Observations of the evolution of the aerosol, cloud and boundary‐layer characteristics during the 1st ACE‐2 Lagrangian experiment

During the 1st Lagrangian experiment of the North Atlantic Regional Aerosol Characterisation Experiment (ACE‐2), a parcel of air was tagged by releasing a smart, constant level balloon into it from the Research Vessel Vodyanitskiy . The Meteorological Research Flight's C‐130 aircraft then followed this parcel over a period of 30 h characterising the marine boundary layer (MBL), the cloud and the physical and chemical aerosol evolution. The air mass had originated over the northern North Atlantic and thus was clean and had low aerosol concentrations. At the beginning of the experiment the MBL was over 1500 m deep and made up of a surface mixed layer (SML) underlying a layer containing cloud beneath a subsidence inversion. Subsidence in the free troposphere caused the depth of the MBL to almost halve during the experiment and, after 26 h, the MBL became well mixed throughout its whole depth. Salt particle mass in the MBL increased as the surface wind speed increased from 8 m s⁻¹ to 16 m s⁻¹ and the accumulation mode (0.1μm to 3.0 μm) aerosol concentrations quadrupled from 50 cm⁻³ to 200 cm⁻³. However, at the same time the total condensation nuclei (>3 nm) decreased from over 1000 cm⁻³ to 750 cm⁻³. The changes in the accumulation mode aerosol concentrations had a significant effect on the observed cloud microphysics. Observational evidence suggests that the important processes in controlling the Aitken mode concentration which, dominated the total CN concentration, included, scavenging of interstitial aerosol by cloud droplets, enhanced coagulation of Aitken mode aerosol and accumulation mode aerosol due to the increased sea salt aerosol surface area, and dilution of the MBL by free tropospheric air.     

Stratigraphy and tectonics of a time-transgressive ophiolite obduction onto the eastern margin of the Pelagonian platform from Late Bathonian until Valanginian time,exemplified in northern Evvoia,Greece

The obduction of an ophiolite sheet onto the eastern Pelagonian carbonate platform complex of the Hellenides began during the Late Bathonian and ended with the final emplacement of the ophiolite during Valanginian time. The early stages of obduction caused subaerial exposure of the platform, recorded by an unconformity of Callovian age, which is marked by laterites overlying folded and faulted, karstic substrates. The laterites have distinct ophiolitic geochemical signatures, indicating that emergent ophiolite had been undergoing lateritic weathering. This unconformity coincides with widespread western Tethyan, Callovian gaps, indicating that the obduction in the Hellenides was probably related to far-reaching plate tectonic processes. Resumed gravitational pull and rollback of the subducted, oceanic leading edge of the temporarily exposed ophiolite. Platform drowning continued into Tithonian–Valanginian time, documented initially by reefal carbonates and then by below-CCD, carbonate-free radiolarian cherts and shales. Subsequently, siliciclastic turbidites, which apparently originated from uplifted Variscan basement, were deposited together with and over the radiolarite as the ophiolite nappe sheet advanced. The nappe substrate underwent tectonic deformations of varying intensity, while polymictic mélange and syntectonic sedimentary debris accreted beneath the ophiolite and at the nappe front. The provenience of the ophiolite nappe complexes of northern Evvoia most probably has to be looked for in the Vardar ocean.     

Quantifying groundwater discharge to a small perennial stream in southern Ontario, Canada

A study of the interaction between groundwater and surface water was undertaken within a small agricultural watershed in southern Ontario, Canada. Groundwater contributions to streamflow were measured along a section of stream during baseflow conditions and during rainfall events. Four techniques were used to estimate the contribution of groundwater to the stream along a 450 m reach (three during baseflow and one during stormflow conditions). Under baseflow conditions, streamflow measurements using the velocity–area technique indicated that the net groundwater flux to the stream during the summer months was 10 ml s⁻¹ m⁻¹. Hydrometric measurements (i.e. hydraulic gradient and hydraulic conductivity) taken using mini-piezometers installed in the sediments beneath the stream resulted in net groundwater flux estimates that were four to five times lower. Seepage meters failed to provide any measurements of water flux into or out of the stream. Therefore, based on these results, the velocity–area technique gives the best estimate of groundwater discharge. Hydrograph separations were conducted using isotopic ratios and electrical conductivity on two large rainfall events with different antecedent moisture conditions in the catchment. Both events showed that pre-event water (generally considered groundwater) dominated streamflow and tile drain flow with 64%–80% of the total discharge contributed by pre-event water. High water table conditions within the catchment resulted in greater stream discharge and a greater contribution of event water in the streamflow than that observed under low water table conditions for similar intensity storm events. The results also showed that differences in riparian zone width, vegetation and surface saturation conditions between the upper and lower catchment can influence the relative magnitude of streamflow response from the two catchment areas.     

Numerical investigation of road salt impact on an urban wellfield

The impact of road salt on a wellfield in a complex glacial moraine aquifer system is studied by numerical simulation. The moraine underlies an extensive urban and industrial landscape, which draws its water supply from >20 wellfields, several of which are approaching or have exceeded the drinking water limit for chloride. The study investigates the mechanisms of road salt infiltration, storage, and transport in the subsurface and assesses the effectiveness of mitigation measures designed to reduce the impact. The three-dimensional transport model accounts for increases in salt loading, as well as growth of the urbanized area and road network over the past 50 years. The simulations, which focus on one impacted wellfield, show chloride plumes originating mainly at arterial roads and migrating through aquitard windows into the water supply aquifers. The results suggest that the aquifer system contains a large and heterogeneously distributed mass of chloride and that concentrations in the aquifer can be substantially higher than the concentrations in the well water. Future impact scenarios indicate that although the system responds rapidly to reductions in salt loading, the residual chloride mass may take decades to flush out, even if road salting were discontinued. The implications with respect to urban wellfields in typical snow-belt areas are discussed.     

Moscow, the global city? The position of the Russian capital within the European system of metropolitan areas

During the 1990s, the city of Moscow was subject to an extraordinary transformation in its political, economic and social structures, which had consequences for the position of Moscow within the national and international hierarchy of cities. This article is concerned with the trends that can be discerned regarding the position of Moscow on the national and European scales. Without a doubt, the development of Moscow is characterized by an increasing separation from the national urban system and a growing international orientation. The Russian capital has no competitors on the national level: measured against the relevant economic indicators it is a long way ahead of the remaining Russian cities, which are primarily integrated into national and regional economic flows, and participate in the global economy only to a limited degree. Moscow, in contrast, is increasingly striving to integrate itself into transnational and international economic structures. Although the concept of Moscow as a global city is often instrumentalized in municipal politics, the ability of the Russian capital to act as a global centre is in fact limited. At present Moscow's most important function, from a Central European perspective, is to act as a bridging link between Central and Western Europe and Russia. There is a danger that the spatial disparities between Moscow on the one hand, and the remaining Russian cities and regions on the other, will continue to grow.     

Laboratory Studies of the Hydrogen Kinetic Isotope Effects (KIES) of the Reaction of Non-Methane Hydrocarbons with the OH Radical in the Gas Phase

The hydrogen kinetic isotope effects (KIEs) of the reactions of 15 non-methane hydrocarbons (NMHCs) with the OH radical were measured at 298 ± 2 K. The measurements were made using NMHCs without artificial isotopic labeling or enrichment. The following average hydrogen KIE values, in per mil (), were obtained: 29.8 ± 2.1 (toluene),51.6 ± 2.1 (n-butane), 97.3± 12.5 (i-butane), 63.2 ± 5.9 (cyclopentane), 10.5 (p-xylene), 26.8 ± 3.5 (ethylbenzene), 65.9± 7.0 (n-pentane), 79.5 ± 9.6 (cyclohexane), 52.8 ± 5.0(n-hexane), 38.9 ± 7.8 (n-heptane), 33.4 ± 3.1 (n-octane), 29.6 ± 1.6(n-nonane), and 29.0 ± 5.3 (n-decane). The KIEs for reactions of two alkenes (cyclohexene and 1-heptene) could not be determined accurately due to interference from reaction with ozone, but nevertheless the results clearly show that the KIEs for reaction of alkenes with OH are significantly lower than those for saturated hydrocarbons. The KIEs for reaction of alkanes are smaller than isotope effects reported in literature for the reactions of NMHCs artificially labeled with deuterium. The main reason for this difference is the reduced probability for reaction at a labeled site for compounds with close to natural deuterium abundance, although some impact of secondary isotope effects cannot be ruled out. Still, the KIEs for NMHCs with natural or close to natural abundance of deuterium are of sufficient magnitude to allow determination of the extent of chemical processing of hydrocarbons in the atmosphere using methods analogous to stable carbon KIE studies. Furthermore, it is shown that combining stable hydrogen and stable carbon isotope ratio data has the potential to also provide valuable information regarding the stable isotope ratios of emissions, and specifically to test one of the key assumptions of the stable isotope hydrocarbon clock, the absence of significant variations of the stable isotope ratio for the emitted NMHCs.     

Well vulnerability: a quantitative approach for source water protection

The concept of vulnerability of drinking water sources is reviewed, and a quantitative approach for assessing well vulnerability for complex three-dimensional ground water systems is developed. The approach focuses on the relative expected impact of potential contaminant sources at unknown locations within a well capture zone, providing relative measures of intrinsic well vulnerability, including the expected times of arrival of a contaminant, the dispersion-related reduction in concentration, the time taken to breach a certain quality objective, and the corresponding exposure times. Thus, the result of the analysis includes the usual advective travel time information used in conventional wellhead protection analysis, plus a set of selected quantitative measures expressing the expected impact. The technique is based on adjoint theory and combines forward- and backward-in-time transport modeling using a standard numerical flow and transport code. The methodology is demonstrated using the case study of a complex glacial multiaquifer system in Ontario. The new approach will be useful in helping water managers develop more physically based and quantitative wellhead protection strategies.     

Measurements of Carbon Monoxide and Nonmethane Hydrocarbons During POPCORN

During the field campaign POPCORN (Photo oxidant formation by plant emitted compounds and OH radicals in North-eastern Germany) in Pennewitt (Mecklenburg-Vorpommern, Germany) in August 1994, carbon monoxide and nonmethane hydrocarbons were measured over a large maize field by in-situ gas chromatography. Throughout the campaign CO and NMHC showed, even for a remote rural area, unexpectedly low mixing ratios. Except a few episodes, CO mixing ratios were around 120 ppb. Ethane was the only hydrocarbon showing mixing ratios exceeding 1 ppb. The mixing ratios of all other NMHC ranged between several hundred ppt and the lower limit of detection which was between 20 and 5 ppt depending on the compound. During three frontal passages CO and NMHC mixing ratios increased significantly, while between August 13 and 16, 1994, polar air masses were encountered with CO and NMHC mixing ratios dropping to values which are typical for North Atlantic background air. During this period average CO mixing ratios were 85 ppb and ethane as the most abundant hydrocarbon decreased to 650 ppt. The large-scale meteorological situation is reflected in an unusual frequency distribution of CO. The distribution shows three maxima which can be assigned to the periods of the frontal passages, to the observation of polar air masses and the rest of the campaign. Two-day backward trajectories were calculated in order to obtain information about the origin of the air masses transported to the site. The observed NMHC and CO data can be attributed to the origin of the air masses and the air mass trajectories. NMHC and CO mixing ratios were well correlated indicating that these compounds originated from similar mostly anthropogenic sources. An exception was isoprene which showed no correlation with CO. With values below 100 ppt the mixing ratio of isoprene, which is emitted by terrestrial vegetation, was also unexpectedly low during the first half of the campaign although the maximum temperatures were around 35°C.     

Isotopic Composition of Non-Methane Hydrocarbons in Emissions from Biomass Burning

The stable carbon isotope ratios of nonmethane hydrocarbons (NMHC) and methyl chloride emitted from biomass burning were determined by analyzing seven whole air samples collected during different phases of the burning process as part of a laboratory study of wood burning. The average of the stable carbon isotope ratios of emitted alkanes, alkenes and aromatic compounds is identical to that of the burnt fuel; more than 50% of the values are within a range of ±1.5 of thecomposition of the burnt fuel wood. Thus for the majority of NMHC emitted from biomass burning stable carbon isotope ratio of the burnt fuel a good first order approximation for the isotopic composition of the emissions. Of the more than twenty compounds we studied, only methyl chloride and ethyne differed in stable carbon isotope ratios by more than a few per mil from the composition of the fuel. Ethyne is enriched in ¹³C by approximately 20–30, and most of the variability can beexplained by a dependence on flame temperature. The ¹³C values decreaseby 0.019 /K (±0.0053/K) with increasing temperature. Methyl chloride is highly depleted in ¹³C, on average by25. However the results cover a wide range of nearly 30. Specifically, in two measurements with wood from Eucalyptus (Eucalyptus delegatensis) as fuel we observed the emission of extremely light methyl chloride (–68.5and–65.5). This coincides with higher than average emission ratiosfor methyl chloride (15.5 × 10^–5 and 18 ×10^–5 mol CH₃Cl/mol CO₂). These high emission ratios are consistent with the highchlorine content of the burnt fuel, although, due to the limited number of measurements, it would be premature to generalize these findings. The limited number of observations also prevents any conclusion on a systematic dependence between chlorine content of the fuel, emission ratios and stable carbon isotope ratio of methyl chloride emissions. However, our results show that a detailed understanding of the emissions of methyl chloride from chloride rich fuels is important for understanding its global budget. It is also evident that the usefulness of stable carbon isotope ratios to constrain the global budget of methyl chloride will be complicated by the very large variability of the stable carbon isotope ratio of biomass burning emissions. Nevertheless, ultimately the large fractionation may provide additional constraints for the contribution of biomass burning emissions to the atmospheric budget of methyl chloride.