Monoterpene emissions from soil in a Sitka spruce forest

A dynamic soil enclosure was used to characterise monoterpene emissions from 3 soil depths within a Picea sitchensis (Sitka spruce) forest. In addition, a dynamic branch enclosure was used to provide comparative emissions data from foliage. In all cases, limonene and α-pinene dominated monoterpene soil emissions, whilst camphene, β-pinene and myrcene were also present in significant quantities. α-Phellandrene, 3-carene and α-terpinene were occasionally emitted in quantifiable amounts whilst cymene and cineole, although tentatively identified, were always non-quantifiable. Total daily mean monoterpene emission rates, normalised to 30°C, varied considerably between soil depths from 33.6 μg m⁻² h⁻¹ (range 28.3–38.4) for undisturbed soil, to 13.0 μg m⁻² h⁻¹ (8.97–16.4) with uppermost layer removed, to 199 μg m⁻² h⁻¹ (157–216) with partially decayed layer removed, suggesting that the surface needle litter was the most likely source of soil emissions to the atmosphere. Relative monoterpene ratios did not vary significantly between layers. Foliar monoterpenes exhibited a similar emission profile to soils with the exceptions of camphene and 3-carene whose contributions decreased and increased, respectively. Emission rates from foliage, normalised to 30°C were found to have a daily mean of 625 ng g⁻¹ dw h⁻¹ (299–1360). On a land area basis however, total soil emissions were demonstrated to be relatively insignificant to total emissions from the forest ecosystem.     

Volatile organic compound emissions from Siberian larch

We determined hourly emissions of isoprene, monoterpenes and sesquiterpenes from Siberian larch, one of the major tree species in Siberian forests. Summer volatile organic compounds (VOCs) emission from Siberian larch consisted mainly of monoterpenes (about 90%). The monoterpene emission spectrum remained constant during the measurement period, almost half was sabinene and other major monoterpenes were Δ³-carene, β- and α-pinene. During spring and summer, about 10% of the VOCs were sesquiterpenes, mainly α-farnesene. The sesquiterpene emissions declined to 3% in the fall. Isoprene, 2-methyl-3-buten-2-ol (MBO) and 1,8-cineole contributed to less than 3% of the VOC emission during the whole period. The diurnal variation of the emissions could be explained using a temperature-dependent parameterization. Emission potentials normalized to 30 °C were 5.2–21 μg g_dw⁻¹ h⁻¹ (using β-value of 0.09 °C⁻¹) for monoterpenes and 0.4–1.8 μg g_dw⁻¹ h⁻¹ (using β-value of 0.143 °C⁻¹, mean of determined values) for sesquiterpenes. Normalized monoterpene emission potentials were highest in late summer and elevated again in late fall. Sesquiterpene emission potentials were also highest in late summer, but decreased towards fall.     

Isoprene and monoterpene fluxes measured above Amazonian rainforest and their dependence on light and temperature

Canopy scale emissions of isoprene and monoterpenes from Amazonian rainforest were measured by eddy covariance and eddy accumulation techniques. The peak mixing ratios at about 10 m above the canopy occurred in the afternoon and were typically about 90 ppt_v of α-pinene and 4–5 ppb_v of isoprene. α-pinene was the most abundant monoterpene in the air above the canopy comprising ≈50% of the total monoterpene mixing ratio. Measured isoprene fluxes were almost 10 times higher than α-pinene fluxes. Normalized conditions of 30°C and 1000 μmol m⁻² s⁻¹ were associated with an isoprene flux of 2.4 mg m⁻² h⁻¹ and a β-pinene flux of 0.26 mg m⁻² h⁻¹. Both fluxes were lower than values that have been specified for Amazon rainforests in global emission models. Isoprene flux correlated with a light- and temperature-dependent emission activity factor, and even better with measured sensible heat flux. The variation in the measured α-pinene fluxes, as well as the diurnal cycle of mixing ratio, suggest emissions that are dependent on both light and temperature. The light and temperature dependence can have a significant effect on the modeled diurnal cycle of monoterpene emission as well as on the total monoterpene emission.     

Seasonal variations in VOC emission rates from gorse (Ulex europaeus)

Seasonal variations of biogenic volatile organic compound (VOC) emission rates and standardised emission factors from gorse (Ulex europaeus) have been measured at two sites in the United Kingdom, from October 1994 to September 1995, within temperature and PAR conditions ranging from 3 to 34°C and 10–1300 μmol m⁻² s⁻¹, respectively. Isoprene was the dominant emitted compound with a relative composition fluctuating from 7% of the total VOC (winter) to 97% (late summer). The monoterpenes α-pinene, camphene, sabinene, β-pinene, myrcene, limonene, trans-ocimene and γ-terpinene were also emitted, with α-pinene being the dominant monoterpene during most the year. Trans-ocimene represented 33–66% of the total monoterpene during the hottest months from June to September. VOC emissions were found to be accurately predicted using existing algorithms. Standard (normalised) emission factors of VOCs from gorse were calculated using experimental parameters measured during the experiment and found to fluctuate with season, from 13.3±2.1 to 0.1±0.1 μg C (g dwt)⁻¹ h⁻¹ in August 1995 and January 1995, respectively, for isoprene, and from 2.5±0.2 to 0.4±0.2 μg C (g dwt)⁻¹ h⁻¹ in July and November 1995, respectively, for total monoterpenes. No simple clear relation was found to allow prediction of these seasonal variations with respect to temperature and light intensity. The effects of using inappropriate algorithms to derive VOC fluxes from gorse were assessed for isoprene and monoterpenes. Although on an annual basis the discrepancies are not significant, monthly estimation of isoprene were found to be overestimated by more than a factor of 50 during wintertime when the seasonality of emission factors is not considered.     

Seasonal soil VOC exchange rates in a Mediterranean holm oak forest and their responses to drought conditions

Available information on soil volatile organic compound (VOC) exchange, emissions and uptake, is very scarce. We here describe the amounts and seasonality of soil VOC exchange during a year in a natural Mediterranean holm oak forest growing in Southern Catalonia. We investigated changes in soil VOC dynamics in drought conditions by decreasing the soil moisture to 30% of ambient conditions by artificially excluding rainfall and water runoff, and predicted the response of VOC exchange to the drought forecasted in the Mediterranean region for the next decades by GCM and ecophysiological models.The annual average of the total (detected) soil VOC and total monoterpene exchange rates were 3.2±3.2 and −0.4±0.3 μg m⁻² h⁻¹, respectively, in control plots. These values represent 0.003% of the total C emitted by soil at the study site as CO₂ whereas the annual mean of soil monoterpene exchange represents 0.0004% of total C. Total soil VOC exchange rates in control plots showed seasonal variations following changes in soil moisture and phenology. Maximum values were found in spring (17±8 μg m⁻² h⁻¹). Although there was no significant global effect of drought treatment on the total soil VOC exchange rates, annual average of total VOC exchange rates in drought plots resulted in an uptake rate (−0.5±1.8 μg m⁻² h⁻¹) instead of positive net emission rates. Larger soil VOC and monoterpene exchanges were measured in drought plots than in control plots in summer, which might be mostly attributable to autotrophic (roots) metabolism.The results show that the diversity and magnitude of monoterpene and VOC soil emissions are low compared with plant emissions, that they are driven by soil moisture, that they represent a very small part of the soil-released carbon and that they may be strongly reduced or even reversed into net uptakes by the predicted decreases of soil water availability in the next decades. In all cases, it seems that VOC fluxes in soil might have greater impact on soil ecology than on atmospheric chemistry.     

Isoprene and monoterpene emission from the coniferous species Abies Borisii-regis—implications for regional air chemistry in Greece

The emission of isoprene has been studied from a forest of Abies Borisii-regis, a Mediterranean fir species previously thought to emit only monoterpenes. Emission studies from two independent enclosure experiments indicated a standardised isoprene emission rate of (18.4±3.8) μg g_dry-weight⁻¹ h⁻¹, similar in magnitude to species such as eucalyptus and oak which are considered to be strong isoprene emitters. Isoprene emission depended strongly on both leaf temperature (2°C–34°C) and photosynthetically active radiation (PAR) below 250 μmol m⁻² s⁻¹, becoming saturated with respect to PAR above this value. The annual isoprene emission rate was estimated to be (132±29) kT yr⁻¹ for those trees growing within Greece, comparable to current estimates of the total isoprene budget of Greece as a whole, and contributing significantly to regional ozone and carbon monoxide budgets. Monoterpene emission exhibited exponential temperature dependence, with 1,8-cineole, α-pinene, β-pinene and limonene forming the primary emissions. A standardised total monoterpene emission rate of (2.7±1.1) μg g_dry-weight⁻¹ h⁻¹ was calculated, corresponding to an annual monoterpene emission rate of (24±12) kT yr⁻¹. Research was conducted as part of the AEROBIC’97 (AEROsol formation from BIogenic organic Carbon) series of field campaigns.     

Volatile organic compounds (VOCs) emitted from 40 Mediterranean plant species:: VOC speciation and extrapolation to habitat scale

Forty native Mediterranean plant species were screened for emissions of the C5 and C10 hydrocarbons, isoprene and monoterpenes, in five different habitats. A total of 32 compounds were observed in the emissions from these plants. The number of compounds emitted by different plant species varied from 19 (Quercus ilex) to a single compound emission, usually of isoprene. Emission rates were normalised to generate emission factors for each plant species for each sampling event at standard conditions of temperature and light intensity. Plant species were categorised according to their main emitted compound, the major groups being isoprene, α-pinene, linalool, and limonene emitters. Estimates of habitat fluxes for each emitted compound were derived from the contributing plant species’ emission factors, biomass and ground cover. Emissions of individual compounds ranged from 0.002 to 505 g ha⁻¹ h⁻¹ (camphene from garrigue in Spain in autumn and isoprene from riverside habitats in Spain in late spring; respectively). Emissions of isoprene ranged from 0.3 to 505 g ha⁻¹ h⁻¹ (macchia in Italy in late spring and autumn; and riverside in Spain in late spring; respectively) and α-pinene emissions ranged from 0.51 to 52.92 g ha⁻¹ h⁻¹ (garrigue in Spain in late spring; and forest in France in autumn; respectively). Habitat fluxes of most compounds in autumn were greater than in late spring, dominated by emissions from Quercus ilex, Genista scorpius and Quercus pubescens. This study contributes to regional emission inventories and will be of use to tropospheric chemical modellers.     

Reference values for structure emissions measured on site in new residential buildings in Finland

A 3-year research project was established in 1999 to create numerical reference data for material emissions during the time of construction and during the first year. Seven buildings, representing the present construction practice in Finland, were investigated. Material emissions were measured by using the field and laboratory cell (FLEC) during the time of construction, in the newly finished, and in the 6- and 12-month-old buildings. The emission rates for volatile organic compounds (VOCs), formaldehyde, and ammonia were determined.The highest total VOCs (TVOC) emissions were measured in the newly finished buildings from the ceiling structure and from some of the PVC floor coverings. These emissions were up to 1300–2000 μg m⁻² h⁻¹. Individual VOCs with emission rates above 50 μg m⁻² h⁻¹ included 2-(2-butoxyethoxy) ethanol and its acetate, C4–C16-substituted alkylbenzenes, and xylenes. The mean TVOC emission decreased at least to the Finnish M1-class level (200 μg m⁻² h⁻¹) from all surfaces and in all the buildings in 6–12 months. The ammonia and formaldehyde emissions from the ceiling structure were 20–60 μg m⁻² h⁻¹ in the newly finished buildings and the M1-levels (30/50 μg m⁻² h⁻¹) were exceeded in some cases. These emissions even increased in some buildings during the follow-up period indicating the difference between emissions measured in the laboratory and on site from real structures. Reference values based on the means and 95th percentile are presented to be utilised in both quality control and while investigating indoor air quality problems which are suspected to be caused by a defect structure.     

Isoprene emission capacity for US tree species

Isoprene emission capacity measurements are presented from 18 North American oak (Quercus) species and species from six other genera previously found to emit significant quantities of isoprene. Sampling was conducted at physiographically diverse locations in North Carolina, Central California, and Northern Oregon. Emissions from several sun leaves of each species were measured at or near standard conditions (leaf temperature of 30°C and photosynthetically active radiation of 1000 μmol m⁻² s⁻¹) using environmentally controlled cuvette systems and gas chromatography with reduction gas detectors. Species mean emission capacity ranged from 39 to 158 μg C g⁻¹ h⁻¹ (mean of 86), or 22 to 79 nmol m⁻² s⁻¹ (mean of 44). These rates are 2–28 times higher than those previously reported from the same species, which were summarized in a recent study where isoprene emission rates were assigned based on published data and taxonomy. These discrepancies were attributed to differences in leaf environment during development, measurement technique (branch or plant enclosure versus leaf enclosure), and lack of environmental measurements associated with some of the earlier branch enclosure measurements. Mass-based emission capacities for 15 of 18 oak species, sweetgum (Liquidambar styraciflua), and poplars (Populus trichocarpa and P. deltoides) were within ranges used in current biogenic volatile organic compound (BVOC) emission models, while measured rates for the remaining three oak species, Nyssa sylvatica, Platanus occidentalis, Robinia pseudoacacia, Salix nigra, and Populus hybrids (Populus trichocarpa × P. deltoides) were considerably higher. In addition, mean specific leaf mass of the oak species was 30% higher than assumed in current emission models. Emission rates reported here and in other recent studies support recent conclusions that isoprene emission capacities for sun leaves of high emitting species may be better represented by a value of 100±50 μg C g⁻¹ h⁻¹ during hot summer conditions. We also find that intermediate isoprene emission rates previously suggested for some tree species may not represent their true emission capacities, and that broadleaf plant species may have either low (<1.0 μg C g⁻¹ h⁻¹) or very high (∼100 μg C g⁻¹ h⁻¹) genetic capacity to emit isoprene when mature foliage is exposed to a high ambient temperature and light environment.     

Pre- and post-catalyst-, fuel-, velocity- and acceleration-dependent benzene emission data of gasoline-driven EURO-2 passenger cars and light duty vehicles

The benzene emission characteristics of six gasoline-driven EURO-2 vehicles, three passenger cars and three light duty vehicles, have been determined by time-resolved chemical ionization mass spectrometry. Aliquots of the exhaust gas were monitored pre- and post-catalyst with two independently operating mass spectrometers. Each vehicle was driven with two different fuels having benzene contents of 1 and 2 vol%. Seven driving cycles—including the European (EDC) and the US (FTP-75) driving cycle—with a total driving time of about 8800 s were studied. Herein, we discuss the average emission characteristics of the entire fleet at transient driving in the velocity range of 0–150 km h⁻¹. The conversion efficiencies of the involved catalytic systems were deduced from the pre- and post-catalyst data. On average, the vehicles showed optimal benzene conversion efficiencies (>95%) in the velocity range of 30–90 km h⁻¹. When driving below 20 or above 100 km h⁻¹ reduced benzene conversion was found (80–82%). No benzene conversion was observed when driving above 130 km h⁻¹. In contrast, the post-catalyst benzene emissions exceeded those of the untreated exhaust gas by 19–49%. Thus on an average, benzene was formed across the catalysts under these conditions. In addition, the influence of the benzene content of the gasoline on the tail-pipe emissions was also studied. The use of the gasoline with 1 vol% benzene instead of 2 vol% induced a 20–30% reduction of the post-catalyst emissions when driving below 50 km h⁻¹. The fuel effect became smaller above 100 km h⁻¹ and was even negative at high engine load (>130 km h⁻¹). Thus under these conditions, when benzene is formed across the catalyst, the amount of the emitted benzene was independent of the benzene level of the fuel.     

Decadal reductions of traffic emissions on a transit route in Austria – results of the Tauerntunnel experiment 1997

Real-world emissions of a traffic fleet on a transit route in Austria were determined in the Tauerntunnel experiment in October 1997. The total number of vehicles and the average speed was nearly the same on both measuring days (465 vehicles 30 min⁻¹ and 76 km h⁻¹ on the workday, 477 and 78 km h⁻¹ on Sunday). The average workday fleet contained 17.6% heavy-duty vehicles (HDV) and the average Sunday fleet 2.8% HDV resulting in up to four times higher emission rates per vehicle per km on the workday than on Sunday for most of the regulated components (CO₂, CO, NO_x, SO₂, and particulate matter-PM10). Emission rates of NMVOC accounted for 200 mg vehicle⁻¹ km⁻¹ on both days. The relative contributions of light-duty vehicles (LDV) and HDV to the total emissions indicated that aldehydes, BTEX (benzene, toluene, ethylbenzene, xylenes), and alkanes are mainly produced by LDV, while HDV dominated emissions of CO, NO_x, SO₂, and PM10. Emissions of NO_x caused by HDV were 16,100 mg vehicle⁻¹ km⁻¹ (as NO₂). Produced by LDV they were much lower at 360 mg vehicle⁻¹ km⁻¹. Comparing the emission rates to the results that were obtained by the 1988 experiment at the same place significant changes in the emission levels of hydrocarbons and CO, which accounted 1997 to only 10% of the levels in 1988, were noticed. However, the decrease of PM has been modest leading to values of 80 and 60% of the levels in 1988 on the workday and on Sunday, respectively. Emission rates of NO_x determined on the workday in 1997 were 3130 mg vehicle⁻¹ km⁻¹ and even higher than in 1988 (2630 mg vehicle⁻¹ km⁻¹), presumable due to the increase of the HD-traffic.     

Acetone and monoterpene emissions from the boreal forest in northern Europe

Acetone is a ubiquitous component of the atmosphere which, by its photolysis, can play an important role in photochemical reactions in the free troposphere. This paper investigates the biogenic source of acetone from Scots pine (Pinus sylvestris) and Norway spruce (Picea abies) in the Scandinavian boreal zone. Branch emission measurements of acetone, monoterpenes, and isoprene were made with an all-Teflon flow-through branch chamber from five specimens of Scots pine at three sites in Sweden and Finland, and from one specimen of Norway spruce at one site in Sweden. Acetone samples were taken with SepPak™ DNPH cartridges, monoterpenes with Tenax TA, and isoprene with 3 l electropolished canisters. Acetone was found to dominate the carbonyl emission of both Scots pine and Norway spruce, as large as the monoterpene emissions and for Norway spruce, as the isoprene emission. The average standard emission rate (30°C) and average β-coefficient for the temperature correlation for 5 specimens of Scots pine were 870 ng C gdw⁻¹ h⁻¹ (gdw=gram dry weight) and 0.12, respectively. For the monoterpenes the values were 900 ng C gdw⁻¹ h⁻¹ and 0.12, respectively. The standard emission rate (30°C) for acetone from Norway spruce was 265 ng C gdw⁻¹ h⁻¹, but the sparsity of data, along with the unusual weather conditions at the time of the measurements, precludes the establishment of a summertime best estimate emission factor.     

Characterization of emissions from portable household combustion devices: particle size distributions,emission rates and factors,and potential exposures

A series of source tests were conducted to characterize emissions of particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO₂), methane (CH₄), and total hydrocarbon (THC ) from five types of portable combustion devices. Tested combustion devices included a kerosene lamp, an oil lamp, a kerosene space heater, a portable gas range, and four unscented candles. All tests were conducted either in a well-mixed chamber or a well-mixed room, which enables us to determine emission rates and emission factors using a single-compartment mass balance model. Particle mass concentrations and number concentrations were measured using a nephelometric particle monitor and an eight-channel optical particle counter, respectively. Real-time CO concentrations were measured with an electrochemical sensor CO monitor. CO₂, CH₄, and THC were measured using a GC-FID technique. The results indicate that all particles emitted during steady burning in each of the tested devices were smaller than 1.0 μm in diameter with the vast majority in the range between 0.1 and 0.3 μm. The PM mass emission rates and emission factors for the tested devices ranged from 5.6±0.1 to 142.3±40.8 mg h⁻¹ and from 0.35±0.06 to 9.04±4.0 mg g⁻¹, respectively. The CO emission rates and emission factors ranged from 4.7±3.0 to 226.7±100 mg h⁻¹ and from 0.25±0.12 to 1.56±0.7 mg g⁻¹, respectively. The CO₂ emission rates and emission factors ranged from 5500±700 to 210,000±90,000 mg h⁻¹ and from 387±45 to 1689±640 mg g⁻¹, respectively. The contributions of CH₄ and THC to emission inventories are expected to be insignificant due both to the small emission factors and to the relatively small quantity of fuel consumed by these portable devices. An exposure scenario analysis indicates that every-day use of the kerosene lamp in a village house can generate fine PM exposures easily exceeding the US promulgated NAAQS for PM_2.5.     

Aerosol scattering properties in northern China

The aerosol scattering properties were investigated at two continental sites in northern China in 2004. Aerosol light scattering coefficient (σ_sp) at 525 nm, PM₁₀, and aerosol mass scattering efficiencies (α) at Dunhuang had a mean value of 165.1±148.8 M m⁻¹, 157.6±270.0 μg m⁻³, and 2.30±3.41 m² g⁻¹, respectively, while these values at Dongsheng were, respectively, 180.2±151.9 M m⁻¹, 119.0±112.9 μg m⁻³, and 1.87±1.41 m² g⁻¹. There existed a seasonal variability of aerosol scattering properties. In spring, at Dunhuang PM₁₀, σ_sp, and α were 184.1±211.548 μg m⁻³, 126.3±89.6 M m⁻¹, and 1.05±0.97 m² g⁻¹, respectively, and these values at Dongsheng were 146.4±142.1 μg m⁻³, 183.4±81.7 M m⁻¹, and 1.98±1.52 m² g⁻¹, respectively. However, in winter at Dunhuang PM₁₀, σ_sp, and α were 158.1±261.4 μg m⁻³, 303.3±165.2 M m⁻¹, and 3.17±1.93 m² g⁻¹, respectively, and these values at Dongsheng were 155.7±170.1 μg m⁻³, 304.4±158.1 M m⁻¹, and 2.90±1.72 m² g⁻¹, respectively. σ_sp and α in winter were higher than that in spring at both the sites, which coincides with the characteristics of dust aerosol and pollution aerosol. Overall, the dominant aerosol types in spring and winter at both sites in northern China are dust aerosol and pollution aerosol, respectively.     

Quantifying natural source mercury emissions from the Ivanhoe Mining District,north-central Nevada,USA

In order to assess the importance of mercury emissions from naturally enriched sources relative to anthropogenic point sources, data must be collected that characterizes mercury emissions from representative areas and quantifies the influence of various environmental parameters that control emissions. With this information, we will be able to scale up natural source emissions to regional areas. In this study in situ mercury emission measurements were used, along with data from laboratory studies and statistical analysis, to scale up mercury emissions for the naturally enriched Ivanhoe Mining District, Nevada. Results from stepwise multi-variate regression analysis indicated that lithology, soil mercury concentration, and distance from the nearest fault were the most important factors controlling mercury flux. Field and lab experiments demonstrated that light and precipitation enhanced mercury emissions from alluvium with background mercury concentrations. Diel mercury emissions followed a Gaussian distribution. The Gaussian distribution was used to calculate an average daily emission for each lithologic unit, which were then used to calculate an average flux for the entire area of 17.1 ng Hg m⁻² h⁻¹. An annual emission of ∼8.7×10⁴ g of mercury to the atmosphere was calculated for the 586 km² area. The bulk of the Hg released into the atmosphere from the district (∼89%) is from naturally enriched non-point sources and ∼11% is emitted from areas of anthropogenic disturbance where mercury was mined. Mercury emissions from this area exceed the natural emission factor applied to mercury rich belts of the world (1.5 ng m⁻² h⁻¹) by an order of magnitude.     

Density of foliage mass and area in the boreal forest cover in Finland,with applications to the estimation of monoterpene and isoprene emissions

The distribution of the density of foliage mass and area in forest canopies throughout Finland (60–70°N) were determined on the basis of the permanent sample plots used in the Finnish National Forest Inventory. These parameters were linked to the long-term monthly mean air temperatures for 1961–1990, which had been converted to hourly temperature and radiation values with the help of a weather simulator in order to calculate the spatial distribution of mean yearly emissions of monoterpene and isoprene over Finland. The mean total density of foliage mass in southern Finland (60°⩽latitude<65°N) was around 500 g m⁻², equivalent to 4–5 m² of total foliage area per m² of land area. In northern Finland (65°⩽latitude<70°N), the maximum values remained below 200–300 g m⁻², or 2–3 m² m⁻². The highest values were achieved in forests dominated by mature Norway spruces. The higher temperatures and longer growing season in southern Finland led to greater emissions than in the rest of the country. Total annual emissions of monoterpene were 1070 kg km⁻² yr⁻¹ in southern Finland and 460 kg km⁻² yr⁻¹ in the north, and those of isoprene from Norway spruce canopies 150 and 40 kg km⁻² yr⁻¹, respectively.     

Measuring emissions of organophosphate flame retardants using a passive flux sampler

Flame retardants are used in polymers to reduce the flammability of building materials, electric appliances, fabric and papers. In recent years, organophosphate flame retardants have been used as substitutes for polybrominated flame retardants (BFRs). In Japan, the amount of organophosphate flame retardants used in 2001 was about five times more than in 2000. Recently, several studies have shown the health concerns for some organophosphate flame retardants. Little research has been performed on the emission of organophosphate flame retardants, especially the relationship between content and emissions. In this study, a new type of passive sampler was developed to measure emissions of organophosphate flame retardants from plastic materials. With this sampler, emissions from polyvinyl chloride wallpaper samples with different content of tris(2-chloroisopropyl)phosphate (TCPP) at different temperatures were examined. The observed maximum emissions of TCPP from 1, 3, 5, 10 and 20 w/w% content wallpaper materials were 262.3, 452.6, 644.8, 1119.1 and 2166.8 μg m⁻² h⁻¹, respectively. Emissions from 5% TCPP content materials at 40 and 60 °C were 1135.7 and 2841.2 μg m⁻² h⁻¹, respectively. A significantly positive correlation between the flux of TCPP and the TCPP content of the wallpaper samples was observed. A linear relationship was found between the inverse of temperature and the logarithm of TCPP emission. The results imply that the use of materials with a high organophosphate flame retardant content can lead to high emission rates in high-temperature indoor environments.     

The physical characteristics of sulfur aerosols

A review of the physical characteristics of sulfur-containing aerosols, with respect to size distribution of the physical distributions, sulfur distributions, distribution modal characteristics, nuclei formation rates, aerosol growth characteristics, and in situ measurement, has been made.Physical size distributions can be characterized well by a trimodal model consisting of three additive lognormal distributions.When atmospheric physical aerosol size distributions are characterized by the trimodal model, the following typical modal parameters are observed:1. Nuclei mode – geometric mean size by volume, DGV_n, from 0.015 to 0.04 μm. σ_gn=1.6, nucler mode volumes from 0.0005 over the remote oceans to 9 μm³ cm⁻³ on an urban freeway.2. Accumulation mode – geometric mean size by volume, DGV_a, from 0.15 to 0.5 μm, σ_ga=1.6–2.2 and mode volume concentrations from 1 for very clean marine or continental backgrounds to as high as 300 μm³ cm⁻³ under very polluted conditions in urban areas.3. Coarse particle mode – geometric mean size by volume, DGV_c, from 5 to 30 μm, σ_gn=2–3, and mode volume concentrations from 2 to 1000 μm³ cm⁻³.It has also been concluded that the fine particles (D_p<2 μm) are essentially independent in formation, transformation and removal from the coarse particles (D_p>2 μm).Modal characterization of impactor-measured sulfate size distributions from the literature shows that the sulfate is nearly all in the accumulation mode and has the same size distribution as the physical accumulation mode distribution.Average sulfate aerodynamic geometric mean dia. was found to be 0.48±0.1 μm (0.37±0.1 μm vol. dia.) and σ_g=2.00±0.29. Concentrations range from a low of about 0.04 μg m⁻³ over the remote oceans to over 8 μg m⁻³ under polluted conditions over the continents.Review of the data on nucleation in smog chambers and in the atmosphere suggests that when SO₂, is present, SO₂-to-aerosol conversion dominates the Aitken nuclei count and, indirectly, through coagulation and condensation, the accumulation mode size and concentration. There are indications that nucleation is ubiquitous in the atmosphere, ranging from values as low as 2 cm⁻³ h⁻¹ over the clean remote oceans to a high of 6×10⁶ cm⁻³ h⁻¹ in a power plant plume under sunny conditions.There is considerable theoretical and experimental evidence that even if most of the mass for the condensational growth of the accumulation mode comes from hydrocarbon conversion, sulfur conversion provides most of the nuclei.     

Engine dynamometer experiments: platinum emissions from differently aged three-way catalytic converters

Depending on the operating conditions and the age of the converter, mean platinum emissions ranged from 7 to 123 ng m^-3 corresponding to emission factors between 9 and 124 ng km^-1. There were no statistically significant differences between the four converter brands tested. The data from new (12–90 ng km^-1) and old catalytic converters (9–26 ng km^-1) installed on a medium-powered gasoline engine (1.8 l 66 kW) showed a tendency towards decreasing platinum emission with increasing use. The platinum emissions increased with rising simulated speed and exhaust temperature. The lowest mean emission from new converters (12 ng km^-1) was found at a constant speed of 80 km h^-1, the highest (90 ng km^-1) at 130 km h^-1. Using the US72 or the US72-EUDC test cycles the emission factors were higher (37 or 19 ng km^-1) than at 80 km h^-1 indicating that additional mechanical or thermal impacts enhance the platinum abrasion at cycle conditions. After installing catalytic converters tested with the 1.8 l engine on a smaller engine (1.4 l 44 kW), the platinum emissions measured at the US72 cycle and a high-speed condition (140 km h^-1) were only 9 and 22 ng km^-1, respectively. Platinum is almost exclusively emitted bound to aluminum oxide particles where (depending on the driving conditions) 43–74% of these emitted particles had aerodynamic diameters >10 μm. The alveolar fraction (<3 μm) was between 11 and 26% (1.8 l engine) and between 21 and 36% (1.4 l engine). If at all, soluble platinum is emitted in only very small quantities (⩽1%).     

Comprehensive assessment of pine needles as bioindicators of PAHs using multivariate analysis. The importance of temporal trends

The importance of the annual and seasonal trends associated to the polycyclic aromatic hydrocarbons (PAHs) biomonitoring by pine needles are studied with a comprehensive use of univariate and multivariate analysis tools. For this purpose, four pine needle sampling campaigns (winter, spring, summer and autumn 2007) were carried out in 29 sites from Portugal. Needles from Pinus pinaster Ait. and Pinus pinea L. trees were collected from all year-classes available in each tree, corresponding to the different shoots of needles coming out every spring and the results of both species were treated separately. Annual trends of polycyclic aromatic hydrocarbons (PAHs) contamination indicate a general increase from the least to the most exposed year-classes, for all seasons. The mean values for the sum of 16 PAHs ranged from 71 ± 33 ng g⁻¹ (dry weight – dw) for new year (2007) needles in the summer to 514 ± 317 ng g⁻¹ (dw) for 2-year needles (2005) in the spring for P. pinea, and between 90 ± 50 ng g⁻¹ (dw) for new year (2007) needles in the summer and 1212 ± 436 ng g⁻¹ (dw) for 3-year needles (2004) in summer for P. pinaster. The seasonal evolution shows the highest concentrations in the winter, then declining to the lowest levels in the summer and rising again from summer to autumn. Principal component analysis confirmed differences between seasons and needle year-classes, more visible for P. pinea samples. The cooler seasons have more affinity towards the lighter more abundant PAHs, as do the older needles. Differences between both pine species are also evident.