Participant-based monitoring of indoor and outdoor nitrogen dioxide,volatile organic compounds,and polycyclic aromatic hydrocarbons among MICA-Air households

The Mechanistic Indicators of Childhood Asthma (MICA) study in Detroit, Michigan introduced a participant-based approach to reduce the resource burden associated with collection of indoor and outdoor residential air sampling data. A subset of participants designated as MICA-Air conducted indoor and outdoor residential sampling of nitrogen dioxide (NO₂), volatile organic compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs). This participant-based methodology was subsequently adapted for use in the Vanguard phase of the U.S. National Children’s Study. The current paper examines residential indoor and outdoor concentrations of these pollutant species among health study participants in Detroit, Michigan.Pollutants measured under MICA-Air agreed well with other studies and continuous monitoring data collected in Detroit. For example, NO₂ and BTEX concentrations reported for other Detroit area monitoring were generally within 10–15% of indoor and outdoor concentrations measured in MICA-Air households. Outdoor NO₂ concentrations were typically higher than indoor NO₂ concentration among MICA-Air homes, with a median indoor/outdoor (I/O) ratio of 0.6 in homes that were not impacted by environmental tobacco smoke (ETS) during air sampling. Indoor concentrations generally exceeded outdoor concentrations for VOC and PAH species measured among non-ETS homes in the study. I/O ratios for BTEX species (benzene, toluene, ethylbenzene, and m/p- and o-xylene) ranged from 1.2 for benzene to 3.1 for toluene. Outdoor NO₂ concentrations were approximately 4.5 ppb higher on weekdays versus weekends. As expected, I/O ratios pollutants were generally higher for homes impacted by ETS.These findings suggest that participant-based air sampling can provide a cost-effective alternative to technician-based approaches for assessing indoor and outdoor residential air pollution in community health studies. We also introduced a technique for estimating daily concentrations at each home by weighting 2- and 7-day integrated concentrations using continuous measurements from regulatory monitoring sites. This approach may be applied to estimate short-term daily or hourly pollutant concentrations in future health studies.     

Preparation and X-ray structural characterization of further stereoisomers of 1,2,5,6,9,10-hexabromocyclododecane

Technical 1,2,5,6,9,10-hexabromocyclododecane (HBCD) consists largely of three diastereomers (α-, β-, and γ-HBCD) produced by the trans addition of bromine to cis,trans,trans-cyclododeca-1,5,9-triene (CDT). However, another seven diastereomers are theoretically possible and may be produced by trans addition of bromine across the double bonds of the other three isomers of 1,5,9-CDT. There are indications that small amounts of the minor HBCD isomers may be present in commercial HBCD mixtures or in products containing this brominated flame retardant (BFR). Such minor components may indeed derive from traces of other 1,5,9-CDTs in the cis, trans, trans starting material, however their formation may also be possible through isomerizations during the processing of this BFR or by bioisomerization subsequent to its release into the environment. Two of the seven additional diastereomers (δ- and ε-HBCD) were synthesized previously from trans,trans,trans-CDT. We now report the preparation of the remaining five diastereomers, ζ-, η-, and θ-HBCD from cis,cis,trans-CDT and ι- and κ-HBCD from cis,cis,cis-CDT, and their characterization by ¹H NMR spectroscopy and X-ray crystallography. The availability of these further diastereomers of HBCD should aid in determining if the minor isomers are present in commercial samples of this BFR, in products containing HBCDs, or in environmental samples. We have also carried out an X-ray crystal structure determination on ε-HBCD, so that crystal structures are now available for all 10 HBCD diastereomers.     

Transcriptional profiles induced by the Aryl Hydrocarbon Receptor agonists 2,3,7,8-tetrachlorodibenzo-p-dioxin, 2,3,7,8-tetrachlorodibenzofuran and 2,3,4,7,8-pentachlorodibenzofuran in primary rat hepatocytes

Toxicogenomics was used to examine mRNA expression profiles obtained from primary rat hepatocytes treated for 24 h with 0.01 or 1.0 nM 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), 0.02 or 2.0 nM 2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PeCDF) and 0.1 or 10 nM 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF). The concentrations of 2,3,4,7,8-PeCDF and 2,3,7,8-TCDF were chosen to be equivalent to 2,3,7,8-TCDD’s concentration based on the toxic equivalency factor/toxic equivalent (TEF/TEQ) method for estimating biological potency. 2,3,7,8-TCDD at 1.0 nM altered the expression of 533 genes; 2,3,4,7,8-PeCDF at 2.0 nM altered 182 genes, and 2,3,7,8-TCDF at 10 nM altered 154 genes. Of these, 57 genes were affected by all three congeners. Agglomerative hierarchical clustering revealed distinct congener-dependent gene subclusters. Principal components analyses of the microarray data revealed that these congeners cluster independently of one another. Data presented here demonstrate that equivalent TEQ concentrations of 2,3,7,8-TCDD, 2,3,4,7,8-PeCDF and 2,3,7,8-TCDF, while altering the expression of a small battery of genes in common, also produce substantial congener specific alterations in gene expression.     

Concentrations and loadings of polybrominated diphenyl ethers in dust from low-income households in California

California residents may experience the highest polybrominated diphenyl ether (PBDE) flame retardant exposures in the United States, the nation with the highest body burdens worldwide. It is hypothesized that Californians' high exposures are due to the state's strict furniture flammability standards. Ingestion of PBDE-contaminated dust, to which children may be particularly susceptible, is a dominant exposure pathway. Low-income populations may also face disparately high exposures due to the presence of older, deteriorated or poorly manufactured furniture treated with PBDEs. We collected up to two dust samples per home (54 samples total), several days apart, from low-income California households in the urban community of Oakland (n=13 homes) and the agricultural community of Salinas (n=15 homes). We measured BDE-47, BDE-99 and BDE-100, the major constituents of the penta-PBDE flame retardant formulation commonly used in furniture. All three PBDE congeners were detected in every sample with concentrations (loadings) ranging from 185 to 126,000ng/g (621-264,000ng/m(2)), 367-220,000ng/g (1550-457,000ng/m(2)), and 84-41,100ng/g (257-85,700ng/m(2)) for BDE-47, BDE-99 and BDE-100, respectively. Median concentrations (loadings) observed in Salinas homes for BDE-47, BDE-99 and BDE-100 were 3100ng/g (10,800ng/m(2)), 5480ng/g (19,500ng/m(2)), and 1060ng/g (3810ng/m(2)), respectively, and in Oakland homes 2780ng/g (10,700ng/m(2)), 4450ng/g (19,100ng/m(2)), and 1050ng/g (4000ng/m(2)), respectively. Maximum concentrations for BDE-47 and BDE-99 are the highest reported to date. Indoor concentrations and loadings did not significantly differ between communities; concentrations and loadings were strongly correlated between collections for all three congeners (Spearman rho=0.79-0.97, p<0.002). We estimated non-dietary ingestion of each congener for one child in each home (n=28 children) and found that estimated intake for BDE-47 and BDE-99 exceeded the U.S. Environmental Protection Agency's recommended chronic reference dose for three and five children, respectively. Children's estimated intake via dust ranged from 1.0 to 599ng/kg/day, 2.0-1065ng/kg/day and 0.5-196ng/kg/day for BDE-47, BDE-99 and BDE-100, respectively. In order to mitigate these exposures, future research must address the factors that contribute to PBDE exposures in low-income homes.     

Air flow and concentration fields at urban road intersections for improved understanding of personal exposure

This paper reviews the state of knowledge on modelling air flow and concentration fields at road intersections. The first part covers the available literature from the past two decades on experimental (both field and wind tunnel) and modelling activities in order to provide insight into the physical basis of flow behaviour at a typical cross-street intersection. This is followed by a review of associated investigations of the impact of traffic-generated localised turbulence on the concentration fields due to emissions from vehicles. There is a discussion on the role of adequate characterisation of vehicle-induced turbulence in making predictions using hybrid models, combining the merits of conventional approaches with information obtained from more detailed modelling. This concludes that, despite advancements in computational techniques, there are crucial knowledge gaps affecting the parameterisations used in current models for individual exposure. This is specifically relevant to the growing impetus on walking and cycling activities on urban roads in the context of current drives for sustainable transport and healthy living. Due to inherently longer travel times involved during such trips, compared to automotive transport, pedestrians and cyclists are subjected to higher levels of exposure to emissions. Current modelling tools seem to under-predict this exposure because of limitations in their design and in the empirical parameters employed.     

Outdoor and indoor cadmium distributions near an abandoned smelting works and their relations to human exposure

The relationship of measured or modelled Cd concentrations in soil, house dust and available to plants with human urinary Cd concentrations were assessed in a population living around a Cd/Pb/Zn smelter in the UK. Modelled air concentrations explained 35% of soil Cd variation indicating the smelter contributed to soil Cd loads. Multi-variate analysis confirmed a significant role of biological and life-style factors in determining urinary Cd levels. Significant correlations of urinary Cd with soil, house dust and modelled plant available Cd concentrations were not, however, found. Potential reasons for the absence of clear relationships include limited environmental contact in urban populations; the role of undefined factors in determining exposure; and the limited spatial scope of the survey which did not sample from the full pollution gradient. Further, the absence of any significant relationship indicates that environmental measures provide limited advantage over atmospheric model outputs for first stage human exposure assessment.     

Temporal variability in dynamic and colloidal metal fractions determined by high resolution in situ measurements in a UK estuary

In recent environmental legislation, such as the Water Framework Directive in the European Union (WFD, 2000/60/EC), the importance of metal speciation and biological availability is acknowledged, although analytical challenges remain. In this study, the Voltammetric In situ Profiler (VIP) was used for high temporal resolution in situ metal speciation measurements in estuarine waters. This instrument simultaneously determines Cd, Cu and Pb species within a size range (ca. <4 nm) that is highly relevant for uptake by organisms. The colloidal metal fraction can be quantified through a combination of VIP measurements and analyses of total dissolved metal concentrations.VIP systems were deployed over tidal cycles in a seasonal study of metal speciation in the Fal Estuary, southwest England. Total dissolved concentrations were 4.97-315 nM Cu, 0.13-8.53 nM Cd and 0.35-5.75 nM Pb. High proportions of Pb (77 ± 17%) and Cu (60 ± 25%) were present as colloids, which constituted a less important fraction for Cd (37 ± 30%). The study elucidated variations in the potentially toxic metal fraction related to river flow, complexation by organic ligands and exchanges between dissolved and colloidal phases and the sediment. Based on published toxicity data, the bioavailable Cu concentrations (1.7-190 nM) in this estuary are likely to severely compromise the ecosystem structure and functioning with respect to species diversity and recruitment of juveniles. The study illustrates the importance of in situ speciation studies at high resolution in pursuit of a better understanding of metal (bio)geochemistry in dynamic coastal systems.     

Characterization of spatial impact of particles emitted from a cement material production facility on outdoor particle deposition in the surrounding community

The objective of this study was to estimate the contribution of a facility that processes steel production slag into raw material for cement production to local outdoor particle deposition in Camden, NJ. A dry deposition sampler that can house four 37-mm quartz fiber filters was developed and used for the collection of atmospheric particle deposits. Two rounds of particle collection (3-4 weeks each) were conducted in 8-11 locations 200-800 m downwind of the facility. Background samples were concurrently collected in a remote area located -2 km upwind from the facility. In addition, duplicate surface wipe samples were collected side-by-side from each of the 13 locations within the same sampling area during the first deposition sampling period. One composite source material sample was also collected from a pile stored in the facility. Both the bulk of the source material and the < 38 microm fraction subsample were analyzed to obtain the elemental source profile. The particle deposition flux in the study area was higher (24-83 mg/m2 x day) than at the background sites (13-17 mg/m2day). The concentration of Ca, a major element in the cement source production material, was found to exponentially decrease with increasing downwind distance from the facility (P < 0.05). The ratio of Ca/Al, an indicator of Ca enrichment due to anthropogenic sources in a given sample, showed a similar trend. These observations suggest a significant contribution of the facility to the local particle deposition. The contribution of the facility to outdoor deposited particle mass was further estimated by three independent models using the measurements obtained from this study. The estimated contributions to particle deposition in the study area were 1.8-7.4% from the regression analysis of the Ca concentration in particle deposition samples against the distance from the facility, 0-11% from the U.S. Environmental Protection Agency (EPA) Chemical Mass Balance (CMB) source-receptor model, and 7.6-13% from the EPA Industrial Source Complex Short Term (ISCST3) dispersion model using the particle-size-adjusted permit-based emissions estimates.     

Ecological effects after an alum treatment in Spring Lake, Michigan

A whole-lake alum treatment was applied to eutrophic Spring Lake during October and November 2005. Eight months later, an ecological assessment of the lake was performed and compared with data collected in 2003 and 2004. Field measurements showed reduced soluble reactive phosphorus (SRP) and total phosphorus (TP) concentrations in the water column the summer after the alum application, but chlorophyll levels and irradiance profiles were not significantly affected. Total macroinvertebrate density declined significantly in 2006 compared with 2004, with chaoborids and oligochaetes experiencing the greatest reductions. Internal phosphorus release rates, measured using sediment cores incubated in the laboratory, ranged from -0.052 to 0.877 mg TP m(-2) d(-1) under anaerobic conditions. These internal loading rates were significantly lower than those measured in 2003 at three out of four sites. Mean porewater SRP concentrations were lower in 2006 than in 2003, but this difference was statistically significant only under aerobic conditions. The NaOH-extractable SRP fraction in the sediment was also significantly lower in 2006 compared with 2003, whereas the HCl-extractable SRP sediment fraction showed the opposite pattern. Overall, these results indicate that the alum treatment effectively reduced internal P loading in Spring Lake. However, water column phosphorus concentrations remain high in this system, presumably due to high external loading levels, and may account for the high chlorophyll levels. An integrated watershed management approach that includes reducing internal and external inputs of P is necessary to address the cultural eutrophication of Spring Lake.     

Enhancement of reproductive success through mate choice in a social rock-wallaby, Petrogale assimilis (Macropodidae) as revealed by microsatellite markers

The reason why a female who is socially paired to one particular male seeks extra-pair copulations (EPCs) with others has important implications in life history models and to the study of behaviour. The Allied rock-wallaby, Petrogale assimilis, lives in spatially isolated colonies in tropical north Queensland, Australia. Extensive observations of a colony at Black Rock showed that intense behavioural bonding occurs between pairs of adult males and females; about two-thirds of males paired with one female, the remainder paired with two females simultaneously. Single-locus microsatellite profiling determined the paternity of 63 offspring from 21 females for which long-term behavioural data were available. One-third of the young were fathered by males which were not paired socially with the mother. The mating system was heterogeneous: (1) all offspring of 11 females were fathered by the mother's partner, (2) all young of 5 females were fathered by extra-pair males, and (3) only some of the young of 5 females were fathered by their regular consort. Analysis of individual longitudinal demographic records showed that females whose young were always fathered by their consort had higher reproductive success than those whose young were always fathered as a result of (EPCs). However, females with some offspring fathered by their regular consort and others via EPCs had the highest probability of raising young to independence. These females were significantly more likely to have an offspring fathered as a result of an EPC if their previous young had failed to survive to pouch emergence. These results are consistent with the hypothesis that females choose mates for their genetic quality. Comparison of the males with which these females sought EPCs and the regular consorts suggested that arm length rather than body weight or testes size was used as the index of genetic quality. Results from a second colony of rock-wallabies in which the reproductive rate was accelerated were also consistent with the genetic-quality hypothesis. These results imply that by choosing better-quality fathers irrespective of social pairing, females are able to maximise their overall lifetime reproductive success, and presumably, those of their offspring. Received: 8 June 1997 / Accepted after revision: 28 February 1998