Modeling speciated terpenoid emissions from the European boreal forest

We present the first estimates of speciated monoterpene emissions from the North European coniferous forests. Measured emission factors and emission profiles of boreal tree species (Picea abies, Pinus sylvestris, Betula pendula, Salix phylicifolia, Populus tremula, and Alnus incana) were used together with detailed satellite land cover information and meteorological data in an emission model based on the Guenther emission algorithms. The variation of the coniferous biomass within the boreal region (60°N to 70°N) was obtained from forest inventory data, and the seasonal variability of the deciduous biomass was taken into account through simple boreal climatology parameterisation. The annual biogenic emissions in the boreal zone are dominated by coniferous species, but in the summer months, the deciduous contribution to the monoterpene and isoprene emissions is considerable. Norway spruce (Picea abies) is the most important isoprene emitter in the north European boreal forests. The biogenic emission fluxes in the South boreal zone are approximately twice as high as fluxes in the North boreal zone. α- and β-pinene, carene, and cineole are the most abundant emitted terpenes, with a strong contribution of isoprene and linalool during the summer months.     

Seasonal variation of polycyclic aromatic hydrocarbons (PAHs) emissions in China

A regression model based on the provincial energy consumption data was developed to calculate the monthly proportions of residential energy consumption compared to the total year volume. This model was also validated by comparing with some survey and statistical data. With this model, a PAHs emission inventory with seasonal variation was developed. The seasonal variations of different sources in different regions of China and the spatial distribution of the major sources in different seasons were also achieved. The PAHs emissions were larger in the winter than in the summer, with a difference of about 1.3-folds between the months with the largest and the smallest emissions. Residential solid fuel combustion dominated the pattern of seasonal variation with the winter-time emissions as much as 1.6 times as that in the summer, while the emissions from wild fires and open fire straw burning was mainly concentrated during the spring and summer.     

Seasonal variations of monoterpene emissions from Pinus densiflora in East Asia

The emission rates and compositions of monoterpene from Pinus densiflora were investigated in the Gumsung (GM) and Worak (WM) mountains. The standard emission rates (ERs: ERs is the monoterpene emission rate at standard temperature, 30 degrees C) from P. densiflora ranged from 0.817 to 1.704 (mugC/gdw-h). The ERs and beta-values of total monoterpene were measured at the two study sites (GM and WM). In the spring and summer, the ERs were the highest, while relatively low values (<0.058mugC/gdw-h) were measured in the autumn and winter. In GM and WM sites the beta-value obtained for the different seasons ranged from 0.047 to 0.179, with an average of 0.09. The major monoterpene compounds from P. densiflora were alpha-pinene, myrcene, beta-phellandrene, d-limonene and alpha-terpinene. The fractional compositions of individual monoterpene compounds were significantly different between the two test sites in the summer and winter. The ERs of the older group (31-40 years) were higher than those in the younger group (21-30 years). However, the monoterpene compositions were similar between the two age groups.     

Emissions of biogenic VOC from forest ecosystems in central Europe: Estimation and comparison with anthropogenic emission inventory

This paper describes a method of estimating emission fluxes of biogenic volatile organic compounds (BVOCs) based on the approach proposed by Guenther et al. (1995) and the high-resolution Corine land-cover 2000 database (1 × 1 km resolution). The computed emission fluxes for the Czech Republic (selected for analysis as being representative of a heavily cultivated, central European country) are compared with anthropogenic emissions, both for the entire country and for individual administrative regions. In some regions, BVOC emissions are as high as anthropogenic emissions; however, in most regions the BVOC emissions are approximately 50% of the anthropogenic emissions. The yearly course of BVOC emissions (represented by monoterpenes and isoprene) is presented, along with the spatial distribution of annual mean values. Differences in emission distributions during winter (January) and summer (June) are also considered.     

Determination and potential importance of diterpene (kaur-16-ene) emitted from dominant coniferous trees in Japan

Reactive volatile organic compounds (VOCs) are known to affect atmospheric chemistry. Biogenic VOCs (BVOCs) have a significant impact on regional air quality due to their large emission rates and high reactivities. Diterpenes (most particularly, kaur-16-ene) were detected in all of the 205 enclosure air samples collected over multiple seasons at two different sites from Cryptomeria japonica and Chamaecyparis obtusa trees, the dominant coniferous trees in Japan,. The emission rate of kaur-16-ene, was determined to be from 0.01 to 7.1 μg dwg⁻¹ h⁻¹ (average: 0.61 μg dwg⁻¹ h⁻¹) employing branch enclosure measurements using adsorbent sampling followed by solid phase-liquid extraction techniques. The emission rate was comparable to that of monoterpenes, which is known major BVOC emissions, collected from the same branches. In addition, total emission of kaur-16-ene at 30 °C was estimated to exceed that of total anthropogenic VOC emissions.     

Seasonal variations of hydroxylated and methoxylated brominated diphenyl ethers in blue mussels from the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) found at high levels in the Baltic biota are mainly natural products, but can also be formed through metabolism or abiotic oxidation of polybrominated diphenyl ethers (PBDEs). The formation of OH-PBDEs is of concern since there is growing evidence of phenolic toxicity. This study investigates seasonal variations in levels of OH-PBDEs and MeO-PBDEs, focusing on an exposed species, the blue mussel (Mytilus edulis), sampled in the Baltic Sea in May, June, August and October of 2008. Both the OH-PBDE and MeO-PBDE levels in the mussels showed seasonal variations from May to October, the highest concentration of each congener appearing in June. The seasonal variation was more marked for OH-PBDEs than in MeO-PBDEs, but all congeners showed the same trends, except 6-MeO-BDE47 and 2′-MeO-BDE68, which did not significantly decline in concentrations after June. Biotic or abiotic debromination is suggested as a possible reason for the rapid decrease in methoxylated penta- and hexa-BDE concentrations observed in blue mussels from June to August, while the tetraBDE concentrations were stable. In addition, 1,3,7/1,3,8-tribrominated dibenzo-p-dioxins showed the same seasonal variation. The seasonal variations indicates natural formation and are unlikely to be due to transformation of anthropogenic precursors. The levels of PBDEs were fairly constant over time and considerably lower than those of the OH-PBDEs and MeO-PBDEs. The timing of the peaks in concentrations suggests that filamentous macro-algae may be important sources of these compounds found in the blue mussels from this Baltic Sea location.     

Direct and indirect impact of sewage sludge compost spreading on Quercus coccifera monoterpene emissions in a Mediterranean shrubland

Monoterpene emissions of Quercus coccifera L. were repeatedly measured during the two years following the spreading of a sewage sludge compost at rates of 50 Mg ha⁻¹ and 100 Mg ha⁻¹, in a twelve-year-old post-fire Mediterranean shrubland. We also monitored the patterns of change in soil and leaf nutrient content, plant water potential, chlorophyll fluorescence, and plant growth. Compost spreading resulted in weak changes in leaf nutrient content and plant water status, and therefore no significant effect on monoterpene emissions at leaf scale, except during one summer sampling, probably related to advanced leaf maturity with the highest compost rate. However, compost increased plant growth, particularly the leaf biomass. The results suggest that compost spreading in Mediterranean shrublands has no strong short-term effect on Q. coccifera monoterpene emissions at leaf level, but may indirectly increase volatile organic compound fluxes at the stand scale, which may contribute to regional ozone pollution.     

Modeling vehicle emissions in different types of Chinese cities: importance of vehicle fleet and local features

We propose a method to simulate vehicle emissions in Chinese cities of different sizes and development stages. Twenty two cities are examined in this study. The target year is 2007. Among the cities, the vehicle emission factors were remarkably different (the highest is 50-90% higher than the lowest) owing to their distinct local features and vehicle technology levels, and the major contributors to total vehicle emissions were also different. A substantial increase in vehicle emissions is foreseeable unless stronger measures are implemented because the benefit of current policies can be quickly offset by the vehicle growth. Major efforts should be focused on all cities, especially developing cities where the requirements are lenient. This work aims a better understanding of vehicle emissions in all types of Chinese cities. The proposed method could benefit national emission inventory studies in improving accuracy and help in designing national and local policies for vehicle emission control.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in urban and suburban areas of Korea

Bulk atmospheric samples (wet and dry) were collected monthly throughout a year at urban and suburban areas of Korea to assess the deposition flux and seasonal variations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The PCDDs/DFs deposition fluxes ranged from 1.0 to 3.7 ng TEQ/m²/year in the urban area and from 0.5 to 4.6 ng TEQ/m²/year in the suburban area. The deposition fluxes of PCDDs/DFs in this study were comparable to or lower than those previously reported at different locations. The atmospheric deposition fluxes of particles and PCDDs/DFs in winter tended to be higher than those in summer. However, monthly variations between particle and PCDDs/DFs deposition fluxes were small, and the correlation coefficients between the deposition fluxes of air particles and each homologue group of PCDDs/DFs varied according to the degree of chlorination of the homologue group. The deposition velocity of PCDDs/DFs in the urban area was estimated at 0.04 cm/s, which is a lower value than those found in other studies. The two most likely factors affecting the monthly variation of deposition fluxes are the ambient temperature and the amount of precipitation. In particular, the ambient temperature had an influence on the lower chlorinated homologues of PCDDs/DFs while precipitation had an influence on the higher chlorinated PCDDs/DFs. The PCDDs/DFs profiles in atmospheric deposition bulk samples showed a similar pattern at the urban and suburban sites. The possibility of the loading of PCDDs/DFs by Asian dust events could be partly confirmed by investigation of homologue profiles.     

Spatial and seasonal variations of polycyclic aromatic hydrocarbons in Haihe Plain, China

A dynamic fugacity model was developed to simulate the spatial and seasonal variations of PAHs in Haihe Plain, China. The calculated and measured concentrations exhibited good consistency in magnitude with deviations within a factor of 4 in air and 2 in soil. The spatial distributions of PAHs in air were mainly controlled by emission while the seasonal variations were dominated by emission and gas-particle partition. In soil, the spatial distributions of PAHs were controlled by the soil organic carbon content while the seasonal variations were insignificant. The severest soil contamination was observed in Shanxi and followed by the southwest of Hebei province. Transfer fluxes of total PAHs between air and soil were calculated. The spatial distribution of air-to-soil flux was closely related to the landcover while the soil-to-air flux changed with soil organic matter content. Monte Carlo simulation was done to evaluate the uncertainty of the estimated results in air.     

Spatial and temporal variations and mobile source emissions of polycyclic aromatic hydrocarbons in Quito, Ecuador

Motor vehicles are a major source of air pollution in Quito, Ecuador; however, little work has been done to characterize spatial and temporal variations in traffic-related pollutants, or to measure pollutants in vehicle emissions. We measured PAH continuously for one year at two residential sites in Quito, and PAH and traffic patterns for one week near a busy roadway. Morning rush-hour traffic and temperature inversions caused daily PAH maxima between 06:00 and 08:00. SO₂, NO_x, CO, and PM_2.5 behaved similarly. At the residential sites PAH levels during inversions were 2-3-fold higher than during the afternoon, and 10-16-fold higher than 02:00-03:00 when levels were lowest. In contrast, at the near-roadway site, PAH concentrations were 3-6-fold higher than at the residential sites, and the effects of inversions were less pronounced. Cars and buses accounted for >95% of PAH at the near-roadway site. Near-roadway PAH concentrations were comparable to other polluted cities.     

Historical estimation of carbonaceous aerosol emissions from biomass open burning in China for the period 1990-2005

Multi-year inventories of carbonaceous aerosol emissions from biomass open burning at a high spatial resolution of 0.5° × 0.5° have been constructed in China using GIS methodology for the period 1990-2005. Black carbon (BC) emissions have increased by 383.03% at an annual average rate of 25.54% from 14.05 Gg in 1990 to 67.87 Gg in 2005; while organic carbon (OC) emissions have increased by 365.43% from 57.37 Gg in 1990 to 267.00 Gg in 2005. Through the estimation period, OC/BC ratio for biomass burning was averagely 4.09, suggesting that it was not the preferred control source from a climatic perspective. Spatial distribution of BC and OC emissions were similar, mainly concentrated in three northeastern provinces, central provinces of Shandong, Jiangsu, Anhui and Henan, and southern provinces of Guangxi, Guangdong, Hunan and Sichuan basin, covering 24.89% of China’s territory, but were responsible for 63.38% and 67.55% of national BC and OC emissions, respectively.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans emissions from open burning of crop residues in China between 1997 and 2004

Annual emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from open burning of crop residues in each province of China mainland between 1997 and 2004 were estimated to be ranged from 1.38x10(3) to 1.52x10(3) g I-TEQ/yr, with the average of 1.50+/-0.08x10(3) g I-TEQ/yr, which contributed to approximately 10% approximately 20% of the total emissions in China. The PCDD/F emissions mainly occurred in the largest crop-producing provinces, especially in those of higher economic levels. The major sources of PCDD/F emissions from open burning in China were found to be cereal residues (i.e. rice, wheat, and corn), which accounted about 70% of the total emissions. Moreover, the first-order one-variable grey differential equation model (GM (1,1) model) for annual emissions of PCDD/Fs was established based on grey system theory. The GM (1,1) model was proved to be robust to predict the annual PCDD/F emissions from crop residue field burning in forthcoming years.     

Seasonal differences and within-canopy variations of antioxidants in mature spruce (Picea abies) trees under elevated ozone in a free-air exposure system

The effect of free-air ozone fumigation and crown position on antioxidants were determined in old-growth spruce (Picea abies) trees in the seasonal course of two consecutive years (2003 and 2004). Levels of total ascorbate and its redox state in the apoplastic washing fluid (AWF) were increased under double ambient ozone concentrations (2xO3), whilst ascorbate concentrations in needle extracts were unchanged. Concentrations of apoplastic and symplastic ascorbate were significantly higher in 2003 compared to 2004 indicating a combined effect of the drought conditions in 2003 with enhanced ozone exposure. Elevated ozone had only weak effects on total glutathione levels in needle extracts, phloem exudates and xylem saps. Total and oxidised glutathione concentrations were higher in 2004 compared to 2003 and seemed to be more affected by enhanced ozone influx in the more humid year 2004 compared to the combined effect of elevated ozone and drought in 2003 as observed for ascorbate.     

An inventory of N(2)O emissions from agriculture in China using precipitation-rectified emission factor and background emission

Fertilized agricultural soils are a major anthropogenic source of atmospheric N₂O. A credible national inventory of agricultural N₂O emission would benefit its global strength estimate. We compiled a worldwide database of N₂O emissions from fertilized fields that were consecutively measured for more than or close to one year. Both nitrogen input (N) and precipitation (P) were found to be largely responsible for temporal and spatial variabilities in annual N₂O fluxes (N₂O–N). Thus, we established an empirical model (N₂O–N = 1.49 P + 0.0186 P · N), in which both emission factor and background emission for N₂O were rectified by precipitation. In this model, annual N₂O emission consists of a background emission of 1.49 P and a fertilizer-induced emission of 0.0186 P · N. We used this model to develop a spatial inventory at the 10 × 10 km scale of direct N₂O emissions from agriculture in China. N₂O emissions from rice paddies were separately quantified using a cropping-specific emission factor. Annual fertilizer-induced N₂O emissions amounted to 198.89 Gg N₂O–N in 1997, consisting of 18.50 Gg N₂O–N from rice paddies and 180.39 Gg N₂O–N from fertilized uplands. Annual background emissions and total emissions of N₂O from agriculture were estimated to be 92.78 Gg N₂O–N and 291.67 Gg N₂O–N, respectively. The annual direct N₂O emission accounted for 0.92% of the applied N with an uncertainty of 29%. The highest N₂O fluxes occurred in East China as compared with the least fluxes in West China.     

Seasonal and spatial variability of polychlorinated biphenyls (PCBs) in vegetation and cow milk from a high altitude pasture in the Italian Alps

The seasonal and spatial variability of polychlorinated biphenyls (PCBs) in vegetation and cow milk was studied in a high altitude pasture in the Alps (1900 m a.s.l.). PCB contamination in vegetation shows a concentration peak in June, which is mainly interpreted as the consequence of a temporary PCB enrichment of the air layer above the ground due to net emission fluxes from the soil. A three compartment dynamic model was developed to test this hypothesis. The North/South enrichment factor in the vegetation was 1.5-1.6 for penta- and hexa-substituted congeners and 1.7 for hepta- and octa-PCBs, according to the effect of temperature on compounds having higher K_oa values. Milk concentrations followed the vegetation seasonal trend. The congener abundance in milk is in agreement with the biotransformation susceptibility, absorption efficiency and residence time of the different congeners in dairy cows.     

Seasonal variations of CH(4) and N(2)O emissions in response to water management of paddy fields located in Southeast China

Water management is one of the most important practices that affect methane (CH₄) and nitrous oxide (N₂O) emissions from paddy fields. A field experiment was designed to study the effects of controlled irrigation (CI) on CH₄ and N₂O emissions from paddy fields, with traditional irrigation (TI) as the control. The effects of CI on CH₄ and N₂O emissions from paddy fields were very clear. The peaks of CH₄ emissions from the CI paddies were observed 1-2 d after the water layer disappeared. Afterward, the emissions reduced rapidly and remained low until the soil was re-flooded. A slight increase of CH₄ emission was observed in a short period after re-flooding. N₂O emissions peaks from CI paddies were all observed 8-10 d after the fertilization at the WFPS ranging from 78.1% to 85.3%. Soil drying caused substantial N₂O emissions, whereas no substantial N₂O emissions were observed when the soil was re-wetted after the dry phase. Compared with TI, the cumulative CH₄ emissions from the CI fields were reduced by 81.8% on the average, whereas the cumulative N₂O emissions were increased by 135.4% on the average. The integrative global warming potential of CH₄ and N₂O on a 100-year horizon decreased by 27.3% in the CI paddy fields, whereas no significant difference in the rice yield was observed between the CI and TI fields. These results suggest that CI can effectively mitigate the integrative greenhouse effect caused by CH₄ and N₂O emissions from paddy fields while ensuring the rice yield.     

Nitrogen isotope variations in camphor (Cinnamomum Camphora) leaves of different ages in upper and lower canopies as an indicator of atmospheric nitrogen sources

Nitrogen isotopic composition of new, middle-aged and old camphor leaves in upper and lower canopies has been determined in a living area, near a motorway and near an industrial area (Jiangan Chemical Fertilizer Plant). We found that at sites near roads, more positive δ¹⁵N values were observed in the camphor leaves, especially in old leaves of upper canopies, and ?δ¹⁵N = δ¹⁵N_upper − δ¹⁵N_lower > 0, while those near the industrial area had more negative δ¹⁵N values and ?δ¹⁵N < 0. These could be explained by two isotopically different atmospheric N sources: greater uptake from isotopically heavy pools of atmospheric NO_x by old leaves in upper canopies at sites adjacent to roads, and greater uptake of ¹⁵N-depleted NH_y in atmospheric deposition by leaves at sites near the industrial area. This study presents novel evidence that ¹⁵N natural abundance of camphor leaves can be used as a robust indicator of atmospheric N sources.     

Comparison of surface emissions and subsurface distribution of cis- and trans-1,3-dichloropropne and chloropicrin in sandy field beds covered with four different plastic films

The purpose of this study was to conduct a field study at a Florida field site on surface emissions and subsurface distribution of cis-and trans-1,3-dichloropropene (1,3-D) and chloropicrin (CP) in raised beds injected with Telone C35 with four replications. A total of 16 beds were applied with Telone C35 by chisel injection and covered with four different plastic films, 4 beds for each film. Each bed was installed with five 20-cm long soil pore air probes and a surface air collection pan at arbitrarily locations along the length of each bed for sampling soil pore air and surface air, respectively, for analysis of the three biologically active compounds, cis- and trans-1,3-D and CP. We found that average concentrations of the three compounds at 20-cm depth among the beds covered with four different plastic films generally were not statistically different. Among the four beds covered with the same plastic film, average concentrations of the three compounds were statistically different only in the four metallic PE covered beds at 5 and 24 hours after injection. Volatilization rates of the three compounds among the beds covered with four different plastic films, with the exception of CP at 48 hours after injection, were not statistically different. It appeared that initial upward diffusion and volatilization flux were influenced by solar radiation. Initial subsurface concentrations of the three compounds and volatilization flux, especially cis-1,3-D, were greater in the beds on the east side of the field than that in the beds on the west side of the field. Whether or not difference in initial subsurface concentrations of the compounds between east side beds and west side beds may influence fumigant efficacy remains to be determined.