Laboratory measurements of the <Superscript>12</Superscript>C/<Superscript>13</Superscript>C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K

The carbon kinetic isotope effects (KIEs) in the reactions of several unsaturated hydrocarbons with chlorine atoms were measured at room temperature and ambient pressure using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). All measured KIEs, defined as the ratio of the rate constants for the unlabeled and labeled hydrocarbon reaction k ₁₂/k ₁₃, are greater than unity or normal KIEs. The KIEs, reported in per mil according to ^Cl ɛ = (k ₁₂/k ₁₃−1) × 1000‰ with the number of experimental determinations in parenthesis, are as follows: ethene, 5.65 ± 0.34 (1); propene, 5.56 ± 0.18 (2); 1-butene, 5.93 ± 1.16 (1); 1-pentene, 4.86 ± 0.63 (1); cyclopentene, 3.75 ± 0.14 (1); toluene, 2.89 ± 0.31 (2); ethylbenzene, 2.17 ± 0.17 (2); o-xylene, 1.85 ± 0.54 (2). To our knowledge, these are the first reported KIE measurements for reactions of unsaturated NMHC with Cl atoms. Relative rate constants were determined concurrently to the KIE measurements. For the reactions of cyclopentene and ethylbenzene with Cl atoms, no rate constant has been reported in refereed literature. Our measured rate constants are: cyclopentene (7.32 ± 0.88) relative to propene (2.68 ± 0.32); ethylbenzene (1.15 ± 0.04) relative to o-xylene (1.35 ± 0.21), all × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. The KIEs in reactions of aromatic hydrocarbons with Cl atoms are similar to previously reported KIEs in Cl-reactions of alkanes with the same numbers of carbon atoms. Unlike the KIEs for previously studied gas-phase hydrocarbon reactions, the KIEs for alkene–Cl reactions do not exhibit a simple inverse dependence on carbon number. This can be explained by competing contributions of normal and inverse isotope effects of individual steps in the reaction mechanism. Implications for the symmetries of the transition state structures in these reactions and the potential relevance of Cl-atom reactions on stable carbon isotope ratios of atmospheric NMHC are discussed.     

Spatial and temporal variation of rainwater stable isotopes in Egypt and the east Mediterranean

Summary ?By analyzing normalized variables, it was found that the latitudinal secular variations of the rainwater deuterium fractionation ratio δ²H, oxygen fractionation ratio δ¹⁸O, vapor pressure, and surface temperature were almost non-linear, occurred in parallel, and decreased with latitude. The rate of depletion around the equator is asymmetric and smaller to the south of 45° S than to the north of 45° N. In the east Mediterranean, the rate of change of δ¹⁸O with height was found to be −.2‰ per 100 m and that of δ²H is comparable with the dry lapse rate in the atmosphere. Analysis of the annual time series of δ²H at Alexandria has indicated that variations show sinusoidal waveform with a major cycle of two years that accounts for 68% of the total variance. Although the quasi-biannual cycle in the atmosphere has small amplitude in the lower layers of the atmosphere at East Mediterranean latitudes, the major cycle in annual series of δ²H or δ¹⁸O may be linked to the quasi-biannual oscillation in the atmosphere. It was also found that the first three Empirical Orthogonal Functions (EOF) account for 72% of the seasonal variation of δ²H and share 68% of the seasonal variation of δ¹⁸O. Share of variances of monthly EOF in the months of the year indicate that the main underlying factors that cause fractionation processes for δ²H and δ¹⁸O are similar across the east Mediterranean especially in late winter and early spring. Received May 13, 2002; revised July 8, 2002; accepted August 6, 2002     

An investigation of the controls on Irish precipitation δ18O values on monthly and event timescales

This two-year study investigates the relative influence of meteorological variables (precipitation amount and temperature), atmospheric circulation, air mass history, and moisture source region on Irish precipitation oxygen isotopes (δ¹⁸O_p) on event and monthly timescales. Single predictor correlations reveal that on the event scale, 20% of δ¹⁸O_p variability is attributable to the amount effect and 7% to the temperature effect while on the monthly timescale the North Atlantic Oscillation accounts for up to 20% of δ¹⁸O_p variability and the amount and temperature effects are not significant. In comparison, multivariate linear regression reveals that the interaction of temperature and precipitation amount explains up to 40% of δ¹⁸O_p variance at event and monthly timescales. Five-day kinematic back trajectories suggest that the amount-weighted mean δ¹⁸O_p value of southerly- and northerly-derived events are lower by 2‰ relative to events derived from the west. Because air mass history and atmospheric circulation appear to influence δ¹⁸O_p in Ireland, Irish paleo-δ¹⁸O_p proxy records are best interpreted as reflecting a combination of parameters, not just paleotemperature or paleorainfall.     

A stable oxygen, but not carbon, isotope chronology of Callitris columellaris reflects recent climate change in north-western Australia

We investigated the dendroclimatic potential of stable carbon (δ¹³C) and oxygen (δ¹⁸O) abundances in tree rings of Callitris columellaris F. Muell. Tree-ring chronologies were constructed from the central Pilbara, north-western Australia and span 1919–1999. Variation in δ¹⁸O was more strongly related to climate than δ¹³C; ecological and physiological factors may have dampened the climate signal in the δ¹³C chronology. Tree-ring δ¹⁸O was most strongly correlated with relative humidity (RH) and rainfall (r = −0.36 and −0.39) of the wettest months of the summer period, January and February. The correlation with RH reflects its effect on evaporative enrichment of leaf water. However, tree-ring δ¹⁸O may also partly reflect the variability in ¹⁸O signatures of rainfall, which are influenced by the amount of rainfall and atmospheric humidity. From the δ¹⁸O chronology, we inferred that from 1919 to 1955 summers were relatively dry and warm, but since 1955, summers in the Pilbara region have become increasingly cooler and more humid. Since 1980, conditions have been the wettest and coolest of the last 80 years. These inferred changes in climate correspond to a measured increase in rainfall since 1980 in north-western Australia associated with a greater intensity of tropical cyclones. We conclude that δ¹⁸O abundances in tree rings of C. columellaris have significant potential for reconstructing the climate of semi-arid Australia, a region for which observational climate records are sparse.     

Annual methane emission from Finnish mires estimated from eddy covariance campaign measurements

Summary  Measurements of landscape-scale methane emission were made over an aapa mire near Kaamanen in Finnish Lapland (69° 8′ N, 27° 16′ E, 155 m ASL). Emissions were measured during the spring thaw, in summer and in autumn. No effect of water table position on CH₄ emission was found as the water table remained at or above the surface of the peat. Methane emission fluxes increased with surface temperature from which an activation energy of −99 kJ mol⁻¹ was obtained. Annual emission from the site, modelled from temperature regression and short-term flux measurements made in three separate years, was calculated to be 5.5 ± 0.4 g CH₄ m⁻² y⁻¹ of which 0.6 ± 0.1 g CH₄ m⁻² y⁻¹ (11%) was released during the spring thaw which lasted 20 to 30 days. The effect of global warming on the CH₄ budget of the site was estimated using the central scenario of the SILMU (Finnish Research Programme on Climate Change) model which predicts annual mean temperature increases of 1.2, 2.4 and 4.4 °C in 2020, 2050 and 2100, respectively. Maximum enhancements in CH₄ emission due to warming were calculated to be 18, 40 and 84% for 2020, 2050 and 2100, respectively. Actual increases may be smaller because prediction of changes in water table are highly uncertain. Received September 17, 1999 Revised October 16, 2000     

Atmospheric inorganic nitrogen in marine aerosol and precipitation and its deposition to the North and South Pacific Oceans

Aerosol and rain samples were collected between 48°N and 55°S during the KH-08-2 and MR08-06 cruises conducted over the North and South Pacific Ocean in 2008 and 2009, to estimate dry and wet deposition fluxes of atmospheric inorganic nitrogen (N). Inorganic N in aerosols was composed of ~68% NH₄⁺ and ~32% NO₃^– (median values for all data), with ~81% and ~45% of each species being present on fine mode aerosol, respectively. Concentrations of NH₄⁺ and NO₃⁻ in rainwater ranged from 1.7–55 μmol L⁻¹ and 0.16–18 μmol L⁻¹, respectively, accounting for ~87% by NH₄⁺ and ~13% by NO₃⁻ of total inorganic N (median values for all data). A significant correlation (r = 0.74, p < 0.05, n = 10) between NH₄⁺ and methanesulfonic acid (MSA) was found in rainwater samples collected over the South Pacific, whereas no significant correlations were found between NH₄⁺ and MSA in rainwater collected over the subarctic (r = 0.42, p > 0.1, n = 6) and subtropical (r = 0.33, p > 0.5, n = 6) western North Pacific, suggesting that emissions of ammonia (NH₃) by marine biological activity from the ocean could become a significant source of NH₄⁺ over the South Pacific. While NO₃⁻ was the dominant inorganic N species in dry deposition, inorganic N supplied to surface waters by wet deposition was predominantly by NH₄⁺ (42–99% of the wet deposition fluxes for total inorganic N). We estimated mean total (dry + wet) deposition fluxes of atmospheric total inorganic N in the Pacific Ocean to be 32–64 μmol m⁻² d⁻¹, with 66–99% of this by wet deposition, indicating that wet deposition plays a more important role in the supply of atmospheric inorganic N than dry deposition.     

Kinetic Study of the Reactions of Ozone with Polycyclic Aromatic Hydrocarbons Adsorbed on Atmospheric Model Particles

In this experimental study, rate constants were measured for the reactions of ozone with 13 polycyclic aromatic hydrocarbons (PAHs) adsorbed on different types of particles. Graphite and silica were chosen to model, respectively, carbonaceous and mineral atmospheric particles. The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate PAH concentrations versus time. Second order rate constants were calculated considering the ozone gaseous concentration. At room temperature, rate constants varied, in the case of graphite particles, between (1.5 ± 0.5) × 10⁻¹⁷ and (1.3 ± 0.7) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ for chrysene and dibenzo[a,l]pyrene, respectively, and, in the case of silica particles, between (1.5 ± 0.3) × 10⁻¹⁷ and (1.4 ± 0.3) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ for fluoranthene and benzo[a]pyrene, respectively. Different granulometric parameters (particle size, pore size) and different PAH concentrations were tested in the case of silica particles. Heterogeneous reactions of ozone with particulate PAHs are shown to be more rapid than those occurring in the gas-phase, and may be competitive with atmospheric photodegradation.     

Rain-aerosol coupling in the tropical atmosphere of Southeast Asia: distribution and scavenging ratios of major ionic species

Both aerosol and rainwater samples were collected and analyzed for ionic species at a coastal site in Southeast Asia over a period of 9 months (January–September 2006) covering different monsoons. In general, the occurrence and distribution of ionic species showed a distinct seasonal variation in response to changes in air mass origins. Real-time physical characterization of aerosol particles during rain events showed changes in particle number distributions which were used to assess particle removal processes associated with precipitation, or scavenging. The mean scavenging coefficients for particles in the range 10–500 nm and 500–10 μm were 7.0 × 10⁻⁵ ± 2.8 × 10⁻⁵ s⁻¹ and 1.9 × 10⁻⁴ ± 1.6 × 10⁻⁵ s⁻¹, respectively. A critical analysis of the scavenging coefficients obtained from this study suggested that the wet removal of aerosol particles was greatly influenced by rain intensity, and was particle size-dependent as well. The scavenging ratios, another parameter used to characterize particle removal processes by precipitation, for NH₄ ⁺, Cl⁻, SO₄ ²⁻, and NO₃ ⁻ were found to be higher than those of Na⁺, K⁺, and Ca²⁺ of oceanic and crustal origins. This enrichment implied that gaseous species NH₃, HCl, and HNO₃ could also be washed out readily. These additional sources of ions in precipitation presumably counter-balanced the dilution effect caused by high total precipitation volume in the marine and tropical area.     

Measurements of surface ozone at semi-arid site Anantapur (14.62°N, 77.65°E, 331 m asl) in India

In the present study, an attempt has been made to examine the governing photochemical processes of surface ozone (O₃) formation in rural site. For this purpose, measurements of surface ozone and selected meteorological parameters have been made at Anantapur (14.62°N, 77.65°E, 331 m asl), a semi-arid zone in India from January 2002 to December 2003. The annual average diurnal variation of O₃ shows maximum concentration 46 ppbv at noon and minimum 25 ppbv in the morning with 1σ standard deviation. The average seasonal variation of ozone mixing ratios are observed to be maximum (about 60 ppbv) during summer and minimum (about 22 ppbv) in the monsoon period. The monthly daytime and nighttime average surface ozone concentration shows a maximum (55 ± 7 ppbv; 37 ± 7.3 ppbv) in March and minimum (28 ± 3.4 ppbv; 22 ± 2.3 ppbv) in August during the study period. The monthly average high (low) O₃ 48.9 ± 7.7 ppbv (26.2 ± 3.5 ppbv) observed at noon in March (August) is due to the possible increase in precursor gas concentration by anthropogenic activity and the influence of meteorological parameters. The rate of increase of surface ozone is high (1.52 ppbv/h) in March and lower (0.40 ppbv/h) in July. The average rate of increase of O₃ from midnight to midday is 1 ppbv/h. Surface temperature is highest (43–44°C) during March and April months leading to higher photochemical production. On the other hand, relative humidity, which is higher during the rainy season, shows negative correlation with temperature and ozone mixing ratio. It can be seen that among the two parameters are measured, correlation of surface ozone with wind speed is better (R ²=0.84) in compare with relative humidity (R ²=0.66).     

Water interaction with MgCl<Subscript>2</Subscript>×6H<Subscript>2</Subscript>O and NaCl surfaces: measurements of the uptake coefficient

The uptake of water vapor on MgCl₂×6H₂O and NaCl salt dry solid films was studied over the temperature range 240 to 340 K and at 1 Torr pressure of helium using a flow reactor coupled to a modulated molecular beam mass spectrometer. The H₂O to salt uptake data were obtained from the kinetics of H₂O loss on salt coated Pyrex rods. The following Arrhenius expression was obtained for the initial uptake coefficient of H₂O on MgCl₂×6H₂O films: γ ₀ (MgCl₂) = (6.5 ± 1.0) × 10⁻⁶ exp[(470 ± 40)/T] (calculated with specific BET surface area, quoted uncertainties are 1σ statistical). The rate of H₂O adsorption on NaCl was found to be much lower than on MgCl₂×6H₂O, and only an upper limit was determined for the corresponding uptake coefficient: γ (NaCl) ≤ 5.6 × 10⁻⁶ at T = 300 K. The results show that the rate of H₂O adsorption to salt surfaces is drastically dependent on the salt sample composition.     

Regional effects of large-scale extreme wind events over orographically structured terrain

Summary ?Above orographically structured terrain considerable differences of the regional wind field may be identified during large-scale extreme wind events. So far, these regional differences could not be resolved by climate models. To determine the relationships between large-scale atmospheric conditions, the influence of orography, and the regional wind field, data measured in the upper Rhine valley within the framework of the REKLIP Regional Climate Project were analyzed and calculations were made using the KAMM mesoscale model. In the area of the upper Rhine valley, ratios of the wind velocity in the Rhine valley at 10 m above ground level, ν_val, and the large-scale flow velocity, ν_lar, are between ν_val/ν_lar ≈ 0.1 and ν_val/ν_lar ≈ 1. The ν_val/ν_lar ratio exhibits a strong dependence on thermal stratification, δ, and decreases from ν_val/ν_lar ≈ 1 at δ = 0 K m⁻¹ to ν_val/ν_lar ≈ 0.2 at δ = 0.0075 K m⁻¹. In areas, where the lateral mountainous border of the Rhine valley is interrupted, the ν_val/ν_lar ratio increases again with increasing stability or decreasing Froude number. This is obviously due to flow around the Black Forest under stable stratification. It is demonstrated by model calculations that a complex wind field develops in the Rhine valley at small Froude numbers (Fr < 1) irrespective of the direction of large-scale flow. The ν_val/ν_lar ratio is characterized by small values in the direct lee side (ν_val/ν_lar ≈ 0.2) and high values on the windward side of the lateral mountainous border of the Rhine valley (ν_val/ν_lar ≈ 0.8). Received October 22, 2001; revised June 18, 2002; accepted June 23, 2002     

Hydrometeorological processes in semi-arid western India: insights from long term isotope record of daily precipitation

Long term (2005–2016) daily precipitation isotope data (δ18O, δD and d-excess) from Ahmedabad in semi-arid Western India are examined in light of various meteorological parameters and air parcel trajectories to identify prominent patterns in the isotopic character and discern the underlying hydrometeorological processes. One of the most prominent and systematic annual patterns is the isotopic depletion (average δ18O: − 2.5‰ in Jun–Jul; − 5.2‰ in Aug–Sept) in the second half of the Indian Summer Monsoon (ISM), which is observed in the 11 out of the 12 years of this study. Four geographically feasible causal factors have been examined if they contribute to observed late monsoon isotopic depletion. These factors are: (1) increased contribution of terrestrially recycled vapor; (2) intra-seasonal change in sea-surface, surface-air and cloud base temperatures; (3) increased rain-out fraction from marine vapor parcel; and (4) increase in relative proportion of convective rain. It is inferred from the present study that isotopic depletion in the second half of ISM is associated with: (1) increased contribution (45% from 36%) of terrestrially recycled moisture; (2) 1.9° C lower cloud base temperature; (3) increased rainout fraction due to decreased wind velocity (6.9 m/s from 8.8 m/s); and (4) an increase of 22.3% in the proportion of convective rain. Daily rain events with atypical isotopic composition (20‰ < d-excess < 0‰) are ascribed mainly to local weather perturbations causing sudden updraft of moist air facilitating terrestrial recycling of water vapor.     

Oxygen and Hydrogen Isotopic Signatures of Large Atmospheric Ice Conglomerations

Specific studies about the stable isotope composition (¹⁸O/¹⁶O and D/H) of atmospheric icy conglomerations are still scarce. The present work offers, for the first time, a very detailed analysis of oxygen and hydrogen isotopic signatures of unusually large ice conglomerations, or “megacryometeors”, that fell to the ground in Spain during January 2000. The hydrochemical analysis is based on the bulk isotopic composition and systematic selective sampling (deuterium isotopic mapping) of eleven selected specimens. δ¹⁸O and δD (V-SMOW) of all samples fall into the Meteoric Water Line matching well with typical tropospheric values. The distribution of the samples on Craig's line suggests either a variation in condensation temperature and/or different residual fractions of water vapour (Rayleigh processes). Three of the largest megacryometeors exhibited unequivocally distinctive negative values (δ¹⁸O = −17.2%₀ and δD = −127 %₀ V-SMOW), (δ¹⁸O = −15.6%₀ and δD = −112%₀ V-SMOW) and (δ¹⁸O = −14.4%₀ and δD = −100%₀ V-SMOW), suggesting an atmospheric origin typical of the upper troposphere. Theoretical calculations indicate that the vertical trajectory of growth was lower than 3.2 km. During the period in which the fall of megacryometeors occurred, anomalous atmospheric conditions were observed to exist: a substantial lowering of the tropopause with a deep layer of saturated air below, ozone depression and strong wind shear. Moreover, these large ice conglomerations occurred during non-thunderstorm conditions, suggesting an alternative process of ice growth was responsible for their formation.     

Measurements of stable carbon isotopic composition of ethane and propane over the western North Pacific and eastern Indian Ocean: A useful indicator of atmospheric transport process

Stable carbon isotopic composition of ethane and propane over the western North Pacific and eastern Indian Ocean between 31°N and 26°S was investigated from February through March 2004. The isotopic composition of ethane ranged from −28 to −18‰ and showed a gradual increase from north to south. Conversely, that of propane was between −31 and −24‰; it showed no systematic latitudinal variation. Investigation of the ethane/propane ratio indicates that ethane and propane that originated from northern mid-latitude countries in the eastern part of Eurasia were both transported into the western North Pacific region. However, the results of the isotopic analyses indicate the contribution of oceanic emission to the atmospheric propane during transport, although that contribution can not be discerned for ethane. A ship based stationary observation conducted in the western equatorial North Pacific showed that the isotopic composition of ethane varied from −25 to −19‰ and showed clear systematic diurnal variation: propane ranged between −32 to −26‰ and no such isotopic diurnal signal was observed. The diurnal variation for ethane is explained by entrainment of free tropospheric air, whereas the variation for propane was influenced by oceanic emissions as well as the entrainment. The contribution of oceanic emissions to the atmospheric propane inventory was considered from our isotopic observation. Isotopic composition of dissolved propane is estimated to be less than −38‰, and the contribution up to 79% was calculated when the isotopic composition of dissolved propane is assumed to be −40‰. Our study demonstrates that isotopic analysis can be more useful than ratio-based analysis to improve our present understanding of transport processes, especially for impact of the oceanic emissions on the atmospheric distribution of low level C₂–C₅ non-methane hydrocarbons such as propane in the remote marine atmosphere.     

Seasonal carbon dioxide balance and respiration of a high-arctic fen ecosystem in NE-Greenland

Summary  Turbulent fluxes of CO₂ were continuously measured by eddy correlation for three months in 1997 over a gramineous fen in a high-arctic environment at Zackenberg (74°28′12″N, 20°34′23″W) in NE-Greenland. The measurements started on 1 June, when there was still a 1–2 m cover of dry snow, and ended 26 August at a time that corresponds to late autumn at this high-arctic site. During the 20-day period with snow cover, fluxes of CO₂ to the atmosphere were small, typically 0.005 mg CO₂ m⁻² s⁻¹ (0.41 g CO₂ m⁻² d⁻¹), wheres during the thawed period, the fluxes displayed a clear diurnal variation. During the snow-free period, before the onset of vegetation growth, fluxes of CO₂ to the atmosphere were typically 0.1 mg CO₂ m⁻² s⁻¹ in the afternoon, and daily sums reached values up to almost 9 g CO₂ m⁻² d⁻¹. After 4 July, downward fluxes of CO₂ increased, and on sunny days in the middle of the growing season, the net ecosystem exchange rates attained typical values of about −0.23 mg m⁻² s⁻¹ at midday and max values of daily sums of −12 g CO₂ m⁻² d⁻¹. Throughout the measured period the fen ecosystem acted as a net-sink of 130 g CO₂ m⁻². Modelling the ecosystem respiration during the season corresponded well with eddy correlation and chamber measurements. On the basis of the eddy correlation data and the predicted respiration effluxes, an estimate of the annual CO₂ balance the calender year 1997 was calculated to be a net-sink of 20 g CO₂ m⁻² yr⁻¹. Received October 6, 1999 Revised May 2, 2000     

A Study of the Reaction of OH Radicals with N-Methyl Pyrrolidinone,N-Methyl Succinimide and N-Formyl Pyrrolidinone

A study of the oxidation mechanism of N-methyl pyrrolidinone (C₅H₉NO, NMP) initiated by hydroxyl radicals was made at EUPHORE at atmospheric pressure (1000 ± 10) mbar of air and ambient temperature (T = 300 ± 5 K). The main products were N-methyl succinimide (NMS) (52 ± 4)% and N-formyl pyrrolidinone (FP) (23 ± 9)%. The relative rate technique was used to determine the rate constants of OH with NMP, NMS and FP, the measured values were (in units of cm³ molecule ^{− 1} s^{− 1}): k_NMP = (2.2 ± 0.4) × 10^{− 11}, k_NMS = (1.4 ± 0.3) × 10^{− 12} and k_FP = (6 ± 1) × 10^{− 12}. The results are presented and discussed in terms of the atmospheric impact.     

Manganese in coastal rainwater: speciation,photochemistry and deposition to seawater

Concentrations of manganese in 56 rain events in Wilmington, NC, USA rainwater from April 1, 2005 to March 31, 2006 were 11 ± 3 nM for dissolved Mn and 1.2 ± 0.4 nM for particulate Mn. Concentrations of both forms of Mn were higher in terrestrial storms relative to marine events. This observation along with the positive correlation of Mn with pollutant indicators suggests anthropogenic inputs to rain at this location, as has been observed at other locations. The ratio of Mn_part/Mn_diss was threefold larger in summer relative to winter rain, which matched the increase of particulate to dissolved Fe in rainwater suggesting influence of Saharan dust during the summer. Like Fe in rain, Mn undergoes photoreduction in rainwater, which has also been shown to be important in Mn cycling in seawater. The flux of Mn removed from the atmosphere via wet deposition is 1.5 × 10⁻⁵ moles m⁻² yr⁻¹ at this location, which is approximately twice the flux reported from two rainwater studies conducted in the early 1980s on Bermuda. Atmospheric input of Mn to the oceans is important because Mn like Fe is an essential and potentially limiting nutrient. Experiments mixing authentic rainwater and seawater demonstrate that rainwater dissolved Mn does not rapidly precipitate in seawater suggesting wet deposition is an important source of soluble, stable Mn to surface seawater.     

Net CO2 exchange of a subarctic mountain birch ecosystem

Summary  Net ecosystem CO₂ exchange was measured over a mountain birch forest in northern Finland throughout the growing season. The maximal net CO₂ uptake rate of about − 0.5 mg(CO₂) m⁻² s⁻¹ was observed at the end of July. The highest nocturnal respiration rates in early August were 0.2 mg(CO₂) m⁻² s⁻¹. The daily CO₂ balances during the time of maximal photosynthesis were about −15 g(CO₂) m⁻² d⁻¹. The mountain birch forest acted as a net sink of CO₂ from 30 June to 28 August. During that period the net CO₂ balance was −448 g(CO₂)m⁻². The interannual representativeness of the observed balances was studied using a simplified daily balance model, with daily mean global radiation and air temperature as the input parameters. The year-to-year variation in the phenological development was parameterised as a function of the cumulative effective temperature sum. The daily balance model was used for estimating the variability in the seasonal CO₂ balances due to the timing of spring and meteorological factors. The sink term of CO₂ in 1996 was lower than the 15-year mean, mainly due to the relatively late emergence of the leaves. Received October 11, 1999 Revised April 25, 2000     

Tropical climates at the Last Glacial Maximum: a new synthesis of terrestrial palaeoclimate data. I. Vegetation, lake-levels and geochemistry

 Palaeodata in synthesis form are needed as benchmarks for the Palaeoclimate Modelling Intercomparison Project (PMIP). Advances since the last synthesis of terrestrial palaeodata from the last glacial maximum (LGM) call for a new evaluation, especially of data from the tropics. Here pollen, plant-macrofossil, lake-level, noble gas (from groundwater) and δ¹⁸O (from speleothems) data are compiled for 18±2 ka (¹⁴C), 32 °N–33 °S. The reliability of the data was evaluated using explicit criteria and some types of data were re-analysed using consistent methods in order to derive a set of mutually consistent palaeoclimate estimates of mean temperature of the coldest month (MTCO), mean annual temperature (MAT), plant available moisture (PAM) and runoff (P-E). Cold-month temperature (MAT) anomalies from plant data range from −1 to −2 K near sea level in Indonesia and the S Pacific, through −6 to −8 K at many high-elevation sites to −8 to −15 K in S China and the SE USA. MAT anomalies from groundwater or speleothems seem more uniform (−4 to −6 K), but the data are as yet sparse; a clear divergence between MAT and cold-month estimates from the same region is seen only in the SE USA, where cold-air advection is expected to have enhanced cooling in winter. Regression of all cold-month anomalies against site elevation yielded an estimated average cooling of −2.5 to −3 K at modern sea level, increasing to ≈−6 K by 3000 m. However, Neotropical sites showed larger than the average sea-level cooling (−5 to −6 K) and a non-significant elevation effect, whereas W and S Pacific sites showed much less sea-level cooling (−1 K) and a stronger elevation effect. These findings support the inference that tropical sea-surface temperatures (SSTs) were lower than the CLIMAP estimates, but they limit the plausible average tropical sea-surface cooling, and they support the existence of CLIMAP-like geographic patterns in SST anomalies. Trends of PAM and lake levels indicate wet LGM conditions in the W USA, and at the highest elevations, with generally dry conditions elsewhere. These results suggest a colder-than-present ocean surface producing a weaker hydrological cycle, more arid continents, and arguably steeper-than-present terrestrial lapse rates. Such linkages are supported by recent observations on freezing-level height and tropical SSTs; moreover, simulations of “greenhouse” and LGM climates point to several possible feedback processes by which low-level temperature anomalies might be amplified aloft. Received: 7 September 1998 / Accepted: 18 March 1999     

A technique for atmospheric measurements of stable carbon isotope ratios of isoprene,methacrolein, and methyl vinyl ketone

A technique was developed to measure stable carbon isotope ratios (¹³C/¹²C) of light volatile organic compounds (VOCs) such as isoprene, methacrolein (MACR) and methyl vinyl ketone (MVK) using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). An automated sampling and cryofocussing system allowed for the extraction of VOCs from air samples of up to 140 L of air collected over 3 h, and the subsequent ¹³C/¹²C analysis of the VOCs by GCC-IRMS. Chromatography using selective transfer between two columns was used to improve the separation for selected compounds, increasing peak resolution and attaining less noisy baselines. Still, some target compounds could not be completely separated from co-eluting peaks. To reduce the bias of isotope ratio determinations, which can result from incomplete peak resolution, a peak-fitting procedure has been developed. In cases of overlapping peaks or substantial baseline drift, this peak fitting allows more accurate determination of isotope ratios than conventional integration schemes. Comparisons between off-line IRMS measurements and a peak-evaluation procedure using a prepared VOC gas-phase standard show that isotope ratios derived from large (>1 ng of carbon per peak) and well-resolved peaks have a reproducibility of ±0.3‰. With smaller masses in the range of 0.1–1 ng of carbon, reproducibility decreased to ±(0.5–0.8)‰. For a 140 L sample of air, such small masses of carbon correspond to mixing ratios in the low pptV range. The developed measurement technique was applied to a small set of ambient air samples taken during hot, sunny periods from late May to early August, 2005, at Forschungszentrum Jülich, Germany, a semi-rural area. The range of δ¹³C values determined for isoprene, benzene, and toluene are consistent with those reported in the literature. GCC-IRMS results of δ¹³C for ambient samples of isoprene, MACR, and MVK, measured at mixing ratios of 15–280 pptV, are presented and discussed.