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.     

Averaging Intervals For Spectral Analysis Of Nonstationary Turbulence

We formulate a method for determining the smallest time interval Tover which a turbulence time series can be averaged to decompose it intoinstantaneous mean and random components. From the random part the method defines the optimal interval (or averaging window) AW over which this part should be averaged to obtain the instantaneous spectrum. Both T and AW vary randomly with time and depend on physical properties of the turbulence. T also depends on the accuracy of the measurements and is thus independent of AW. Interesting features of the method are its real-time capability and the non-equality between AW and T.     

The ‘ultimate objective’ of the framework convention on climate change requires a new approach in climate change research

In the Framework Convention on Climate Change an ultimate objective is formulated that calls for stabilization of the concentrations of greenhouse gases in the atmosphere at a level that would allow ecosystems to adapt naturally, safeguard food supply and enable sustainable development to proceed in a sustainable manner. This paper addresses the possible contribution of science to translate this rather vague and ambiguous objective into more practicable terms. We propose a regionalized, risk-based six-step approach that couples an analysis of ecosystem vulnerability to the results of simulations of climate change. An ultimate objective level could be determined in terms of stabilized concentrations of greenhouse gases in the atmosphere. The level and timing of this stabilization would be determined by a political appreciation of associated risks for managed and unmanaged ecosystems. These risks would be assessed by region in an internationally coordinated scientific effort, followed by a global synthesis.     

The impact of climate change on the river rhine: A scenario study

This paper concerns the impact of human-induced global climate change on the River Rhine discharge. For this purpose a model for climate assessment, named ESCAPE, is coupled to a water balance model, named RHINEFLOW. From climate scenarios, changes in regional annual water availability and seasonal discharge in the River Rhine Basin are estimated. The climate scenarios are based on greenhouse gases emissions scenarios. An assessment is made for best guess seasonal discharge changes and for changes in frequencies of low and high discharges in the downstream reaches of the river. In addition, a quantitative estimation of the uncertainties associated with this guess is arrived at.The results show that the extent and range of uncertainty is large with respect to the best guess changes. The uncertainty range is 2–3 times larger for the Business-as-Usual than for the Accelerated Policies scenarios. This large range stems from the doubtful precipitation simulations from the present General Circulation Models. This scenario study showed the precipitation scenarios to be the key-elements within the present range of reliable climate change scenarios.For the River Rhine best guess changes for annual water availability are small according to both scenarios. The river changes from a present combined snow-melt-rain fed river to an almost entirely rain fed river. The difference between present-day large average discharge in winter and the small average discharge in autumn should increase for all scenarios. This trend is largest in the Alpine part of the basin. Here, winter discharges should increase even for scenarios forecasting annual precipitation decreases. Summer discharge should decrease. Best guess scenarios should lead to increased frequencies of both low and high flow events in the downstream (Dutch) part of the river. The results indicate changes could be larger than presently assumed in worst case scenarios used by the Dutch water management authorities.     

Carbon dioxide emissions in a methane economy

Increasing reliance on natural gas (methane) to meet global energy demands holds implications for atmospheric CO₂ concentrations. Analysis of these implications is presented, based on a logistic substitution model viewing energy technologies like biological species invading an econiche and substituting in case of superiority for existing species. This model suggests gas will become the dominant energy source and remain so for 50 years, peaking near 70 percent of world supply. Two scenarios of energy demand are explored, one holding per capita consumption at current levels, the second raising the global average in the year 2100 to the current U.S. level. In the first (efficiency) scenario concentrations peak about 450 ppm, while in the second (long wave) they near 600 ppm. Although projected CO₂ concentrations in a methane economy are low in relation to other scenarios, the projections confirm that global climate warming is likely to be a major planetary concern throughout the twenty-first century. A second finding is that data on past growth of world per capita energy consumption group neatly into two pulses consistent with longwave theories in economics.     

Periodicity of annual precipitation in different climate regions of Croatia

Summary The periodicity of a 100-year series of annual precipitation over Croatia has been studied by means of power spectrum analysis at 3 stations representing the different climatic regions of Croatia. The annual precipitation variance spectra in the continental lowland (Osijek) and at the north East Adriatic coast (Crikvenica) can be fitted by Markov white noise continuum, but in the transitional region between the Dinaric Alps and the Pannonian lowland (Zagreb-Gri) a non-white noise continuum is necessary. Quasi-periodic oscillations appear in two spectra ranges: short (2.2 and 4.7 years) and medium (25.0 and 33.3 years). These results are compared with those of other authors for other parts of the Europe.With 2 Figures     

Eddy energy dissipation rate and puff diffusion during calms

The paper considers a puff diffusion in its inertial stage when particle separation obeys the laws of the inertial subrange and depends only on eddy energy dissipation rate . The can be determined in the surface layer by the turbulent kinetic energy equation. Similarity equations connect with diffusion measure .A simple analytical model has been deduced to estimate pollutants diffusion during calms.     

On the inner-layer scale height of boundary-layer flow over low hills

Jackson and Hunt's (1975) equation for the depth of the inner layer of flows over low hills does not depend on any closure assumption as contrarily supposed in literature. This equation contains a constant which can arbitrarily be specified. It is suggested that this inner-layer constant should be determined from experimental data. A preliminary check with some data from the Askervein experiment suggests that Jackson and Hunt's equation fits these data almost as well as Jensen's equation provided that fitted inner-layer constants are used.     

Vulnerability of Island Tropical Montane Cloud Forests to Climate Change, with Special Reference to East Maui, Hawaii

Island tropical montane cloud forests may be among the most sensitive of the world's ecosystems to global climate change. Measurements in and above a montane cloud forest on East Maui, Hawaii, document steep microclimatic gradients. Relatively small climate-driven shifts in patterns of atmospheric circulation are likely to trigger major local changes in rainfall, cloud cover, and humidity. Increased interannual variability in precipitation and hurricane incidence would provide additional stresses on island biota that are highly vulnerable to disturbance-related invasion of non-native species. Because of the exceptional sensitivity of these microclimates and forests to change, they may provide valuable listening posts for detecting the onset of human-induced global climate change.     

Limits of warm and cold bioclimatic stress in different climatic regions

Summary Limits of warm and cold stress in different climatic regions are determined by means of temperature, wind speed and humidity for the period 1976–1985. These values are measured at 2 PM local time during July for warm stress and at 7 AM local time during January for cold stress. Hvar (20 m ASL) is used to represent maritime climate, Zavian on the top of Mount Velebit (1594 m ASL) and Skrad (668 m ASL) in Gorski Kotar are representative of mountainous climate, and Zagreb (128 m ASL) is representative of continental low-land climate. Values of a biometeorological Temperature-Wind Speed-Humidity (TWH)-index higher than the 98% value of the theoretical distribution fitted to empirical data represent above normal extreme conditions at a given location, and TWH values less than 2% value of the theoretical distribution represent below normal extreme conditions. For similar temperatures, it will be extremely above normal at the top of Mount Velebit (Zavian) whilst normal on the coast (Hvar), and similarly, it will be extremely below normal in Hvar but normal at Zavian.With 4 Figures     

Effects of heat and water vapor transport on eddy covariance measurement of CO2 fluxes

Flux densities of carbon dioxide were measured over an arid, vegetation-free surface by eddy covariance techniques and by a heat budget-profile method, in which CO₂ concentration gradients were specified in terms of mixing ratios. This method showed negligible fluxes of CO₂, consistent with the bareness of the experimental site, whereas the eddy covariance measurements indicated large downward fluxes of CO₂. These apparently conflicting observations are in quantitative agreement with the results of a recent theory which predicts that whenever there are vertical fluxes of sensible or latent heat, a mean vertical velocity is developed. This velocity causes a mean vertical convective mass flux (= _cw for CO₂, in standard notation). The eddy covariance technique neglects this mean convective flux and measures only the turbulent flux _c w. Thus, when the net flux of CO₂ is zero, the eddy covariance method indicates an apparent flux which is equal and opposite to the mean convective flux, i.e., _c w = – _c w. Corrections for the mean convective flux are particularly significant for CO₂ because _cw and _c w are often of similar magnitude. The correct measurement of the net CO₂ flux by eddy covariance techniques requires that the fluxes of sensible and latent heat be measured as well.     

The effect of synoptic-scale advection on the performance of the Priestley-Taylor evaporation formula

Measurements of the appropriate parameters for the calculation of the latent heat flux over a black spruce forest in northern Quebec were carried out in August, 1980. Values of the Priestley-Taylor parameter, , were derived by exploiting the Bowen-ratio-energy-balance (BREB) technique. Derived values of are then related to synoptic-scale warm air advection, derived from surface synoptic charts and tephigrams of the planetary boundary layer. It is found that when warm air advection is present, > 1.26, especially when the surface is wet. When advection enhancement is removed, however, values of approach unity. A new approach to calculating the latent heat flux, when warm air advection is present, is therefore proposed.     

Statistical properties of 49 years of rainfall rate events

Summary The paper presents a detailed investigation of magnitudes and properties pertaining to the large population of rainfall events recorded during 49 years at the Fabra Observatory in Barcelona. The study includes a statistical analysis of event durationT and rainfall quantityQ together with the statistical rainfall rate parameters: , ²(R) and maximum Rm within an event. The decorrelation time is also analysed. It is found thatQ, T, and can be well modelled by a lognormal distribution, but , ² and Rm are only so for a limited range of precipitation ratesR. The regression analysis between pairs of logarithms of the magnitudes investigated is generally good and a regression coefficient is often better than 0.9. Comparison with published work is also carried out. An attempt is made to discriminate between heavy and non-heavy rainfall rates, and the 50 mm/h threshold is used for the study. The twelve-monthly running average indicates that the rainfall amount has a small increasing trend over the fifty year period. However, this trend is reversed when considering heavy rains. Finally, the return period in years to exceeding a thresholdR within an event is also investigated and the distribution of the population of annual extremes is found to be Gumbel II.With 6 Figures     

Estimation of impact of climate change on the peak discharge probability of the river Rhine

RHINEFLOW is a GIS based water balance model that has been developed to study the changes in the water balance compartments of the river Rhine basin on a monthly time basis. The model has been designed to study the sensitivity of the Rhine discharge to a climate change. The calculated discharge has been calibrated and validated on the period 1956 to 1980. For this period the model efficiency of RHINEFLOW is between 0.74 and 0.81 both for the entire Rhine and for its tributaries. Also calculated values for variations in other compartments, e.g. snow storage and actual evapotranspiration, were in good agreement with the measured values.Since a high correlation between monthly discharge and peak discharge was found for the period 1900–1980 The RHINEFLOW model is used to assess the probability of exceedence for discharge peaks under possible future climate conditions.The probabilities of exceedence were calculated from the conditional probabilities of peak discharges for a series of 15 classes of monthly discharges. Comparison of a calculated frequency distribution of high discharge peaks with observed peaks in a test series showed that the method performs well.Scenarios for temperature changes between 0 °C and plus 4 °C and precipitation changes between plus 20% and minus 20% have been applied. Within this range flood frequencies are more sensitive for a precipitation change than for a temperature change. The present two-year return period peak flow (6500–7000 m³/s) decreases by about 6% due to a temperature rise of 4 °C; a precipitation decrease of 20% leads to 30% lower two-year peaks whilst 20% precipitation increase raises them by approximately 30%.Application of a Business As Usual (BAU) and an Accelerated Policy (AP) climate scenario resulted in a significant increase in probability of peak flows for the BAU scenario, while for the AP scenario no significant change could be found. Due to sampling errors, accurate estimations of recurrence times of discharge peaks7000 m³/s require a longer sampling time series than 90 years. For management purposes the method can be applied to estimate changes of probabilities of events with a relatively long recurrence time.     

In Search of Warmer Climates? The Impact of Climate Change on Flows of British Tourists

This paper investigates the impact of climate change on the chosendestinations of Britishtourists. Destinations are characterised in terms of attractors includingclimate variables, traveland accommodation costs. These variables are used to explain the currentobserved pattern ofoverseas travel in terms of a model based upon the idea of utilitymaximisation. The approachpermits the trade-offs between climate and holiday expenditure to be analysedand effectivelyidentifies the optimal climate for generating tourism. The findings are usedto predict the impactof various climate change scenarios on popular tourist destinations.     

Effect of finite sampling on atmospheric spectra

The effect of a finite averaging time on variances is well known, but its effect on power spectra is less clearly understood. We present numerical solutions for the spectral distortion arising from sampling over a finite time interval T and show that the commonly used filter function (1 – sinc²f T), valid for variances, is a reasonable approximation for power spectra only when T 10 _m , where f is the cyclic frequency, and _m is the dominant time scale of the process. Our results exhibit an increasingly steeper low-frequency roll-off as T decreases relative to _m , indicating that the measured spectrum is subject to a greater suppression of the lower frequencies (f > 1/T) than predicted by (1 – sinc²f T). This suppression is, in a sense, compensated by an overestimation of spectral estimates in the frequency range f 1/T.     

Mechanisms of shrubland expansion: land use,climate or CO2?

Encroachment of trees and shrubs into grasslands and the thicketization of savannas has occurred worldwide over the past century. These changes in vegetation structure are potentially relevant to climatic change as they may be indicative of historical shifts in climate and as they may influence biophysical aspects of land surface-atmosphere interactions and alter carbon and nitrogen cycles. Traditional explanations offered to account for the historic displacement of grasses by woody plants in many arid and semi-arid ecosystems have centered around changes in climatic, livestock grazing and fire regimes. More recently, it has been suggested that the increase in atmospheric CO₂ since the industrial revolution has been the driving force. In this paper we evaluate the CO₂ enrichment hypotheses and argue that historic, positive correlations between woody plant expansion and atmospheric CO₂ are not cause and effect.Please direct all correspondence to the senior author.     

Scavenging Efficiency of ‘Aerosol Carbon’ and Sulfate in Supercooled Clouds at Mt. Sonnblick (3106 m a.s.l., Austria)

Cloud water and interstitial aerosol samples collected at Mt. Sonnblick (SBO) were analyzed for sulfate and aerosol carbon to calculate in-cloud scavenging efficiencies. Scavenging efficiencies for sulfate (_SO) ranged from 0.52 to 0.99 with an average of 0.80. Aerosol carbon was scavenged less efficiently with an average value (_AC) of 0.45 and minimum and maximum values of 0.14 and 0.81, respectively. Both _SO and _AC showed a marked, but slightly different, dependence on the liquid water content (LWC) of the cloud. At low LWC, _SO increased with rising LWC until it reached a relatively constant value of 0.83 above an LWC of 0.3 g/m³. In the case of aerosol carbon, we obtained a more gradual increase of _AC up to an LWC of 0.5 g/m³. At higher LWCs, _{_} remained relatively constant at 0.60. As the differences between _SO and _A varied across the LWC range observed at SBO, we assume that part of the aerosol carbon was incorporated into the cloud droplets independently from sulfate. This hypothesis is supported by size classified aerosol measurements. The differences in the size distributions of sulfate and total carbon point to a partially external mixture. Thus, the different chemical nature and the differences in the size and mixing state of the aerosol particles are the most likely candidates for the differences in the scavenging behavior.     

Small-Scale Variability in the Coastal Atmospheric Boundary Layer

The influence of the main large-scale wind directions on thermally driven mesoscale circulations at the Baltic southwest coast, southeast of Sweden, is examined. The aim of the study is to highlight small-scale alterations in the coastal atmospheric boundary layer. A numerical three-dimensional mesoscale model is used in this study, which is focused on an overall behaviour of the coastal jets, drainage flows, sea breezes, and a low-level eddy-type flow in particular. It is shown that synoptic conditions, together with the moderate terrain of the southeast of Sweden (max. height h₀ 206 m), governs the coastal mesoscale dynamics triggered by the land-sea temperature difference T. The subtle nature of coastal low-level jets and sea breezes is revealed; their patterns are dictated by the interplay between synoptic airflow, coastline orientation, and T.The simulations show that coastal jets typically occur during nighttime and vary in height, intensity and position with respect to the coast; they interact with downslope flows and the background wind. For the assigned land surface temperature (varying ±8 K from the sea temperature) and the opposing constant geostrophic wind 8 m s^-1, the drainage flow is more robust to the opposing ambient flow than the sea breeze later on. Depending on the part of the coast under consideration, and the prevailing ambient wind, the sea breeze can be suppressed or enhanced, stationary at the coast or rapidly penetrating inland, locked up in phase with another dynamic system or almost independently self-evolving. A low-level eddy structure is analyzed. It is governed by tilting, divergence and horizontal advection terms. The horizontal extent of the coastal effects agrees roughly with the Rossby radius of deformation.     

Changing thermal topography of the Baltimore-Washington corridor: 1950–1979

A study of the temperature field for the Baltimore-Washington region reveals that since 1950 there has been the development of an urban heat corridor. Trend surface analysis shows that there has been an inversion of the thermal topography in the region as a saddle of rising temperatures has emerged, replacing a trough of lowered temperatures through three decades. Steady population growth throughout the area is seen to be the most important contributor. The strengthening of the heat corridor is best expressed in the summer months and weakest during the winter months. As population continues to grow in this region, the thermal topography is sure to be modified even further.It is recommended that further study be devoted to temperature and precipitation changes in regions experiencing urban growth.