Profiling the spatial concentration of allethrin and piperonyl butoxide using passive sorptive sampling and thermal desorption capillary GC-MS

Spatial concentration distribution of a chemical in an indoor environment is an important factor in the evaluation of chemical nuisances. However, straightforward techniques for the determination of this distribution are not very common and usually limited in their application. Sorptive sampling using polydimethylsiloxane-coated stir bars and the combination of active and diffusive sampling were shown to allow uncomplicated spatial concentration profiling of multiple compounds in an indoor environment. The validity of the approach was demonstrated in the analysis of the spatial concentration distribution of a pyrethroid insecticide in a common bedroom. The relative concentrations of allethrin and piperonyl butoxide were profiled throughout the room upon the application of an insecticide vaporizer.     

Real-time measurements of jet aircraft engine exhaust

Particulate-phase exhaust properties from two different types of ground-based jet aircraft engines--high-thrust and turboshaft--were studied with real-time instruments on a portable pallet and additional time-integrated sampling devices. The real-time instruments successfully characterized rapidly changing particulate mass, light absorption, and polycyclic aromatic hydrocarbon (PAH) content. The integrated measurements included particulate-size distributions, PAH, and carbon concentrations for an entire test run (i.e., "run-integrated" measurements). In all cases, the particle-size distributions showed single modes peaking at 20-40nm diameter. Measurements of exhaust from high-thrust F404 engines showed relatively low-light absorption compared with exhaust from a turboshaft engine. Particulate-phase PAH measurements generally varied in phase with both net particulate mass and with light-absorbing particulate concentrations. Unexplained response behavior sometimes occurred with the real-time PAH analyzer, although on average the real-time and integrated PAH methods agreed within the same order of magnitude found in earlier investigations.     

The effect of mass transport on biostimulation of algal growth

A model is proposed to account for mass transport limitation to the uptake of major nutrients. A thin film diffusion resistance layer is hypothesized. In an example using Cyclotella nana (a diatom), diffusion resistance was calculated to result in a maximum decrease of 40% in phosphorus uptake rate. Transport limitation was demonstrated experimentally. The growth of Chlorella pyrenoidosa (a green alga) was found to be stimulated by shaking the cultures.Using similar mathematical techniques, the internal resistance to the uptake of nutrients in algal cell aggregates was also modeled.     

Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.     

Characterization of exhaust particles from military vehicles fueled with diesel,gasoline, and JP-8

Diluted exhaust from selected military aircraft ground-support equipment (AGE) was analyzed for particulate mass, elemental carbon (EC) and organic carbon (OC), SO4(2-), and size distributions. The experiments occurred at idle and load conditions and utilized a chassis dynamometer. The selected AGE vehicles operated on gasoline, diesel, and JP-8. These military vehicles exhibited concentrations, size distributions, and emission factors in the same range as those reported for nonmilitary vehicles. The diesel and JP-8 emission rates for PM ranged from 0.092 to 1.1 g/kg fuel. The EC contributed less and the OC contributed more to the particulate mass than reported in recent studies of vehicle emissions. Overall, the particle size distribution varied significantly with engine condition, with the number of accumulation mode particles and the count median diameter (CMD) increasing as engine load increased. The SO4(2-) analyses showed that the distribution of SO4(2-) mass mirrored the distribution of particle mass.     

Evaluation of NO(x) flue gas analyzers for accuracy and their applicability for low-concentration measurements

The requirements of the Texas State Implementation Plan of the U.S. Clean Air Act for the Houston-Galveston Ozone Nonattainment Area stipulate large reductions in oxides of nitrogen (NO(x)) emissions. A large number of sources at Dow Chemical Co. sites within the nonattainment area may require the addition of continuous emission monitoring systems (CEMS) for online analysis of NO(x), CO, and O2. At the outset of this work, it was not known whether the analyzers could accurately measure NO(x) as low as 2 ppm. Therefore, NO(x) CEMS analyzers from five different companies were evaluated for their ability to reliably measure NO(x) in the 2-20 ppm range. Testing was performed with a laboratory apparatus that accurately simulated different mixtures of flue gas and, on a limited basis, simulated a dual-train sampling system on a gas turbine. The results indicate that this method is a reasonable approach for analyzer testing and reveal important technical performance aspects for accurate NO(x) measurements. Several commercial analyzers, if installed in a CEMS application with sampling conditioning components similar to those used in this study, can meet the U.S. Environmental Protection Agency's measurement data quality requirements for accuracy.