Laboratory and field investigations of particulate and carbon monoxide emissions from traditional and improved cookstoves

We implemented a program in which emission characterization is enabled through collaborations between academic, US and international non-governmental entities that focus on evaluation, dissemination, and in-use testing, of improved cookstoves. This effort resulted in a study of field and laboratory emissions from traditional and improved biofuel cookstoves. We found that field measured particulate emissions of actual cooking average three times those measured during simulated cooking in the laboratory. Emission factors are highly dependent on the care and skill of the operator and the resulting combustion; these do not appear to be accurately reproduced in laboratory settings. The single scattering albedo (SSA) of the emissions was very low in both lab and field measurements, averaging about 0.3 for lab tests and around 0.5 for field tests, indicating that the primary particles are climate warming. Over the course of three summers in Honduras, we measured field emissions from traditional cookstoves, relatively new improved cookstoves, and “broken-in” improved cookstoves. We found that well-designed improved cookstoves can significantly reduce PM and CO emission factors below traditional cookstoves. For improved stoves, the presence of a chimney generally resulted in lower emission factors but left the SSA unaffected. Traditional cookstoves had an average PM emission factor of 8.2 g kg^?1 – significantly larger than previous studies. Particulate emission factors for improved cookstoves without and with chimneys averaged about 6.6 g kg^?1 and 4.5 g kg^?1, respectively. The elemental carbon (EC) fraction of PM varied significantly between individual tests, but averaged about 25% for each of the categories.     

Ethnicity,housing and personal factors as determinants of VOC exposures

Previous studies investigating effects of personal, demographic, housing and other factors on exposures to volatile organic compounds (VOC) have focused on mean or median exposures, and generally not the high exposures that are of great interest. This paper identifies determinants of personal VOC exposures on a quantile-specific basis using a nationally representative sample. The NHANES 1999–2000 VOC dataset was merged with personal, demographic, housing, smoking and occupation variables. Bivariate analyses tested for differences in geometric means and quantiles across levels of potential exposure determinants. Multivariate sample-weighted ordinary least-squares (OLS) and quantile regression (QR) models were then used to adjust for covariates. We identify a number of exposure determinants, most of which varied by exposure quantile. The most striking finding was the much higher exposures experienced by Hispanics and Blacks for aromatic VOCs (BTEX: benzene, toluene, ethylbenzene and xylenes), methyl tert-butyl ether (MTBE), and 1,4-dichlorobenzene (DCB). Exposure to gasoline, paints or glues, and having a machine-related occupation also were associated with extremely high BTEX and MTBE exposures. Additional determinants included the presence of attached garages and open windows, which affected exposures of BTEX (especially at lower quantiles) and MTBE (especially at higher quantiles). Smoking also increased BTEX exposures. DCB was associated with air freshener use, and PERC with dry-cleaned clothing. After adjusting for demographic, personal and housing factors, age and gender were not significant predictors of exposure. The use of QR in conjunction with OLS yields a more complete picture of exposure determinants, and identifies subpopulations and heterogeneous exposure groups in which some individuals experience very elevated exposures and which are not well represented by changes in the mean. The high exposures of Hispanics and Blacks are perplexing and disturbing, and they warrant further investigation.     

A dynamic hydrological Monte Carlo simulation model to inform decision-making at Lake Toolibin,Western Australia

Lake Toolibin, an ephemeral lake in the agricultural zone of Western Australia, is under threat from secondary salinity due to land clearance throughout the catchment. The lake is extensively covered with native vegetation and is a Ramsar listed wetland, being one of the few remaining significant migratory bird habitats in the region. Currently, inflow with salinity greater than 1000 mg/L TDS is diverted from the lake in an effort to protect sensitive lakebed vegetation. However, this conservative threshold compromises the frequency and extent of lake inundation, which is essential for bird breeding. It is speculated that relaxing the threshold to 5000 mg/L may pose negligible additional risk to the condition of lakebed vegetation. To characterise the magnitude of improvement in the provision of bird breeding habitat that might be generated by relaxing the threshold, a dynamic water and salt balance model of the lake was developed and implemented using Monte Carlo simulation. Results from best estimate model inputs indicate that relaxation of the threshold increases the likelihood of satisfying habitat requirements by a factor of 9.7. A second-order Monte Carlo analysis incorporating incertitude generated plausible bounds of [2.6, 37.5] around the best estimate for the relative likelihood of satisfying habitat requirements. Parameter-specific sensitivity analyses suggest the availability of habitat is most sensitive to pan evaporation, lower than expected inflow volume, and higher than expected inflow salt concentration. The characterisation of uncertainty associated with environmental variation and incertitude allows managers to make informed risk-weighted decisions.     

Calibration of two passive air sampler configurations for monitoring concentrations of hexabromocyclododecanes in indoor air

While polyurethane foam (PUF) disk passive air samplers are employed increasingly to monitor persistent organic pollutants in indoor air, they essentially sample only the vapour phase. As a previous investigation of the vapour : particle phase partitioning of hexabromocyclododecanes HBCDs in (outdoor) air reported them to be present largely in the particulate phase, we monitored three offices using active air samplers. In each, approximately 65% of HBCDs were present in the vapour phase, suggesting PUF disk passive samplers are suitable for monitoring HBCDs in indoor air. Concentrations in the three offices (239-359 pg Sigma HBCD m(-3)) exceed substantially those reported in outdoor air from the United States (2.1-11 pg Sigma HBCD m(-3)), but are in line with outdoor air from Stockholm. The relative abundance of the three principal diastereomers in office air was closer to that found in technical HBCD formulations (i.e. predominantly gamma-HBCD) than in most US outdoor air samples. Time integrated air concentrations of alpha-, beta-, and gamma-HBCD were obtained for an office using a low volume sampler operated over a 50 d period alongside PUF disk samplers. This calibration exercise yielded the following passive air sampling rates for both a fully- and part-sheltered PUF disk sampler design: for alpha-, beta-, and gamma-HBCD, 0.87, 0.89, and 0.91 m3 d(-1) respectively (fully-sheltered) and 1.38, 1.54, and 1.55 m3 d(-1) respectively (part-sheltered). Deployment of the part-sheltered configuration yielded concentrations approximately 35% lower than those obtained using a high volume sampler, consistent with PUF disk samplers measuring primarily the vapour phase.     

Novel brominated flame retardants: a review of their analysis, environmental fate and behaviour

This review summarises current knowledge about production volumes, physico-chemical properties, analysis, environmental occurrence, fate and behaviour and human exposure to the "novel" brominated flame retardants (NBFRs). We define the term NBFRs as relating to BFRs which are new to the market or newly/recently observed in the environment. Restrictions and bans on the use of some polybrominated diphenyl ether (PBDE) formulations, in many jurisdictions, have created a market for the use of NBFRs. To date, most data on NBFRs have arisen as additional information generated by research designed principally to study more "traditional" BFRs, such as PBDEs. This has led to a wide variety of analytical approaches for sample extraction, extract purification and instrumental analysis of NBFRs. An overview of environmental occurrence in abiotic matrices, aquatic biota, terrestrial biota and birds is presented. Evidence concerning the metabolism and absorption of different NBFRs is reviewed. Human exposure to NBFRs via different exposure pathways is discussed, and research gaps related to analysis, environmental sources, fate, and behaviour and human exposure are identified.     

Concentrations of polybrominated diphenyl ethers in blood serum from New Zealand

Polybrominated diphenyl ethers (PBDEs) were measured in samples of human blood serum taken from 23 donors in Wellington, New Zealand. Concentrations expressed as the sum of congeners 47, 99, 100, 153, 154, and 183 (SigmaPBDE) were - at an average of 7.17 ng SigmaPBDE g (lipid)(-1) - within the range reported for human tissues in Europe, but lower than in Australia and North America. The most likely source of this contamination is considered to be the release of PBDEs from imported consumer goods. The congener pattern observed is in line with that reported for human tissues outside North America, but shows a lower contribution of PBDE 47 to SigmaPBDE than observed in North Americans. No significant (p>0.1) differences between concentrations in males and females were detected, and no relationship between donor age and SigmaPBDE concentration was observed. One donor displayed concentrations that were significantly elevated (i.e. > average +2 standard deviations) above those in others in this study.     

A review of studies performed to assess metal uptake by earthworms

Earthworms perform a number of essential functions in soil; the impacts of metals on earthworms are often investigated. In this review we consider the range of earthworm species, types of soil and forms of metal for which metal uptake and accumulation have been studied, the design of these experiments and the quantitative relationships that have been derived to predict earthworm metal body burden. We conclude that there is a need for more studies on earthworm species other than Eisenia fetida in order to apply the large existing database on this earthworm to other, soil dwelling species. To aid comparisons between studies agreement is needed on standard protocols that define exposure and depuration periods and the parameters, such as soil solution composition, soil chemical and physical properties to be measured. It is recommended that more field or terrestrial model ecosystem studies using real contaminated soil rather than metal-amended artificial soils are performed.     

Rapid determination of ETS markers with a prototype field-portable GC employing a microsensor array detector

The adaptation of a portable gas chromatograph (GC) prototype with several unique design features to the determination of vapor-phase markers of environmental tobacco smoke (ETS) is described. This instrument employs a dual-stage adsorbent preconcentrator, two series-coupled separation columns that can be independently temperature programmed, and a detector consisting of an array of nanoparticle-coated chemiresistors, whose response patterns are used together with retention times for vapor recognition. An adsorbent pre-trap was developed to remove semi-volatile organics from the sample stream. Conditions were established to quantitatively capture two ETS markers, 2,5-dimethylfuran (2,5-DMF) and 4-ethenylpyridine (4-EP, as a surrogate for 3-EP), and to separate them from the 34 most prominent co-contaminants present in ETS using ambient air as the carrier gas. A complete analysis can be performed every 15 min. Projected detection limits are 0.58 and 0.08 ppb for 2,5-DMF and 4-EP, respectively, assuming a 1 L sample volume, which are sufficiently low to determine these markers in typical smoking-permitted environments.     

Continuous, intermittent and passive sampling of airborne VOCs

Long sampling periods are often advantageous or required for measuring air quality and characterizing exposures. However, sampling periods exceeding 8 to 24 h using thermally desorbable adsorbent tube (TDT) samplers for the measurement of airborne volatile organic compounds (VOCs) face several challenges, including maintaining stable and low flow rates, and avoiding breakthrough of the adsorbent. These problems may be avoided using intermittent sampling; however, the literature contains few if any reports that have evaluated this technique in environmental, occupational or other applications. The purpose of this study is to evaluate continuous, intermittent and passive sampling methods using both laboratory and real-world tests. Laboratory tests compared continuous and intermittent (active) samplers in a controlled dynamic test gas generation system. Field tests used side-by-side active and passive samplers in an office, home workshop and four smokers' homes. All samples were analyzed for a wide range of VOCs by GC-MS. In most instances, intermittent sampling yielded better reproducibility (duplicate precision of 10 +/- 6%) than continuous low-flow sampling (18 +/- 5%), in part due to difficulty maintaining low flows. Concentrations obtained using intermittent sampling agreed with those for continuous sampling, with downward biases resulting primarily from errors in flow rate measurements. In the field, more VOC species were detected using active rather than passive sampling. Passive measurements were 12% lower than continuous measurements, a difference attributed to declining uptake rates at higher concentrations over the 3 to 4 d sampling period. Overall, most measurements obtained using the three sampling methods agreed within 20% for a wide range of concentrations (0.1 to 230 microg m(-3)). Both passive and intermittent sampling approaches are suitable for long sampling periods, but intermittent sampling provides greater flexibility with respect to sampling period, and permits the use of multi-bed adsorbents that can capture a wider range of VOCs.