A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Whole effluent toxicity assessment at a wastewater treatment plant upgraded with a full-scale post-ozonation using aquatic key species

Ozonation as final wastewater (WW) polishing step, following conventional activated sludge treatment is increasingly implemented in sewage treatment for contaminant degradation to prevent surface water pollution. While the oxidative degradation of chemicals has been extensively investigated, the in vivo toxicological characteristics of ozonated whole effluents are rarely a matter of research.In the present study, whole effluents were toxicologically evaluated with an in vivo test battery before and after full-scale ozonation and subsequent sand filtration on site at a treatment plant. One aquatic plant (duckweed, Lemna minor) and five invertebrate species of different systematic groups (Lumbriculus variegatus, Chironomus riparius, Potamopyrgus antipodarum, Daphnia magna) were exposed to the effluents in a flow-through-designed test system with a test duration of 7-28 d.None of the considered toxicity endpoints correlated with the pollutant elimination. A tendency towards an increased toxicity after ozonation was apparent in three of the test systems showing [statistically] significant adverse effects in the L. variegatus toxicity test (decrease in reproduction and biomass). After sand filtration, adverse effects were reduced to a similar level like after conventional treatment. Solely the Daphnia reproduction test revealed beneficial effects after ozonation in combination with sand filtration.Results of the test battery indicate the formation of adverse oxidation products during WW ozonation. L. variegatus appeared to be the most sensitive of the five test species. Sand filtration effectively removes or detoxifies toxic oxidation products, as toxic effects were subsequently reduced to the level after conventional treatment.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Monobromo and higher brominated congeners of the marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1)

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) is widely distributed in the environment. In this study, we screened samples which have previously been found to contain remarkably high residues of Q1 (blubber of marine mammals from Australia, samples from Antarctica, human milk from the Faroe Island) for the additional presence of mixed chlorinated and brominated congeners. Using GC/ECNI-MS, all samples tested were positive and many contained four out of five possible bromohexachloro congeners (BrCl6-MBPs), five out of 14 possible dibromopentachloro congeners (Br2Cl5-MBPs), five of 21 possible tribromotetrachloro-congeners (Br3Cl4-MBPs), as well as several higher brominated congeners. About 20 heptahalo congeners of Q1 are described for the first time in the scientific literature. Isomers eluted within about one minute, respectively. Hence it is possible, that the peak clusters identified may be composed of more, co-eluting congeners. Similarities in the GC/ECNI-MS mass spectra with polychlorinated biphenyls (PCBs) were addressed. We also suggest an acronym system similar to that in use for polychlorinated biphenyls that may simplify the use of this substance class in scientific papers. In the samples from Australia, BrCl6-MBPs and Br2Cl5-MBPs amounted for 7-27.5% and 0.4-4.2% of Q1, respectively whereas Br3Cl4-MBPs and higher brominated MBPs were found in the range of <1% of Q1 or less.     

Techniques for the stabilization and assessment of treated copper-, chromium-, and arsenic-contaminated soil

Remediation mainly based on excavation and burial of the contaminated soil is impractical with regard to the large numbers of sites identified as being in need of remediation. Therefore, alternative methods are needed for brownfield remediation. This study was conducted to assess a chemical stabilization procedure of CCA-contaminated soil using iron (Fe)-containing blaster sand (BS) or oxygen-scarfing granulate (OSG). The stabilization technique was assessed with regard to the feasibility of mixing ameliorants at an industrial scale and the efficiency of the stabilization under different redox conditions. The stability was investigated under natural conditions in 1-m3 lysimeters in a field experiment, and the effect of redox conditions was assessed in a laboratory experiment (10 L). The treatments with high additions of ameliorant (8% and 17%) were more successful in both the laboratory and field experiments, even though there was enough Fe on a stochiometric basis even at the lowest addition rates (0.1% and 1%). The particle size of the Fe and the mixing influenced the stabilization efficiency. The development of anaerobic conditions, simulated by water saturation, increases the fraction of arsenic (AsIII) and, consequently, As mobility. The use of high concentrations of OSG under aerobic conditions increased the concentrations of nickel (Ni) and copper (Cu) in the pore water. However, under anaerobic conditions, it decreased the As leaching compared with the untreated soil, and Ni and Cu leaching was not critical. The final destination of the treated soil should govern the amendment choice, that is, an OSG concentration of approximately 10% may be suitable if the soil is to be landfilled under anaerobic conditions. Alternatively, the soil mixed with 1% BS could be kept under aerobic conditions in a landfill cover or in situ at a brownfield site. In addition, the treatment with BS appeared to produce better effects in the long term than treatment with OSG.     

Increases of dissolved organic carbon in temperate and boreal lakes in Quebec, Canada

Purpose  

Increases in dissolved organic carbon (DOC) concentrations have been reported in surface waters worldwide in the last 10 to 20 years. The causes behind these increases have been attributed to many factors, including climate change and decreasing depositions of atmospheric sulphate ( \textSO₄^{2 -} {\text{SO}}_4^{{{2} - }} ). Trends in DOC concentrations and their potential causal factors were examined in a network of 30 lakes lying in undisturbed temperate and boreal catchments in the province of Quebec, Canada.     

On-road and simulated driving: concurrent and discriminant validation

Introduction

A converging pair of studies investigated the validity of a simulator for measuring driving performance/skill.

Study 1

A concurrent validity study compared novice driver performance during an on-road driving test with their performance on a comparable simulated driving test.

Results

Results showed a reasonable degree of concordance in terms of the distribution of driving errors on-road and errors on the simulator. Moreover, there was a significant relationship between the two when driver performance was rank ordered according to errors, further establishing the relative validity of the simulator. However, specific driving errors on the two tasks were not closely related suggesting that absolute validity could not be established and that overall performance is needed to establish the level of skill.

Study 2

A discriminant validity study compared driving performance on the simulator across three groups of drivers who differ in their level of experience - a group of true beginners who had no driving experience, a group of novice drivers who had completed driver education and had a learner's permit, and a group of fully licensed, experienced drivers.

Results

The findings showed significant differences among the groups in the expected direction -- the various measures of driving errors showed that beginners performed worse than novice drivers and that experienced drivers had the fewest errors. Collectively, the results of the concurrent and discriminant validity studies support the use of the simulator as a valid measure of driving performance for research purposes.

Impact on industry

These findings support the use of a driving simulator as a valid measure of driving performance for research purposes. Future research should continue to examine validity between on-road driving performance and performance on a driving simulator and the use of simulated driving tests in the evaluation of driver education/training programs.     

Development of an indirect-cost calculation model suitable for workplace use

Introduction: Occupational Health and Safety (OHS) stakeholders rarely factor the cost of workplace accidents into prevention spending decisions. The lack of consideration of this key information is related to the fact that the scientific literature has failed to provide OHS stakeholders with a cost-calculation tool that is both sufficiently accurate and does not require a data-collection stage ill-suited to the time constraints of workplace decision-makers. Method: This study reviews the recent literature to identify key elements that should foster the use of indirect-cost calculation methods by decision makers. Results: A “local” approach currently appears to be the best method for calculating indirect costs of workplace incidents or accidents in comparison to “bottom-up” or “top-down” approach. This paper discusses four criteria that this type of approach must satisfy to be compatible with the time constraints and accuracy demands of OHS stakeholders in organizations. In addition, four bases for the development of a new indirect cost estimation model are presented and discussed. Impact on industry: this study provides bases and criteria to help the development of indirect-cost calculation models better suited to workplace use than those currently available.     

Disclosure of climate risk information by the world’s largest companies

The risks related to global climate change are seen as threats to companies, taking into consideration their impact on the return on investment. In order to mitigate climate risk and introduce new opportunities to financiers, companies need to identify, manage, and report climate risks. The purpose of this paper is to investigate the climate risks disclosed by the 100 largest companies in the world, according to the Bloomberg and Price Waterhouse Coopers (PwC 2015) classification, and identify some characteristics of these companies that explain the disclosure level of such information. Preliminary results revealed that of the companies investigated, 14% did not disclose any climate risk information in the Carbon Disclosure Program (CDP) report. Also, from the companies that disclosed information according to the Global Reporting Initiative (GRI), 9.9% did not provide information regarding policies, actions, and strategies for mitigating the risks related to climate change. The results shown by the content analysis suggested that, in general, there is still a low level of disclosure about climate risks by these companies. The final results through econometric instruments and statistical tests indicate that the size of the company or the fact that corporations are from developed countries do not necessarily explain the level of information disclosed. However, the activity sector, the continent, and the efficiency of the Board of Directors are factors that strongly explain the level of climate risk disclosure. We conclude that more effort is needed to encourage an engaging attitude from corporations to develop actions, policies, and strategies to mitigate climate change risks and threats. In addition, the world’s largest companies should make a greater investment in climate risk disclosure.     

Accuracy assessment of land surface temperature retrievals from Landsat 7 ETM + in the Dry Valleys of Antarctica using iButton temperature loggers and weather station data

The McMurdo Dry Valleys of Antarctica are the largest snow/ice-free regions on this vast continent, comprising 1 % of the land mass. Due to harsh environmental conditions, the valleys are bereft of any vegetation. Land surface temperature is a key determinate of microclimate and a driver for sensible and latent heat fluxes of the surface. The Dry Valleys have been the focus of ecological studies as they arguably provide the simplest trophic structure suitable for modelling. In this paper, we employ a validation method for land surface temperatures obtained from Landsat 7 ETM + imagery and compared with in situ land surface temperature data collected from four transects totalling 45 iButtons. A single meteorological station was used to obtain a better understanding of daily and seasonal cycles in land surface temperatures. Results show a good agreement between the iButton and the Landsat 7 ETM + product for clear sky cases. We conclude that Landsat 7 ETM + derived land surface temperatures can be used at broad spatial scales for ecological and meteorological research.