Indoor organophosphate and polybrominated flame retardants in Tokyo

In Japan, organophosphate and polybrominated flame retardants are used in building materials and electric appliances to protect them from fire hazards. In this study, to identify the emission sources of these flame retardants to indoor air, the migration rates (flux) of organophosphate and polybrominated flame retardants from building materials and electrical appliances to solid extraction disks that were placed in contact with the interior surfaces were measured. In addition to the migration test, indoor air and outdoor air concentrations of these flame retardants were investigated. With regard to building materials in a newly built house, triethylphosphate (TEP) and tributylphosphate (TBP) were detected in the wall and ceiling coverings, and tris(2-butoxyethyl)phosphate (TBEP) was detected in the wooden flooring cleaned with a floor polish agent. With regard to electrical appliances, triphenylphosphate (TPHP) was predominantly detected in computer monitors and tris(2-chloroethyl) phosphate (TCEP) in television (TV) sets, with the highest median levels. Among the polybrominated compounds, only 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) was detected from a few old TV sets manufactured before 1995. In an indoor and outdoor air survey, nine organophosphates and nine polybrominated flame retardants were detected from indoor air. In outdoor air, only four organophosphate flame retardants were detected. The maximum level of indoor organophosphate compounds was 1260 ng/m(3) with tris(2-chloro-1-methylethyl) phosphate (TCPP), and that of polybrominated compounds was 29.5 ng/m(3) with hexabromocyclododecane (HBCD). Tetrabromobisphenol A (TBBPA) was not detected in this study, although it has the largest demand among flame retardants in Japan. The results of the migration test and the indoor air survey revealed that in indoor air, organophosphate compounds were more predominant than polybrominated compounds in Tokyo. PRACTICAL IMPLICATIONS: Polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE) are commonly used as flame retardants in plastics. The use of these two compounds in electric appliances will be banned in 2007 by the EU Directives on waste electrical and electronic equipment (WEEE) and on the restriction of the use of certain hazardous substances (RoHS) in electrical and electronic equipment. In Japan, the use of PBB was banned and that of PBDE diminished in the early 1990s by the self-imposed controls of the Japanese Flame Retardants Conference (Akutu and Hori, 2004). In Japan, the predominantly used organic flame retardants were tetrabromobisphenol A and organophosphate compounds. Tetrabromobisphenol A has been reported to disrupt endocrine systems (Kitamura et al., 2005), and some organophosphate flame retardants were recently reported to have neurochemical hazardous effects. Furthermore, organophosphate compounds were suspected to cause endocrine-disrupting effects (Fang et al., 2003; Ohyama et al., 2005) or attention deficit hyperactivity disorder (ADHD) (Winrow et al., 2003). In this study, organophosphate and polybrominated flame retardants were surveyed in indoor environments in Tokyo.     

Relationships between estimated flame retardant emissions and levels in indoor air and house dust

A significant number of consumer goods and building materials can act as emission sources of flame retardants (FRs) in the indoor environment. We investigate the relationship between the emission source strength and the levels of 19 brominated flame retardants (BFRs) and seven organophosphate flame retardants (OPFRs) in air and dust collected in 38 indoor microenvironments in Norway. We use modeling methods to back‐calculate emission rates from indoor air and dust measurements and identify possible indications of an emission‐to‐dust pathway. Experimentally based emission estimates provide a satisfactory indication of the relative emission strength of indoor sources. Modeling results indicate an up to two orders of magnitude enhanced emission strength for OPFRs (median emission rates of 0.083 and 0.41 μg h^?1 for air‐based and dust‐based estimates) compared to BFRs (0.52 and 0.37 ng h^?1 median emission rates). A consistent emission‐to‐dust signal, defined as higher dust‐based than air‐based emission estimates, was identified for four of the seven OPFRs, but only for one of the 19 BFRs. It is concluded, however, that uncertainty in model input parameters could potentially lead to the false identification of an emission‐to‐dust signal.     

Temporal trends of decabromodiphenyl ether and emerging brominated flame retardants in dust,air and window surfaces of newly built low‐energy preschools

The envelope of low‐energy buildings is generally constructed with significant amounts of plastics, sealants and insulation materials that are known to contain various chemical additives to improve specific functionalities. A commonly used group of additives are flame retardants to prevent the spread of fire. In this study, decabromodiphenyl ether (BDE‐209) and fourteen emerging brominated flame retardants (BFRs) were analyzed in indoor dust, air and on the window surface of newly built low‐energy preschools to study their occurrence and distribution. BDE‐209 and decabromodiphenyl ethane (DBDPE) were frequently detected in the indoor dust (BDE‐209: <4.1‐1200 ng/g, DBDPE: <2.2‐420 ng/g) and on window surfaces (BDE‐209: <1000‐20 000 pg/m², DBDPE: <34‐5900 pg/m²) while the other thirteen BFRs were found in low levels (dust: <0.0020‐5.2 ng/g, window surface: 0.0078‐35 pg/m²). In addition, the detection frequencies of BFRs in the indoor air were low in all preschools. Interestingly, the dust levels of BDE‐209 and DBDPE were found to be lower in the environmentally certified low‐energy preschools, which could be attributed to stricter requirements on the chemical content in building materials and products. However, an increase of some BFR levels in dust was observed which could imply continuous emissions or introduction of new sources.     

Determining source strength of semivolatile organic compounds using measured concentrations in indoor dust

Consumer products and building materials emit a number of semivolatile organic compounds (SVOCs) in the indoor environment. Because indoor SVOCs accumulate in dust, we explore the use of dust to determine source strength and report here on analysis of dust samples collected in 30 US homes for six phthalates, four personal care product ingredients, and five flame retardants. We then use a fugacity‐based indoor mass balance model to estimate the whole‐house emission rates of SVOCs that would account for the measured dust concentrations. Di‐2‐ethylhexyl phthalate (DEHP) and di‐iso‐nonyl phthalate (DiNP) were the most abundant compounds in these dust samples. On the other hand, the estimated emission rate of diethyl phthalate is the largest among phthalates, although its dust concentration is over two orders of magnitude smaller than DEHP and DiNP. The magnitude of the estimated emission rate that corresponds to the measured dust concentration is found to be inversely correlated with the vapor pressure of the compound, indicating that dust concentrations alone cannot be used to determine which compounds have the greatest emission rates. The combined dust‐assay modeling approach shows promise for estimating indoor emission rates for SVOCs.     

Plastics additives in the indoor environment--flame retardants and plasticizers

Phthalic acid esters and phosphororganic compounds (POC) are generally known as semivolatile organic compounds (SVOCs) and are frequently utilized as plasticizers and flame retardants in commercial products. In the indoor environment, both compound groups are released from a number of sources under normal living conditions and accumulate in air and dust. Therefore, inhalation of air and ingestion of house dust have to be considered as important pathways for the assessment of exposure in living habitats. Especially in the case of very young children, the oral and dermal uptake from house dust might be of relevance for risk assessment. A critical evaluation of indoor exposure to phthalates and POC requires the determination of the target compounds in indoor air and house dust as well as emission studies. The latter are usually carried out under controlled conditions in emission test chambers or cells. Furthermore, chamber testing enables the determination of condensable compounds by fogging sampling. In the case of automobiles, specific scenarios have been developed to study material emissions on a test stand or to evaluate the exposure of users while the vehicle is driving. In this review, results from several studies are summarized and compared for seven phthalic esters and eight POC. The available data for room air and dust differ widely depending on investigated compound and compartment. Room air studies mostly include only a limited number of measurements, which makes a statistical evaluation difficult. The situation is much better for house dust measurements. However, the composition of house dust is very inhomogeneous and the result is strongly dependent on the particle size distribution used for analysis. Results of emission studies are presented for building products, electronic equipment, and automobiles. Daily rates for inhalation and dust ingestion of phthalic esters and POC were calculated from 95-percentiles or maximum values. A comparison of the data with results from human biomonitoring studies reveals that only a small portion of intake takes place via the air and dust paths.     

The effect of reduction measures on concentrations of hazardous semivolatile organic compounds in indoor air and dust of Swedish preschools

Young children spend a substantial part of their waking time in preschools. It is therefore important to reduce the load of hazardous semivolatile organic compounds (SVOCs) in the preschools’ indoor environment. The presence and levels of five SVOC groups were evaluated (1) in a newly built preschool, (2) before and after renovation of a preschool, and (3) in a preschool where SVOC-containing articles were removed. The new building and the renovation were performed using construction materials that were approved with respect to content of restricted chemicals. SVOC substance groups were measured in indoor air and settled dust and included phthalates and alternative plasticizers, organophosphate esters (OPEs), brominated flame retardants, and bisphenols. The most abundant substance groups in both indoor air and dust were phthalates and alternative plasticizers and OPEs. SVOC concentrations were lower or of the same order of magnitude as those reported in comparable studies. The relative Cumulative Hazard Quotient (HQ_cum) was used to assess the effects of the different reduction measures on children's SVOC exposure from indoor air and dust in the preschools. HQ_cum values were low (1.0–6.1%) in all three preschools and decreased further after renovation and article substitution. The SVOCs concentrations decreased significantly more in the preschool renovated with the approved building materials than in the preschool where the SVOC-containing articles were removed.     

Chlorinated ethyl and isopropyl phosphoric acid triesters in the indoor environment--an inter-laboratory exposure study

The chlorinated organo-phosphate triesters, tris(2-chloroethyl)-phosphate (TCEP) and tris(monochloroisopropyl)-phosphate (TCPP), are employed in consumer articles for indoor usage, e.g. flame retardants and plasticizers in foam material as well as in paints, varnishes and wallpapers. As a result of this widespread usage, employing domestic dust as a matrix, both chemicals have been detected in the indoor environment. TCEP was present in 85% of a total of 983 samples, whereas TCPP was found in 60-90% of 436 cases (with levels ranging from 0.1 to 375 mg/kg). Since TCEP and TCPP residues in domestic dust are assumed to be condensates arising from primary sources, spot check analysis of various indoor materials was performed. The results show that soft foams, paints and wallpapers contained mainly TCEP, whereas in insulation and sealant foams high levels of TCPP were found. Moreover, TCEP can also be detected in indoor air in concentrations up to 6,000 ng/m3. On the basis of this data, we estimated the levels of indoor exposure via oral and inhalative ingestion.     

How to measure and evaluate volatile organic compound emissions from building products. A perspective

The primary emissions of VOCs (e.g. solvents) from building products influence the perceived indoor air quality during the initial decay period. However, secondary emissions will continue thereafter (chemical or physical degradation, e.g. oxidation, hydrolysis, mechanical wear, maintenance), in addition to sorption processes. Emission testing for primary VOC emissions is necessary, but insufficient to characterise the impact of building products in their entire life span on the perceived air quality. Methods to distinguish between the two types of emissions are required. Also, the influence of climate parameters on the emission rates is necessary to know for proper testing. Future product development and selection strategies of new building products should consider the secondary emissions, in addition to the contribution from the use of auxiliary agents for cleaning, maintenance, and other potential impacts either physical or chemical in nature. Some of the requirements for emission testing are discussed in terms of secondary vs. primary emissions in order to develop 'healthier/better' building products for the indoor environment. In addition, some of the assumptions about the possible impact of VOCs on health and comfort in the indoor environment are presented. Odour thresholds for VOCs are one or more orders of magnitude lower than the corresponding airway irritation estimates, and it also appears that chemically non-reactive VOCs are not sufficiently strong irritants to cause airway irritation at concentrations normally encountered indoors. Finally, future requirements for analytical laboratory performances is proposed to accommodate the increasing need to establish which VOCs may be responsible for the perception of odour intensity from building products.     

磷系阻燃聚乙烯热降解动力学研究

采用热重分析方法研究纯聚乙烯、阻燃聚乙烯在空气气氛中的热降解行为,并采用Kissinger法和Flynn-Wall-Ozawa(FWO)法计算其热降解动力学参数。计算结果表明,阻燃聚乙烯的活化能高于纯聚乙烯,阻燃剂的加入提高了聚乙烯的热稳定性。     

Polybrominated diphenyl ether (PBDE) concentrations and resulting exposure in homes in California: relationships among passive air,surface wipe and dust concentrations,and temporal variability

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in furniture foam, electronics, and other home furnishings. A field study was conducted that enrolled 139 households from California, which has had more stringent flame retardant requirements than other countries and areas. The study collected passive air, floor and indoor window surface wipes, and dust samples (investigator collected using an HVS3 and vacuum cleaner) in each home. PentaBDE and BDE209 were detected in the majority of the dust samples and many floor wipe samples, but the detection in air and window wipe samples was relatively low. Concentrations of each PBDE congener in different indoor environmental media were moderately correlated, with correlation coefficients ranging between 0.42 and 0.68. Correlation coefficients with blood levels were up to 0.65 and varied between environmental media and age group. Both investigator‐collected dust and floor wipes were correlated with serum levels for a wide range of congeners. These two sample types also had a relatively high fraction of samples with adequate mass for reliable quantification. In 42 homes, PBDE levels measured in the same environmental media in the same home 1 year apart were statistically correlated (correlation coefficients: 0.57–0.90), with the exception of BDE209 which was not well correlated longitudinally.     

A general mechanistic model for predicting the fate and transport of phthalates in indoor environments

A mechanistic model that considers particle dynamics and their effects on surface emissions and sorptions was developed to predict the fate and transport of phthalates in indoor environments. A controlled case study was conducted in a test house to evaluate the model. The model‐predicted evolving concentrations of benzyl butyl phthalate in indoor air and settled dust and on interior surfaces are in good agreement with measurements. Sensitivity analysis was performed to quantify the effects of parameter uncertainties on model predictions. The model was then applied to a typical residential environment to investigate the fate of di‐2‐ethylhexyl phthalate (DEHP) and the factors that affect its transport. The predicted steady‐state DEHP concentrations were 0.14 μg/m³ in indoor air and ranged from 80 to 46 000 μg/g in settled dust on various surfaces, which are generally consistent with the measurements of previous studies in homes in different countries. An increase in the mass concentration of indoor particles may significantly enhance DEHP emission and its concentrations in air and on surfaces, whereas increasing ventilation has only a limited effect in reducing DEHP in indoor air. The influence of cleaning activities on reducing DEHP concentration in indoor air and on interior surfaces was quantified, and the results showed that DEHP exposure can be reduced by frequent and effective cleaning activities and the removal of existing sources, though it may take a relatively long period of time for the levels to drop significantly. Finally, the model was adjusted to identify the relative contributions of gaseous sorption and particulate‐bound deposition to the overall uptake of semi‐volatile organic compounds (SVOCs) by indoor surfaces as functions of time and the octanol‐air partition coefficient (K_oa) of the chemical. Overall, the model clarifies the mechanisms that govern the emission of phthalates and the subsequent interactions among air, suspended particles, settled dust, and interior surfaces. This model can be easily extended to incorporate additional indoor source materials/products, sorption surfaces, particle sources, and room spaces. It can also be modified to predict the fate and transport of other SVOCs, such as phthalate‐alternative plasticizers, flame retardants, and biocides, and serves to improve our understanding of human exposure to SVOCs in indoor environments.     

The biofiltration of indoor air: implications for air quality

An alternative method of maintaining indoor air quality may be through the biofiltration of air recirculating within the structure rather than the traditional approach of ventilation. This approach is currently being investigated. Prior to its acceptance for dealing with volatile organic compounds (VOCs) and CO2, efforts were made to determine whether the incorporation of this amount of biomass into the indoor space can have an (negative) impact on indoor air quality. A relatively large ecologically complex biofilter composed of a ca. 10 m2 bioscrubber, 30 m2 of plantings and a 3,500 litre aquarium were established in a 160 m2 'airtight' room in a recently constructed office building in downtown Toronto. This space maintained ca. 0.2 air changes per hour (ACH) compared to the 15 to 20 ACH (with a 30% refresh rate) of other spaces in the same building. Air quality parameters of concern were total VOCs (TVOCs), formaldehyde and aerial spore counts. TVOC and formaldehyde levels in the biofilter room were the same or significantly less than other spaces in the building despite a much slower refresh rate. Aerial spore levels were slightly higher than other indoor spaces but were well within reported values for 'healthy' indoor spaces. Levels appeared to be dependent on horticultural management practices within the space. Most genera of fungal spores present were common indoors and the other genera were associated with living or dead plant material or soil. From these results, the incorporation of a large amount of biomass associated with indoor biofilters does not in itself lower indoor air quality.     

光催化型过滤器分解有机化合物的实验研究

以TVOC及甲醛为测试对象对光催化型过滤器分解VOCs的性能进行了实验测试。结果显示:光催化型空调过滤器能有效分解VOCs,能在较短的时间内(12h)使室内VOCs的浓度达到GB/T-18883-2002的要求;其平均反应速率及分解效率随着过滤器层数的增加而增加,并且其分解效率随面风速的增加而略有降低(当面风速从0.42m/s增加至0.8m/s时,在第3小时,分解效率下降了约5%);对于室内VOCs浓度较低的民用建筑,光催化分解过程中的反应速率与反应浓度成正比。     

Modeling the formation and growth of organic films on indoor surfaces

Emission, transport, and fate of semi‐volatile organic compounds (SVOCs), which include plasticizers, flame retardants, pesticides, biocides, and oxidation products of volatile organic compounds, are influenced in part by their tendency to sorb to indoor surfaces. A thin organic film enhances this effect, because it acts as both an SVOC sink and a source, thus potentially prolonging human exposure. Unfortunately, our ability to describe the initial formation and subsequent growth of organic films on indoor surfaces is limited. To overcome this gap, we propose a mass transfer model accounting for adsorption, condensation, and absorption of multiple gas‐phase SVOCs on impervious, vertical indoor surfaces. Further model development and experimental research are needed including more realistic scenarios accounting for surface heterogeneity, non‐ideal organic mixtures, and particle deposition.     

Determination of Exposure-Response Relationships for Emissions from Building Products

Abstract Building products have been shown to affect the perceived indoor air quality in buildings. Consequently, there is a need for characterizing the emissions from building products in sensory terms to evaluate their impact on the perceived air quality. Determining the exposure-response relationship between concentration of the emission from a building product and human response is recommended. A practical method is proposed based on an air-dilution system connected to the exhaust of a ventilated small-scale test chamber. The method was used to determine the exposure-response relationships for eight building products. For each building product, samples were placed in a test chamber. A typical room was used as a reference to calculate a building-realistic area-specific ventilation rate in the test chamber. A sensory panel assessed the immediate acceptability of polluted air at four different concentrations 3, 10 and 29 days after samples of the building products were placed in the test chambers. The exposure-response relationships show that the impact of dilution of polluted air on the perceived air quality varies between building products. For some building products it may only be possible in practice to improve the perceived air quality marginally by increasing dilution. The results of the present study suggest that for such building products, source control is recommended as the remedy for poor indoor air quality, rather than an increase of the ventilation rate.     

Mass balance modeling of building recirculation rates and filtration efficiencies effects on secondary organic aerosols derived from ozone-initiated chemistry

Recirculation of conditioned air is a common practice in regions with hot and humid climate. This is due to the need to reduce sensible and latent cooling loads in buildings. However, recirculating used indoor air may influence indoor air chemical reactions and products derived from the chemistry. Example of such products is secondary organic aerosols (SOA) derived from ozone initiated indoor chemistry. This present study was conducted using mass balance model to examine the impacts of four recirculation rates on ozone (of outdoor origin) and SOA derived from the ozone initiated indoor chemistry. At steady-states, it was observed that the higher the recirculation rate, the lower the ozone and SOA concentration for all modeled scenarios. At steady-state, outdoor to indoor transport of ozone, indoor ozone and SOA concentrations were found to increase with increasing outdoor ozone levels. Increase in ventilation rate was found to increase outdoor to indoor transport of ozone and steady-state indoor ozone concentration. However, higher ventilation rate resulted in lower SOA concentration at steady-state. Increasing ozone filtration efficiency of activated carbon (AC) filter was found to be effective in reducing indoor ozone and SOA concentrations. This study is relevant to building sustainability in terms of health and comfort of building occupants.     

建筑材料用硬质聚氨酯泡沫(PUR)的燃烧特性与防火对策

介绍了当前在日本建筑市场上面向建筑材料所使用的聚氨酯产品的种类以及具有代表性的应用实例。对高分子聚合物的燃烧特性以及在建筑领域一般火灾安全性方面的问题进行了说明。同时，对与节能相关的建筑材料的情况进行了描述。对PUR／PIR泡沫以及由此生产出的建筑材料的燃烧性能，末端客户的使用条件及依据阻燃规定的讨论仍在进行中。如何向末端客户提供符合使用条件的具有燃烧特性的PUR／PIR泡沫将成为满足今后环境保护与节能措施技术要求的新课题。     

Indoor gaseous air pollutants determinants in office buildings—The OFFICAIR project

The aim of this study was to identify determinants of aldehyde and volatile organic compound (VOC) indoor air concentrations in a sample of more than 140 office rooms, in the framework of the European OFFICAIR research project. A large field campaign was performed, which included (a) the air sampling of aldehydes and VOCs in 37 newly built or recently retrofitted office buildings across 8 European countries in summer and winter and (b) the collection of information on building and offices’ characteristics using checklists. Linear mixed models for repeated measurements were applied to identify the main factors affecting the measured concentrations of selected indoor air pollutants (IAPs). Several associations between aldehydes and VOCs concentrations and buildings’ structural characteristic or occupants’ activity patterns were identified. The aldehyde and VOC determinants in office buildings include building and furnishing materials, indoor climate characteristics (room temperature and relative humidity), the use of consumer products (eg, cleaning and personal care products, office equipment), as well as the presence of outdoor sources in the proximity of the buildings (ie, vehicular traffic). Results also showed that determinants of indoor air concentrations varied considerably among different type of pollutants.     

Spatial and temporal variability in VOC levels within a commercial retail building

A study was performed to characterize the concentration of dozens of volatile organic compounds (VOCs) at 10 locations within a single large building and track these concentrations over a 2-year period. The study was performed at a shopping center (strip mall) in New Jersey. A total of 130 indoor air samples were collected from 10 retail stores within the shopping center and analyzed for 60 VOCs by US EPA Method TO-15. Indoor concentrations of up to 55,100 microg/m(3) were measured for individual VOCs. The indoor/outdoor ratio (I/O) was as high as 1500 for acetone and exceeded 100 at times for various compounds, indicating that significant indoor air sources were present. A large degree of spatial variability was observed between stores within the building, with concentrations varying by three to four orders of magnitude for some compounds. The spatial variability was dependent on the proximity of the sampling locations to the indoor sources. A large degree of temporal variability also was observed for compounds emitted from indoor sources, but the temporal variability generally did not exceed two standard deviations (sigma). For compounds not emitted from indoor sources at significant rates, both the spatial and temporal variability tended to range within an order of magnitude at each location. PRACTICAL IMPLICATIONS: Many cross-sectional studies have been published where the levels of volatile organic compounds (VOCs) were measured in indoor air at one or two locations for houses or offices. This study provides longitudinal data for a commercial retail building and also addresses spatial variability within the building. The data suggest that spatial and temporal variability are important considerations for compounds emitted from indoor sources. Elevated concentrations were found in retail spaces with no apparent emission sources due to their proximity to other retail spaces with emission sources.     

Occurrence and human exposure assessment of organophosphate flame retardants in indoor dust from various microenvironments of the Rhine/Main region,Germany

We analyzed organophosphate flame retardants (OPFRs) in 74 indoor dust samples collected from seven microenvironments (building material markets, private cars, daycare centers, private homes, floor/carpet stores, offices, and schools) in the Rhine/Main region of Germany. Ten of 11 target OPFRs were ubiquitously detected, some with more than 97% detection frequency, including tris(1,3‐dichloroisopropyl)phosphate (TCIPP), tris(2‐butoxyethyl)phosphate (TBOEP), triphenyl phosphate (TPHP), and tris(isobutyl) phosphate (TIBP). Total concentrations (∑OPFRs) ranged from 5.9 to 4800 μg/g, with TBOEP and TCIPP being the most abundant congeners. The ∑OPFRs in schools, private cars, offices, and daycare centers were significantly (P<.05) higher than in private homes. The ∑OPFRs for building material markets (19 μg/g) and floor/carpet stores (20 μg/g) showed no significant difference to the other microenvironments, likely because of forced ventilation. The profiles of OPFRs in dust samples from offices and private homes were highly similar, while profiles from the other five microenvironments were substantially different. Comparison of our results with previous studies indicates a significant global variation in OPFR concentrations and their profiles, reflecting distinct fire safety regulations in different countries and/or different sampling strategies. Dust ingestion constitutes the major exposure pathway to OPFRs for toddlers, while air inhalation is the major pathway for adults.