Determination of mercury biogeochemical fluxes in the remote Mackenzie River Basin,northwest Canada,using speciation of sulfur and organic carbon

The Mackenzie River Basin (MRB) in NW Canada is one of the least human-impacted large watersheds in the world. The western and eastern sub-basins of the MRB are also marked by contrasting geology, geomorphology, hydrology, and biology. These remarkable differences in a remote river basin provide a unique opportunity to probe the biogeochemical processes governing the sources, transport, and bioavailability of Hg at the terrestrial-marine interface and ultimately in the Arctic Ocean. Based on a large dataset of the concentration and speciation of Hg, S and organic matter in surface sediments across the MRB, a source-apportioned budget was constructed for Hg in the MRB. The results indicate that the Hg flux in the basin originates primarily from the weathering of sulfide minerals in the western mountainous sub-basin (∼78% of the total), followed by the erosion of coal deposits along the mainstream of the Mackenzie River (∼10%), with the remainder split between atmospheric inputs and organic matter-bound Hg (6% and 5%, respectively). Although the Hg flux from the eastern peatland sub-basin only accounts for ∼10% of the total riverine Hg flux, Hg in this region correlates strongly with labile organic matter, and will likely have a much stronger influence on local biota.     

Studying the humification degree and evolution of peat down a Holocene bog profile (Inuvik, NW Canada): A petrological and chemical perspective

The process of the transformation of fresh organic matter (OM) into more stable and recalcitrant humic substances is still not completely clear. Understanding how OM humification evolves in northern bog environments is extremely important, especially considering that they represent one of the largest terrestrial carbon pools.Structural changes of OM occurring during the humification process have been generally evaluated by indirect measurements of the degree of humification. Several approaches have been used, often providing contrasting results probably because humification is a complex process that evolves differently according to varying pedoclimatic conditions.In the present work, the authors followed the evolution of peat OM along a 165 cm bog profile (covering the mid- to late Holocene) correlating results obtained from both organic petrological and chemical investigation. Data clearly underline a significant agreement between the two perspectives, both showing either a quite immature peat material or the presence of three distinct zones along the profile. In detail, both spectroscopic (i.e., FT-IR and three dimensional fluorescence spectra, humification indexes), and Rock-Eval pyrolysis results (low residual organic carbon content and high hydrogen and oxygen index values) showed the occurrence of a central zone (from 20-30 cm to 120 cm depth) often characterized by high heterogeneity and a low degree of humification when compared to the upper ∼20 and bottom 40 cm sections.     

Characterization of organic matter in surface sediments of the Mackenzie River Basin, Canada

The particulate organic matter in < 63 µm surface sediments from the Mackenzie River and its main tributaries was studied using Rock-Eval pyrolysis and organic petrology. The organic matter in the sediments is dominated by refractory residual organic carbon (RC) of mainly terrigenous nature, as indicated by abundant inertinite, vitrinite, and type III kerogen. Sediments from the tributaries contained significantly more algal-derived organic matter than from the main channel of the river, highlighting the importance of low-energy system dynamics in the tributaries, which allows modest algal production, more accumulation, and better preservation of autochthonous organic matter. This is particularly true for tributaries fed by lacustrine systems, which showed the highest S1 and S2 fractions, and consequently higher total particulate organic carbon (POC) in the basin. Organic petrology of the sediment samples confirms abundant liptinitic materials (i.e., fat-rich structured algae, spores and pollen, cuticles, and resins). Forest fire and coal deposits are also confirmed to contribute to the basin. Assuming that suspended and fine surfacial sediments have a similar OC composition, the Mackenzie River is estimated to deliver a total POC flux of 1.1 Mt C/yr to its delta, of which 85% is residual carbon with liptinitic OC (S1 + S2) and S3 accounting for another 9% and 6%, respectively.     

Analysis of large thermal maturity datasets: Examples from the Canadian Arctic Islands

This paper describes an approach for verifying thermal maturity data in a large historical dataset from the Canadian Arctic Islands. A compilation of more than 6000 maturity measurements (vitrinite reflectance and Rock-Eval Tmax) collected over the span of three decades involved a rigorous assessment of data quality. Some common anomalies in interpreting thermal maturity dataset include: (i) elevated thermal maturity due to Cretaceous igneous intrusion in the region, (ii) reworking of refractory material from older rocks into younger strata during the Triassic period, (iii) suppression of vitrinite reflectance and Tmax in hydrogen-rich samples, (iv) low maturity values due to cross-contamination by the younger sediments during drilling process (caving), and (v) offset maturity values obtained from different maturity measurements. The study discusses various independent checks to verify the obtained maturity parameters. The comparison between thermal maturity data with the sonic velocity of shale resulted in a satisfactory correlation. While such a correlation may vary in different sedimentary basins, it produces a useful independent assessment of thermal maturity. The results indicate that increased heat flow during the Jurassic–Early Cretaceous rifting of the Canada Basin may have caused the elevated maturity beyond the expected burial level as suggested by the discrepancy between thermal maturity and sonic velocity data. Given the fact that vitrinite reflectance records only the maximum temperature to which the enclosing rocks were exposed, deviation of the collected reflectance values from the current depth of burial serves as an indicator for the amount of geological uplift.     

Characterization of diatom-derived lipids and chlorophyll within Holocene laminites, Saanich Inlet, British Columbia, using conventional and laser scanning fluorescence microscopy

Conventional fluorescence microscopy and visible light region fluorescence microspectrometry have been combined with laser scanning fluorescence microscopy (LSFM) to examine and characterize soluble sedimentary organic matter (SOM) in Holocene diatomaceous laminites from ODP core 1034, Saanich Inlet, British Columbia, Canada. Microscopic SOM in the laminites is dominated by two components: red-fluorescing chlorophyllinite, and yellow-fluorescing, diatom-derived oils. Both are commonly preserved within the interior of siliceous diatom auxospores and appear as an abundant and intense stain on mineral matter throughout the laminites. The mineral stain is classified as matrix chlorophyllinite and matrix oil, respectively. Accessory insoluble SOM consists of dinoflagellate, prasinophyte and coccoidal alginites, and rare woody huminite, funginite, and sporinite. Visible light region fluorescence microspectrometry of chlorophyllinite reveals a predominance at λ max 670–675 nm, which is consistent with a chlorophyll a source based on comparison with reference samples of chlorophyll a and b. The consistency in λmax and spectral character of chlorophyllinite with increasing depth in Saanich Inlet correlates with a high degree of chlorophyll preservation. Its distribution in the laminites is readily imaged by LSFM using either UV (363 nm) or blue (488 nm) laser excitation and >665 nm emission. Yellow-fluorescing diatom oils have λmax ranging from 485 to 520 nm, suggesting that they may comprise up to 70% saturates. The distribution of entrapped yellow-fluorescing diatom oils as well as matrix oils is also readily imaged with LSFM using a combination of UV laser excitation (363 nm) and 510 ±40 nm emission. Laminae in the Saanich Inlet samples which are highly enriched in both diatom oils and ‘reproductive’ auxospore cells are interpreted as recording intense episodic spring diatom blooms. The observations reported here document microscopically, in situ, possibly pristine preservation of diatom oils (including possible fatty acids) at appreciable depths within Holocene organic-rich laminites. Their recognition in recent and older strata is important, for they serve as potential biomarkers for assessing long term geo-environmental changes such as water temperature. The periodic presence of anomalously high amounts of diatom-derived biological oils in laminae within the recent sediments may mark times of unusually high nutrient levels and paleoproductivity.     

Geochemistry of coals from the Elk Valley coalfield, British Columbia, Canada

The Elk Valley coalfield of British Columbia is one of the major coal producing areas in Canada. The coals are of Cretaceous and Jurassic–Cretaceous age and range in rank from high-volatile to low-volatile bituminous (%Ro_max: 0.8–1.6). Coal seams from outcrops and active mines in this coalfield were analysed for rank and maceral composition using reflected light microscopy, for geochemistry using AAS, INAA, and ICPES, and also by proximate and ultimate analyses. The Elk Valley coal seams contain low average concentrations of hazardous elements such as As, Mo, Pb, and Se. However, there are seams that contain relatively high concentrations of some of these elements, such as 8 mg/kg and 108 mg/kg of arsenic. When the geochemistry of coal seams is compared within the different parts of the coalfield, the elemental composition amongst the seams from various sections located in the central area of the coalfield is similar. Coal seams in the northern area of the coalfield have different geochemistry than coal seams in other areas of the coalfield; seams in the northern area have much higher As, Br, Cr, Cu, Fe, K, and Na content, but contain less Ca.