Terpenoid and carbonyl emissions from Norway spruce in Finland during the growing season

We present spring and summer volatile organic compound (VOC) emission rate measurements from Norway spruce (Picea abies L. Karst) growing in a boreal forest in southern Finland. The measurements were conducted using in situ gas chromatograph with 1 to 2 h time resolution to reveal quantitative and qualitative short-term and seasonal variability of the emissions. The measurements cover altogether 14 weeks in years 2011, 2014 and 2015. Monoterpene (MT) and sesquiterpene (SQT) emission rates were measured all the time, but isoprene only in 2014 and 2015 and acetone and C-4-C-10 aldehydes only in 2015. The emission rates of all the compounds were low in spring, but MT, acetone, and C-4-C-10 aldehyde emission rates increased as summer proceeded, reaching maximum emission rates in July. Late summer mean values (late July and August) were 29, 17, and 33 ng g(dw)(-1) h(-1) for MTs, acetone, and aldehydes respectively. SQT emission rates increased during the summer and highest emissions were measured in late summer (late summer mean value 84 ng g(dw)(-1) h(-1)) concomitant with highest linalool emissions most likely due to stress effects. The between-tree variability of emission pattern was studied by measuring seven different trees during the same afternoon using adsorbent tubes. Especially the contributions of limonene, terpinolene, and camphene were found to vary between trees, whereas proportions of alpha-pinene (25 +/- 5 %) and beta-pinene (7 +/- 3 %) were more stable. Our results show that it is important to measure emissions at canopy level due to irregular emission pattern, but reliable SQT emission data can be measured only from enclosures. SQT emissions contributed more than 90% of the ozone reactivity most of the time, and about 70% of the OH reactivity during late summer. The contribution of aldehydes to OH reactivity was comparable to that of MT during late summer, 10-30% most of the time.Peer reviewe

Seasonal influences on surface ozone variability in continental South Africa and implications for air quality

Although elevated surface ozone (O-3) concentrations are observed in many areas within southern Africa, few studies have investigated the regional atmospheric chemistry and dominant atmospheric processes driving surface O-3 formation in this region. Therefore, an assessment of comprehensive continuous surfaceO(3) measurements performed at four sites in continental South Africa was conducted. The regional O-3 problem was evident, with O-3 concentrations regularly exceeding the South African air quality standard limit, while O-3 levels were higher compared to other background sites in the Southern Hemisphere. The temporal O-3 patterns observed at the four sites resembled typical trends for O-3 in continental South Africa, with O-3 concentrations peaking in late winter and early spring. Increased O-3 concentrations in winter were indicative of increased emissions of O-3 precursors from household combustion and other low-level sources, while a spring maximum observed at all the sites was attributed to increased regional biomass burning. Source area maps of O-3 and CO indicated significantly higher O-3 and CO concentrations associated with air masses passing over a region with increased seasonal open biomass burning, which indicated CO associated with open biomass burning as a major source of O-3 in continental South Africa. A strong correlation between O-3 on CO was observed, while O-3 levels remained relatively constant or decreased with increasing NOx, which supports a VOC-limited regime. The instantaneous production rate of O-3 calculated at Welgegund indicated that similar to 40 % of O-3 production occurred in the VOC- limited regime. The relationship between O-3 and precursor species suggests that continental South Africa can be considered VOC limited, which can be attributed to high anthropogenic emissions of NOx in the interior of South Africa. The study indicated that the most effective emission control strategy to reduce 03 levels in continental South Africa should be CO and VOC reduction, mainly associated with household combustion and regional open biomass burning.Peer reviewe

Rapid changes in biomass burning aerosols by atmospheric oxidation

Peer reviewe

Spatial, temporal and source contribution assessments of black carbon over the northern interior of South Africa

After carbon dioxide (CO2) aerosol black carbon (BC) is considered to be the second most important contributor to global warming. This paper presents equivalent black carbon (eBC) (derived from an optical absorption method) data collected from three sites in the interior of South Africa where continuous measurements were conducted, i.e. Elandsfontein, Welgegund and Marikana, as well elemental carbon (EC) (determined by evolved carbon method) data at five sites where samples were collected once a month on a filter and analysed offline, i.e. Louis Trichardt, Skukuza, Vaal Triangle, Amersfoort and Botsalano. Analyses of eBC and EC spatial mass concentration patterns across the eight sites indicate that the mass concentrations in the South African interior are in general higher than what has been reported for the developed world and that different sources are likely to influence different sites. The mean eBC or EC mass concentrations for the background sites (Welgegund, Louis Trichardt, Skukuza, Botsalano) and sites influenced by industrial activities and/or nearby settlements (Elandsfontein, Marikana, Vaal Triangle and Amersfoort) ranged between 0.7 and 1.1, and 1.3 and 1.4 ae gm 3, respectively. Similar seasonal patterns were observed at all three sites where continuous measurement data were collected (Elandsfontein, Marikana and Welgegund), with the highest eBC mass concentrations measured from June to October, indicating contributions from household combustion in the cold winter months (June-August), as well as savannah and grassland fires during the dry season (May to mid-October). Diurnal patterns of eBC at Elandsfontein, Marikana and Welgegund indicated maximum concentrations in the early mornings and late evenings, and minima during daytime. From the patterns it could be deduced that for Marikana and Welgegund, household combustion, as well as savannah and grassland fires, were the most significant sources, respectively. Possible contributing sources were explored in greater detail for Elandsfontein, with five main sources being identified as coal-fired power stations, pyrometallurgical smelters, traffic, household combustion, as well as savannah and grassland fires. Industries on the Mpumalanga Highveld are often blamed for all forms of pollution, due to the NO2 hotspot over this area that is attributed to NOx emissions from industries and vehicle emissions from the Johannesburg-Pretoria megacity. However, a comparison of source strengths indicated that household combustion as well as savannah and grassland fires were the most significant sources of eBC, par-ticularly during winter and spring months, while coal-fired power stations, pyrometallurgical smelters and traffic contribute to eBC mass concentration levels year round.Peer reviewe

Continuous isoprene measurements in a UK temperate forest for a whole growing season: effects of drought stress during the 2018 heatwave

Isoprene concentrations were measured at four heights below, within and above the forest canopy in Wytham Woods (UK) throughout the summer of 2018 using custom-built gas chromatographs (the iDirac). These observations were complemented with selected ancillary variables, including air temperature, photosynthetically active radiation (PAR), occasional leaf gas exchange measurements and satellite retrievals of normalized difference vegetation and water indices (NDVI and NDWI). The campaign overlapped with a long and uninterrupted heatwave accompanied by moderate drought. Peak isoprene concentrations during the heatwave-drought were up to a factor of 4 higher than those before or after. Higher temperatures during the heatwave could not account for all the observed isoprene; the enhanced abundances correlated with drought stress. Leaf-level emissions confirmed this and also included compounds associated with ecosystem stress. This work highlights that a more in-depth understanding of the effects of drought stress is required to better characterize isoprene emissions

Temporal assessment of volatile organic compounds at a site with high atmospheric variability in the North–West Province

Thesis (MSc (Environmental Sciences))--North-West University, Potchefstroom Campus, 2013Volatile organic compounds (VOCs) are emitted into the atmosphere from biogenic and anthropogenic sources with atmospheric lifetimes ranging from minutes to months, depending on the specific VOC compound considered. It is estimated that biogenic VOCs (BVOCs) (e.g. isoprenes, terpenes) make up 90% of the global atmospheric VOC budget. However, in highly industrialised regions, anthropogenic VOCs (e.g. benzene, toluene, ethylbenzene and xylene, combined abbreviated as BTEX) might dominate. VOCs have various reversible and irreversible effects on human health. They also have environmental impacts that range from changes in the population of terrestrial and aquatic ecosystems to the extinction of vulnerable species. VOCs are precursors for the formation of ozone (O3) during solar radiation initiated reactions in the presence of NOx. Tropospheric O3 is considered a pollutant, with negative impacts on human health, ecosystems and food security. O3 is also a short-lived greenhouse gas. Through reactions with radical species, VOCs lead to the formation of higher molecular weight organic compounds, which produce carbon monoxide (CO), peroxyacytyl nitrate (PAN) and ultimately secondary organic aerosol (SOA) particles. SOA particles impact directly on air quality and visibility, as well as directly and indirectly on the radiation balance of the earth that contributes to the regulation of climate. Notwithstanding the importance of atmospheric VOCs, limited data is available for VOCs in South Africa. In this study, a comprehensive dataset of BVOC and anthropogenic VOC species was obtained at the Welgegund measurement station in the North West Province, South Africa. Measurements were conducted from 9 February 2011 to 4 February 2012. Samples were collected on Tenax-TA and Carbopack-B adsorption tubes twice a week for two hours during day time and two hours during night time. The first 1.25m of the stainless steel sampling inlet was heated to 120ºC to remove O3 that could lead to sample degradation. Analyses of the sampled adsorption tubes were conducted by thermal desorption, cryofocusing, re-desorption, followed by gas chromatography separation and analysis with a mass selective detector (GC-MS). The results indicated that toluene was the most abundant aromatic hydrocarbon and heptane the most abundant alkane. Benzene is currently the only VOC listed as a criteria pollutant in the South African Air Quality Act with an annual average standard of 1.6ppb. The annual median benzene concentration was 0.13 ppb, while the highest daily benzene concentration measured was 8.7 ppb. No distinct seasonal cycles were identified for anthropogenic VOC species measured, i.e. aromatic hydrocarbons and alkanes. However, air mass history analysis indicated that air masses that passed over the Mpumalanga Highveld, the Vaal Triangle and the Johannesburg-Pretoria conurbation (collectively referred to as Area I) had significantly higher concentrations of these anthropogenic VOCs compared to air masses that passed over the western and eastern Bushveld Igneous Complex, and a region over which air masses typically followed an anti-cyclonic movement pattern (collectively referred to as Area II). Anthropogenic VOC levels in air masses that passed over the regional background (areas with no large point sources) had levels similar to air masses that had passed over Area II. Relatively good interspecies correlations (r > 0.8) between most of the aromatic hydrocarbons in air masses that had passed over Area I, with the exception of benzene, indicated that these species had common sources. Benzene, however, correlated well with CO, indicating that sources associated with incomplete combustion were most likely the origin of benzene in air masses that had passed over Area I. The interspecies concentration ratios for plumes passing over Area I indicated that this source region is relatively close to the Welgegund monitoring station and air masses that passed over this source region were substantially influenced by anthropogenic activities. The concentration ratios for plumes that passed over Area II and the Regional Background indicated that these were aged air masses. Furthermore, the concentration ratios of toluene, ethylbenzene and o,m,p-xylene (TEX) to the total aromatic concentration for air masses that passed over the various source regions showed a greater contribution to the total VOC concentration during periods of higher temperature, i.e. summer. This proved that the evaporation of solvents contributes significantly to VOC levels during the months with higher temperatures. The relative contribution of aromatic hydrocarbons to photochemical O3 formation in air masses that passed over the various source regions indicated the highest contribution was observed for air masses that passed over Area I, with Area II and the Regional Background in the same order of magnitude. The annual temporal variations of the measured BVOCs indicated that 2-methyl-3-buten-2-ol (MBO) and isoprene exhibited distinct seasonal patterns, i.e. higher values in summer and lower values in winter. The monoterpenes (MT) and the sesquiterpenes (SQT) did not follow distinct seasonal patterns. BVOC concentrations correlated relatively well to seasonal variations in temperature, photosynthetically active radiation (PAR), rainfall, relative humidity (RH) and CO2 flux. This proved that biogenic activity is responsible for BVOCs emitted. The most abundant MT was -pinene, while -caryophyllene was the most abundant SQT with annual median concentrations of 0.468 ppb and 0.022 ppb, respectively. Pollution roses for isoprene showed a dominance of sources from the north-west to the north-east, as well as the south-east. These directions correlated to areas where pockets of the savannah biome are located.Master

Regional atmospheric Cr(VI) pollution from the Bushveld Complex, South Africa

Hexavalent chromium, Cr(VI), is a proven human carcinogen. Of interest in this paper was the regional atmospheric pollution of Cr(VI) from the ferrochromium and related industries located in the western Bushveld Complex (wBC) of South Africa. A significant fraction of the world's ferrochromium and platinum group metals is produced in this region. Particulate matter (PM), in two size fractions, i.e. PM2.5 (≤2.5 μm) and PM2.5−10 (2.5–10 μm), was sampled for a full calendar year at a regional background site, which is situated downwind of the wBC on the dominant anti-cyclonic recirculation route of air mass over the South African interior. Results indicated that Cr(VI) concentrations in air masses that had passed over the regional background were below the detection limit of the analytical technique applied, but that Cr(VI) in air masses that had passed over the wBC were elevated and had a median concentration of 4.6 ng/m3. The majority of Cr(VI) was found to be in the finer size fraction (PM2.5), which could be explained by the nature of Cr(VI)-containing PM being emitted by the sources in the wBC and the atmospheric lifetimes of different PM size fractions. The results further indicated that it is possible that not only pyrometallurgical sources in the wBC, but also other combustion sources outside the wBC contributed to the observed atmospheric Cr(VI) concentration