Three million years of monsoon variability over the northern Sahara

We present a 3 million year record of aeolian dust supply into the eastern Mediterranean Sea, based on hematite contents derived from magnetic properties of sediments from Ocean Drilling Program Site 967. Our record has an average temporal resolution of 400 years. Geochemical data validate this record of hematite content as a proxy for the supply of aeolian dust from the Sahara. We deduce that the aeolian hematite in eastern Mediterranean sediments derives from the eastern Algerian, Libyan, and western Egyptian lowlands located north of the central Saharan watershed (21°N). In corroboration of earlier work, we relate dust flux minima to penetration of the African summer monsoon front to the north of the central Saharan watershed. This would have enhanced soil humidity and vegetation cover in the source regions, in agreement with results from green Sahara climate models. Our results indicate that this northward monsoon penetration recurred during insolation maxima throughout the last 3 million years. As would be expected, this orbital precession-scale mechanism is modulated on both short (100-kyr) and long (400-kyr) eccentricity time scales. We also observe a strong expression of the 41-kyr (obliquity) cycle, which we discuss in terms of high- and low-latitude mechanisms that involve Southern Hemisphere meridional temperature contrasts and shifts in the latitudes of the tropics, respectively. We also observe a marked increase in sub-Milankovitch variability around the mid-Pleistocene transition (0.95 Ma), which suggests a link between millennial-scale climate variability, including monsoon dynamics, and the size of northern hemisphere ice sheets.     

Characteristics of the ozone decline in the northern polar and middle latitudes during the winter-spring

Summary The total ozone decline during the past twenty years, especially strong during the winter-spring season poleward from 50° N, is well established with known average trends of 5–7% per decade. This study presents a number of additional characteristics such as ozone-mass deficiency (O₃MD) from the pre- 1976 base average, and areal extent with negative deviations greater than2 and3. Gridded satellite data combined with ground-based total ozone maps, permit calculations of daily and regional ozone deficiencies from the anthropogenically undisturbed average ozone levels of the 1960s and early 1970s. Then the quantity of the O₃MD and the changes in surface area, with deficiencies larger than-10 and-15% are integrated for the 1 January to 15 April period for each of the last 20 years, and compared. In addition, the polar vortex extent during the last 10 years is determined using the PV at 475°K. The quantity of the O₃MD within the sunlit part of the vortex is shown to contribute from15 to 35% of the overall ozone deficiency within the-10% contours over the area 35–90°N. The ozone deficiency, integrated for the first 105 days of each year, has increased dramatically from 2,800Mt in the early 1980s to7,800Mt in the 1990s, exceeded 12,000Mt in the winter-springs of 1993 and 1995. The latter quantity is comparable with the average O₃MD over the same Southern latitudes in the last ten austral springs. During the 1990s over the 35–90° latitudes the average ozone deficiency in the Southern hemisphere belt is less than over the Northern hemisphere belt by40%. It is known that the main ozone decline is observed in the lower stratosphere and the ozone loss over the Arctic is very sensitive to decreasing stratospheric temperatures; negative 50hPa monthly anomalies greater than 4°C have occurred during 7 of the springs in the last decade, thus possibly facilitating doubling the area with negative ozone deviations greater than-10% in the 1990s to5,000.10⁶km² and nearly tripling the O₃MD as stated above. The changes in total eddy heat fluxes as a proxy indicator of the long wave perturbations are positively correlated with the ozone deficiency in the 45–75°N. The strong anticorrelation between the ozone deficiency in the region>55° N. versus the 35–50° N belt is discussed in relation to possible transport of air masses with low ozone from the sub-tropics, which in some years are the dominant reason for the observed ozone deficiency.With 11 Figures     

A study of the sensitivity of bare soil evaporation schemes to soil surface wetness,using the coupled soil moisture and surface temperature prediction model,BARESOIL

Summary The performance of evaporation schemes with and approach and their combination within resistance representation of evaporation from bare soil surface is discussed. For this purpose nine schemes, based on different functions of or , on the ratio of the volumetric soil moisture content and its saturated value are used.The quality of the chosen schemes has been evaluated using the results of time integration by the coupled soil moisture and surface temperature prediction model, BARESOIL, using in situ data. A sensitivity analysis was made using two sets of data derived from the volumetric soil moisture content of the top soil layer. One with values below the wilting point (0.17 m³m^–3) and the second with values above 0.20m³m^–3. Data sets were obtained at the experimental site Rimski anevi, Yugoslavia, from the bare surface of a chernozem soil.With 4 Figures     

Bioaccumulation of Cobalt in Parmelia sulcata

Six locations across mainland Portugal were selected for exposing Parmelia sulcata, for a one-year period (8 months for one site), with simultaneous measurement of total (dry + wet) deposition (one-month periods). The exposed lichens and the total (dry + wet) deposition were analysed for cobalt contents by INAA (instrumental neutron activation analysis) and ICP-MS (inductively coupled plasma mass spectroscopy), respectively. The designated wet deposition was evaluated through the collected water volume; the designated dry deposition was assessed after the (dried) residual mass of the wet deposition. An excellent agreement between Co contents in exposed lichens and the cumulative (1) Co contents in the dry deposition, (2) dry deposition, and (3) wet deposition has been found for the locations with alternate drought and precipitation months, high dry deposition, and high Co contents in the latter. Continuous rainfall was found to hinder the Co accumulation in the lichen due to its release from the lichen and/or lower Co contents in the dry deposition. At three locations, P. sulcata Co contents, after subtraction of the background (before exposure), equalled or exceeded the Co contents in the cumulative dry deposition at the end of the exposure time. The optimal exposure period for this species likely depends on the exposure conditions.     

Background ozone and anthropogenic ozone enhancement at niwot ridge,Colorado

The mixing ratios for ozone and NO_x (NO+NO₂) have been measured at a rural site in the United States. From the seasonal and diurnal trends in the ozone mixing ratio over a wide range of NO_x levels, we have drawn certain conclusions concerning the ozone level expected at this site in the absence of local photochemical production of ozone associated with NO_x from anthropogenic sources. In the summer (June 1 to September 1), the daily photochemical production of ozone is found to increase in a linear fashion with increasing NO_x mixing ratio. For NO_x mixing ratios less than 1 part per billion by volume (ppbv), the daily increase is found to be (17±3) [NO_x]. In contrast, the winter data (December 1 to March 1) indicate no significant increase in the afternoon ozone level, suggesting that the photochemical production of ozone during the day in winter approximately balances the chemical titration of ozone by NO and other pollutants in the air. The extrapolated intercept corresponding to [NO_x]=0 taken from the summer afternoon data is 13% less than that observed from the summer morning data, suggesting a daytime removal mechanism for O₃ in summer that is attributed to the effects of both chemistry and surface deposition. No significant difference is observed in the intercepts inferred from the morning and afternoon data taken during the winter.The results contained herein are used to deduce the background ozone level at the measurement site as a function of season. This background is equated with the natural ozone background during winter. However, the summer data suggest that the background ozone level at our site is elevated relative to expected natural ozone levels during the summer even at low NO_x levels. Finally, the monthly daytime ozone mixing ratios are reported for 0[NO_x]0.2 ppbv, 0.3 ppbv[NO_x]0.7 ppbv and 1 ppbv[NO_x]. These monthly ozone averages reflect the seasonal ozone dependence on the NO_x level.     

Gas and Particle Products Distribution from the Reaction of β-Caryophyllene with Ozone

Gas and particulate reaction products from the ozonolysis of -caryophyllene (I) in the presence of atmospheric air were investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). A Scanning Mobility Particle Sizer system (3936, TSI) and a Condensation Particle Counter (3025A, TSI) were used to study secondary organic aerosol formation. The nighttime oxidation was carried out in a large outdoor smog chamber (190 m³). A wide range of ring retaining and ring opening products in the gas and particle phase are reported over the course of the reaction. On average, measured gas and particle phase products accounted for 64% of the reacted -caryophyllene (I) carbon. Measurements show that a number of reaction products with low vapor pressure (e.g., -caryophyllone aldehyde (IV), -norcaryophyllone aldehyde (V), -caryophyllonic acid (VIII), -14-hydroxycaryophyllonic acid (XIV)) were found in the sample taken during the first 20 min of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.     

Gaseous and Particulate Oxidation Products Analysis of a Mixture of α-pinene + β-pinene/O3/Air in the Absence of Light and α-pinene + β-pinene/NOx/Air in the Presence of Natural Sunlight

The gas and particle phase reaction products of a mixture of the atmospherically important terpenes -pinene and -pinene with the atmospheric oxidants O₃ and OH/NO_x were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of a mixture of -pinene and -pinene in the presence of O₃/air, and the daytime oxidation of a mixture of -pinene + -pinene with NO_x air in the presence of natural sunlight were carried out in the University of North Carolina's large outdoor smog chamber (190 m³) located in Chatham County, North Carolina. Mass balances for gaseous and aerosol reaction products are reported over the course of the reaction. More than twenty-nine products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 74 to 80% of the reacted -pinen/-pinene mixture carbon. Measurements show that a number of reaction products were found in both O₃ and NO_x system [pinonaldehyde, pinic acid, pinonic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxy-nopinone, 3-hydroxy-nopinone, and nopinone]. Pinonic acid, pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, and 10-hydroxypinonic acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols.     

Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O₂ of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with O₂ versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, (H)=(H_{decomposition}–H_{O 2 reaction}), between these two reactions pathways. For (H)[22–0.5(H_{O 2 reaction})], alkoxy radical decomposition dominates over the reaction with O₂ at room temperature and atmospheric pressure of air, while for (H)[25-0.5(H_{O 2 reaction})], the O₂ reaction dominates over decomposition (where the units of H are in kcal mol^–1). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed.     

Monoterpene concentrations in and above a forest of scots pine

Diurnal and vertical ambient air measurements of the monoterpenes have been made in and above a Scots pine (Pinus sylvestris) forest of central Sweden, within the boreal northern coniferous biome. Sampling was done with Tenax TA, and analysis by GC and ion trap detection. Daytime mixing ratios were on the order of tenths of a ppbv from the forest floor to the top of the forest, and a factor of 2 or 3 lower above the forest. Mixing ratios at night were at the ppbv level, highest near the forest floor and the crown, and decreased with height above the forest. The highest total concentration observed was 8 ppbv inside the forest at 3 am (GMT). The average terpene composition was 3-carene 32%, -pinene 29%, limonene 18%, -pinene 10%, -phellandrene 7%, camphene 5%, and sabinene at less than 2%. The 3-carene/-pinene ratio varied with wind direction and speed, relative humidity, and wet/dry vegetation, but not with ozone or NO₂ concentration, solar radiation, or temperature. Variations in the observed terpene composition at the sampling site are mainly caused by the influence of other vegetation in the vicinity of the site. It would seem that wet Scots pine emits more 3-carene relative to -pinene than does dry pine.     

Trace gas exchange at the air/water interface: Measurements of mass accommodation coefficients

A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO₃ (0.01), N₂O₅ (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.     

Carbonyl sulfide emissions from biomass burning in the tropics

Carbonyl sulfide emissions from biomass burning have been studied during field experiments conducted both in an African savanna area (Ivory Coast) and rice fields, central highland pine forest and savanna areas in Viet-Nam. During these experiments CO₂, CO and C₂H₂ or CH₄ have also been also monitored. COS values range from 0.6 ppbv outside the fires to 73 ppbv in the plumes. Significant correlations have been observed between concentrations of COS and CO (R ²=0.92,n=25) and COS and C₂H₂ (R ²=0.79,n=26) indicating a COS production during the smoldering combustion. COS/CO₂ emission factors (COS/CO₂) during field experiments ranged from 1.2 to 61×10^–6 (11.4×10^–6 mean value). COS emission by biomass burning was estimated to be up to 0.05 Tg S/yr in tropics and up to 0.07 Tg S/yr on a global basis, contributing thus about 10% to the global COS flux. Based on the S/C ratio measured in the dry plant biomass and the COS/CO₂ emission factor, COS can account for only about 7% of the sulfur emitted in the atmosphere by biomass burning.     

Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products

Atmospheric oxidation of monoterpenes contributes to formation of tropospheric ozone and secondary organic aerosol, but their products are poorly characterized. In this work, we report a series of outdoor smog chamber experiments to investigate both gaseous and particulate products in the ozone oxidation of four monoterpenes: -pinene, -pinene, ³-carene, and sabinene. More than ten oxygenated products are detected and identified in each monoterpene/O₃ reaction by coupling derivatization techniques and GC/MS detection. A denuder/filter pack sampling system is used to separate and simultaneously collect gas and aerosol samples. The identified products, consisting of compounds containing carbonyl, hydroxyl, and carboxyl functional groups, are estimated to account for about 34–50%, 57%, 29–67%, and 24% of the reacted carbon mass for -pinene, sabinene, -pinene, and ³-carene, respectively. The identified individual products account for >83%, 100%, >90%, and 61% of the aerosol mass produced in the ozone reaction of -pinene, sabinene, -pinene, and ³-carene. The uncertainty in the yield data is estimated to be ±50%. Many of the products partition between gas and aerosol phases, and their gas-aerosol partitioning coefficients are determined and reported here. Reaction schemes are suggested to account for the products observed.     

Experiments On Buoyant Plume Dispersion In A Laboratory Convection Tank

Plume dispersion in the convective boundary layer (CBL) is investigated experimentally in a laboratory convection tank. The focusis on highly-buoyant plumes that loft near or become trapped in the CBL capping inversion and resistdownward mixing. Such plumes are defined by dimensionless buoyancy fluxes F_* 0.1, where F_* = F_b/(U w_* ² z_i), F_b is the stack buoyancy flux,U is the mean wind speed, w_* is the convective velocity scale, and z_i is the CBL depth. The aim is to obtain statistically-reliable mean (C) and root-mean-square (rms, _c) concentration fields as a function of F_* and the dimensionless distance X = w_*x/(U z_i), where x is the distance downstream of the source.The experiments reveal the following mainresults: (1) For 3 X 4and F_* 0.1, the crosswind-integrated concentration (CWIC) fields exhibit distinctly uniform profiles below z_i with a CWIC maximum aloft, in contrast to the nonuniform profiles obtained earlier by Willis and Deardorff. (2) The lateral dispersion (_y) variation with X is consistent with Taylor's theory for _* 0.1 and a buoyancy-enhanced dispersion, _y/z_i F_* ^1/3X^2/3, forF_* = 0.2 and 0.4. (3) The entrapment, the plume fraction above z_i, has a mean (E) that follows a systematic variationwith X and F_*, and a variability (_e/E) that is broad ( 0.3 to 2) near the source but subsides to 0.25 far downstream. (4) Vertical profiles of the concentration fluctuation intensity (c/C) are uniform for z < z_i and X > 1.5, but exhibit significant increases: (a) at the surface and close to the source (X 1.5), and(b) in the entrainment zone. (5) The cumulative distribution functions (CDFs) of the scaled concentration fluctuations (c/_c) separate into mixed-layer and entrainment-layer CDFs for X 2, with the mixed-layer group collapsing to a single distribution independent of z.These are the first experiments to obtain all components of the lateral and vertical dispersion parameters (rms meander, relative dispersion, total dispersion) for continuous buoyant releases in a convection tank. They also are the first tank experiments to demonstrate agreement with field observations of: (1) the scaled ground-level concentration along the plume centreline, and (2) the dimensionless lateral dispersion _y/z_i of buoyant plumes.     

Gas-Particle Partitioning of Nitric Acid Modulated by Alkaline Aerosol

The role of alkaline mineral aerosol in controlling HNO₃ partitioning between gas and aerosol phases is explored using a comprehensive, process oriented three-dimensional model. Simulation results for March 1994, a period from the PEM West B experiment, are presented. It is found that in the dust impacted regions of the boundary layer and free troposphere, more than 50% of HNO₃ ispartitioned onto dust particles; while 1050% of HNO₃ in the boundarylayer and 10 30% of HNO₃ in the free troposphere is partitionedonto sea-salt particles. This higher capacity of mineral dust to uptake HNO₃ is due to the fact that carbonate in the dust particles is more volatile (thus easily replaced by nitrate) than chloride in the sea-salt particles. When this process of nitric acid partitioning onto alkaline particles is included in the analysis, model predicted HNO₃-to-NO_x ratios are much closer to observed valuesthat typically range between 1 and 9.     

On the transfer of stratospheric ozone into the troposphere near the north pole

A series of nearly daily ozone vertical profiles obtained at station T-3 on Fletcher's Ice Island (85°N, 90°W) during the period January-March 1971 shows several significant ozone intrusions into the troposphere. These intrusions are not only associated with enhanced ozone amounts in the stratosphere but also require tropopause folding events to transport ozone into the troposphere. These folds in the Arctic tropopause appear to be capable of contributing significantly to the ozone budget of the Arctic troposphere during the late winter and spring seasons. The importance of tropopause folding for bringing ozone into the troposphere seen in the daily ozone profiles confirms the results found in the Arctic Gas and Aerosol Sampling Program aircraft flights.     

Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons

Measurements of aerosol formation during thephotooxidation of -pinene, -pinene,d-3-carene, d-limonene, ocimene, linalool, terpinene-4-ol, andtrans-caryophyllene were conducted in anoutdoor smog chamber. Daylight experiments in thepresence of and dark experiments withelevated ozone concentrations were performed. Theevolution of the aerosol was simulated by theapplication of a gas/particle absorption model inconnection with a chemical reaction mechanism. Thefractional aerosol yield is shown to be a function ofthe organic aerosol mass concentration andtemperature. Ozone and, for selected hydrocarbons, theNO₃ reaction of the compounds were found torepresent efficient routes to the formation ofcondensable products. For initial hydrocarbon mixingratios of about 100 ppb, the fractional aerosol yieldsfrom daylight runs have been estimated to be 5%for open-chain hydrocarbons, such as ocimene andlinalool, 5–25% for monounsaturated cyclicmonoterpenes, such as -pinene, d-3-carene, orterpinene-4-ol, and 40% for a cyclic monoterpenewith two double bonds like d-limonene. For the onlysesquiterpene investigated, trans-caryophyllene, afractional aerosol yield of close to 100% wasobserved. The majority of the compounds studied showedan even higher aerosol yield during dark experimentsin the presence of ozone.     

Characterization and Temporal Variation of Asian Dust Aerosol from a Site in the Northern Chinese Deserts

Time series for total aerosol mass and the concentrations of nineteen elements, and the mass particle-size distributions of the elements, were determined for samples collected from a site in the northern deserts of China -Zhenbeitai, one of ground sites of the Asia-Pacific Regional Aerosol Characterization Experiment (ACE-Asia). Nine dust storm (DS) events were observed during the spring of 2001, lasting a combined total of twenty-six days. Peak mass loadings greatly exceeded the average (260 g m^–3), and higher than average dust-element concentrations and wind speeds were also observed during the three-month study. Material balance calculations showed that 82% mass of the total aerosol particles could be ascribed to Asian dust, of which Al, Ca, Fe, K, Mn, Si and Ti accounted for 7%, 6%, 4%, 2%, 0.1%, 32% and 1% by weight, respectively. Modelcalculated dry deposition velocities for 7 dust-elements during dust storm periods averaged 17 cm s^–1 and ranged from 14 to 21 cm s^–1. The estimated dry depositiona of Asian dust for the spring of 2001 was 189 g m^–2, of which 85% was due to dust storms. Factor analysis indicated that 89% of the dust loading during this period was due to remote or regional transport; 11% to local or background dust.     

An observational aircraft-based study of sea-breeze frontogenesis

In the summer of 1988/89 flights were carried out in the Coorong coastal area of South Australia to investigate sea-breeze fronts. The flights yielded data sets of the structure of the fronts in the cross-frontal direction with a spatial resolution of approximately 3 m. The study is focused on the budgets of sensible and latent heat in the vicinity of the front and on frontogenesis/frontolysis processes which are closely related to budget considerations.The frontogenesis relationships and the budgets were established on a 2 km length scale by low-pass filtering of the space series. As the wind components were measured with high accuracy, all processes which determine frontogenesis could be evaluated and are displayed in x,z-cross-sections: these are the confluence, shear and diabatic effects, all of which play a role in q/x-, q/z-, /x- as well as /z-frontogenesis. A detailed analysis is given for two different states of frontal development. The presented results shed much light on the governing physical processes in the frontal region with strong emphasis on the effects of confluence-generated updrafts, on shear instabilities causing bulges and clefts in the frontal surface as well as producing the elevated frontal head, and on processes related to differential heating and moistening.     

Re-analysis of the nuclear winter phenomenon

Summary An analysis of the report of the (U.S.) National Academy of Sciences (NAS) on atmospheric effects of a nuclear exchange leads to conclusions that differ from those of the NAS and of the earlier TTAPS and AMBIO studies. Any cooling of the earth's surface is likely to beshort-lived because of rapid removal of the smoke clouds originating from nuclear burst-initiated fires, andminor because of appreciable green-house effects due to several distinct physical causes. (One of these, neglected in prior analyses, is the infrared absorption from cirrus clouds produced directly by the nuclear bursts.) Taken together, these effects may even induce slight surface warming (nuclear summer) instead of cooling (nuclear winter). The consequences to atmospheric ozone are similarly ambiguous; depending on the detailed nuclear scenario, the net ozone content may increase-rather than decrease as argued by TTAPS. Experiments could settle some uncertainties.With 2 Figures     

The behaviour of aerosol optical depth during clear summer days in Athens,Greece

Summary The integral aerosol optical depths (k ) at the hour of 08:20 Local Standard Time (LST), are compared with those calculated previously at 11:20 and 14:20 LST, for clear days during summer in Athens over the period 1962–1988. The mean values at 08:20 LST were consistently lower than the values at 11:20 and 14:20 LST. The influence of the vertical wind profile on the values ofk was also investigated. A comparison was made of the wind profiles at 02:00 and 14:00 LST, for days in which the 11:20 and 14:20 LST values ofk were 0.200 andk 0.350, respectively. The corresponding bulk wind shear s was also found for the period 1980–1988. The most significant results occurred with the first category of days. The resultant wind velocities from the surface to the 900 hPa level, in each hour were higher by 2–4 m·s^–1 with respect to the corresponding values for the second category. At 02:00 LST the bulk wind shear showed a considerable difference (1.8) between the two categories of days in the surface to 700 hPa layer at 02:00 LST. Finally, the associated weather conditions that appear to initiate a period of low values ofk (k 0.200) at 11:20 and 14:20 LST were examined for the period 1980–1988. Fifteen such cases were identified and it was found that they all occurred after the passage of weak cold fronts.With 6 Figures