A Preparative Method for the Isolation and Fractionation of Dissolved Organic Acids from Bitumen-influenced Waters

The surface mining of oil sands north of Fort McMurray, Alberta produces considerable tailings waste that is stored in large tailings ponds on industrial lease sites. Viable strategies for the detoxification of oil sands process affected water (OSPW) are under investigation. In order to assess the toxic potential of the suite of dissolved organics in OSPW, a method for their extraction and fractionation was developed using solid phase extraction. The method successfully isolated organic compounds from 180 L of an aged OSPW source. Using acidic- or alkaline-conditioned non-polar ENV+ resin and soxhlet extraction with ethyl acetate and methanol, three fractions (F1–F3) were generated. Chemical characterization of the generated fractions included infusion to electrospray ionization ultrahigh-resolution mass spectrometry (ESI-UHRMS), liquid chromatography quadrupole time-of-flight mass spectrometry, gas chromatography triple quadrupole time-of-flight mass spectrometry, and synchronous fluorescence spectroscopy (SFS). Additionally, ESI-UHRMS class distribution data and SFS identified an increased degree of oxygenation and aromaticity, associated with increased polarity. Method validation, which included method and matrix spikes with surrogate and labelled organic mono carboxylic acid standards, confirmed separation according to acidity and polarity with generally good recoveries (average 76%). Because this method is capable of extracting large sample volumes, it is amenable to thorough chemical characterization and toxicological assessments with a suite of bioassays. As such, this protocol will facilitate effects-directed analysis of toxic components within bitumen-influenced waters from a variety of sources

The effect of organic retarders on grout thickening and setting during deep borehole disposal of high-level radioactive waste

Deep borehole disposal (DBD) is being increasingly seen as a viable and potentially superior alternative to comparatively shallow mined repository concepts for disposal of some high-level radioactive wastes. We report here details of proof-of-concept investigations into the use of cementitious grouts as sealing/ support matrices for use in low temperature DBD scenarios. Using the cementitious grout to fill annular space within the disposal zone will not only support waste packages during placement, but will also provide a low permeability layer around them which will ultimately enhance the safety case for DBD. Grouts based on Class G oil well cement are being developed. The use of retarders to delay the accelerated onset of thickening and setting (caused by the high temperature and pressure in the borehole) is being investigated experimentally. Sodium gluconate and a polycarboxylate additive each provide suf- ficient retardation over the range 90e140 °C in order to be considered for this application. Phosphonate and sulphonate additives provide desirable retardation at 90 °C. The additives did not affect grout composition at 14 days curing and the phases formed are durable at elevated temperature and pressure

Advances in Distinguishing Groundwater Influenced by Oil Sands Process-Affected Water (OSPW) from Natural Bitumen-Influenced Groundwater

The objective of this study was to advance analytical methods for detecting oil sands process-affected water (OSPW) seepage from mining containments and discriminating any such seepage from the natural bitumen background in groundwaters influenced by the Alberta McMurray formation. Improved sampling methods and quantitative analyses of two groups of monoaromatic acids were employed to analyze OSPW and bitumen-affected natural background groundwaters for source discrimination. Both groups of monoaromatic acids showed significant enrichment in OSPW, while ratios of O /O containing heteroatomic ion classes of acid extractable organics (AEOs) did not exhibit diagnostic differences. Evaluating the monoaromatic acids to track a known plume of OSPW-affected groundwater confirmed their diagnostic abilities. A secondary objective was to assess anthropogenically derived artificial sweeteners and per- and polyfluoroalkyl substances (PFAS) as potential tracers for OSPW. Despite the discovery of acesulfame and PFAS in most OSPW samples, trace levels in groundwaters influenced by general anthropogenic activities preclude them as individual robust tracers. However, their inclusion with the other metrics employed in this study served to augment the tiered, weight of evidence methodology developed. This methodology was then used to confirm earlier findings of OSPW migrations into groundwater reaching the Athabasca River system adjacent to the reclaimed pond at Tar Island Dyke

Preparative isolation, fractionation and chemical characterization of dissolved organics from natural and industrially derived bitumen-influenced groundwaters from the Athabasca River watershed

Recent analytical advances have provided evidence that groundwater affected by oil sands process-affected water (OSPW) is reaching the Athabasca River at one location. To understand and discriminate the toxicological risks posed by OSPW-influenced groundwater relative to groundwaters associated with natural oil sands deposits, these highly complex mixtures of soluble organics were subjected to toxicological characterization through effects directed analysis. A recently-developed preparative fractionation methodology was applied to bitumen-influenced groundwaters and successfully isolated dissolved organics from both industrial and natural sources into three chemically distinct fractions (F1, F2, F3), enabling multiple toxicological assessments. Analytical techniques included electrospray ionization high resolution mass spectrometry (ESI-HRMS), liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF/MS), gas chromatography mass spectrometry (GC–MS), and synchronous fluorescence spectroscopy (SFS) methods, which did not reveal obvious differences between sources. Comparisons between fractions within each source consistently demonstrated that F3 contained compounds with greater polarity than F2, which in turn was more polar than F1. The abundance of O2 species was confined to F1, including naphthenic acids often cited for being the primary toxicants within bitumen-influenced waters. This result is consistent with earlier work on aged OSPW, as well as with other extraction methods, suggesting that additional factors other than molecular weight and the presence of acid functionalities play a prominent role in defining compound polarities and toxicities within complex bitumen-derived organic mixtures. The similarities in organic abundances, chemical speciation, aromaticity, and double bond equivalents, concomitant with inorganic mixture similarities, demonstrate the resemblances of bitumen-influenced groundwaters regardless of the source, and reinforce the need for more advanced targeted analyses for source differentiation.This work was funded under the Oil Sands Monitoring Program, and is a contribution to the Program, but does not necessarily reflect the position of the Program. Internal resources from Environment and Climate Change Canada were also used to fund this research

In the social factory? Immaterial labour, precariousness and cultural work

This article introduces a special section concerned with precariousness and cultural work. Its aim is to bring into dialogue three bodies of ideas -- the work of the autonomous Marxist 'Italian laboratory'; activist writings about precariousness and precarity; and the emerging empirical scholarship concerned with the distinctive features of cultural work, at a moment when artists, designers and (new) media workers have taken centre stage as a supposed 'creative class' of model entrepreneurs. The paper is divided into three sections. It starts by introducing the ideas of the autonomous Marxist tradition, highlighting arguments about the autonomy of labour, informational capitalism and the 'factory without walls', as well as key concepts such as multitude and immaterial labour. The impact of these ideas and of Operaismo politics more generally on the precarity movement is then considered in the second section, discussing some of the issues that have animated debate both within and outside this movement, which has often treated cultural workers as exemplifying the experiences of a new 'precariat'. In the third and final section of the paper we turn to the empirical literature about cultural work, pointing to its main features before bringing it into debate with the ideas already discussed. Several points of overlap and critique are elaborated -- focusing in particular on issues of affect, temporality, subjectivity and solidarity

Stealth-spectacles: the discursive waves of the nuclear Asian seascape

When compared to the bombast of nuclear tests, nuclear submarines come with the relatively quiet fantasy of victory-to-come against neighbouring nuclear adversaries. Such political expressions are making their mark in Indian popular culture that hitherto had little commentary to offer on submarines. Outlets such as film and digital media on submarines rest on an aporia that resonates across the pleats and folds of secrecy and publicity: there is a felt need to keep covert underwater vessels under wraps, yet also an irrepressible desire to glorify the technological achievement and political posturings enabled by thesecond strike capability of a nuclear armed and powered submarine. Highlighting the tensile allure of both stealth and spectacle, the article considers the ways submarines make a mark in Indian audio-visual and digital media alongside the affective resonance of submarines more widely. By understanding their hegemonic dynamics, we can begin to raise questions about the ongoing nuclearisation of the Asian region and neighbouring arterial seas described here as the Asian seascape