through multiple episodes of internal hydrocarbon migration in response to evolving temperature and pressure conditions during burial and uplift. Migrated fluid signatures can be recognized using stable carbon isotope and PVT compositional data from produced samples representative of in-situ petroleum fluids. Such samples, however, are seldom collected due to operational complexity and high cost. Here, we use carbon isotope and PVT data from co-produced hydrocarbon gas and liquid to provide evidence for widespread migration of gas-condensate in the Montney unconventional petroleum system of western Canada. Extended C1-C33 isotopic profiles exhibit convex upward signatures with C4-C5 maxima at low molecular weight, and increasing or nearly uniform signatures at high molecular weight. Additionally, recombination PVT compositional data show C6-C15 condensate concentrations are higher than expected for unmodified oils. The combined convex upward and increasing or uniform isotopic signatures are interpreted as mixing profiles formed by the introduction of high-maturity gas-condensate (C1-C15) to shallower zones with in-situ hydrocarbon fluids of lower thermal maturity. The recognition of widespread gas-condensate migration adds to the complex history of internal hydrocarbon migration within the Montney tight-petroleum system including previously identified migration episodes of early oil and late-stage methane-rich gas.

Synchrotron-radiation-induced oxidation of selenite to selenate in coal-derived fly ash.

Systematic changes observed in consecutive XANES spectra of selenium in samples of fly ash from a power plant in Alberta, Canada, burning subbituminous coal have been interpreted as arising from synchrotron-radiation-induced oxidation of a selenite species to selenate. It was estimated that about 15-20% of the selenite was oxidized to selenate during the 2 h exposure of the fly ash to the synchrotron beam. In contrast, the XANES spectra of arsenic (and other trace elements not documented herein) showed no variation. It is believed that this is the first time that radiation-induced changes have been observed for an element in coal-derived fly ash.

High mercury accumulation in deep-ocean hadal sediments.

Ocean sediments are the largest sink for mercury (Hg) sequestration and hence an important part of the global Hg cycle1. Yet accepted global average Hg flux data for deep-ocean sediments (> 200 m depth) are not based on measurements on sediments but are inferred from sinking particulates2. Mercury fluxes have never been reported from the deepest zone, the hadal (> 6 km depth). Here we report the first measurements of Hg fluxes from two hadal trenches (Atacama and Kermadec) and adjacent abyssal areas (2-6 km). Mercury concentrations of up to 400 ng g-1 were the highest recorded in marine sediments remote from anthropogenic or hydrothermal sources. The two trench systems differed significantly in Hg concentrations and fluxes, but hadal and abyssal areas within each system did not. The relatively low recent mean flux at Kermadec was 6-15 times higher than the inferred deep-ocean average1,3, while the median flux across all cores was 22-56 times higher. Thus, some hadal and abyssal sediments are Hg accumulation hot-spots. The hadal zone comprises only ~ 1% of the deep-ocean area, yet a preliminary estimate based on sediment Hg and particulate organic carbon (POC) fluxes suggests total hadal Hg accumulation may be 12-30% of the estimate for the entire deep-ocean. The few abyssal data show equally high Hg fluxes near trench systems. These results highlight a need for further research into deep-ocean Hg fluxes to better constrain global Hg models.

Genesis of solid bitumen.

This paper presents a new schematic model for generation and timing of multiple phases of solid bitumen throughout the continuum of organic matter maturation in source and tight reservoir rocks. Five distinct stages in the evolution of solid bitumen are proposed: (1) diagenetic solid bitumen (or degraded bituminite), which is not a secondary maceral resulting from the thermal cracking of kerogen. Instead it is derived from degradation of bituminite in the diagenesis stage (Ro < 0.5%); (2) initial-oil solid bitumen, is a consolidated form of early catagenetically generated bitumen at the incipient oil window (Ro ~ 0.5-0.7%); (3) primary-oil solid bitumen is derived from thermally generated bitumen and crude oil in the primary oil window (Ro ~ 0.7-1.0%); (4) late-oil solid bitumen (solid-wax) is derived from the waxy bitumen separated from the mature paraffinic heavy oil in the primary- and late-oil windows; and (5) pyrobitumen, which is mainly a non-generative solid bitumen, is evolved from thermal cracking of the remaining hydrocarbon residue and other types of solid bitumen in the dry gas window and higher temperature (Ro > 1.4%). This model shows concurrence of multi-populations solid bitumen with oil, bitumen, and other phases of fluid hydrocarbon residue during most of the maturity continuum.