Tracing industrial sulfur contributions to atmospheric sulfate deposition in the Athabasca oil sands region,Alberta, Canada

Anthropogenic S emissions in the Athabasca oil sands region (AOSR) in Alberta, Canada, affect SO₄ deposition in close vicinity of industrial emitters. Between May 2008 and May 2009, SO₄-S deposition was monitored using open field bulk collectors at 15 sites and throughfall collectors at 14 sites at distances between 3 and 113 km from one of the major emission stacks in the AOSR. At forested plots >90 km from the operations, SO₄ deposition was ∼1.4 kg SO₄-S ha⁻¹ yr⁻¹ for bulk deposition and ∼3.3 kg SO₄-S ha⁻¹ yr⁻¹ for throughfall deposition. Throughfall SO₄ deposition rates in the AOSR exceeded bulk deposition rates at all sites by a factor of 2–3, indicating significant inputs of dry deposition especially under forest canopies. Both bulk and throughfall SO₄ deposition rates were elevated within 29 km distance of the industrial operations with deposition rates as high as 11.7 kg SO₄-S ha⁻¹ yr⁻¹ for bulk deposition and 39.2 kg SO₄-S ha⁻¹ yr⁻¹ for throughfall at industrial sites. Sulfur isotope ratio measurements of atmospheric SO₄ deposited in the AOSR revealed that at a few selected locations ³⁴S-depleted SO₄, likely derived from H₂S emissions from tailing ponds contributes to local atmospheric SO₄ deposition. In general, however, δ³⁴S values of SO₄ deposition at distant forested plots (>74 km) with low deposition rates were not isotopically different from δ³⁴S values at sites with high deposition rates in the AOSR and are, therefore, not suitable to determine industrial S contributions. However, O isotope ratios of atmospheric SO₄ in bulk and throughfall deposition in the AOSR showed a distinct trend of decreasing δ¹⁸O-SO₄ values with increasing SO₄ deposition rates allowing quantification of industrial contributions to atmospheric SO₄ deposition. Two-end-member mixing calculations revealed that open field bulk SO₄ deposition especially at industrial sites in close proximity (<29 km) to the operations is significantly (17–59%) affected by industrial S emissions and that throughfall generally contained 49–100% SO₄ of industrial origin. Hence, it is suggested that δ¹⁸O values of SO₄ may constitute a suitable tracer for quantifying industrial contributions to atmospheric SO₄ deposition in the AOSR.     

Quantifying saline groundwater seepage to surface waters in the Athabasca oil sands region

Western Canadian oil sands contain over 170 billion barrels of proven unconventional petroleum reserves currently extracted at 1.8 million barrels per day by either surface mining, or by in situ techniques that require subsurface injection of steam and hydrocarbon solvents. Natural high-salinity springs are known to add water and entrained inorganic and organic constituents to the Athabasca River and its tributaries in the region of ongoing bitumen production. However, the magnitude and synoptic distribution of these saline inputs has remained unquantified. Here, a chloride mass balance is used to estimate saline groundwater discharge to the Athabasca River from 1987 to 2010. Results show that the highest saline water discharge rate to the Athabasca River occurs between Ft. McMurray and the Peace-Athabasca Delta, supported by subcrop exposure of lower Cretaceous- and Devonian-aged formations bearing saline waters. Further, the input of saline groundwater is found to be an important control on the chemistry of the lower Athabasca River, despite comprising 10⁻¹ to 3% of the Athabasca River’s discharge. The flux of natural saline groundwater entering the Athabasca does not appear to have increased or decreased from 1987 to 2010. The origin of seep salinity is interpreted as relict subglacial meltwater that has dissolved Devonian-aged evaporites, supported by saline Na-Cl type waters with low ¹⁸O/¹⁶O and ²H/¹H ratios relative to modern precipitation. The magnitude of groundwater discharge and its impact on the Athabasca River’s chemistry in the area of ongoing bitumen development warrants the incorporation of natural groundwater seepages into surface water quality monitoring networks.     

Sources of polycyclic aromatic hydrocarbons (PAHs) to northwestern Saskatchewan lakes east of the Athabasca oil sands

The past several decades have witnessed a significant expansion of mining activities in the Athabasca oil sands region, raising concerns about their impact on the surrounding boreal forest ecosystem. To better understand the extent to which distal sites are impacted by oil sands-derived airborne contaminants, we examine sources of polycyclic aromatic hydrocarbons (PAHs) in surface sediments and dated sediment cores from Saskatchewan lakes situated ∼100–220 km east–northeast of the main area of bitumen mining activities. The concentrations and fluxes of both parent and alkylated PAHs are low and show considerable variability over the past 70–100 years. Small yet discernible increases in PAH concentrations and fluxes occurred over the past 30 years, a trend which coincides with the rapid growth in bitumen production. However, several lines of evidence point to wildfires as the principal source of PAHs to these lakes: (1) the significant co-variations in most cores between retene (1-methyl-7-isopropyl phenanthrene) and other groups of parent and alkylated PAHs, (2) the similarity in compound specific δ¹³C signatures of the parent PAHs phenanthrene and pyrene in recently deposited surficial sediments and those corresponding to time intervals considerably pre-dating the large scale development of the oil sands and (3) the discernible up-core increases in the proportion of refractory carbon (i.e., char) in Rock-Eval 6 data. The collective evidence points to softwood combustion from boreal forest fires as the principal source of retene in sediments and the general increase in forest fire activity in this region over the past several decades as the source of refractory carbon. Mining activities associated with the Athabasca oil sands are thus not considered a major source of PAHs to these lakes.     

Physicochemical gradients,diffusive flux,and sediment oxygen demand within oil sands tailings materials from Alberta,Canada

The Athabasca Oil Sands contain one of the world's largest oil reserves consisting of approximately 168 billion barrels of currently recoverable bitumen. With 20% recoverable through open pit mining methods, this extraction process produces a considerable amount of fluid fine tailings (FFT) waste material, which must be deposited on site in tailings ponds. These ponds allow the waste sand, clay and residual bitumen to settle out of the water column, allowing for the water to be recycled for use again in the extraction process. It is vital to gain a better understanding of the processes contributing to the development of physicochemical gradients (pH, Eh, Oxygen etc…) that form in these tailings ponds over time, with the goal of remediation and subsequent construction of end-pit lake systems once oil extraction has ceased. To differentiate between the impacts of biotic and abiotic processes in fresh (newly processed material) and mature FFT (∼38 year old tailings) over a 52-week study, a specific experimental design was utilized in accordance with novel microsensor profiling techniques. The sulfide diffusive fluxes within mature biotic systems measured 37.6 μmol m⁻² day⁻¹ at the onset of the experiment, decreasing over time, as FeS mineralization progressed. In addition, DO fluxes also showed strong correlation to the physical affects of consolidation, and overall biological consumption of O₂ at the FFT-water interface. This holistic study comparing different tailings pond materials provides insight regarding biotransformation and physicochemical controls effecting sediment oxygen demand associated with reclaimed wetlands and end pit lake development.     

Relationship between DOC photochemistry and mercury redox transformations in temperate lakes and wetlands

We compared diurnal variations in dissolved gaseous mercury (DGM) concentration and in losses of dissolved organic carbon fluorescence (DOCF) in four boreal Canadian Shield lakes, in one beaver pond, and in filtered and unfiltered water from a wetland in Lake St. Pierre, a fluvial lake of the St. Lawrence River. These systems were chosen to represent a spectrum of DOC. We also determined the contribution of UVB, UVA and visible light on DGM photo-induced production in the four lakes. Our results showed a strong relationship between DGM concentrations and light intensity and between DGM production and losses in DOCF, in all study sites. We also observed higher rates of DGM formation and of DOCF bleaching in the presence of UV radiation. Under UVB light, production of DGM was higher in clear lakes than in the humic ones. Inversely, in the UVA range, DGM production tended to be higher in humic lakes. We suggest that DOCF bleaching can be used as a proxy for the rate of formation of reactive species that may alter the redox state of mercury in surface waters. We also have indications that DGM production is more important in clear than in humic waters.     

Economic and environmental risks and uncertainty in frontier resource development: Case study of the Athabasca oil sands

Resource extraction projects in frontier regions may give rise to many problems concerning their economic viability and also their impact on the environment. The mining and processing activity in the oil sands of Alberta is a case in point. This area comprises one of the largest reservoirs of oil in the world. Long-run supply considerations in both Canada and the rest of the world should lead to further development of these oil sands. However, a review of the first two projects reveals considerable economic and environmental uncertainty. The economics of the project currently under way are questionable mainly because of inflated costs on one hand and uncertain future oil prices on the other. Controversy has developed over aspects of the land, water, and atmospheric environmental impacts of the projects partly because development proceeded before extensive studies were done. All these concerns have led to uncertainty concerning future projects and also the price the people of Alberta and Canada will pay, in economic and environmental terms, for development in this area.     

The distribution of total and methylmercury concentrations in soils near the Idrija mercury mine, Slovenia, and the dependence of the mercury concentrations on the chemical composition and organic carbon levels of the soil

Although the mining activity of the Idrija mine in Slovenia ceased in 1995, a large amount of mining dregs containing high concentrations of mercury remains in the area. The mining dregs were transported with river flow and deposition along the Idrija River. To estimate the dispersion and change in the chemical form of mercury, a total of 28 soil core samples were taken around the river. The individual core samples were separated into layers for the analysis of their chemical composition, carbon contents, total mercury (T-Hg) and methylmercury (MeHg) concentrations. The chemical composition measured by X-ray fluorescence spectrometry was useful to estimate the dispersion of tailings: the fluvial terrace soil had a chemical composition similar to that of the tailings and could be distinguished clearly from the forest soil. The highest T-Hg concentration, 1,100 mg kg⁻¹, was observed in the fluvial terrace soil near the mine. Although the concentration decreased gradually along with distance from the mine, concentrations higher than 200 mg kg⁻¹ of T-Hg were still observed in the fluvial terrace soil approximately 20 km downstream from the mine. In the vertical distribution of T-Hg in the hillslope soil, a higher value was observed in the upper layers, which suggests the recent atmospheric deposition of mercury. The concentration of MeHg was the lowest at the riverside and higher in the hillslope soil, which was the opposite of the T-Hg distribution. The total organic carbon content tracked similarly with the distribution of MeHg and a linear relation with a significantly high correlation coefficient was obtained. The distinction may be related to the different dispersion process of mercury, and the organic carbon contents may be an important factor for MeHg formation.     

Sandstone grain size characteristics of the Upper Jurassic Emuerhe Formation in the western region,Mohe Basin (NE China)

The Upper Jurassic Emuerhe Formation was developed with abundant sedimentary facies types in the western section of the Mohe Basin. Based on the systematic sampling and detailed observation on the Emuerhe Formation of this section, the research on the sandstone grain size characteristics of the Emuerhe Formation was carried out with the grain size parameters features (Mz, SK₁, K_G and σ₁), the sensitive components parameters features (SCPGS, SCGSR and SCPV) and the grain size analytical graphs features (grain size frequency curves, grain size cumulative curves, probability cumulative curves and C–M plots). The comprehensive analytical results illustrate that the hydrodynamic energy of the Emuerhe Formation (three times fan delta facies, two times sandy shallow lake microfacies and five times turbidite deposit) in the western section gradually reduced from bottom to top. In addition, the hydrodynamic energy of each fan delta facies gradually enhanced from bottom to top. Based on the analysis of the hydrodynamic conditions of the Emuerhe Formation in the western section, the hydrodynamic conditions evolution history of this section can be divided into five sedimentary phases, namely respectively for the fan delta sedimentary phase, the first‐time sandy shallow lake microfacies sedimentary phase, the short‐term deep lake subfacies sedimentary phase, the second‐time sandy shallow lake microfacies sedimentary phase and the relatively stable deep lake subfacies sedimentary phase from bottom to top. Copyright © 2015 John Wiley & Sons, Ltd.     

Relationship between mercury and arsenic mineralization in the Sarasa ore zone (Gornyy Altay)

Granite gneiss, gneiss, and granite domes of Central Karelia are developed near the junction zone between two tectonic structures, the Western anticlinorium of the Belomorides and the East Karelian zone of the Karelides, The established regular restriction of both shows and deposits of a number of mineral resources to the surroundings of the domes is of importance in forecasting and the future direction of exploration work in this region. —Authors.     

Geochemical correlations between effusive and explosive silicic volcanics in the Saraykent region (Yozgat), central Anatolia,Turkey

Two main volcanic events are distinguished between Saraykent and Akçakışla in the Yozgat province of central Anatolia: (1) early Late Cretaceous–Palaeocene effusive activity, that produced a sequence of intermediate to felsic ‘basal lavas’; and (2) marginally later Palaeocene explosive activity that formed a series of covering ignimbrite flows. Due to their close temporal and spatial relation, geochemical comparisons were made between the silicic members of the lavas and ignimbrites, to identify chemical groups and their relative petrogenesis. The basal lavas range from calc‐alkaline basaltic andesites to dominant rhyolites. Based on trace element correlations three main geochemical groups were identified: the Akçakışla rhyolites (present as domes); Akçakışla rhyodacites‐dacites (lava flows); and Ozan‐Saraykent rhyolites (lava flows). Large‐ion lithophile elements have been mobile in all the groups, but mainly in the Akçakışla rhyolites. Rare earth element (REE) patterns show marked similarity between the Ozan and Saraykent basal lavas. The Akçakışla dome rhyolites are more fractionated with lower La_N/Yb_N ratios (c.10), whereas the Akçakışla basal lavas have much higher La_N/Yb_N ratios (c.30). The chemical coherence and petrographic similarities between the Saraykent and Ozan lavas suggest a single suite related via fractionation. Three geochemical groups were also established for the ignimbrites: Saraykent ignimbrite; Bağlıca ignimbrite‐Toklu‐Kızıldağ crystal tuffs; and Keklikpınar ignimbrite. The ignimbrites, like the basal lavas, display a pronounced depletion in Ba on ORG‐normalized plots. Relative to the basal lavas, chondrite‐normalized patterns for the ignimbrites are different in displaying negative Eu anomalies that indicate feldspar fractionation. The lack of geochemical overlap or coherence between any of the lava and ignimbrite groups suggests that they represent distinct eruptive events and are not related in any simple volcanic development and cogenetic sense. Two geochemical features are common to all the volcanic rock groups: (1) the presence of a Nb‐Ta anomaly, which is generally accepted as a crustal signature; and (2) the relatively low Y abundances which appear characteristic for the region as a whole. These fundamental features of the local silicic volcanism largely reflect source composition and effects. Copyright © 2002 John Wiley & Sons, Ltd.     

Mid-Holocene climate change in the eastern Xinjiang region indicated by the grain size and stable isotope record from Lake Barkol, northwest China

A sediment core from Lake Barkol located in the eastern Xinjiang autonomous region, northwest China, provided a high-resolution record of environmental change covering the last ~8.6 cal ka BP. Three major climate stages, 8.6–7.1, 7.1–2.0 and from 2.0 cal ka BP to the present, were divided by grain size and the authigenic carbonate stable isotope of the lake sediment. Climatic drought during the period 7.1–4.5 cal ka BP, deduced from Lake Barkol, prevailed in the mid-Holocene climate in northern Xinjiang and northwest Mongolia. In contrast, it was wet in central Xinjiang, northwest India and the Middle East during the same period. The climatic difference between northern and southern arid central Asia demonstrates the southward shifting of the Westerlies, which indicates the potential contribution of the Siberian high in the mid-Holocene.     

Deglaciation ages and meltwater routing in the Fort McMurray region,northeastern Alberta and northwestern Saskatchewan,Canada

A field-based reconstruction of the deglacial paleogeography in the Fort McMurray area permits: 1) constraining the timing of meltwater routing to the Arctic from the present Hudson Bay drainage basin; and 2) minimum-age estimates for ice-margin positions that can be used to constrain ice-sheet modeling results. A downslope recession of the Laurentide Ice Sheet resulted in a series of proglacial lakes forming between the ice margin and higher land to the southwest. The paleogeography of these lakes is poorly constrained in part from the masking effect of boreal forest vegetation and map-scale issues. However, recent space-shuttle based DEMs increase the number and spatial extent of moraines identified within the study area resulting in a coherent pattern of ice margin retreat focused on the Athabasca River valley. An intensive lake-coring program resulted in a minimum ten-fold increase in the radiocarbon database used to limit moraine ages. Results indicate that deglaciation in this region was younger than previously reported, and it is likely that the meltwater could not drain northward to the Arctic Ocean from any source southeast of the Fort McMurray area until approximately 9850–9660 ¹⁴C BP.     

Comparison of metal(loid) concentrations in water, sediments and fish from two large shallow lakes

Hulun Lake and Taihu Lake are both large shallow lakes in China. In summer and winter of 2009, water, sediments and fish samples were collected from the two lakes and the concentrations of metal(loids) were analyzed. The results demonstrated that aqueous concentrations of arsenic (As), chromium (Cr), cadmium (Cd), nickel (Ni) and copper (Cu) in Hulun Lake were significantly higher than those in Taihu Lake. Especially, the As concentrations (about 130 μg/L) in Hulun Lake dramatically exceeded the permissible level of drinking water. Compared with Taihu Lake, metal(loid) concentrations in the sediments of Hulun Lake were significantly lower, which might have less impacts on the metal exchanges between water and sediments. In contrast, concentrations of the measured metal(loids) (including As) in fish from Hulun Lake and Taihu Lake were comparable, suggesting that the dramatic difference in aqueous and sediment metal(loid) concentrations had less influence on the metal(loid) bioavailability. The higher concentrations of dissolved organic carbon (DOC) and cations (e.g., Na⁺, K⁺ and Mg²⁺) in lake water might contribute to the reduced metal(loid) bioavailability to fish in Hulun Lake.     

Architecture of pre-vegetation sandy-braided perennial and ephemeral river deposits in the Paleoproterozoic Athabasca Group, northern Saskatchewan, Canada as indicators of Precambrian fluvial style

The Late Paleoproterozoic Athabasca Basin contains more than 1.5 km of predominantly sandy strata, most of which are of braided fluvial origin. In the eastern part of the basin, at McClean Lake, sandstones and minor conglomerates of the Read Formation at the base of the succession are preserved within a steep-walled valley system. They consist predominantly of meter-scale sheet elements, characterized by massive and flat-laminated fine- to very coarse-grained sandstone with minor discontinuous cobble and boulder conglomerate along lower set boundaries. These are interpreted as sheet-flood and stream-flood deposits of a terminal dry-land system, deposited in an arid climatic setting. Analysis of closely spaced drill-core indicates that late stage run-off was confined to small shallow channels, typically only a few tens of meters wide and a few meters deep. Overlying strata of the Bird Member of the Manitou Falls Formation are predominantly coarse- to very coarse-grained sandstones with abundant small-scale cross-stratification and minor granule and small pebble conglomerate. At McClean Lake, these appear to have been deposited as sheet-elements by semi-ephemeral to perennial braided rivers under more humid conditions. At Key Lake, 160 km to the southwest, architectural analysis of a 184 m wide section indicates that at least part of the Bird Member was deposited in deeper, sandy-braided rivers characterized by seasonally varied flow. The closest modern analogue is the South Saskatchewan River, in which large simple flow-transverse bedforms become exposed and dissected during falling stage, and act as nuclei for sand-flat development. The presence of numerous low-relief 4th order surfaces suggests continued reworking of bar-tops during rising stage. The incremental character of downstream accretionary elements suggests periodic migration of barforms during peak-flood stages, separated by periods of low flow. This indicates similarities with modern perennial braided systems, and is counter to the idea that all pre-Devonian fluvial systems should consist of stacked sheets formed by individual flood events. Thin gravel layers accumulated as lags on fourth order surfaces, with discontinuous mud layers suggesting deposition within temporary ponds in channel thalwegs after major floods. Strata in overlying units indicate a return to semi-perennial conditions.     

Relationship between crude-oil properties and geology in some oil and gas fields in the Niigata basin,Japan

The crude oil separately sampled from every producing well in the two fields in the Niigata Neogene sedimentary basin was analysed chemically and tested physically. The data obtained were interpreted, taking the geological conditions of the reservoir fully into consideration.     

Pliocene subaqueous fans and Gilbert-type deltas in maar crater lakes, Hopi Buttes, Navajo Nation (Arizona), USA

Maar craters of the Mio-Pliocene Hopi Buttes volcanic field of Arizona formed within a broad playa system, and accumulated a variety of lacustrine sedimentary deposits. Many craters initially held isolated, groundwater-fed lakes. Ephemeral streams crossing the playa entered some of the lake-filled craters, and built coarse grained Gilbert-type deltas and subaqueous fans along the margins of these craters. The small, coarse grained fans and deltas have many features in common with much larger coarse grained deltaic and fan deltaic deposits. However, the local production of coarse grained volcanic sediment, low gradients in the local stream catchment, steep subaqueous relief and the small size of the receiving ‘basins’resulted in a unique combination of features. Cone-shaped subaqueous fans initially formed at the mouths of incised feeder streams. The fans are small accumulations of steeply dipping gravelly tephra that consist almost entirely of overlapping lobes constructed by density-modified grain flows. Gravelly Gilbert-type tephra deltas formed in brimfull craters fed by a freely migrating feeder stream. They are concave lakeward, mimicking the underlying crater wall topography. Complex deltaic geometries are defined by topset strata that steeply onlap tall foreset beds. They suggest that feeding stream floods caused rapid and comparatively large variations in lake level within the small crater lakes. Bed-specific carbonate alteration is common, and probably resulted from both influx of detrital carbonate across the playa and alteration of tephra beds by carbonate-saturated lakewaters during between flood periods of high net evaporation.     

Methylmercury and total mercury distribution in the sediments of Baihua Reservoir, Guizhou Province, China

Mercury is an important pollutant in lakes. Methylmercury （MeHg）, the most toxic mercury species, which can be formed from inorganic mercury in lakes, can be bioaccumulated into high concentration in food chain and result in a potential threat to human beings. Sediments play an important role for the Hg biogeochemistry in the aquatic systems： Mercury methylation has been shown to be fastest in the surfacial sediments, where the microbial activity is highest. The formation of MeHg in lakes suggests that sediments and/or near-shore wetlands can be the sources of MeHg in aquatic environments. The Baihua Reservoir, located in the suburb of Guiyang, was impounded in 1966. From the 1970s to the 1990s, Guizhou Organic Chemical Plant which used inorganic mercury as catalyst to produce acetic acid, was responsible for the discharge of waste water with high mercury content.