Aerobic degradation of di- and trichlorobenzenes by two bacteria isolated from polluted tropical soils

Two polychlorinated biphenyl (PCBs)-degrading bacteria were isolated by traditional enrichment technique from electrical transformer fluid (Askarel)-contaminated soils in Lagos, Nigeria. They were classified and identified as Enterobacter sp. SA-2 and Pseudomonas sp. SA-6 on the basis of 16S rRNA gene analysis, in addition to standard cultural and biochemical techniques. The strains were able to grow extensively on dichloro- and trichlorobenzenes. Although they failed to grow on tetrachlorobenzenes, monochloro- and dichlorobenzoic acids, they were able to utilize all monochlorobiphenyls, and some dichlorobiphenyls as sole sources of carbon and energy. The effect of incubation with axenic cultures on the degradation of 0.9 mM 1,4-dichlorobenzene, 0.44 mM 1,2,3- and 0.43 mM 1,3,5-trichlorobenzene in mineral salts medium was studied. Approximately, 80-90% of these xenobiotics were degraded in 200 h, concomitant with cell increase of up to three orders of magnitude, while generation times ranged significantly (P<0.05) from 17-32 h. Catechol 1,2-dioxygenase and catechol 2,3-dioxygenase activities were detected in crude cell-free extracts of cultures pre-grown with benzoate, with the latter enzyme exhibiting a slightly higher activity (0.15-0.17 micromolmin(-1) mg of protein(-1)) with catechol, suggesting that the meta-cleavage pathway is the most readily available catabolic route in the SA strains. The wider substrate specificity of these tropical isolates may help in assessing natural detoxification processes and in designing bioremediation and bioaugmentation methods.     

Interference with xenobiotic metabolic activity by the commonly used vehicle solvents dimethylsulfoxide and methanol in zebrafish (Danio rerio) larvae but not Daphnia magna

Organic solvents, such as dimethylsulfoxide (DMSO) and methanol are widely used as vehicles to solubilise lipophilic test compounds in toxicity testing. However, the effects of such solvents upon innate detoxification processes in aquatic organisms are poorly understood. This study assessed the effect of solvent exposure upon cytochrome P450 (CYP)-mediated xenobiotic metabolism in Daphnia magna and zebrafish larvae (4 d post fertilisation). Adult D. magna were demonstrated to have a low, but detectable, metabolism of ethoxyresorufin in vivo and this activity was not modulated by pre-exposure to DMSO or methanol (24 h, up to 0.1% and 0.05% v/v, respectively). In contrast, the metabolism of ethoxyresorufin in zebrafish larvae was significantly reduced by both solvents (0.1% and 0.05% v/v, respectively) after 24 h of exposure. In zebrafish, these observed decreases in activity towards ethoxyresorufin were accompanied by decreased expression of a variety of genes coding for drug metabolising enzymes (corresponding to CYP1, CYP2, CYP3 and UDP-glucuronyl transferase [UGT] family enzymes), measured by quantitative PCR. Reduction of gene expression and CYP1 enzyme activities by methanol (0.05% v/v) in zebrafish larvae was partially reversed by co-exposure with Aroclor 1254 (100 μg L⁻¹). Overall this study suggests that relatively low concentrations of organic solvents can impact upon the biotransformation of certain xenobiotics in zebrafish larvae, and that this warrants consideration when assessing compounds for metabolism and toxicity in this species.     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in breast milk of first-time Irish mothers: impact of the 2008 dioxin incident in Ireland

The 2008 dioxin incident in Ireland resulted in elevated concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in Irish pork and pork products, due to the consumption of contaminated animal feed by pigs. In order to investigate any resulting impact on the Irish population, these contaminants were measured in pooled breast milk samples from 109 first-time mothers, collected in 2010. A comparison of the results with similar data from 2002 revealed generally lower concentrations of PCDD/Fs and dioxin-like PCBs in the 2010 samples, confirming the declining trend reported by many authors. Contaminant concentration levels for both 2002 and 2010 were generally slightly lower than those reported internationally, with a mean combined PCDD/F and PCB WHO-TEQ of 9.66 pg g⁻¹ fat, for an overall pooled sample of milk from 2010. An apparent slight increase in PCDFs was observed between 2002 and 2010 (from 2.73 pg WHO-TEQ g⁻¹ fat to 3.21 pg WHO-TEQ g⁻¹ fat), with the main contributory congener being 2,3,4,7,8-PentaCDF. While it cannot be totally discounted that the slight increase in 2,3,4,7,8-PentaCDF and in the overall PCDF WHO-TEQ in breast milk could be attributable to consumption of Irish pork during the 2008 incident, we consider that it is more likely that this was due to other factors, including the predominantly urban/industrial sampling locations for the 2010 samples, compared to 2002.     

Migrating an incident reporting system to a CCPS process safety metrics model

A major chemical company established a formal incident investigation and reporting system several years ago. The original system focused heavily on worker-related injuries, illnesses, and near-misses and was used primarily to track statistics reportable to the Occupational Safety and Health Administration (OSHA). This Occupational Injury and Illness (OII) approach has been recognized to be an ineffective tool for measuring, predicting, and preventing process safety incidents. The Center for Chemical Process Safety (CCPS) recently published guidelines on how to establish safety metrics for the measurement and reduction of process safety incidents. The process safety metrics approach relies upon leading and lagging metrics to improve organization process safety. This paper is a case study of the analysis of one organization’s incident database, which represents approximately five years of data from over a dozen facilities. The aim of this investigation was to extract useful process safety metrics from the incident investigation and reporting system, which would be pertinent to the types of process units and process functions at these facilities. This paper will discuss the approach taken to extract process incident information from an OII-based database and present the difficulties of performing an analysis on such a database. This paper provides guidance on how to migrate an existing OII-based reporting system to a program that includes process safety metrics in accordance with industry best practices.     

Simulation of a 100-MW solar-powered thermo-chemical air separation system combined with an oxy-fuel power plant for bio-energy with carbon capture and storage (BECCS)

The combination of concentrated solar power–chemical looping air separation (CSP-CLAS) with an oxy-fuel combustion process for carbon dioxide (CO₂) capture is a novel system to generate electricity from solar power and biomass while being able to store solar power efficiently. In this study, the computer program Advanced System for Process Engineering Plus (ASPEN Plus) was used to develop models to assess the process performance of such a process with manganese (Mn)-based oxygen carriers on alumina (Al₂O₃) support for a location in the region of Seville in Spain, using real solar beam irradiance and electricity demand data. It was shown that the utilisation of olive tree prunings (Olea europaea) as the fuel—an agricultural residue produced locally—results in negative CO₂ emissions (a net removal of CO₂ from the atmosphere). Furthermore, it was found that the process with an annual average electricity output of 18 MW would utilise 2.43% of Andalusia’s olive tree prunings, thereby capturing 260.5 k-tonnes of CO₂, annually. Drawbacks of the system are its relatively high complexity, a significant energy penalty in the CLAS process associated with the steam requirements for the loop-seal fluidisation, and the gas storage requirements. Nevertheless, the utilisation of agricultural residues is highly promising, and given the large quantities produced globally (~?4 billion tonnes/year), it is suggested that other novel processes tailored to these fuels should be investigated, under consideration of a future price on CO₂ emissions, integration potential with a likely electricity grid system, and based on the local conditions and real data.

     

Safe speed limits for a safe system: The relationship between speed limit and fatal crash rate for different crash types

Objective: The objective of this article is to provide empirical evidence for safe speed limits that will meet the objectives of the Safe System by examining the relationship between speed limit and injury severity for different crash types, using police-reported crash data.

Method: Police-reported crashes from 2 Australian jurisdictions were used to calculate a fatal crash rate by speed limit and crash type. Example safe speed limits were defined using threshold risk levels.

Results: A positive exponential relationship between speed limit and fatality rate was found. For an example fatality rate threshold of 1 in 100 crashes it was found that safe speed limits are 40 km/h for pedestrian crashes; 50 km/h for head-on crashes; 60 km/h for hit fixed object crashes; 80 km/h for right angle, right turn, and left road/rollover crashes; and 110 km/h or more for rear-end crashes.

Conclusions: The positive exponential relationship between speed limit and fatal crash rate is consistent with prior research into speed and crash risk. The results indicate that speed zones of 100 km/h or more only meet the objectives of the Safe System, with regard to fatal crashes, where all crash types except rear-end crashes are exceedingly rare, such as on a high standard restricted access highway with a safe roadside design.     

Hydrocarbon emission fingerprints from contemporary vehicle/engine technologies with conventional and new fuels

The present paper presents results from the analysis of 29 individual C₂–C₉ hydrocarbons (HCs) specified in the European Commission Ozone Directive. The 29 HCs are measured in exhaust from common, contemporary vehicle/engine/fuel technologies for which very little or no data is available in the literature. The obtained HC emission fingerprints are compared with fingerprints deriving from technologies that are being phased out in Europe. Based on the total of 138 emission tests, thirteen type-specific fingerprints are extracted (Mean ± SD percentage contributions from individual HCs to the total mass of the 29 HCs), essential for receptor modelling source apportionment. The different types represent exhaust from Euro3 and Euro4 light-duty (LD) diesel and petrol-vehicles, Euro3 heavy-duty (HD) diesel exhaust, and exhaust from 2-stroke preEuro, Euro1 and Euro2 mopeds. The fuels comprise liquefied petroleum gas, petrol/ethanol blends (0–85% ethanol), and mineral diesel in various blends (0–100%) with fatty acid methyl esters, rapeseed methyl esters palm oil methyl esters, soybean oil methyl or sunflower oil methyl esters. Type-specific tracer compounds (markers) are identified for the various vehicle/engine/fuel technologies.An important finding is an insignificant effect on the HC fingerprints of varying the test driving cycle, indicating that combining HC fingerprints from different emission studies for receptor modelling purposes would be a robust approach.The obtained results are discussed in the context of atmospheric ozone formation and health implications from emissions (mg km^?1 for LD and mopeds and mg kW h^?1 for HD, all normalised to fuel consumption: mg dm^?3 fuel) of the harmful HCs, benzene and 1,3-butadiene.Another important finding is a strong linear correlation of the regulated “total” hydrocarbon emissions (tot-HC) with the ozone formation potential of the 29 HCs (ΣPO₃ = (1.66 ± 0.04) × tot-RH; r² = 0.93). Tot-HC is routinely monitored in emission control laboratories, whereas C₂–C₉ are not. The revealed strong correlations broadens the usability of data from vehicle emission control laboratories and facilitates the comparison of the ozone formation potential of HCs in exhaust from of old and new vehicle/engine/fuel technologies.     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.