Extraction behavior of the synergistic system 2,6-bis-(benzoxazolyl)-4-dodecyloxylpyridine and 2-bromodecanoic acid using Am and Eu as radioactive tracers

In this study, the extraction properties of a synergistic system consisting of 2,6-bis-(benzoxazolyl)-4-dodecyloxylpyridine (BODO) and 2-bromodecanoic acid (HA) in tert-butyl benzene (TBB) have been investigated as a function of ionic strength by varying the nitrate ion and perchlorate ion concentrations. The influence of the hydrogen ion concentration has also been investigated. Distribution ratios between 0.03-12 and 0.003-0.8 have been found for Am(III) and Eu(HI), respectively, but there were no attempts to maximize these values. It has been shown that the distribution ratios decrease with increasing amounts of ClO4-, NO3-, and H+. The mechanisms, however, by which the decrease occurs, are different. In the case of increasing perchlorate ion concentration, the decrease in extraction is linear in a log-log plot of the distribution ratio vs. the ionic strength, while in the nitrate case the complexation between nitrate and Am or Eu increases at high nitrate ion concentrations and thereby decreases the distribution ratio in a non-linearway. The decrease in extraction could be caused by changes in activity coefficients that can be explained with specific ion interaction theory (SIT); shielding of the metal ions, and by nitrate complexation with Am and Eu as competing mechanism at high ionic strengths. The separation factor between Am and Eu reaches a maximum at similar to1 M nitrate ion concentration. Thereafter the values decrease with increasing nitrate ion concentrations.

The advection of high-resolution tracers by low-resolution winds

The usefulness of any simulation of atmospheric tracers using low-resolution winds relies on both the dominance of large spatial scales in the strain and time dependence that results in a cascade in tracer scales. Here, a quantitative study on the accuracy of such tracer studies is made using the contour advection technique. It is shown that, although contour stretching rates are very insensitive to the spatial truncation of the wind field, the displacement errors in filament position are sensitive. A knowledge of displacement characteristics is essential if Lagrangian simulations are to be used for the inference of airmass origin. A quantitative lower estimate is obtained for the tracer scale factor (TSF): the ratio of the smallest resolved scale in the advecting wind field to the smallest “trustworthy” scale in the tracer field. For a baroclinic wave life cycle the TSF = 6.1 ± 0.3 while for the Northern Hemisphere wintertime lower stratosphere the TSF = 5.5 ± 0.5, when using the most stringent definition of the trustworthy scale. The similarity in the TSF for the two flows is striking and an explanation is discussed in terms of the activity of potential vorticity (PV) filaments. Uncertainty in contour initialization is investigated for the stratospheric case. The effect of smoothing initial contours is to introduce a spinup time, after which wind field truncation errors take over from initialization errors (2–3 days). It is also shown that false detail from the proliferation of finescale filaments limits the useful lifetime of such contour advection simulations to 3σ−1 days, where σ is the filament thinning rate, unless filaments narrower than the trustworthy scale are removed by contour surgery. In addition, PV analysis error and diabatic effects are so strong that only PV filaments wider than 50 km are at all believable, even for very high-resolution winds. The minimum wind field resolution required to accurately simulate filaments down to the erosion scale in the stratosphere (given an initial contour) is estimated and the implications for the modeling of atmospheric chemistry are briefly discussed.

Establishing Lagrangian connections between observations within air masses crossing the Atlantic during the International Consortium for Atmospheric Research on Transport and Transformation experiment

The ITCT-Lagrangian-2K4 (Intercontinental Transport and Chemical Transformation) experiment was conceived with an aim to quantify the effects of photochemistry and mixing on the transformation of air masses in the free troposphere away from emissions. To this end, attempts were made to intercept and sample air masses several times during their journey across the North Atlantic using four aircraft based in New Hampshire (USA), Faial (Azores) and Creil (France). This article begins by describing forecasts from two Lagrangian models that were used to direct the aircraft into target air masses. A novel technique then identifies Lagrangian matches between flight segments. Two independent searches are conducted: for Lagrangian model matches and for pairs of whole air samples with matching hydrocarbon fingerprints. The information is filtered further by searching for matching hydrocarbon samples that are linked by matching trajectories. The quality of these "coincident matches'' is assessed using temperature, humidity and tracer observations. The technique pulls out five clear Lagrangian cases covering a variety of situations and these are examined in detail. The matching trajectories and hydrocarbon fingerprints are shown, and the downwind minus upwind differences in tracers are discussed.

A case study of boundary layer ventilation by convection and coastal processes

It is often assumed that ventilation of the atmospheric boundary layer is weak in the absence of fronts, but is this always true? In this paper we investigate the processes responsible for ventilation of the atmospheric boundary layer during a nonfrontal day that occurred on 9 May 2005 using the UK Met Office Unified Model. Pollution sources are represented by the constant emission of a passive tracer everywhere over land. The ventilation processes observed include shallow convection, turbulent mixing followed by large-scale ascent, a sea breeze circulation and coastal outflow. Vertical distributions of tracer are validated qualitatively with AMPEP (Aircraft Measurement of chemical Processing Export fluxes of Pollutants over the UK) CO aircraft measurements and are shown to agree impressively well. Budget calculations of tracers are performed in order to determine the relative importance of these ventilation processes. Coastal outflow and the sea breeze circulation were found to ventilate 26% of the boundary layer tracer by sunset of which 2% was above 2 km. A combination of coastal outflow, the sea breeze circulation, turbulent mixing and large-scale ascent ventilated 46% of the boundary layer tracer, of which 10% was above 2 km. Finally, coastal outflow, the sea breeze circulation, turbulent mixing, large-scale ascent and shallow convection together ventilated 52% of the tracer into the free troposphere, of which 26% was above 2 km. Hence this study shows that significant ventilation of the boundary layer can occur in the absence of fronts (and thus during high-pressure events). Turbulent mixing and convection processes can double the amount of pollution ventilated from the boundary layer.

A description of the FAMOUS (version XDBUA) climate model and control run

FAMOUS is an ocean-atmosphere general circulation model of low resolution, capable of simulating approximately 120 years of model climate per wallclock day using current high performance computing facilities. It uses most of the same code as HadCM3, a widely used climate model of higher resolution and computational cost, and has been tuned to reproduce the same climate reasonably well. FAMOUS is useful for climate simulations where the computational cost makes the application of HadCM3 unfeasible, either because of the length of simulation or the size of the ensemble desired. We document a number of scientific and technical improvements to the original version of FAMOUS. These improvements include changes to the parameterisations of ozone and sea-ice which alleviate a significant cold bias from high northern latitudes and the upper troposphere, and the elimination of volume-averaged drifts in ocean tracers. A simple model of the marine carbon cycle has also been included. A particular goal of FAMOUS is to conduct millennial-scale paleoclimate simulations of Quaternary ice ages; to this end, a number of useful changes to the model infrastructure have been made.

Dispersion Experiments in Central London: The 2007 DAPPLE project

In the event of a release of toxic gas in the center of London, the emergency services would need to determine quickly the extent of the area contaminated. The transport of pollutants by turbulent flow within the complex street and building architecture of cities is not straightforward, and we might wonder whether it is at all possible to make a scientifically-reasoned decision. Here we describe recent progress from a major UK project, ‘Dispersion of Air Pollution and its Penetration into the Local Environment’ (DAPPLE, www.dapple.org.uk). In DAPPLE, we focus on the movement of airborne pollutants in cities by developing a greater understanding of atmospheric flow and dispersion within urban street networks. In particular, we carried out full-scale dispersion experiments in central London (UK) during 2003, 2004, 2007, and 2008 to address the extent of the dispersion of tracers following their release at street level. These measurements complemented previous studies because (i) our focus was on dispersion within the first kilometer from the source, when most of the material was expected to remain within the street network rather than being mixed into the boundary layer aloft, (ii) measurements were made under a wide variety of meteorological conditions, and (iii) central London represents a European, rather than North American, city geometry. Interpretation of the results from the full-scale experiments was supported by extensive numerical and wind tunnel modeling, which allowed more detailed analysis under idealized and controlled conditions. In this article, we review the full-scale DAPPLE methodologies and show early results from the analysis of the 2007 field campaign data.

Cloud-radar observations of insects in the UK convective boundary layer

Radar has been applied to the study of insect migration for almost 40 years, but most entomological radars operate at X-band (9.4 GHz, 3.2 cm wavelength), and can only detect individuals of relatively large species, such as migratory grasshoppers and noctuid moths, over all of their flight altitudes. Many insects (including economically important species) are much smaller than this, but development of the requisite higher power and/or higher frequency radar systems to detect these species is often prohibitively expensive. In this paper, attention is focussed upon the uses of some recently-deployed meteorological sensing devices to investigate insect migratory flight behaviour, and especially its interactions with boundary layer processes. Records were examined from the vertically-pointing 35 GHz ‘Copernicus’ and 94 GHz ‘Galileo’ cloud radars at Chilbolton (Hampshire, England) for 12 cloudless and convective occasions in summer 2003, and one of these occasions (13 July) is presented in detail. Insects were frequently found at heights above aerosol particles, which represent passive tracers, indicating active insect movement. It was found that insect flight above the convective boundary layer occurs most often during the morning. The maximum radar reflectivity (an indicator of aerial insect biomass) was found to be positively correlated with maximum screen temperature.

On the dependence of boundary-layer ventilation on frontal type

Case study simulations with idealized tracers have been used to determine the relationship between the dynamics and conceptual representations of different midlatitude frontal systems and the amount, distribution, and time scale of boundary layer ventilation by these systems. The key features of ventilation by a kata– and ana–cold frontal system are found to be quantitatively and also often qualitatively similar to the main ventilation pathways, which are the conveyor belts, cloud head, and other convection. The conveyor belts and cloud head occur within cloud, implying that they can be identified using satellite imagery. Differences in the transport by the two systems can be related to their conceptual representations and include a sensitive dependence on the diurnal cycle for the kata- but not the ana-cold frontal case.

Mechanisms of midlatitude cross-tropopause transport using a potential vorticity budget approach

[ 1] A potential vorticity (PV) budget method has been used to attribute vertical transport across the near-tropopause ( 1 PVU surface) in extratropical weather systems to radiative, latent heating and cooling, and mixing processes. Sources and sinks of PV due to nonconservative processes are calculated online and advected as passive tracers. There is reasonable agreement between the spatial distribution of transport determined from the PV budget method and the transport across the 1 - 2 PVU zone from a passive tracer and trajectories, but different aspects of exchange can be diagnosed with each method. Stratosphere-to-troposphere transport occurred in the broad upper level PV anomalies and was attributed mainly to latent heating and cooling processes; troposphere-to-stratosphere transport occurred toward the tail of a PV filament and in a ridge region and was attributed mainly to radiative processes. The contribution of mixing processes to transport was comparatively small. Using the PV budget method, the domain integrated exchange across the 1 PVU surface was from stratosphere to troposphere, and the magnitude of 1 x 10(15) kg over a 2 day winter integration in a large North Atlantic domain is consistent with stratosphere-troposphere exchange calculations from other studies. This exchange arises from an approximate balance between the dominant stratosphere-to-troposphere transport due to latent heating and cooling processes and troposphere-to-stratosphere transport due to radiative processes. The direction of transport across the tropopause in a fold was found to be critically dependent on the PV surface considered to represent the tropopause.

Mechanisms of ocean heat uptake in a coupled climate model and the implications for tracer based predictions of ocean heat uptake

The distribution of tracers in the ocean is often taken as an indication of the ventilation pathways for oceanic water masses. It has been suggested that under anthropogenic forcing heat will be taken up into the interior of the ocean along isopycnal ventilation pathways. This notion is investigated by examining distributions of potential temperature and a passive anomaly temperature tracer in a coupled climate experiment where CO2 is increased at a rate of 2% per year. We show that interior temperature changes cannot be explained solely by passive tracer transport along isopycnals. Heat uptake is strongly affected by changes in circulation and has a substantial diapycnal component.

Suprathermal electron evolution in a Parker spiral magnetic field

Suprathermal electrons (>70 eV) form a small fraction of the total solar wind electron density but serve as valuable tracers of heliospheric magnetic field topology. Their usefulness as tracers of magnetic loops with both feet rooted on the Sun, however, most likely fades as the loops expand beyond some distance owing to scattering. As a first step toward quantifying that distance, we construct an observationally constrained model for the evolution of the suprathermal electron pitch-angle distributions on open field lines. We begin with a near-Sun isotropic distribution moving antisunward along a Parker spiral magnetic field while conserving magnetic moment, resulting in a field-aligned strahl within a few solar radii. Past this point, the distribution undergoes little evolution with heliocentric distance. We then add constant (with heliocentric distance, energy, and pitch angle) ad-hoc pitch-angle scattering. Close to the Sun, pitch-angle focusing still dominates, again resulting in a narrow strahl. Farther from the Sun, however, pitch-angle scattering dominates because focusing is effectively weakened by the increasing angle between the magnetic field direction and intensity gradient, a result of the spiral field. We determine the amount of scattering required to match Ulysses observations of strahl width in the fast solar wind, providing an important tool for inferring the large-scale properties and topologies of field lines in the interplanetary medium. Although the pitch-angle scattering term is independent of energy, time-of-flight effects in the spiral geometry result in an energy dependence of the strahl width that is in the observed sense although weaker in magnitude.

Cross-hemispheric transport of Central African biomass burning pollutants: Implications for downwind ozone production

Pollutant plumes with enhanced concentrations of trace gases and aerosols were observed over the southern coast of West Africa during August 2006 as part of the AMMA wet season field campaign. Plumes were observed both in the mid and upper troposphere. In this study we examined the origin of these pollutant plumes, and their potential to photochemically produce ozone (O3) downwind over the Atlantic Ocean. Their possible contribution to the Atlantic O3 maximum is also discussed. Runs using the BOLAM mesoscale model including biomass burning carbon monoxide (CO) tracers were used to confirm an origin from central African biomass burning fires. The plumes measured in the mid troposphere (MT) had significantly higher pollutant concentrations over West Africa compared to the upper tropospheric (UT) plume. The mesoscale model reproduces these differences and the two different pathways for the plumes at different altitudes: transport to the north-east of the fire region, moist convective uplift and transport to West Africa for the upper tropospheric plume versus north-west transport over the Gulf of Guinea for the mid-tropospheric plume. Lower concentrations in the upper troposphere are mainly due to enhanced mixing during upward transport. Model simulations suggest that MT and UT plumes are 16 and 14 days old respectively when measured over West Africa. The ratio of tracer concentrations at 600 hPa and 250 hPa was estimated for 14–15 August in the region of the observed plumes and compares well with the same ratio derived from observed carbon dioxide (CO2) enhancements in both plumes. It is estimated that, for the period 1–15 August, the ratio of Biomass Burning (BB) tracer concentration transported in the UT to the ones transported in the MT is 0.6 over West Africa and the equatorial South Atlantic. Runs using a photochemical trajectory model, CiTTyCAT, initialized with the observations, were used to estimate in-situ net photochemical O3 production rates in these plumes during transport downwind of West Africa. The mid-troposphere plume spreads over altitude between 1.5 and 6 km over the Atlantic Ocean. Even though the plume was old, it was still very photochemically active (mean net O3 production rates over 10 days of 2.6 ppbv/day and up to 7 ppbv/day during the first days) above 3 km especially during the first few days of transport westward. It is also shown that the impact of high aerosol loads in the MT plume on photolysis rates serves to delay the peak in modelled O3 concentrations. These results suggest that a significant fraction of enhanced O3 in mid-troposphere over the Atlantic comes from BB sources during the summer monsoon period. According to simulated occurrence of such transport, BB may be the main source for O3 enhancement in the equatorial south Atlantic MT, at least in August 2006. The upper tropospheric plume was also still photochemically active, although mean net O3 production rates were slower (1.3 ppbv/day). The results suggest that, whilst the transport of BB pollutants to the UT is variable (as shown by the mesoscale model simulations), pollution from biomass burning can make an important contribution to additional photochemical production of O3 in addition to other important sources such as nitrogen oxides (NOx) from lightning.

Forest fire plumes over the North Atlantic: p-TOMCAT model simulations with aircraft and satellite measurements from the ITOP/ICARTT campaign

Intercontinental Transport of Ozone and Precursors (ITOP) (part of International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)) was an intense research effort to measure long-range transport of pollution across the North Atlantic and its impact on O3 production. During the aircraft campaign plumes were encountered containing large concentrations of CO plus other tracers and aerosols from forest fires in Alaska and Canada. A chemical transport model, p-TOMCAT, and new biomass burning emissions inventories are used to study the emissions long-range transport and their impact on the troposphere O3 budget. The fire plume structure is modeled well over long distances until it encounters convection over Europe. The CO values within the simulated plumes closely match aircraft measurements near North America and over the Atlantic and have good agreement with MOPITT CO data. O3 and NOx values were initially too great in the model plumes. However, by including additional vertical mixing of O3 above the fires, and using a lower NO2/CO emission ratio (0.008) for boreal fires, O3 concentrations are reduced closer to aircraft measurements, with NO2 closer to SCIAMACHY data. Too little PAN is produced within the simulated plumes, and our VOC scheme's simplicity may be another reason for O3 and NOx model-data discrepancies. In the p-TOMCAT simulations the fire emissions lead to increased tropospheric O3 over North America, the north Atlantic and western Europe from photochemical production and transport. The increased O3 over the Northern Hemisphere in the simulations reaches a peak in July 2004 in the range 2.0 to 6.2 Tg over a baseline of about 150 Tg.

Quantifying mesoscale variability in ocean transient tracer fields

A powerful way to test the realism of ocean general circulation models is to systematically compare observations of passive tracer concentration with model predictions. The general circulation models used in this way cannot resolve a full range of vigorous mesoscale activity (on length scales between 10–100 km). In the real ocean, however, this activity causes important variability in tracer fields. Thus, in order to rationally compare tracer observations with model predictions these unresolved fluctuations (the model variability error) must be estimated. We have analyzed this variability using an eddy‐resolving reduced‐gravity model in a simple midlatitude double‐gyre configuration. We find that the wave number spectrum of tracer variance is only weakly sensitive to the distribution of (large scale slowly varying) tracer sources and sinks. This suggests that a universal passive tracer spectrum may exist in the ocean. We estimate the spectral shape using high‐resolution measurements of potential temperature on an isopycnal in the upper northeast Atlantic Ocean, finding a slope near k −1.7 between 10 and 500 km. The typical magnitude of the variance is estimated by comparing tracer simulations using different resolutions. For CFC‐ and tritium‐type transient tracers the peak magnitude of the model variability saturation error may reach 0.20 for scales shorter than 100 km. This is of the same order as the time mean saturation itself and well over an order of magnitude greater than the instrumental uncertainty.

Constraining a North Atlantic Ocean general circulation model with chlorofluorocarbon observations

Measurements of anthropogenic tracers such as chlorofluorocarbons and tritium must be quantitatively combined with ocean general circulation models as a component of systematic model development. The authors have developed and tested an inverse method, using a Green's function, to constrain general circulation models with transient tracer data. Using this method chlorofluorocarbon-11 and -12 (CFC-11 and -12) observations are combined with a North Atlantic configuration of the Miami Isopycnic Coordinate Ocean Model with 4/3 degrees resolution. Systematic differences can be seen between the observed CFC concentrations and prior CFC fields simulated by the model. These differences are reduced by the inversion, which determines the optimal gas transfer across the air-sea interface, accounting for uncertainties in the tracer observations. After including the effects of unresolved variability in the CFC fields, the model is found to be inconsistent with the observations because the model/data misfit slightly exceeds the error estimates. By excluding observations in waters ventilated north of the Greenland-Scotland ridge (sigma (0) < 27.82 kg m(-3); shallower than about 2000 m), the fit is improved, indicating that the Nordic overflows are poorly represented in the model. Some systematic differences in the model/data residuals remain and are related, in part, to excessively deep model ventilation near Rockall and deficient ventilation in the main thermocline of the eastern subtropical gyre. Nevertheless, there do not appear to be gross errors in the basin-scale model circulation. Analysis of the CFC inventory using the constrained model suggests that the North Atlantic Ocean shallower than about 2000 m was near 20% saturated in the mid-1990s. Overall, this basin is a sink to 22% of the total atmosphere-to-ocean CFC-11 flux-twice the global average value. The average water mass formation rates over the CFC transient are 7.0 and 6.0 Sv (Sv = 10(6) m(3) s(-1)) for subtropical mode water and subpolar mode water, respectively.