Heidi Hellén

Influence of residential wood combustion on local air quality.

The importance of wood combustion to local air quality was estimated by measuring different air pollutants and conducting chemical mass balance modelling. PM10, PM2.5, PAHs and VOC concentrations in ambient air were measured in a typical Finnish residential area. Measurements were conducted in January-March 2006. For some compounds, wood combustion was clearly the main local source at this site. The effect of wood combustion was more clearly seen for organic compounds than for fine particle mass. For fine particles, background concentrations dominated. However, very high, short-lived concentration peaks were detected, when the wind direction and other weather conditions were favourable. For organic compounds, the effect of wood combustion was seen in diurnal and in two-week average concentrations. PAH-concentrations were often several times higher at the residential area than in the background. Benzene concentrations showed similar diurnal pattern as the use of wood and benzene/toluene ratios indicated that wood combustion is the most important source. A chemical mass balance model was used for studying the effect of wood combustion on the measured concentrations of VOCs. Model results showed that the main local sources for VOCs at Kurkimäki are wood combustion and traffic. Wood combustion was clearly the most important source for many compounds (e.g., benzene).

OH reactivity measurements within a boreal forest: evidence for unknown reactive emissions.

Boreal forests emit large amounts of volatile organic compounds (VOCs) which react with the hydroxyl radical (OH) to influence regional ozone levels and form secondary organic aerosol. Using OH reactivity measurements within a boreal forest in Finland, we investigated the budget of reactive VOCs. OH reactivity was measured using the comparative reactivity method, whereas 30 individual VOCs were measured using proton transfer reaction mass spectrometry, thermal-desorption gas chromatography mass spectrometry, and liquid chromatography mass spectrometry, in August 2008. The measured OH reactivity ranged from below detection limit (3.5 s(-1)), to approximately 60 s(-1) in a single pollution event. The average OH reactivity was approximately 9 s(-1) and no diel variation was observed in the profiles. The measured OH sinks (approximately 30 species) accounted for only 50% of the total measured OH reactivity, implying unknown reactive VOCs within the forest. The five highest measured OH sinks were: monoterpenes (1 s(-1)), CO (0.7 s(-1)), isoprene (0.5 s(-1)), propanal and acetone (0.3 s(-1)), and methane (0.3 s(-1)). We suggest that models be constrained by direct OH reactivity measurements to accurately assess the impact of boreal forest emissions on regional atmospheric chemistry and climate.

Size distribution and chemical composition of airborne particles in south-eastern Finland during different seasons and wildfire episodes in 2006.

The inorganic main elements, trace elements and PAHs were determined from selected PM(1), PM(2.5) and PM(10) samples collected at the Nordic background station in Virolahti during different seasons and during the wildfire episodes in 2006. Submicron particles are those most harmful to human beings, as they are able to penetrate deep into the human respiratory system and may cause severe health effects. About 70-80%, of the toxic trace elements, like lead, cadmium, arsenic and nickel, as well as PAH compounds, were found in particles smaller than 1 microm. Furthermore, the main part of the copper, zinc, and vanadium was associated with submicron particles. In practice, all the PAHs found in PM(10) were actually in PM(2.5). For PAHs and trace elements, it is more beneficial to analyse the PM(2.5) or even the PM(1) fraction instead of PM(10), because exclusion of the large particles reduces the need for sample cleaning to minimize the matrix effects during the analysis. During the wildfire episodes, the concentrations of particles smaller than 2.5 microm, as well as those of submicron particles, increased, and also the ratio PM(1)/PM(10) increased to about 50%. On the fire days, the mean potassium concentration was higher in all particle fractions, but ammonium and nitrate concentrations rose only in particles smaller than 1.0 microm. PAH concentrations rose even to the same level as in winter.

Determination of source contributions of NMHCs in Helsinki (60°N, 25°E) using chemical mass balance and the Unmix multivariate receptor models

Abstract A chemical mass balance (CMB) receptor model and a multivariate receptor model (Unmix) were used for the determination of the contributions of different non-methane hydrocarbon (NMHC) sources in Helsinki. C2–C10 hydrocarbon measurements were conducted in the Helsinki city area during four different seasons in 2001 in order to get a data set for CMB modelling. The samples were collected using 24-h passive canister sampling simultaneously with 2-h pumped adsorbent samples. The emission profiles of the NMHC sources were also determined. Source contributions were estimated for different seasons of the year and weekly and diurnal variations were examined using the CMB model. According to the CMB analysis major sources of C2–C10 NMHCs were traffic (gasoline exhaust 33%, gasoline vapour 9% and liquid gasoline 12%) and emissions from distant sources, advected to the study area in long-range transported air masses (37%). City gas (2%), solvents (3%), biogenic compounds (1%) and diesel exhaust (0.2%) were minor contributions. Unmix was used to confirm that the major sources were included in the CMB calculations. For C6–C10 hydrocarbons the major sources in both CMB and Unmix analyses were gasoline exhaust, accounting for 52% and 53% of the NMHCs, respectively.

Aromatic hydrocarbon and methyl tert-butyl ether measurements in ambient air of Helsinki (Finland) using diffusive samplers.

The diffusive sampling method was evaluated for measuring benzene, toluene, ethylbenzene, xylenes, styrene, propylbenzene, ethyltoluenes, trimethylbenzenes and methyl tert-butyl ether (MTBE) in the urban air of Helsinki, Finland. Concentrations were measured in 2-week periods at four different sites during the year 2000. Tube type adsorbent tubes were pre-packed with Carbopack-B (60/80). Analysis was conducted using thermal desorption and gas chromatograph coupled to a mass spectrometer. In different seasons, during five diffusive sampling periods, parallel measurements were conducted using pumped and online sampling. The compared techniques agreed reasonably well for other compounds than trimethylbenzenes. Based on comparisons, diffusive uptake rates for ethyltoluenes, styrene, propylbenzene and MTBE were determined, and for trimethylbenzenes, uptake rates were revised. The concentrations of aromatic compounds in Helsinki metropolitan area were also compared to the concentrations of a rural, forested site in Central Finland.

Strong sesquiterpene emissions from Amazonian soils

The Amazon rainforest is the world’s largest source of reactive volatile isoprenoids to the atmosphere. It is generally assumed that these emissions are products of photosynthetically driven secondary metabolism and released from the rainforest canopy from where they influence the oxidative capacity of the atmosphere. However, recent measurements indicate that further sources of volatiles are present. Here we show that soil microorganisms are a strong, unaccounted source of highly reactive and previously unreported sesquiterpenes (C15H24; SQT). The emission rate and chemical speciation of soil SQTs were determined as a function of soil moisture, oxygen, and rRNA transcript abundance in the laboratory. Based on these results, a model was developed to predict soil–atmosphere SQT fluxes. It was found SQT emissions from a Terra Firme soil in the dry season were in comparable magnitude to current global model canopy emissions, establishing an important ecological connection between soil microbes and atmospherically relevant SQTs.Recent measurements in the Amazon rainforest indicate missing sources of volatile organic compounds (VOCs). Here the authors show that soil microorganisms are a strong, unaccounted source of highly reactive sesquiterpenes, a class of VOCs that can regulate ozone chemistry within the forest canopy.

New perspectives on CO2, temperature and light effects on BVOC emissions using online measurements by PTR-MS and cavity ring-down spectroscopy

Volatile organic compounds (VOC) play important roles in atmospheric chemistry, plant ecology, and physiology, and biogenic VOC (BVOC) emitted by plants is the largest VOC source. Our knowledge about how environmental drivers (e.g., carbon, light, and temperature) may regulate BVOC emissions is limited because they are often not controlled. We combined a greenhouse facility to manipulate atmospheric CO2 ([CO2]) with proton-transfer-reaction mass spectrometry (PTR-MS) and cavity ring-down spectroscopy to investigate the regulation of BVOC in Norway spruce. Our results indicate a direct relationship between [CO2] and methanol and acetone emissions, and their temperature and light dependencies, possibly related to substrate availability. The composition of monoterpenes stored in needles remained constant, but emissions of mono-(linalool) and sesquiterpenes (β-farnesene) increased at lower [CO2], with the effects being most pronounced at the highest air temperature. Pulse-labeling suggested an immediate incorporation of recently assimilated carbon into acetone, mono- and sesquiterpene emissions even under 50 ppm [CO2]. Our results provide new perspectives on CO2, temperature and light effects on BVOC emissions, in particular how they depend on stored pools and recent photosynthetic products. Future studies using smaller but more seedlings may allow sufficient replication to examine the physiological mechanisms behind the BVOC responses.

Amines in boreal forest air at SMEAR II station in Finland

We measured amines in boreal forest air in Finland both in gas and particle phases with 1 h time resolution using an online ion chromatograph (instrument for Measuring AeRosols and Gases in Ambient Air – MARGA) connected to an electrospray ionization quadrupole mass spectrometer (MS). The developed MARGA-MS method was able to separate and detect seven different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA), and butylamine (BA). The detection limits of the method for amines were low (0.2–3.1 ng m−3), the accuracy of ICMS analysis was 11–37 %, and the precision 10–15 %. The proper measurements in the boreal forest covered about 8 weeks between March and December 2015. The amines were found to be an inhomogeneous group of compounds, showing different seasonal and diurnal variability. Total MMA (MMA(tot)) peaked together with the sum of ammonia and ammonium ions already in March. In March, monthly means for MMA were< 2.4 and 6.8± 9.1 ng m−3 in gas and aerosol phases, respectively, and for NH3 and NH+4 these were 52± 16 and 425± 371 ng m−3, respectively. Monthly medians in March for MMA(tot), NH3, and NH+4 were < 2.4, 19 and 90 ng m−3, respectively. DMA(tot) and TMA(tot) had summer maxima indicating biogenic sources. We observed diurnal variation for DMA(tot) but not for TMA(tot). The highest concentrations of these compounds were measured in July. Then, monthly means for DMA were < 3.1 and 8.4± 3.1 ng m−3 in gas and aerosol phases, respectively, and for TMA these were 0.4± 0.1 and 1.8± 0.5 ng m−3. Monthly medians in July for DMA were below the detection limit (DL) and 4.9 ng m−3 in gas and aerosol phases, respectively, and for TMA these were 0.4 and 1.4 ng m−3. When relative humidity of air was > 90 %, gas-phase DMA correlated well with 1.1–2 nm particle number concentration (R2 = 0.63) suggesting that it participates in atmospheric clustering. EA concentrations were low all the time. Its July means were < 0.36 and 0.4± 0.4 ng m−3 in gas and aerosol phases, respectively, but individual concentration data correlated well with monoterpene concentrations in July. Monthly means of PA and BA were below detection limits at all times.