Phthalate and PAH concentrations in dust collected from Danish homes and daycare centers

As part of the Danish Indoor Environment and Children’s Health (IECH) study, dust samples were collected from 500 bedrooms and 151 daycare centers of children (ages 3 to 5) living on the island of Fyn. The present paper reports results from the analyses of these samples for five phthalate esters (diethyl phthalate (DEP), di(n-butyl) phthalate (DnBP), di(isobutyl) phthalate (DiBP), butyl benzyl phthalate (BBzP), di(2-ethylhexyl) phthalate (DEHP)) and three PAHs (pyrene, benz[a]anthracene (B[a]A) and benzo[a]pyrene (B[a]P)). The three PAHs and DEHP were detected in dust samples from all sites, while DEP, DnBP, DiBP and BBzP were detected in more than 75% of the bedrooms and more than 90% of the daycare centers. The dust mass-fractions of both phthalates and PAHs were log-normally distributed. With the exception of DEP, the mass-fractions of phthalates in dust were higher in daycare centers than homes; PAH mass-fractions in dust were similar in the two locations. There was no correlation among the different phthalates in either homes or daycare centers. In contrast, the PAH were correlated with one another – more strongly so in homes (R² = 0.80–0.90) than in daycare centers (R² = 0.28–0.45). The dust levels of several phthalates (BBzP, DnBP and DEHP) were substantially lower than those measured in a comparable study conducted 6–7 years earlier in Sweden. Although usage patterns in Denmark differ from those in Sweden, the current results may also reflect a change in the plasticizers that are used in common products including toys. PAH levels were roughly an order of magnitude lower than those measured in Berlin and Cape Cod residences, suggesting that the Danish sites are less impacted by motor vehicle emissions.     

The Effect of Building Fan Operation on Indoor-Outdoor Dust Relationships

As part of an energy conservation program recently implemented by the Bell System, fans in many telephone equipment buildings now operate only when necessary to bring the temperature within allowable limits, rather than continuously. In the study reported here the effects of fan operation on indoor-outdoor dust relationships were monitored at 2 representative telephone offices. Automatic dichotomous samplers were used to collect fine and coarse aerosol particles inside telephone equipment buildings at Wichita, KS and Lubbock, TX. At both sites, outdoor samples (roof top) were collected at the same time as the indoor samples. During the tests the building fans were repetitively cycled between 2-week intervals of continuous fan operation and 2-week intervals of intermittent fan operation. The indoor dust concentrations typically increased when the fans were off. The results indicate that this increase was due to loss of constant filtration, but not due to loss of building pressurlzation (i.e., filtration of the recirculated air is largely responsible for the lower dust levels when the fans are running continuously). An expression is derived for the relative dust increase when the building fans are switched off. Among other factors, the relative increase is directly proportional to the efficiency of the building filters and to the rate at which air is recirculated through them. The present findings can be extended to similar buildings.     

Indoor Ozone Exposures

Indoor and outdoor ozone concentrations were measured from late May through October at three office buildings with very different ventilation rates. The indoor values closely tracked the outdoor values, and, depending on the ventilation rate, were 20 to 80 percent of those outdoors. The Indoor/outdoor data are adequately described with a mass balance model. The model can also be coupled with reported air exchange rates to estimate indoor/outdoor ratios for other structures. The results from this and previous studies indicate that Indoor concentrations are frequently a significant fraction of outdoor values. These observations, and the fact that most people spend greater than 90 percent of their time indoors, indicate that indoor ozone exposure (concentration × time) is greater than outdoor exposure for many people. Relatively Inexpensive strategies exist to reduce indoor ozone levels, and these could be implemented to reduce the public’s total ozone exposure.     

Indoor/outdoor connections exemplified by processes that depend on an organic compound's saturation vapor pressure

Outdoor and indoor environments are profitably viewed as parts of a whole connected through various physical and chemical interactions. This paper examines four phenomena that share a dependence on vapor pressure—the extent to which an organic compound in the gas phase sorbs on airborne particles, sorbs on surfaces, sorbs on particles collected on a filter or activates trigeminal nerve receptors. It also defines a new equilibrium coefficient for the partitioning of organic compounds between an airstream and particles collected by a filter in that airstream. Gas/particle partitioning has been studied extensively outdoors, but sparingly indoors. Gas/surface partitioning occurs primarily indoors while gas/filter partitioning occurs at the interface between outdoors and indoors. Activation of trigeminal nerve receptors occurs at the human interface. The logarithm of an organic compound's saturation vapor pressure correlates in a linear fashion with the logarithms of equilibrium coefficients characteristic of each of these four phenomena. Since, to a rough approximation, the log of an organic compound's vapor pressure scales with its molecular weight, molecular weight can be used to make first estimates of the above processes. For typical indoor conditions, only larger compounds with lower-saturation vapor pressures (e.g., tetracosane, pentacosane, or di-2-ethylhexyl phthalate) have airborne particle concentrations comparable to or larger than gas phase concentrations. Regardless of a compound's vapor pressure, the total mass sorbed on indoor airborne particles is quite small compared to the total sorbed on indoor surfaces, reflecting the large difference in surface areas between particles within a room and surfaces within a room. If the actual surface areas are considered, accounting for roughness and porosity, the surface concentration of organics sorbed on typical airborne particles appears to be comparable to the surface concentration of organics sorbed on indoor carpets, walls and other materials (based on data from several studies in the literature). Mirroring the importance of phase distributions outdoors, an organic compound's indoor lifetime, fate and even health impacts depend on its distribution between phases and among surfaces.     

SVOC partitioning between the gas phase and settled dust indoors

Semivolatile organic compounds (SVOCs) are a major class of indoor pollutants. Understanding SVOC partitioning between the gas phase and settled dust is important for characterizing the fate of these species indoors and the pathways by which humans are exposed to them. Such knowledge also helps in crafting measurement programs for epidemiological studies designed to probe potential associations between exposure to these compounds and adverse health effects. In this paper, we analyze published data from nineteen studies that cumulatively report measurements of dustborne and airborne SVOCs in more than a thousand buildings, mostly residences, in seven countries. In aggregate, measured median data are reported in these studies for 66 different SVOCs whose octanol-air partition coefficients (K_oa) span more than five orders of magnitude. We use these data to test a simple equilibrium model for estimating the partitioning of an SVOC between the gas phase and settled dust indoors. The results demonstrate, in central tendency, that a compound’s octanol-air partition coefficient is a strong predictor of its abundance in settled dust relative to its gas phase concentration. Using median measured results for each SVOC in each study, dustborne mass fractions predicted using K_oa and gas-phase concentrations correlate reasonably well with measured dustborne mass fractions (R² = 0.76). Combined with theoretical understanding of SVOC partitioning kinetics, the empirical evidence also suggests that for SVOCs with high K_oa values, the mass fraction in settled dust may not have sufficient time to equilibrate with the gas phase concentration.     

Experiments probing the influence of air exchange rates on secondary organic aerosols derived from indoor chemistry

Reactions between ozone and terpenes have been shown to increase the concentrations of submicron particles in indoor settings. The present study was designed to examine the influence of air exchange rates on the concentrations of these secondary organic aerosols as well as on the evolution of their particle size distributions. The experiments were performed in a manipulated office setting containing a constant source of d-limonene and an ozone generator that was remotely turned “on” or “off” at 6 h intervals. The particle number concentrations were monitored using an optical particle counter with eight-channels ranging from 0.1–0.2 to>2.0 μm diameter. The air exchange rates during the experiments were either high (working hours) or low (non-working hours) and ranged from 1.6 to>12 h⁻¹, with intermediate exchange rates. Given the emission rates of ozone and d-limonene used in these studies, at an air exchange rate of 1.6 h⁻¹ particle number concentration in the 0.1–0.2 μm size-range peaked 1.2 h after the ozone generator was switched on. In the ensuing 4.8 h particle counts increased in successive size-ranges up to the 0.5–0.7 μm diameter range. At higher air exchange rates, the resulting concentrations of total particles and particle mass (calculated from particle counts) were smaller, and at exchange rates exceeding 12 h⁻¹, no excess particle formation was detectable with the instrument used in this study. Particle size evolved through accretion and, in some cases, coagulation. There was evidence for coagulation among particles in the smallest size-range at low air exchange rates (high particle concentrations) but no evidence of coagulation was apparent at higher air exchange rates (lower particle concentrations). At higher air exchange rates the particle count or size distributions were shifted towards smaller particle diameters and less time was required to achieve the maximum concentration in each of the size-ranges where discernable particle growth occurred. These results illustrate still another way in which ventilation affects human exposures in indoor settings. However, the ultimate effects of these exposures on health and well being remain to be determined.     

Changes in indoor pollutants since the 1950s

Over the past half-century there have been major changes in building materials and consumer products used indoors. Composite-wood, synthetic carpets, polymeric flooring, foam cushioning, plastic items and scented cleaning agents have become ubiquitous. The same is true for mechanical and electrical appliances such as washer/dryers, TVs and computers. These materials and products emit an array of chemicals including solvents, unreacted monomers, and additives. The consequent changes in emission profiles for indoor pollutants have been accompanied by modifications in building operations. Residences and non-residences are less ventilated than they were decades ago. Air-conditioned buildings are more numerous, especially in certain parts of the world. Most of these recirculate a high fraction of their air. The personal habits of building occupants, including the fraction who smoke indoors, have also changed. Taken together, these changes have altered the kind and concentrations of chemicals that occupants are exposed to in their homes, workplaces and schools. Since the 1950s, levels of certain indoor pollutants (e.g., formaldehyde, aromatic and chlorinated solvents, chlorinated pesticides, PCBs) have increased and then decreased. Levels of other indoor pollutants have increased and remain high (e.g., phthalate esters, brominated flame-retardants, nonionic surfactants and their degradation products). Many of the chemicals presently found in indoor environments, as well as in the blood and urine of occupants, were not present 50 years ago. Given the public's exposure to such species, there would be exceptional value in monitoring networks that provided cross-sectional and longitudinal information regarding pollutants found in representative buildings.     

Impact of climate change and seasonal trends on the fate of Arctic oil spills

We investigated the effects of a warmer climate, and seasonal trends, on the fate of oil spilled in the Arctic. Three well blowout scenarios, two shipping accidents and a pipeline rupture were considered. We used ensembles of numerical simulations, using the OSCAR oil spill model, with environmental data for the periods 2009–2012 and 2050–2053 (representing a warmer future) as inputs to the model. Future atmospheric forcing was based on the IPCC’s A1B scenario, with the ocean data generated by the hydrodynamic model SINMOD. We found differences in “typical” outcome of a spill in a warmer future compared to the present, mainly due to a longer season of open water. We have demonstrated that ice cover is extremely important for predicting the fate of an Arctic oil spill, and find that oil spills in a warming climate will in some cases result in greater areal coverage and shoreline exposure.     

Indoor Fine Particles: The Role of Terpene Emissions from Consumer Products

Abstract

Consumer products can emit significant quantities of terpenes, which can react with ozone (O₃). Resulting byproducts include compounds with low vapor pressures that contribute to the growth of secondary organic aerosols (SOAs). The focus of this study was to evaluate the potential for SOA growth, in the presence of O₃, following the use of a lime-scented liquid air freshener, a pine-scented solid air freshener, a lemon-scented general-purpose cleaner, a wood floor cleaner, and a perfume. Two chamber experiments were performed for each of these five terpene-containing agents, one at an elevated O₃ concentration and the other at a lower O₃ concentration. Particle number and mass concentrations increased and O₃ concentrations decreased during each experiment. Experiments with terpene-based air fresheners produced the highest increases in particle number and mass concentrations. The results of this study clearly demonstrate that homogeneous reactions between O₃ and terpenes from various consumer products can lead to increases in fine particle mass concentrations when these products are used indoors. Particle increases can occur during periods of elevated outdoor O₃ concentrations or indoor O₃ generation, coupled with elevated terpene releases. Human exposure to fine particles can be reduced by minimizing indoor terpene concentrations or O₃ concentrations.