Emissions of Polycyclic aromatic hydrocarbons by savanna fires

Although Polycyclic aromatic hydrocarbons (PAH) are known as anthropogenic compounds arising from the combustion or the pyrolysis of fossil fuels, they may be also emitted by the combustion of vegetation. A field study was carried out in January 1991 at Lamto (Ivory Coast) as part of the FOS DECAFE experiment (Fire Of Savanna). Some ground samplings were devoted to the qualitative and quantitative characterization of atmospheric emissions by savanna fires during prescribed burns and under background conditions. Specific collections for gaseous and particulate PAHs have shown that the African practice of burning the savanna biomass during the winter months is an important source of PAHs. These compounds are emitted mainly in gaseous form but a significant fraction, essentially heavy PAHs, is associated with fine carbonaceous particles and can therefore represent a hazard for human health, since some of these compounds are mutagenic and carcinogenic. Twelve compounds were identified during the fire episodes and in the atmospheric background. The total concentration in the fires is of the order of 10 ng m^–3 for the gas phase and from 0.1 to 1 ng m^–3 in the aerosols. In the atmospheric background the mean concentrations are regular, 0.15 ng m^–3 and 2 pg m^–3, respectively. These concentrations are comparable with what is observed in European rural zones. The particulate emissions of PAHs by the savanna fires are distinguished by the abundance of some compounds which can be considered as tracers, although they are also slightly emitted by fossil fuel sources. These compounds are essentially pyrene, chrysene and coronene. In the gas phase, although no individual PAH may be considered as specific of the biomass combustion emissions, the relative abundances of the main PAHs are characteristic of the biomass burning. The concentrations of pyrene and fluorene are always predominant; these compounds could be considered as characteristic emission products of smoldering and flaming episodes, respectively. In the background the PAH composition shows that in a tropical region the air consists of a mixture coming from the various sources, but the biomass combustion is by far the most important source.The fluxes of total PAH emitted by savanna biomass burning in Africa were estimated to be of the order of 17 and 600 ton yr^–1, respectively, for the particulate PAHs and the gaseous PAHs, respectively.     

210Po in savanna burning plumes

During the FOS-DECAFE experiment at Lamto (Ivory Coast) in January 1991 aerosols samples were collected at ground level above fires in order to investigate the possibility of using²¹⁰Po as a tracer of biomass burning. The concentration of this radionuclide in plants is studied as a function of its content in soils and in the atmospheric background. It is shown that it depends strongly on the atmospheric content in²¹⁰Po, due to dry deposition of the aerosols. The mean concentration of plants at Lamto is found to be about 4.4 pCi of²¹⁰Po/gC during the fire season and falls down to less than 1pCi/gC outside this period. The budget of²¹⁰Po is evaluated taking into account its complete volatilization during the flaming phase, the (²¹⁰Po)_ash/(²¹⁰Po)_plants ratio, which is measured to be about 14% and the percentage of submicron particles in the plume, about 91%. The inferred flux of²¹⁰Po is 3850 Ci/yr for the African savanna, and 5800 Ci/yr for the global savanna. From this flux, fluxes of Ct and Cs are estimated to be 8.4 and 1.1 Tg of C/yr for the worldwide savanna.     

Particulate content of savanna fire emissions

As part of the FOS-DECAFE experiment at Lamto (Ivory Coast) in January 1991, various aerosol samples were collected at ground level near prescribed fires or under local background conditions, to characterize the emissions of particulate matter from the burning of savanna vegetation. This paper deals with total aerosol (TPM) and carbon measurements. Detailed trace element and polycyclic hydrocarbon data are discussed in other papers presented in this issue.Near the fire plumes, the aerosols from biomass burning are primarily of a carbonaceous nature (C%70% of the aerosol mass) and consist predominantly of submicron particles (more than 90% in mass.) They are characterized by their organic nature (black to total carbon ratio Cb/Ct in the range 3–20%) and their high potassium content (K/Cb0.6). These aerosols undergo aging during their first minutes in the atmosphere causing slight alterations in their size distribution and chemical composition. However, they remain enriched in potassium (K/Cb=0.21) and pyrene, a polycyclic aromatic hydrocarbon, such that both of these species may be used as tracers of savanna burning aerosols. We show that during this period of the year, the background atmosphere experiences severe pollution from both terrigenous sources and regional biomass burning (44% of the aerosol). Daynight variations of the background carbon concentrations suggest that fire ignition and spreading occur primarily during the day. Simultaneous TPM and CO₂ real-time measurements point to a temporal and spatial heterogeneity of the burning so that the ratio of the above background concentrations (TPM/CO₂) varies from 2 to 400 g/kg C. Smoldering processes are intense sources of particles but particulate emissions may also be important during the rapidly spreading heading fires in connection with the generation of heavy brown smoke. We propose emission factor values (EF) for aerosols from the savanna biomass burning aerosols: EF (TPM)=11.4±4.6 and 69±25 g/kg C_{dry plant} and EF(Ct)=7.4±3.4 and 56±16 g C/kg C_{dry plant} for flaming and smoldering processes respectively. In these estimates, the range of uncertainty is mostly due to the intra-fire variability. These values are significantly lower than those reported in the literature for the combustion of other types of vegetation. But due to the large amounts of vegetation biomass being burnt in African savannas, the annual flux of particulate carbon into the atmosphere is estimated to be of the order of 8 Tg C, which rivals particulate carbon emissions from anthropogenic activities in temperate regions.     

Aerosol black carbon measurements in the Arctic haze during AGASP-II

During the second Arctic Gas and Aerosol Sampling Program conducted in April 1986, we performed measurements of the optically absorbing carbonaceous component of the ambient aerosol from the NOAA WP-3D aircraft operating between sea level and 10 km altitude. We collected the aerosol of filters that were exposed for several hours; we also operated the aethalometer to measure the concentration of aerosol black carbon in real time. The filter analyses represent averages over the altitude range and time span during which the filter was collecting. The real-time results were sorted by altitude to calculate vertical profiles of black carbon concentration. Values typically ranged from 300 to 500 ng m^–3 at lower altitudes, decreasing gradually to 25 to 100 ng m^–3 at 8–10 km. Strong stratification at lower altitudes was frequently observed. The magnitude of these concentrations suggests that the sources are distant regions of considerable fuel consumption. The presence of this material in the tropospheric column and its probable deposition to the high-albedo surface may result in perturbations of the solar radiation balance. The concentrations measured at the highest altitudes may mean that particulate carbon and accompanying emissions for which it is a tracer are mixing into the stratosphere.     

Stable carbon and nitrogen isotopic characteristics of PM2.5 and PM10 in Delhi,India

This study presents the chemical composition (carbonaceous and nitrogenous components) of aerosols (PM_2.5 and PM₁₀) along with stable isotopic composition (δ¹³C and δ¹⁵N) collected during winter and the summer months of 2015–16 to explore the possible sources of aerosols in megacity Delhi, India. The mean concentrations (mean?±?standard deviation at 1σ) of PM_2.5 and PM₁₀ were 223?±?69 µg m^?3 and 328?±?65 µg m^?3, respectively during winter season whereas the mean concentrations of PM_2.5 and PM₁₀ were 147?±?22 µg m^?3 and 236?±?61 µg m^?3, respectively during summer season. The mean value of δ¹³C (range: ??26.4 to ??23.4‰) and δ¹⁵N (range: 3.3 to 14.4‰) of PM_2.5 were ??25.3?±?0.5‰ and 8.9?±?2.1‰, respectively during winter season whereas the mean value of δ¹³C (range: ??26.7 to ??25.3‰) and δ¹⁵N (range: 2.8 to 11.5‰) of PM_2.5 were ??26.1?±?0.4‰ and 6.4?±?2.5‰, respectively during the summer season. Comparison of stable C and N isotopic fingerprints of major identical sources suggested that major portion of PM_2.5 and PM₁₀ at Delhi were mainly from fossil fuel combustion (FFC), biomass burning (BB) (C-3 and C-4 type vegitation), secondary aerosols (SAs) and road dust (SD). The correlation analysis of δ¹³C with other C (OC, TC, OC/EC and OC/WSOC) components and δ¹⁵N with other N components (TN, NH₄⁺ and NO₃^?) are also support the source identification of isotopic signatures.

     

Carbonaceous materials in size-segregated atmospheric aerosols from urban and coastal-rural areas at the Western European Coast

A high-volume cascade impactor, equipped with a PM10 inlet, was used to collect size-segregated aerosol samples during the summer of 2004 at two Portuguese locations: a coastal-rural area (Moitinhos) and an urban area (Oporto). Concentrations of airborne particulate matter (PM), total carbon (TC), organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were determined for the following particle size ranges: < 0.49, 0.49–0.95, 0.95–3.0, and 3.0–10 µm. The total PM mass concentrations at the urban and coastal-rural sites ranged from 22.8 to 79.6 μg m^− 3 and 19.9 to 28.2 μg m^− 3, respectively, and more than 56% of the total aerosol mass was found in the fractions below 3.0 μm. At both locations the highest concentrations of OC and EC were found in the submicrometer size range. The regional variability for the OC and EC concentrations, with the highest concentrations being found in the urban area, was related to the contribution of local primary sources (mostly traffic emissions). It was also verified an enrichment of the small size particles in WSOC, representing on average 37.3(± 12.4)% and 59.7(± 18.0)% of OC in the very fine aerosol at the coastal-rural and urban areas, respectively. The amount of secondary OC calculated by the minimum OC/EC ratio method indicates that secondary organic aerosol formation was important throughout the study at both sites. The obtained results suggest that long-range transport and favourable summer conditions for photochemical oxidation are key factors determining secondary OC formation in the coastal-rural and urban areas. The ultraviolet absorption properties of the chromophoric constituents of the WSOC fractions were also different among the different particle size ranges and also between the two sampling locations, thus suggesting the strong impact of the diverse emission sources into the composition of the size-segregated organic aerosol.     

Trace elements in tropical African savanna biomass burning aerosols

As a part of the FOS/DECAFE experiment, aerosol particles emitted during prescribed savanna fires were collected in January 1991 at Lamto (Ivory Coast), either close to the emission or in ambient air. Analytical transmission electron microscopy pointed out the presence of sub-micrometer soots, salt condensates, vegetation relicts and soil derived particles. The samples were also analyzed for their total particulate matter (TPM) content and elemental composition by PIXE or XRF. At the emission, high concentrations of soil derived elements (Fe and Al) pointed out an intense remobilization process during the fires. Biomass burning emissions contributed to more than 90% of the measured concentrations, of P, Cl, S, K, Cu and Zn, which were found primarily in the fine fraction with the exception of P. Near the emission, K was mainly present as KCl, evolving to K₂SO₄ in the ambient samples. Trace elements emission factors were obtained for the first time for the African savanna burning and their annual emissions were estimated: our median K emission factor (0.78 g/kg of C) is higher than estimates for other ecosystems (0.2–0.58 g/kg of C); Zn emissions (0.008 Tg/year) account for 4 to 11% of the global anthropogenic emissions.     

Application of Lead Isotopic Ratios in Atmospheric Pollution Studies in the Valley of Mexico

Lead isotopic studies of airborne particulate matter, gasoline and other environmental samples have been carried out to determine possible sources of lead pollution in the Metropolitan Zone of the Valley of Mexico. ²⁰⁶Pb/²⁰⁷Pb ratio in gasoline was 1.1395 ± 0.0165 and 1.071 ± 0.008 for industrially-derived lead as a mean. Natural lead is more radiogenic with values from 1.2082 ± 0.022 to 1.211 ± 0.108. The measured Pb isotopic signature of airborne particulate matter reflects the relative importance of each of these sources. The ²⁰⁶Pb/²⁰⁷Pb ratio was 1.179 ± 0.105 as a mean. The relative importance of gasoline has decreased, and, therefore, other sources (natural and industrial) can be identified by means of isotopic studies. This is a consequence of the introduction of unleaded gasoline as mandaped by strictest environmental regulation.     

Isoprene emissions from vegetation and hydrocarbon emissions from bushfires in tropical Australia

Information from a variety of sources, including an airborne field expedition in November 1985, is used to produce estimates of the annual emissions of some hydrocarbons from bushfires, and isoprene from trees, in tropical Australia. For the continent north of 23° S the annual bushfires (biomass burning) input was estimated, in units of Tg carbon, to be 2 TgC (uncertainty range 0.8–5 TgC), emitted predominantly during the May to October dryseason. Isoprene emissions during this period were estimated also to be 2 TgC (uncertainty range 0.5–8 TgC), but were estimated to be an order of magnitude higher during the November to April wet season, at a level of 23 TgC (uncertainty range 6–100 TgC).The large annual emission of isoprene over the tropical part of the Australian continent yields ppbv levels of isoprene measured at the surface in summertime. Isoprene reactivity with hydroxyl radical is such that at these concentrations isoprene must be a dominant factor in controlling the concentration of OH radical in the convective boundary layer. Simple arguments based on the convective velocity scale suggest that the shape of the isoprene vertical profile in November 1985 would be consistent with available data on the OH-isoprene reaction rate if OH concentration in the boundary layer averaged about 2.5×10⁶ cm^-3 over the middle part of the day.Temporarily at the International Meteorological Institute, Stockholm University, S-106 91, Stockholm, Sweden.     

Fluxes of gases and particles above a deciduous forest in wintertime

Eddy-correlation measurements of the vertical fluxes of ozone, carbon dioxide, fine particles with diameter near 0.1 m, and particulate sulfur, as well as of momentum, heat and water vapor, have been taken above a tall leafless deciduous forest in wintertime. During the experimental period of one week, ozone deposition velocities varied from about 0.1 cm s^–1 at night to more than 0.4 cm s^-1 during the daytime, with the largest variations associated primarily with changes in solar irradiation. Most of the ozone removal took place in the upper canopy. Carbon dioxide fluxes were directed upward due to respiration and exhibited a strong dependence on air temperature and solar heating. The fluxes were approximately zero at air temperatures less than 5 °C and approached 0.8 mg m^–2 s^–1 when temperatures exceeded 15 °C during the daytime. Fine-particle deposition rates were large at times, with deposition velocities near 0.8 cm s^–1 when turbulence levels were high, but fluxes directed upward were found above the canopy when the surface beneath was covered with snow. Diffusional processes seemed to dominate fine-particle transfer across quasilaminar layers and subsequent deposition to the upper canopy. Deposition velocities for particulate sulfur were highly variable and averaged to a value small in magnitude as compared to similar measurements taken previously over a pine forest in summer.     

Global transport and inter-reservoir exchange of carbon dioxide with particular reference to stable isotopic distributions

A two-dimensional model of global atmospheric transport is used to relate estimated air-to-surface exchanges of carbon dioxide (CO₂) to spatial and temporal variations of atmospheric CO₂ concentrations and isotopic composition. The atmospheric model coupled with models of the biosphere and mixed layer of the ocean describes the gross features of the global carbon cycle. In particular this paper considers the change in isotopic composition due to interreservoir exchanges and thus the potential application and measurement requirements of new isotopic observational programs.A comparison is made between the model-generated CO₂ concentration variation and those observed on secular, interannual and seasonal time scales and spatially through the depth of the troposphere and meridionally from pole-to-pole.The relationship between isotopic and concentration variation on a seasonal time-scale is discussed and it is shown how this can be used to quantitatively estimate relative contributions of biospheric and oceanic CO₂ exchange. Further, it is shown that the interhemispheric gradient of concentration and isotopic ratio results primarily from the redistribution of fossil fuel CO₂. Both isotopic and concentration data indicate that tropical deforestation contributes less than 2 Gt yr^-1 of carbon to the atmosphere.The study suggests that changes in the rate of change of the ratio of ¹³C to ¹²C in the atmosphere of less than 0.03 yr^-1 might be expected if net exchanges with the biosphere are the cause of interannual variations of CO₂ concentrations.     

Seasonal trend of particulate PAHs at Gosan, a background site in Korea between 2001 and 2002 and major factors affecting their levels

The concentrations of particulate Polycyclic aromatic hydrocarbons (PAHs) were measured at Gosan, a background site in Korea for 1 year between November 2001 and November 2002. The total concentrations of 14 PAH compounds at Gosan were between 0.52 and 14.76 ng m^− 3 and about 3–15 times higher than those at other rural or remote sites in the world. Seasonal trend was observed for particulate PAHs concentrations at Gosan with higher levels during heating season due to increased fossil fuel usage and the movement of air parcels from Asian continent. Principal component factor analysis (PCF) for PAHs showed three factors; combination of coal combustion and vehicular emission, natural gas combustion, and unidentified one. However, PCF for the combined data of PAHs, inorganic ions, and elements revealed that the unidentified factor consists of crustal species, sea salts, and four PAH compounds. Thus, this factor is thought to be transport of crustal species with organics from combustion sources. The major variables which determine the sources of PAHs are the heating season and the movement of air parcels from Asian continent.     

Light hydrocarbons in the surface water of the mid-Atlantic

During a cruise of RV Polarstern over the Atlantic in September/October 1988, C₂–C₄ hydrocarbons were measured in surface sea water. The ship passed through three different ocean regions divided by divergences at 8° N and 3° S. Hydrocarbon concentrations differed considerably in these regions. The highest values were obtained for ethene with mean concentrations of 246 pMol/l between 35° N and 8° N, 165 pMol/l between 8° N and 3° S, and 63 pMol/l between 3° S and 30° S. Low values were found for i- and n-butane and acetylene between 32 pMol/l and 1 pMol/l. The alkene concentrations were in general higher than the concentrations of their saturated homologs. Concentrations decreased with increasing carbon numbers. The various alkenes were well correlated with one another as were the various alkanes. Oceanic emission rates of the light hydrocarbons were calculated from their sea water concentrations using an ocean atmosphere exchange model. The averaged fluxes ranged from about 10⁸ molec cm^-2 s^-1 for the alkenes and ethane to less than 10⁷ molec cm^-2 s^-1 for the C₄ alkanes. Acetylene emissions were below 3×10⁶ molec cm^-2 s^-1. Based upon these rates budget estimates of NMHC in the ocean surface layer were made with a simple model considering production and destruction processes in the water. The emissions to the atmosphere appear to be the dominant loss process between 35° N and 8° N, whereas destruction in the water seems to be dominant in the latitude ranges 8° N-3° S and 3° S-30° S.     

Laboratory studies of some environmental variables controlling sulfur emissions from plants

Several trace sulfur gases that can have a significant influence on atmospheric chemistry are emitted from biological systems. In order to begin to address biological questions on the mechnisms of production of such gases, laboratory-scale experiments have been developed that reproduce such emissions under controlled conditions. Using a flux chamber technique, flats containing soil, or soil plus plants were sampled for the net fluxes of sulfur gases. The major sulfur gas emitted from all the plants tested (corn, alfalfa, and wheat) was dimethyl sulfide (DMS). Alfalfa and wheat also emitted lesser amounts of methanethiol, variable amounls of hydrogen sulfide, and in some experiments wheat emitted carbon disulfide. The use of a plant incubator allowed a systematic study of the effects of variables such as temperature, photon flux, and carbon dioxide levels, on these emissions. Fluxes of all the emitted sulfur gases increased exponentially with increasing air temperature, and increased with increasing photon flux up to a saturation level of \~300 E/m^–2 sec^-1. Three to four-fold changes in DMS flux were observed during light to dark or dark to light transitions. By varying the CO₂ content of the chamber flush gas, it was shown that the observed sulfur fluxes from corn and alfalfa were not related to the CO₂ concentration. Growing these crop plants through holes in a Teflon soil-covering film allowed a separate determination of soil and foliage emissions and substantiation of the light dependent uptake of COS by growing vegetation observed in previous field studies.     

太平洋海气CO2通量对气候事件的响应

应用一个嵌套了海洋生物地球化学循环的太平洋环流碳循环模式,分析了1960～2000年太平洋不同海区海气碳通量随时间的变化。模拟结果显示,赤道太平洋为大气CO₂的排放区,南、北太平洋(南、北纬15°至模式计算区域南、北边界)为吸收区。3个海区海气碳通量随时间均存在显著的波动,其中赤道太平洋海气碳通量年际波动最显著。3个海区海气碳通量年际波动对气候事件的响应并不一致,在El Niño年赤道太平洋冷舌的强度和总溶解无机碳(DIC)的浓度以及输出生产力均会受到上升流减弱的影响而降低,La Niña年这些海气碳通量控制要素的分布情况则正好相反,但在南北太平洋副热带以及高纬度海区,El Niño和La Niña对这些要素带来的影响却并不一定相反,对输出生产力的影响甚至是一致的。以海表温度(SST)为例考察海气碳通量与物理场之间的关系表明,在赤道太平洋上升流对DIC的影响是控制海气碳通量变化的主要因素,而在其他海区,尤其是副热带海区,由于垂直运动的年际变化较小,且生物生产力水平较低,SST的波动对海气碳通量年际变化的影响更加重要。     

Variations of δ^18 O in Precipitation along Vapor Transport Paths

Three sampling cross sections along the south path starting from the Tropics through the vapor passage in the Yunnan-Guizhou Plateau to the middle-low reaches of the Yangtze River, the north path from West China, via North China, to Japan under the westerlies, and the plateau path from South Asia over the Himalayas to the northern Tibetan Plateau, are set up, based on the IAEA (International Atomic Energy Agency)/WMO global survey network and sampling sites on the Tibetan Plateau. The variations, and the relationship with precipitation and temperature, of the δ^18 O in precipitation along the three cross sections are analyzed and compared. Along the south path, the seasonal differences of mean δ^18 O in precipitation are small at the stations located in the Tropics, but increase markedly from Bangkok towards the north, with the 51so in the rainy season smaller than inthe dry season. The δ^18 O sovalues in precipitation fluctuate on the whole, which shows that there are different vapor sources. Along the north path, the seasonal differences of the mean δ^18 O in precipitation for the stations in the west of Zhengzhou are all greater than in the east of Zhengzhou. During the cold half of the year, the mean δ^18 O in precipitation reaches its minimum at Uriimqi with the lowest temperature due to the wide, cold high pressure over Mongolia, then increases gradually with longitude, and remains at roughly the same level at the stations eastward from Zhengzhou. During the warm half of the year, the δ^18 O values in precipitation are lower in the east than in the west, markedly influenced by the summer monsoon over East Asia. Along the plateau path, the mean δ^18 O values in precipitation in the rainy season are correspondingly high in the southern parts of the Indian subcontinent, and then decrease gradually with latitude. A sharp depletion of the stable isotopic compositions in precipitation takes place due to the very strong rainout of the stable isotopic compositions in vapor in the process of lifting over the southern slope of the Himalayas. The low level of the δ^18 O in precipitation is from Nyalam to the Tanggula Mountains during the rainy season,but δ^18 O increases persistently with increasing latitude from the Tanggula Mountains to the northern Tibetan Plateau because of the replenishment of vapor with relatively heavy stable isotopic compositions originating from the inner plateau. During the dry season, the mean δ^18 O values in precipitation basically decrease along the path from the south to the north. Generally, the mean δ^18 O in precipitation during the rainy season is lower than in the dry season for the regions controlled by the monsoons over South Asia or the plateau, and opposite for the regions without a monsoon or with a weak monsoon.     

Measurement of Carbon Dioxide Emissions Plumes from Prudhoe Bay, Alaska Oil Fields

Large carbon dioxide plumes with concentrations up to 45 ppm aboveambient levels were measured about 15 km downwind of the Prudhoe Bay, Alaskamajor oil production facilities, located at 70° N Lat. above the ArcticCircle. The measured emissions were 1.3 × 10³ metrictons (C) hour^-1 (11.4× 10⁶ metric tons(C) year^-1), six times greater than the combustion emissionsassumed by Jaffe and coworkers in J. Atmos. Chem. 20 (1995), 213–227,based on 1989 reported Prudhoe Bay oil facility fuel consumption data, andfour times greater than the total C emissions reported by the oil facilitiesfor the same months as the measurement time periods. Variations in theemissions were estimated by extrapolating the observed emissions at a singlealtitude for all tundra research transect flights conducted downwind of theoil fields. These 30 flights yielded an average emission rate of1.02 × 10³ metric tons (C) hour^-1 with astandard deviation of 0.33 × 10³. These quantity ofemissions are roughly equivalent to the carbon dioxide emissions of7–10 million hectares of arctic tussock tundra (Oechel and Vourlitis,Trends in Ecol. Evolution 9 (1994), 324–329).     

The Stable Carbon Isotope Ratio of Biogenic Emissions of Isoprene and the Potential Use of Stable Isotope Ratio Measurements to Study Photochemical Processing of Isoprene in the Atmosphere

A technique was developed that allows the determination of the stable carbon isotope ratio of isoprene in air. The method was used for a limited number of ambient measurements as well as laboratory studies of isoprene emitted from Velvet Bean (Mucana pruriens L. var. utilis), including the light and temperature dependence. The mean stable carbon isotope ratio ( ¹³C) of isoprene emitted from Velvet Bean (Mucana pruriens L. var. utilis) for all our measurements is –27.7 ± 2.0 (standard deviation for 23 data points). Our results indicate a small dependence of the stable carbon isotope ratios on leaf temperature and photosynthetic photon flux density (PPFD). The light dependence is 0.0026 ± 0.0012/( mol of photons m^–2 s^–1) for the studied range from 400 to 1700 mol of photons m^–2 s^–1. The temperature dependence is 0.16 ± 0.09/K. On average, the emitted isoprene is 2.6 ± 0.9 lighter than the leaf carbon. An uncertainty analysis of the possibility to use stable carbon isotope ratio measurements of isoprene for estimates of its mean photochemical age suggests that meaningful results can be obtained. This is supported by the results of a small number of measurements of the stable carbon isotope composition of ambient isoprene at different locations. The results range from approximately –29 to –16. They are consistent with vegetation emissions of isoprene that is slightly depleted in ¹³C relative to the plant material and enrichment of ¹³C in the atmosphere due to isotope fractionation associated with the reaction with OH-radicals. The stable carbon isotope ratio of ambient isoprene at locations directly influenced by isoprene emissions is very close to the values we found in our emission studies, whereas at sites located remote from isoprene emitting vegetation we find substantial enrichment of ¹³C. This suggests that stable carbon isotope ratio measurements will be a valuable, quantitative method to determine the extent of photochemical processing of isoprene in ambient air.     

The First Global Carbon Dioxide Flux Map Derived from TanSat Measurements

Space-borne measurements of atmospheric greenhouse gas concentrations provide global observation constraints for top-down estimates of surface carbon flux.Here,the first estimates of the global distribution of carbon surface fluxes inferred from dry-air CO_2 column (XCO_2) measurements by the Chinese Global Carbon Dioxide Monitoring Scientific Experimental Satellite (Tan Sat) are presented.An ensemble transform Kalman filter (ETKF) data assimilation system coupled with the GEOS-Chem global chemistry transport model is used to optimally fit model simulations with the Tan Sat XCO_2 observations,which were retrieved using the Institute of Atmospheric Physics Carbon dioxide retrieval Algorithm for Satellite remote sensing (IAPCAS).High posterior error reduction (30%–50%) compared with a priori fluxes indicates that assimilating satellite XCO_2 measurements provides highly effective constraints on global carbon flux estimation.Their impacts are also highlighted by significant spatiotemporal shifts in flux patterns over regions critical to the global carbon budget,such as tropical South America and China.An integrated global land carbon net flux of 6.71±0.76 Gt C yr~(-1) over12 months (May 2017–April 2018) is estimated from the Tan Sat XCO_2 data,which is generally consistent with other inversions based on satellite data,such as the JAXA GOSAT and NASA OCO-2 XCO_2 retrievals.However,discrepancies were found in some regional flux estimates,particularly over the Southern Hemisphere,where there may still be uncorrected bias between satellite measurements due to the lack of independent reference observations.The results of this study provide the groundwork for further studies using current or future Tan Sat XCO_2 data together with other surfacebased and space-borne measurements to quantify biosphere–atmosphere carbon exchange.     

Carbon cycle variations on the Earth's surface during the last two glacial cycles

Data concerning carbon cycle variations on the earth's surface during the past 200,000 years are reviewed.The variations of the surface temperature (T) and concentration of carbon dioxide (CO₂) in the atmosphere of Antarctica are compared to those of the isotopic ratios of oxygen ¹⁸O/¹⁶O (δ¹⁸O) and of carbon ¹³C/¹²C (°¹³C) of waters in the deep oceans for the two last glacial cycles. This comparison shows that the decrease of the atmospheric CO₂ concentration is accompanied by a carbon transferase from the continental biosphere to the oceanic deep waters. At the glacial maximum this transfer is estimated to be about 500 GtC (1 GtC = 10¹⁵g of carbon) equivalent to 25% of the carbon storage of the biosphere. It occurs mainly in the high latitudes of the Southern Hemisphere by incorporation of CO₂ into particulate matter during photosynthesis. It is shown that the mean oceanic productivity does not increase with a supplementary supply of ions such as phosphate (PO₄³⁻) or nitrate (NO₃⁻) but that the intensity of the thermohaline circulation is certainly reduced. As the warming up of the oceans and the melting of the ice-sheet begin carbon transfer takes place to restore the continental biosphere.Another carbon transfer of a much more important intensity is also at work in the sea shore environment. Its intensity could be sufficient to renew the entire carbon of the continental biospheric, atmospheric and oceanic reservoirs in a length of time comparable to a glacial cycle. This fact shows the importance of studying the deposition of carbon in oceanic zones which are uncovered with drops in sea level. At the present time data on the coastal environment in relation to the global carbon cycle are very scarce and warrants more research in this area.