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# Journal Publications

This section contains all refereed journal publications that have some connection either with the Mace Head Research Station or with members, both present and past, of the Atmospheric Physics Research Cluster at NUI, Galway.

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## Documents

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 Date added: 08/07/2003 Date modified: 07/23/2009 Filesize: 34.15 kB
Fleming, Z.L.; Monks, P.S.; Rickard, A.R.; Heard, D.E.; Stills, T; Sommariva, R; Brough, N; Penkett, S.A.; Lewis, A.C.; Lee, J.D.Peroxy radical formation at Mace Head during NAMBLEX [EGU04-A-04097].

Abstract

Analysis of peroxy radical (HO$_2$ + $\Sigma$RO$_2$) data taken using the dual inlet Leicester/UEA PEroxy Radical Chemical Amplification (PERCA) instrument during the North Atlantic Marine Boundary Layer Experiment (NAMBLEX 2002) at the Mace Head Atmospheric Research Station in county Galway, on the west coast of Ireland will be presented.
Photolysis rate coefficients of a variety of compounds (including ozone, formaldehyde and nitrous acid), measured using a spectral radiometer were seen to explain to a large extent the shape of the diurnal variation in the peroxy radicals. In the evening, (after the ozone photolysis is no longer significant) on many days there was still a large amount of radical production appearing to come from formaldehyde photolysis. On a minute timescale, NO$\rm _x$ is shown to suppress radical production but for the averaged peroxy radicals versus NO$\rm _x$ the relationship in daylight hours

there is a maximum in radical production at a NO$\rm _x$ level of just less than 0.5 ppbv and a marked shape to these plots. At nighttime, evidence for an increase in radical production with increasing NO$\rm _x$ shows that NO$_3$ chemistry is a contributor to radical production. Net photochemical ozone production and destruction rates were calculated using amongst other measurements, the peroxy radical data and showed that there were few periods during daylight hours when more ozone was destroyed than produced. In general there was usually a small overall production of ozone. The highest ozone producing periods were when the radical concentrations were high and the NO$\rm _x$ relatively low. HO2 data was compared with total peroxy radical data to examine the ratios of organic to hydrogen peroxy radicals. As the NO$\rm _x$ concentration increased, the proportion of HO$_2$ increased. Examining the contribution of a variety of VOCs to radical production (via their reaction with OH) may explain the variation in
the HO$_2$ : RO$_2$ ratio.

### Non-Methane hydrocarbon measurements in Ireland

 Date added: 08/06/2003 Date modified: 07/27/2009 Filesize: 32.07 kB
Noone, C A.Non-methane hydrocarbon measurements in Ireland [EGU04-A-05179].

Abstract

The measurement of non-methane hydrocarbons (NMHCs) has become increasingly important in recent years in light of their role as precursors in the formation of ozone and their potential impact on human health. In this poster, observations of diurnal and seasonal cycles of NMHCs (C$_2$-C$_8$) are reported for measurements observed at Mace Head, Ireland from 2002-2003. The remote coastal research station of Mace Head, Co. Galway is unique in Europe offering an opportunity to study the Northern Hemispheric background atmosphere, as well as emissions from Europe. Continuous ground-based data collected at Mace Head allows air mass characterisation and model estimates of ozone production with polluted

### Source apportionment of individual aerosol particles by using time-of-flight mass spectrometry

 Date added: 08/06/2003 Date modified: 08/18/2008 Filesize: 7.67 kB

M. Dall Osto , R. M. Harrison , D. Beddows , R. P. Kinnesley , R. J. Donovan  and M. R. Heal, Source apportionment of individual aerosol particles by using time-of-flight mass spectrometry, 2003

### Measurement of OH and HO2 in the Troposphere

 Date added: 08/06/2003 Date modified: 07/23/2009 Filesize: 669.08 kB

D. E. Heard and M. J. Pilling, "Measurement of OH and HO2 in the troposphere," Chem. Rev. 103, 5163-5198 (2003).

Abstract

Volatile organic compounds (VOCs), emitted into the atmosphere, react with a range of oxidants, of which the most important are OH, NO3, and ozone. Under most atmospheric conditions, and during the day, the removal of VOCs is dominated by their reaction with OH. This ability of the atmosphere to “cleanse itself”, and to continue doing so into the future, affects many processes. The concentration of methane, and hence its contribution to radiative forcing, is determined by the balance between its rate of emission and the rate of its removal by reaction with OH. The global distribution and seasonal variability of methane depend on the interaction between emission and reaction with OH. Tropospheric oxidation is also responsible for the formation of groundlevel ozone and photochemical smog and for the production of secondary organic aerosols. The spatial distribution and concentrations of oxidants, such as OH, depend on a wide range of factors, including emissions of both volatile organic compounds and nitrogen ooxides and the interaction of atmospheric transport and chemical kinetics. Oxidation is a complex chemical process, which proceeds through a series of partially oxidized intermediates; the primary emitted compounds and the intermediates have a wide range of atmospheric lifetimes, from minutes to years, depending, in most cases, on their rate constants for reaction with OH and the OH  concentration, [OH]. Thus, the concentrations of photochemically active radical precursors, such as acetone in the upper troposphere, depend on their formation by oxidation of VOCs emitted at the surface, their atmospheric lifetimes, and their rate of vertical transport. Clearly, OH plays a central role in tropospheric chemistry. The in situ measurement of its concentration has long been a goal, but its short lifetime and consequently low concentration provide a seriouschallenge. Considerable progress has been made, however, over the last 10 years, and there are now several OH instruments which are actively used for both ground- based and aircraft-based campaigns, employing principally laser-induced fluorescence, laser absorption, and chemical ionization. Some of these instruments can also be used to measure HO2, which is closely coupled to OH; [OH]:[HO2] depends sensitively on the chemical composition of the atmosphere and particularly on the concentrations of VOCs and NOx. The atmospheric lifetime of OH is 1 s or less, and it has been argued that its concentration is determined only by the local concentrations of longer-lived species such as O3, VOCs, and NOx, and is not affected directly by atmospheric transport. Thus, field measurements of [OH] can be interpreted through zero-dimensional chemical box models, in which the concentrations of longer-lived species are constrained to simultaneous, co-located measured values. This approach has led to the use of measurements of [OH], coupled with contemporaneous measurements of other species, as a way of evaluating chemical mechanisms for atmospheric oxidation. The interpretation of the box models has also provided a means of investigating the interaction of component reactions in the chemical mechanisms under a range of differing but representative chemical environments.

### Measurement and interpretation of OH and HO2 radicals during NAMBLEX

 Date added: 08/06/2003 Date modified: 07/23/2009 Filesize: 8.76 kB
Lee, J.; Smith, S.; Bloss, W.; Heard, D.; Johnson, G.Measurement and interpretation of OH and HO2 radicals during NAMBLEX

Abstract

We present measurements of the hydroxyl, OH, and hydroperoxyl, HO2, radicals obtained during the summer 2002 North Atlantic Marine Boundary Layer Experiment at the Mace Head Atmospheric Research Station, Ireland. Direct  easurements
of [OH] were made using laser-induced fluorescence (LIF) at 308 nm, whilst measurements of [HO2] were made possible subsequent to chemical conversion to OH using NO. Calibration of the measurements of both species was carried out

using a technique based on the photolysis of H2O by a mercury lamp at 184.9 nm. Measurements of OH and HO2 were made on 24 and 13 days respectively, and the noon-time maxima in [OH] and [HO2] were found to vary between 3 - 8 x 10ˆ6 and 1.5 - 2.1 x 10ˆ8 molecule cm-3 respectively for j(O1D) in the range 0.5 - 2.2 x 10ˆ-5 s-1. There is significant evidence to support the presence of night-time HO2 radicals with concentrations in the range 2 - 3 x 10ˆ7 molecule cm-3 (mean [HO2] night-time detection limit 9.65 x 10ˆ6 molecule cm-3). The limited data available for [OH] at night suggest that there is some evidence for the presence of the species above its night-time detection limit (mean night-time [OH]  detection limit = 5.74 x 10ˆ4 molecule cm-3). The data set was used along with a wide range of supporting measurements to carry out a detailed study of chemistry in a range of clean and semi-polluted air masses. A strong correlation between [OH] and the rate of its primary production, P(OH), has been illustrated in both types of air mass with a reduction in dependence as [NOx] increases. A simple steady state calculation has also shown relatively good agreement highlighting the dominance of the CO and CH4 destruction routes in the Marine Boundary Layer (MBL). An analysis of the functional dependence of [OH], [HO2] and the ratio [HO2] / [OH] on [NOx] illustrated the non linear relationship between HOx and NOx radicals. Steady state modelling of [OH] versus [NOx] gave results within the error of the measurements. Similar modelling of [HO2] and [HO2] / [OH] versus [NOx] agreed well at higher [NOx], but showed discrepancies of increasing magnitude for [NOx] < 900 pptv. The effect of the reaction of halogen monoxide species (IO and BrO) with HO2 is also investigated. Observed levels of IO and BrO during NAMBLEX are such that the XO + HO2 reaction can account for up to 40 % of the total sink for HO2 radicals during clean marine air (low NOx) episodes, and to make a significant contribution to the production of OH via the photolysis of HOX.

### Low Molecular Weight Organic Compounds in Maritime Air Recent Results from NAMBLEX Experiment,

 Date added: 08/06/2003 Date modified: 07/24/2009 Filesize: 13.55 kB
Read, K.; Hopkins, J.; Lewis, A., "Low Molecular Weight Organic Compounds in Maritime Air: Recent Results from NAMBLEX Experiment, Mace Head, Ireland", Geophysical Research Abstracts Volume 5, 2003.

Abstract

A dual channel GC-FID for the simultaneous measurement of C2-C7 non-methane hydrocarbons (NMHC), dimethyl sulphide (DMS) and some previously unmeasured oxygenated hydrocarbons (O-VOC) in the atmosphere has been developed and run alongside an established single channel GC-FID measuring NMHC. The instruments were implemented in the field as part of the NAMBLEX (North Atlantic Marine Boundary Layer Experiment) campaign to investigate the role of these trace species in the marine boundary layer. Oxygen containing species such as aldehydes, ketones and alcohols although well known to be highly significant in atmospheric reactions, have in the past been poorly

understood from both distribution and source perspectives. They exist from a combination of both biogenic and anthropogenic emissions together with a secondary source from hydrocarbon oxidation. Under all maritime conditions the organic composition was dominated by acetone, methanol and acetaldehyde with the sum of these compounds contributing up to 85% of the carbon mass of organics in air and up to 80% of the normalised OH radical sink. The relative contribution of NMHC was only comparable when isoprene emissions from terrestrial sources were present. In marine air masses a positive correlation was seen between average zonal surface wind speed and DMS concentration in air in line with previous studies. No equivalent behaviour was recreated for either acetone or acetaldehyde indicating that in this region the ocean is not a significant atmospheric source. These O-VOC compounds appeared to follow the general trends of anthropogenic NMHC tracers such as acetylene indicating a common terrestrial origin for these compounds. Methanol however showed strong anti correlation with averaged wind speed directly indicating that the surface ocean was acting as a sink.

### Free-radical chemistry in the coastal marine boundary layer Measurements and modelling at Mace

 Date added: 08/06/2003 Date modified: 07/24/2009 Filesize: 21.42 kB

D. E. Heard et al. (NAMBLEX team), "Free-radical chemistry in the coastal marine boundary layer: Measurements and modelling at Mace Head, Ireland, during the NAMBLEX campaign", Geophysical Research Abstracts, European Geophysical Society, 5, 11843 (2003).

Abstract

The coastal marine boundary layer provides an ideal location to study the background chemistry of the remote troposphere, and also the effects of perturbations due to biogenic emissions from the inter-tidal zone. The North Atlantic Marine Boundary Layer EXperiment (NAMBLEX), involving ca. 50 scientists, took place at the Mace Head Atmospheric Research Station in July--September 2002. Measurements were made of a number of free-radical species, including OH, HO_2 and RO_2, together with a comprehensive suite of supporting measurements of longer-lived species and radiative parameters that define their rates of formation and destruction. This paper focuses on a comparison of the concentrations of OH and HO_2, measured using laser-induced fluorescence at low pressure, and RO_2, measured using a dual-channel peroxy radical amplifier, under predominantly clean westerly conditions ([NO] < 20 pptv), but also during polluted episodes. Full diurnal profiles were measured on a large number of days, allowing a detailed analysis of the correlations between the free-radical concentrations and the controlling variables, for example, J(O^1D), NO_x and VOCs. A zero-dimensional model, based on the Master Chemical Mechanism (v3), and constrained by measurements of CO, CH_4, H_2, O_3, H_2O, speciated non-methane hydrocarbons, oxygenated hydrocarbons, peroxides, HCHO, NO, NO-2, photolysis frequencies (determined using a scanning spectral-radiometer) and temperature, is used to calculate OH, HO_2 and RO_2. A comparison between measured and calculated levels of free-radicals is made over a range of NO levels. Agreement for OH is better than in previous campaigns at Mace Head. The destruction of OH is dominated by reaction with CO (> 50%), but reaction with the previously unmeasured oxygenated VOCs (in particular acetaldehyde) is found to be more important than reaction with CH_4 or NMHC, with significant implications for the chemistry of the marine boundary layer.

### DOAS measurements of I2, BrO,IO, OIO and NO3 at mace head, ireland

 Date added: 08/06/2003 Date modified: 07/27/2009 Filesize: 33.33 kB

Saiz-Lopez, A., Shillito, J. A., Coe, H., and Plane, J. M. C.: Measurements and modelling of I2, IO, OIO, BrO and NO3 in the mid-latitude marine boundary layer, Atmos. Chem. Phys. Discuss., 5, 9731-9767, 2005.

Abstract

Time series observations of molecular iodine (I2), iodine oxides (IO, OIO), bromine oxide (BrO), and the nitrate radical (NO3) in the mid-latitude coastal marine boundary layer (MBL) are reported. Measurements were made using a new long-path DOAS instrument during a summertime campaign at Mace Head on the west coast of Ireland. I<2 was detected using the B3Π(0+u)−X1Σxg electronic transition between 535 and 575 nm. The I2 mixing ratio was found to vary from below the detection limit (~5 ppt) up to a nighttime maximum of 93 ppt. Along with I2, observations of IO, OIO and NO3 were also made during the night. Surprisingly, IO and OIO were detected at mixing ratios up to 2.5 and 10.8 ppt, respectively. A model is employed to show that the reaction between I2 and NO3 is the likely nighttime source of these radicals. The BrO mixing ratio varied from below the detection limit at night (~1 ppt) to a maximum of 6 ppt in the first hours after sunrise. A model shows that this diurnal behaviour can be explained by halogen recyling in sea-salt aerosol building up photolabile precursors of atomic Br during the preceding night. In the same campaign a zenith sky DOAS was employed to determine the column density variation of NO3 as a function of solar zenith angle (SZA) during sunrise, from which vertical profiles of NO3 through the troposphere were obtained. On several occasions a positive gradient of NO3 was observed over the first 2 km, possibly due to dimethyl sulphide (DMS) removing NO3 at the ocean surface.

### Atmospheric measurements of OH, HO2 and NO by laser-induced fluorescence spectroscopy

 Date added: 08/06/2003 Date modified: 07/27/2009 Filesize: 16.18 kB

Bloss, W. J.; Floquet, C.; Gravestock, T. J.; Heard, D. E.; Ingham, T.; Johnson, G. P.; Lee, J. D.,Atmospheric measurements of OH, HO2 and NO by laser-induced fluorescence spectroscopy using a compact all solid-state laser system,EGS - AGU - EUG Joint Assembly, Abstracts from the meeting held in Nice, France, 6 - 11 April 2003, abstract #10521

Abstract

Free-radicals are key intermediates that control the budgets of many trace gases, for example ozone, greenhouse gases and harmful pollutants. Measurement of radicals and comparison with model calculations constitutes an important test of our understanding of the underlying chemistry. There is a greater need for compact and lightweight instruments for the in situ measurement of free-radical species that are suitable for deployment from a number of field-platforms. A new field instrument has been developed that incorporates an all solid-state Nd:YAG pumped titanium sapphire laser that is capable of generating radiation at high pulse-repetition-frequency for the detection of OH, HO_2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF). The system offers advantages of wide wavelength tunability, compactness, low weight, greater long-term stability (fibre-optic delivery) and short warm-up time. The instrument was successfully deployed during 2002 in the NAMBLEX field campaign at Mace Head with detection limits for OH and HO_2 (measured simultaneously with laser operation at 308 nm) of 3.1 x 10^5 molecule cm-3 (0.012 ppt) and 2.6 x 10^6 molecule cm-3 (0.09 pptv) respectively. Diurnal profiles of OH have been recorded over a period of 5 weeks. NO controls the HO_2/OH ratio and is the critical parameter in the production of tropospheric ozone, yet measurements in the boundary layer are restricted to a single indirect technique based on chemiluminescent analysers. Measurements of NO in the atmosphere have been made by LIF using the new instrument operating at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a commercial chemiluminescent analyser. Whilst operating at 445 nm, the instrument has detected the IO radical in the laboratory, with a projected detection limit that is well below previously measured atmospheric concentrations of IO. A second instrument to be deployed on an aircraft platform is currently being developed.

### ATMOSPHERIC MEASUREMENTS OF OH, HO2

 Date added: 08/06/2003 Date modified: 07/09/2009 Filesize: 16.18 kB

Bloss, W. J.; Floquet, C.; Gravestock, T. J.; Heard, D. E.; Ingham, T.; Johnson, G. P.; Lee, J. D.,Atmospheric measurements of OH, HO2 and NO by laser-induced fluorescence spectroscopy using a compact all solid-state laser system,EGS - AGU - EUG Joint Assembly, Abstracts from the meeting held in Nice, France, 6 - 11 April 2003, abstract #10521

Abstract

Free-radicals are key intermediates that control the budgets of many trace gases, for example ozone, greenhouse gases and harmful pollutants. Measurement of radicals and comparison with model calculations constitutes an important test of our understanding of the underlying chemistry. There is a greater need for compact and lightweight instruments for the in situ measurement of free-radical species that are suitable for deployment from a number of field-platforms. A new field instrument has been developed that incorporates an all solid-state Nd:YAG pumped titanium sapphire laser that is capable of generating radiation at high pulse-repetition-frequency for the detection of OH, HO_2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF). The system offers advantages of wide wavelength tunability, compactness, low weight, greater long-term stability (fibre-optic delivery) and short warm-up time. The instrument was successfully deployed during 2002 in the NAMBLEX field campaign at Mace Head with detection limits for OH and HO_2 (measured simultaneously with laser operation at 308 nm) of 3.1 x 10^5 molecule cm-3 (0.012 ppt) and 2.6 x 10^6 molecule cm-3 (0.09 pptv) respectively. Diurnal profiles of OH have been recorded over a period of 5 weeks. NO controls the HO_2/OH ratio and is the critical parameter in the production of tropospheric ozone, yet measurements in the boundary layer are restricted to a single indirect technique based on chemiluminescent analysers. Measurements of NO in the atmosphere have been made by LIF using the new instrument operating at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a commercial chemiluminescent analyser. Whilst operating at 445 nm, the instrument has detected the IO radical in the laboratory, with a projected detection limit that is well below previously measured atmospheric concentrations of IO. A second instrument to be deployed on an aircraft platform is currently being developed.

### Application of a compact all solid-state laser system to the in situ detection of atmospheric OH, HO

 Date added: 08/06/2003 Date modified: 07/27/2009 Filesize: 184.19 kB
W. J. Bloss, T. J. Gravestock, D. E. Heard, T. Ingham,G. P. Johnson and J. D. Lee, "Application of a compact all solid-state laser system to the in situ detection of atmospheric OH, HO2, NO and IO by laser-induced fluorescence", Journal of Environmental Monitoring., 5, 21-28 (2003).

Abstract

A tuneable, high pulse-repetition-frequency, solid state Nd:YAG pumped titanium sapphire laser capable of generating radiation for the detection of OH, HO2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF) has been developed. The integration of the laser system operating at 308 nm into a field measurement apparatus for the simultaneous detection of hydroxyl and hydroperoxy radicals is described, with detection limits of 3.1 6 105 molecule cm23 (0.012 pptv in the boundary layer) and 2.6 6 106 molecule cm23 (0.09 pptv) achieved for OH and HO2 respectively (30 s signal integration, 30 s background integration, signalto- noise ratio ~ 1). The system has been field tested and offers several advantages over copper vapour laser pumped dye laser systems for the detection of atmospheric OH and HO2 radicals by LIF, with benefits of greater tuning range and ease of use coupled with reduced power consumption, instrument footprint and warm-up time. NO has been detected in the atmosphere at y 1 ppbv by single photon LIF using the A 2S1 B X 2P1/2 (0,0) transition at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a chemiluminescence analyser. With some improvements in performance, particularly with regard to laser power, the theoretical detection limit for NO is projected to be y 2 6 106 molecule cm23 (0.08 pptv). Whilst operating at 445 nm, the laser system has been used to readily detect the IO radical in the laboratory, and although it is difficult to project the sensitivity in the field, an estimate of the detection limit is v 1 6 105 molecule cm23 (v 0.004 pptv), well below previously measured atmospheric concentrations of IO.

### Application of a compact all solid-state laser system to the in situ detection of atmospheric OH, HO

 Date added: 08/06/2003 Date modified: 06/30/2009 Filesize: 184.19 kB
W. J. Bloss, T. J. Gravestock, D. E. Heard, T. Ingham,G. P. Johnson and J. D. Lee, "Application of a compact all solid-state laser system to the in situ detection of atmospheric OH, HO2, NO and IO by laser-induced fluorescence", Journal of Environmental Monitoring., 5, 21-28 (2003).

Abstract

A tuneable, high pulse-repetition-frequency, solid state Nd:YAG pumped titanium sapphire laser capable of generating radiation for the detection of OH, HO2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF) has been developed. The integration of the laser system operating at 308 nm into a field measurement apparatus for the simultaneous detection of hydroxyl and hydroperoxy radicals is described, with detection limits of 3.1 6 105 molecule cm23 (0.012 pptv in the boundary layer) and 2.6 6 106 molecule cm23 (0.09 pptv) achieved for OH and HO2 respectively (30 s signal integration, 30 s background integration, signalto- noise ratio ~ 1). The system has been field tested and offers several advantages over copper vapour laser pumped dye laser systems for the detection of atmospheric OH and HO2 radicals by LIF, with benefits of greater tuning range and ease of use coupled with reduced power consumption, instrument footprint and warm-up time. NO has been detected in the atmosphere at y 1 ppbv by single photon LIF using the A 2S1 B X 2P1/2 (0,0) transition at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a chemiluminescence analyser. With some improvements in performance, particularly with regard to laser power, the theoretical detection limit for NO is projected to be y 2 6 106 molecule cm23 (0.08 pptv). Whilst operating at 445 nm, the laser system has been used to readily detect the IO radical in the laboratory, and although it is difficult to project the sensitivity in the field, an estimate of the detection limit is v 1 6 105 molecule cm23 (v 0.004 pptv), well below previously measured atmospheric concentrations of IO.

### Aircraft Measurements During NAMBLEX (the SNAP campaign)

 Date added: 08/06/2003 Date modified: 07/27/2009 Filesize: 33.65 kB
Purvis R.M., Lewis A.C., McQuaid J.B. & Lee J.D. "Aircraft Measurements During NAMBLEX (the SNAP campaign)." Geophys Res. Abs. 6 (2004):

Abstract

The spatial distribution of a number of trace species has been determined in marine boundary layer (MBL) and free troposphere (FT) air around the Mace Head Atmospheric Research Station, Ireland. CO and ozone measurements were made onboard the NERC Dornier 228-101 research aircraft operated by the Airborne Remote Sensing Facility during the SNAP (Supporting NAMBLEX from an Airborne Platform) campaign in August 2002. High frequency whole air samples taken from onboard the aircraft with ground analysis using GC-FID were used for C2 - C6 hydrocarbons mixing ratios. The campaign was conducted in conjunction with the ground based NAMBLEX (North Atlantic Marine Boundary Layer Experiment) campaign carried out at Mace Head during the summer of 2002. The distribution of trace species was investigated in both coastal regions and above the deep waters beyond the continental shelf. A vertical gradient in concentration of hydrocarbon and sulphur species with known oceanic sources was observed in the MBL over both oceanic regions when compared to anthropogenic tracers such as acetylene and CO. Under clear sky conditions typical maximum mixing ratios were MBL ethene 78 pptV: FT ethene 10 pptV: MBL DMS: 89 pptV: FT DMS 21 pptV.

Elevated mixing ratios of species with oceanic origin were observed in the lower most  FT in regions experiencing strong convective activity associated with cumulus cells. Vertical profiles centred over the field site showed good agreement between ground based and airborne hydrocarbon measurements taken within the MBL. The MBL upwind of Mace Head appeared well mixed with respect to both NMHCs,CO and ozone. Above 2 km showed distinct layers with free  tropospheric ozone values of 50 ppbV contrasting typical MBL values of less than 30 ppbV. Flights indicate a boundary layer height of approximately 1200 m. The observations confirm that for these species the surface site measurements are generally representative of the marine boundary layer as a whole but not of the air mass above.

### Airborne trace gas measurements over open ocean and coastal regions upwind of Mace Head, Irelan

 Date added: 08/06/2003 Date modified: 07/27/2009 Filesize: 13.7 kB

Ruth Purvis, Ally Lewis, Jim McQuaid, "Airborne Trace Gas Measurements Over Open Ocean and Coastal Regions Upwind of Mace Head, Ireland", Geophysical Research Abstracts Volume 5, 2003.

Abstract

The spatial distribution of a number of trace species has been determined in marine boundary layer (MBL) and free troposphere (FT) air around the Mace Head Atmospheric Research Station, Ireland. CO and ozone measurements were made onboard NERC Dornier 228-101 research aircraft operated by the Airborne Remote Sensing Facility during the SNAP (Supporting NAMBLEX from an Airborne Platform) campaign in August 2002. High frequency whole air sampling from the aircraft with ground analysis using GC-FID was used for C2 - C6 hydrocarbons mixing ratios. The campaign was conducted in conjunction with the ground based NAMBLEX (North Atlantic Marine Boundary Layer Experiment) campaign carried out at Mace Head. The distribution of trace species was investigated in both coastal regions and above the deep waters beyond the continental shelf. A vertical gradient in concentration of hydrocarbonand sulphur species with known oceanic sources was observed in the MBL over both oceanic regions when compared to anthropogenic tracers such as acetylene and CO. Under clear sky conditions typical maximum mixing ratios were MBL ethene 78 pptV: FT ethene 10 pptV: MBL DMS: 89 pptV: FT DMS 21 pptV. Elevated mixing ratios of species with oceanic origin were observed in the lower most FT in regions experiencing strong convective activity associated with cumulus cells. Vertical profiles centred over the field sit showed good agreement between ground based and airbornehydrocarbon measurements taken within the MBL. The MBL upwind of Mace Head appeared well mixed with respect to both NMHCs, CO and ozone. Above 2 km showed distinct layers with free tropospheric ozone values of 50 ppbV contrasting typical MBL values of less than 30 ppbV. Flights indicate aboundary layer height of approximately 1200 m. The observations confirm that for these species the surface site measurements are generally representative of the marine boundary layer as a whole but not of the air mass above.

### Marine organohalogens in the atmosphere over the Atlantic and Southern Oceans

 Date added: 08/06/2003 Date modified: 07/24/2009 Filesize: 564.21 kB

Carpenter, L. J., P. S. Liss, and S. A. Penkett (2003), Marine organohalogens in the atmosphere over the Atlantic and Southern Oceans, J. Geophys. Res., 108(D9), 4256, doi:10.1029/2002JD002769.

Abstract

Reactive halogen species (RHS) such as the halogen oxide radicals IO and BrO influence tropospheric oxidation processes in both polar and temperate regions. Oceanic photolabile halocarbons have been shown to be strong sources of RHS in midlatitudes. However, the global source strengths of these halocarbon precursors and the relative importance of the coastal and pelagic oceans on their concentrations are highly uncertain. Here we present atmospheric measurements of the reactive organic halogens CH3I, CH2I2, CH2ClI, CH2IBr, CHIBr2, CHBr3, CH2Br2, and CHBr2Cl made at Mace Head, Ireland, during the Particle Formation and Fate in the Coastal Environment campaign in September 1998 and at Cape Grim, Tasmania, during the Southern Ocean Atmospheric Photochemistry Experiment 2 campaign in January/February 1999. Mace Head is strongly influenced by local macroalgae, whereas Cape Grim, owing to its cliff-top location, suffers much less impact from seaweeds. The very reactive halocarbons CH2I2, CH2IBr, and CHIBr2 observed at Mace Head were below detection limits at Cape Grim, although CH2ClI was detected at both locations. Mixing ratios of CH3I, CH2ClI, CHBr3, CHBr2Cl, and CH2Br2 at Cape Grim were on average 25–50% of those at Mace Head. Concentrations of the polybromomethanes correlated well at both sites. Using these correlations, we estimate molar source strengths of CHBr2Cl and CH2Br2 to be between 3 and 6% and between 15 and 25% of the global CHBr3 flux, respectively. These values fall within ranges estimated independently from concentration and lifetime data.

### Atmospheric Methyl Iodide at Cape Grim, Tasmania, from AGAGE Observations

 Date added: 08/05/2003 Date modified: 07/27/2009 Filesize: 264.04 kB

Cohan, D.S., G.A. Sturrock, A.P. Biazar, and P.J. Fraser, Atmospheric methyl iodide at Cape Grim, Tasmania from AGAGE  observations, J. Atmos. Chem., 44, 131-150, 2003.

Abstract

Atmospheric mixing ratios of methyl iodide (CH3I) and other methyl halides have been measured at Cape Grim, Tasmania (41°S, 145°E), since early 1998 as part of the Advanced Global Atmospheric Gases Experiment (AGAGE). This paper analyses about 1700 ambient air CH3I measurements from the 14-month period (March 1998–April 1999). Mixing ratios peaked during the summer, despite faster photolytic loss, suggesting local oceanic emissions were about 2.2–3.6 times stronger in summer than in winter. Back trajectories show that CH3I levels are strongly dependent on air mass origin, with highest mixing ratios in air from the Tasman Sea/Bass Strait region and lowest levels in air originating from the Southern Ocean at higher latitudes. CH3I mixing ratios were not well correlated with other methyl halides in unpolluted marine air. The large variations with season and air mass origin suggest that high frequency, continuous data from key locations will make a significant contribution to the understanding of sources and sinks of this important short-lived atmospheric species.

### New Particle Formation from Photooxidation of Diiodomethane (CH2I2)

 Date added: 08/01/2003 Date modified: 07/03/2009 Filesize: 1.27 MB

Jimenez, J.L., R. Bahreini, D. R. Cocker III, H. Zhuang, V. Varutbangkul, R. C. Flagan, and J. H. Seinfeld, C.D. O'Dowd, T. Hoffmann, New Particle Formation from Photooxidation of Diiodomethane (CH2I2), in press, J. Geophys. Research, 2003.

Abstract

Photolysis of CH2I2 in the presence of O3 has been proposed as a mechanism leading to intense new particle formation in coastal areas. We report here a comprehensive laboratory chamber study of this system. Rapid homogeneous nucleation was observed over three orders of magnitude in CH2I2 mixing ratio, down to a level of 15 ppt (∼4 × 108 molec. cm−3) comparable to the directly measured total gas-phase iodine species concentrations in coastal areas. After the nucleation burst, the observed aerosol dynamics in the chamber was dominated by condensation of additional vapors onto existing particles and particle coagulation. Particles formed under dry conditions are fractal agglomerates with mass fractal dimension, D f ∼ 1.8–2.5. Higher relative humidity (65%) does not change the nucleation or growth behavior from that under dry conditions, but results in more compact and dense particles (D f ∼ 2.7). On the basis of the known gas-phase chemistry, OIO is the most likely gas-phase species to produce the observed nucleation and aerosol growth; however, the current understanding of this chemistry is very likely incomplete. Chemical analysis of the aerosol using an Aerodyne Aerosol Mass Spectrometer reveals that the particles are composed mainly of iodine oxides but also contain water and/or iodine oxyacids. The system studied here can produce nucleation events as intense as those observed in coastal areas. On the basis of comparison between the particle composition, hygroscopicity, and nucleation and growth rates observed in coastal nucleation and in the experiments reported here, it is likely that photooxidation of CH2I2, probably aided by other organic iodine compounds, is the mechanism leading to the observed new particle formation in the west coast of Ireland.

 Date added: 08/01/2003 Date modified: 07/24/2009 Filesize: 1.51 MB

Mace Head Atmospheric Research Station – characterization of aerosol radiative parameters S. Gerard Jennings, C. Kleefeld, C. D. O'Dowd, C. Junker, T.G. Spain, P. O'Brien, A.F Roddy, and T.C. O'Connor Boreal Environ. Res., 8, 303-314, 2003.

Abstract

A fairly concise description and a short history of the Mace Head atmospheric research station, at 53°N, 10°W, on the west coast of Ireland is reported. The relatively high latitude site is representative of background marine air in the Northern Atlantic on the western periphery of Europe. The site is ideally located to measure the prevailing (about 52% of the time) westerly-southwesterly air from the Atlantic, as well as polluted air under anticyclonic conditions from sources east of the site within Ireland, from the UK and from mainland Europe. Three years of aerosol radiative data, over a period from January 2000 to December 2002, are indicative of the medium to longterm measurement programme at the site. These include aerosol scattering coefficient, aerosol absorption coefficient, aerosol optical depth and single scattering albedo, supported by meteorological and air mass trajectory input. Variability in aerosol parameters are shown to be dependent on air mass origin, season and meteorological conditions. Measurements indicate that the dominant contribution to aerosol optical depth is due to scattering, with single scattering albedo in the range 0.941 to 0.997. Measured aerosol optical depth for marine air over the 3 year period varies between 0.03 and 0.38 with a mean value of 0.11 and standard deviation of ±0.06. These values are in fair agreement with other data for the North Atlantic region.

### Light backscattering and scattering by non-spherical sea-salt aerosols

 Date added: 08/01/2003 Date modified: 07/24/2009 Filesize: 483.03 kB

Chamaillard K., Jennings S.J., Kleefeld C., Ceburnis D. and Yoon Y.J. Light backscattering and scattering by non-spherical sea-salt aerosols. J. of Quantitative Spectroscopy & Radiative Transfer, Vol. 79-80, 577-597, 2003.

Abstract

The scattering coefficient, single-scatter albedo, and up-scatter fraction are key parameters in direct climate forcing by aerosols. Usually the contribution of sea-salt is estimated using Mie theory, assuming that these particles are spherical. The optical properties of particles are known to strongly depend on the shape of the particles. The question of the applicability of using Mie theory in recent studies is mainly devoted to nonspherical dust-like tropospheric aerosols. In this study, we attempt to quantify the relative contribution of nonspherical sea-salt to measured scattering and backscattering coefficients. The shape of nonspherical sea-salt is assumed to be cubic. The discrete dipole approximation model is applied to estimate the optical properties of the nonspherical particles. Measurements are then compared to Mie theory calculations and to DDA cubic calculations. The results are presented for two wavelengths: λ=0.55 μm and 0.7 μm, It is found that the size of particles responsible for scattering is larger than 0.3 μm. The backscattering coefficient, unlike the scattering coefficient, is very sensitive to particle shape. Cubic particles give better agreement to the measurements. Compared to spherical particles, the cubic approach underestimates the backscattering coefficient in contrast to prolate spheroidal calculations.

### Averaging periods for indoor-outdoor ratios of pollution in naturally ventilated non-domestic buildings near a busy road

 Date added: 08/01/2003 Date modified: 06/30/2009 Filesize: 387.68 kB

Ni Riain, C, Mark, D., Davies, M., Harrison, R.M. and Byrne, M.A. Averaging periods for indoor-outdoor ratios of pollution in naturally ventilated non-domestic buildings near a busy road. Atmos Env, Vl 37, pp 4121-4132 , 2003.

Abstract

Continuous measurements of carbon monoxide (CO) and particulate matter (PM10, PM2.5 and PM1) were made inside and outside two naturally ventilated (NV) and two mechanically assisted (MV) spaces overlooking the same six-lane highway in Central London. The indoor/outdoor (I/O) ratio was calculated for each site for the whole monitoring period in the usual way, and then cumulatively at each hourly time-step from the start of monitoring up to the whole period in order to track the evolution of the I/O ratio with length of monitoring or averaging period. Hourly data were also sorted by wind speed and direction and I/O ratios calculated for each direction/speed set from ensemble means. I/O ratios for the whole period were generally lower in the NV spaces than the MV, however, the indoor-outdoor relationship in the NV spaces was found to vary substantially with wind direction. For a constant above-roof wind speed, I/O ratios of CO varied by 50-60% about the mean value with direction, and by 20-30% for particulate matter. Consequently, I/O ratios for NV spaces depended on the distribution of wind direction within the calculation period and, hence, on the length of monitoring period. The I/O ratio in one NV space changed by a factor of three between the early stages and final stages of monitoring, with a stable final value (±5%) achieved after 900 h of monitoring. By contrast, in the MV spaces under constant fan speed, constant values for the I/O ratio were achieved for CO within 4 h of the start of monitoring. It is argued here that field assessments of the filtration performance of naturally ventilated spaces need to consider exposure to and distribution of natural ventilation drivers within the monitoring period in order to draw meaningful comparisons for design and exposure assessment purposes.

### The Hohenpeissenberg aerosol formation experiment (HAFEX): a long-term study including size-resolved

 Date added: 07/27/2003 Date modified: 07/27/2009 Filesize: 514.79 kB

Birmili W, Berresheim H, Plass-Dulmer C, Elste T, Gilge S, Wiedensohler A, Uhrner U, 2003. The Hohenpeissenberg aerosol formation experiment (HAFEX): a longterm study including size-resolved aerosol, H2SO4, OH, and monoterpenes measurements. Atmos. Chem. Phys. 3: 361–376.

Abstract

Ambient aerosol size distributions (> 3 nm) and OH, H2SO4, and terpene concentrations were measured from April 1998 to August 2000 at a rural continental site in southern Germany. New particle formation (NPF) events were detected on 18% of all days, typically during midday hours under sunny and dry conditions. The number of newly formed particles correlated significantly with solar irradiance and ambient levels of H2SO4. A pronounced anticorrelatation of NPF events with the pre-existing particle surface
area was identified in the cold season, often associated with the advection of dry and relatively clean air masses from southerly directions (Alps). Estimates of the particle formation rate based on observations were around 1 cm−3 s−1, being in agreement with the predictions of ternary homogeneous H2SO4-NH3-H2O nucleation within a few orders of magnitude. The experimentally determined nucleation mode particle growth rates were on average 2.6 nm h−1, with a fraction of 0.7 nm h−1 being attributed to the cocondensation of H2SO4-H2O-NH3. The magnitude of nucleation mode particle growth was neither significantly correlated
to H2SO4, nor to the observed particle formation rate. Turn-over rate calculations of measured monoterpenes and aromatic hydrocarbons suggest that especially the oxidation products of monoterpenes have the capacity to contribute to the growth of nucleation mode particles. Although a large number of precursor gases, aerosol and meteorological parameters were measured, the ultimate key factors controlling the occurence of NPF events could not be identified.

### Measurements of gas-phase hydrogen peroxide and methyl hydroperoxide in the coastal environment duri

 Date added: 09/14/2002 Date modified: 07/02/2009 Filesize: 313.1 kB
Morgan, R. B., and A. V. Jackson (2002), Measurements of gas-phase hydrogen peroxide and methyl hydroperoxide in the coastal environment during the PARFORCE project, J. Geophys. Res., 107(D19), 8109, doi:10.1029/2000JD000257.

Abstract

Ambient gas-phase hydrogen peroxide (H2O2) and organic hydroperoxides (ROOHs) were measured at Mace Head Atmospheric Monitoring Station during September 1998 and June 1999. These measurements formed part of the New Particle Formation and Fate in the Coastal Environment (PARFORCE) campaign with the intention of assisting with the elucidation of potential oxidation pathways that lead to the production of new particles. A reflux concentrator sampled ambient air prior to on-site analysis by a peroxidase fluorescence technique with specific peroxide detection. Hydrogen peroxide, methyl hydroperoxide (CH3OOH), and several hydroperoxide species were detected. The highest H2O2 concentrations were observed during periods of clean maritime air, and a significant correlation exists between H2O2 concentration and tidal cycle during days when air masses had advected over inter tidal zones upwind of Mace Head. Peak H2O2 concentrations were observed around low tide on these days, coincident with particle events.

### Comparisons of box model calculations and measurements of formaldehyde from the 1997 North Atlantic

 Date added: 08/31/2002 Date modified: 07/01/2009 Filesize: 953.85 kB
Frost, G. J., et al. (2002), Comparisons of box model calculations and measurements of formaldehyde from the 1997 North Atlantic Regional Experiment, J. Geophys. Res., 107(D8), 4060, doi:10.1029/2001JD000896.

Abstract

Formaldehyde (CH2O) measurements from two independent instruments are compared with photochemical box model calculations. The measurements were made on the National Oceanic and Atmospheric Administration P-3 aircraft as part of the 1997 North Atlantic Regional Experiment (NARE 97). The data set considered here consists of air masses sampled between 0 and 8 km over the North Atlantic Ocean which do not show recent influence from emissions or transport. These air masses therefore should be in photochemical steady state with respect to CH2O when constrained by the other P-3 measurements, and methane oxidation was expected to be the predominant source of CH2O in these air masses. For this data set both instruments measured identical CH2O concentrations to within 40 parts per trillion by volume (pptv) on average over the 0–800 pptv range, although differences larger than the combined 2σ total uncertainty estimates were observed between the two instruments in 11% of the data. Both instruments produced higher CH2O concentrations than the model in more than 90% of this data set, with a median measured-modeled [CH2O] difference of 0.13 or 0.18 ppbv (depending on the instrument), or about a factor of 2. Such large differences cannot be accounted for by varying model input parameters within their respective uncertainty ranges. After examining the possible reasons for the model-measurement discrepancy, we conclude that there are probably one or more additional unknown sources of CH2O in the North Atlantic troposphere.

### Temporal patterns, sources, and sinks of C8-C16 hydrocarbons in the atmosphere of Mace Head, Ireland

 Date added: 08/30/2002 Date modified: 03/07/2010 Filesize: 758.23 kB
Sartin, J. H., C. J. Halsall, L. A. Robertson, R. G. Gonard, A. R. MacKenzie, H. Berresheim, and C. N. Hewitt (2002), Temporal patterns, sources, and sinks of C8-C16 hydrocarbons in the atmosphere of Mace Head, Ireland, J. Geophys. Res., 107(D19), 8099, doi:10.1029/2000JD000232.

Abstract

During the 1999 New Particle Formation and Fate in the Coastal Environment (PARFORCE) field campaign, 16 C8-C16 volatile organic compounds (VOCs) were identified in the coastal atmosphere of Mace Head, Ireland. Sampling took place over 24 days, with 12 VOCs routinely quantified. Concentrations were observed in the low <10–150 parts per trillion by volume range, with levels typically in the order of aldehydes > ketones ≥ n-alkanes. Concentrations of these compounds were also measured in shoreline surface seawater. No relationship was observed between atmospheric concentrations and high/low tide events. Many VOCs revealed a temporal pattern in the atmosphere, with highest concentrations measured during the early morning and lowest concentrations in the afternoon. The strongest pattern was observed for the n-alkanes. However, this was dependent on the prevailing air mass direction and the local meteorology. A Lagrangian box model was applied to assess this diurnal cycle, using seawater emissions as a source (based on the seawater concentrations and observed wind speeds), and depletion via OH radicals and dilution by entrainment as sinks (using measured [OH] and boundary layer height data). The model gave good agreement to the observed concentrations for selected air mass types, predicting the daytime decrease in VOC concentrations due to OH radical chemistry and boundary layer growth, and the subsequent increase in VOC concentrations toward evening as both oxidation chemistry diminished and the mixing layer height fell.

### The origin of high particulate concentrations over the United Kingdom, March 2000

 Date added: 08/07/2002 Date modified: 07/23/2009 Filesize: 1.45 MB

Ryall, D.B., R.G Derwent, A.J. Manning, A.L. Redington, J. Corden, W. Millington, P.G. Simmonds, S. O’Doherty, N. Carslaw and G.W. Fuller (2002), The origin of high particulate concentrations over the United Kingdom, March 2000, Atmos. Environ. 36, 1363-1378.

Abstract

An episode of exceptionally high PM10 and PM2.5 levels was observed during the night of the 2-3 March 2000 throughout England and Wales. The weather was characterised by strong westerly winds and widespread rainfall associated with a low pressure system to the north of Scotland, conditions usually associated with relatively clean, unpolluted air. Possible sources included volcanic ash from an eruption on 26 February 2000 in Iceland, or dust from large sandstorms over the Sahara. A combination of atmospheric transport modelling using the Lagrangian dispersion model NAME, an analyses of satellite imagery and observational data from Mace Head has shown that the most likely origin of the episode was long range transport of dust from the Sahara region of North Africa. Further modelling studies have revealed a number of previously unidentified dust episodes, and indicate that transport of dust from the Sahara can occur several times a year. Dust episodes are of interest for a number of reasons, particulate levels can be elevated over a wide area and in some instances can significantly exceeded current air quality standards. If a natural source is identified over which there can be no control, there are implications for the setting of air quality standards.

### Long-term measurements of atmospheric mercury at Mace Head, Irish west coast, between 1995 and

 Date added: 08/07/2002 Date modified: 07/24/2009 Filesize: 236.55 kB

Long-term measurements of atmospheric mercury at Mace Head, Irish west coast, between 1995 and 2001 R. Ebinghaus, H.H. Kock, A.M. Coggins, T.G. Spain, S.G. Jennings, C. Temme Atmos. Environ., 36, 5267-5276, 2002

Abstract

Monitoring of atmospheric mercury concentrations has been carried out at the Mace Head atmospheric research station on the west coast of Ireland between September 1995 and December 2001. Measurements were carried out with a time resolution of 15 min. No trend in the concentration levels has been detected during the measurement period, with the annual average concentrations remaining constant at 1.75 ng m−3. A slight increase in the concentration levels is derived, if only clean sector filtered air masses clearly of marine origin are used.

The Mace Head data set shows a seasonal pattern with higher monthly mean concentrations in the winter months. Comparison with two continental sites in Sweden shows, that atmospheric mercury concentrations at the western inflow boundary are on an average higher than those at the two continental sites, expressing a west to east decreasing concentration gradient.

At Mace Head, no indications for so-called Mercury Depletion Events (MDEs), recently reported for a number of sites in the Arctic and in the Antarctic, have been found between 1995 and 2001.

### Emission rates of C8–C15 VOCs from seaweed and sand in the inter-tidal zone at Mace Head, Irela

 Date added: 08/07/2002 Date modified: 07/27/2009 Filesize: 167.86 kB

Emission rates of C8 - C15 VOCs from seaweed and sand in the inter-tidal zone at Mace Head, Ireland (2002) J.H. Sartin, C.J. Halsall, S. Hayward and C.N. Hewitt, Atmospheric Environment , 36, 5311 - 5321

Abstract

Emission fluxes for a range of C8-C15 volatile organic compounds (VOCs) were determined from the seaweed Fucus spiralis (spiral wrack) and an adjacent sand surface during low tide on the coastline of Mace Head, Ireland. These two surface types, assessed using dynamic flux chamber systems, are typical of the Mace Head inter-tidal zone. A range of n-alkanes and oxygenates were routinely identified in the measurement of chamber air. Examination of the odd/even n-alkane ratios and use of the carbon preference index (CPI) suggested a biogenic source for these compounds (CPIs >2 in for all samples). Fluxes of n-pentadecane, the most predominant n-alkane, ranged from 0.2 to 5.1gm-2h-1 (0.9-24nmolm-2h-1), while oxygenates such as nonanal and decanal had fluxes ranging from <0.1 to 4.4gm-2h-1 (<0.1-31nmolm-2h-1) and <0.1 to 4.6gm-2h-1 (<0.1-30nmolm-2h-1), respectively. Seaweed emission rates for n-pentadecane were correlated with photosynthetically active radiation (PAR) (rs=0.94) while emissions from sand showed correlation with temperature (rs=0.85). This suggests a possible biochemical route controlling the release of n-pentadecane from spiral wrack, and temperature-driven volatilisation from sand. Volatilisation from residual seawater trapped in the sand may explain the comparable flux of both n-alkanes and oxygenates from this surface. Unlike the n-alkanes, oxygenate fluxes from sand correlate with PAR, suggesting a photodependent production from organic carbon residues present in seawater. Comparison with previous flux estimates from coastal seawater indicates that the two source types (Fucus spiralis and bare sand) are significant but not dominant sources of these VOCs.

### IOP John A McClelland

 Date added: 08/07/2002 Date modified: 08/07/2008 Filesize: 3.28 MB
pg 176 - 185 by Tom O Connor

### Transatlantic transport of pollution and its effects on surface ozone in Europe and North Ameri

 Date added: 08/07/2002 Date modified: 07/23/2009 Filesize: 7.5 MB
Li, Q., et al. (2002), Transatlantic transport of pollution and its effects on surface ozone in Europe and North America, J. Geophys. Res., 107(D13), 4166, doi:10.1029/2001JD001422.

Abstract

We examine the transatlantic transport of anthropogenic ozone and its impact on surface ozone in Europe and North America by using a 5-year (1993–1997) simulation with the GEOS-CHEM global three-dimensional model of tropospheric chemistry. Long-term time series of ozone and CO at Mace Head (Ireland) and Sable Island (Canada) are used to evaluate transatlantic transport in the model. North American anthropogenic emissions contribute on average 5 ppbv to surface ozone at Mace Head, and up to 10–20 ppbv during transatlantic transport events, which are forerunners of broader events in Europe. These events are associated with low-level westerly flow driven by an intense Icelandic low between Iceland and the British Isles. North American influence on ozone at Mace Head is strongly correlated with the North Atlantic Oscillation (NAO), implying that the NAO index can be used to forecast transatlantic transport of North American pollution to Europe. European anthropogenic emissions contribute on average less than 2 ppbv to surface ozone at Sable Island but up to 5–10 ppbv during transatlantic transport events. These events are associated with low-level easterly flow established by anomalous low pressure at 45°N over the North Atlantic. North American anthropogenic emissions enhance surface ozone in continental Europe by 2–4 ppbv on average in summer and by 5–10 ppbv during transatlantic transport events; transport in the boundary layer and subsidence from the free troposphere are both important mechanisms. We find in the model that 20% of the violations of the European Council ozone standard (55 ppbv, 8-hour average) in the summer of 1997 over Europe would not have occurred in the absence of anthropogenic emissions from North America. North American influence on surface ozone in Europe is particularly strong at the thresholds used for the European standards (55–65 ppbv).

### The background atmospheric concentrations of cyclic perfluorocarbon tracers determined by negat

 Date added: 08/07/2002 Date modified: 07/23/2009 Filesize: 164.57 kB

Simmonds, P. G., Greally, B. R., Olivier, S., Nickless, G., Cooke, K. M., and Dietz, R. N.  The background atmospheric concentrations of cyclic perfluorocarbon tracers determined by negative ion-chemical ionization mass spectrometry.  Atmos. Environ. 36, 2147-2156 (2002).

Abstract

The background atmospheric mixing ratios for a range of cyclic perfluorocarbons (cyclic-PFCs), widely used in atmospheric dispersion studies, have been measured by gas chromatography-mass spectrometry in negative ion-chemical ionization mode. Background concentrations range from <1fll-1 to >10fll-1, where femtolitre is expressed as parts in 1015 (ppqv). Because of their very long atmospheric lifetimes (>3000yr) the present day concentrations represent the accumulated emissions from all sources, although significant commercial production did not commence until the 1960s. Cyclic-PFCs are potent greenhouse gases; however, their atmospheric concentrations are currently so low as to make an insignificant contribution to global warming.

### Marine biogenic and anthropogenic contributions to non-sea-salt sulfate in the marine boundary

 Date added: 08/06/2002 Date modified: 07/24/2009 Filesize: 376.92 kB

Savoie, D. L., R. Arimoto, W. C. Keene, J. M. Prospero, R. A. Duce, and J. N. Galloway (2002), Marine biogenic and anthropogenic contributions to non-sea-salt sulfate in the marine boundary layer over the North Atlantic Ocean, J. Geophys. Res., 107(D18), 4356, doi:10.1029/2001JD000970.

Abstract

### Hygroscopic properties of nucleation mode and Aitken mode particles during nucleation bursts an

 Date added: 08/06/2002 Date modified: 07/24/2009 Filesize: 925.58 kB

Väkevä, M., K. Hämeri, and P. P. Aalto (2002), Hygroscopic properties of nucleation mode and Aitken mode particles during nucleation bursts and in background air on the west coast of Ireland, J. Geophys. Res., 107(D19), 8104, doi:10.1029/2000JD000176.

Abstract

The hygroscopic and cloud condensation nuclei (CCN) properties of submicrometer atmospheric aerosol particles were investigated using an Ultrafine Tandem Differential Mobility Analyzer (UF-TDMA) and a CCN counter at the Mace Head Monitoring Station on the west coast of Ireland during the New Particle Formation and Fate in the Coastal Environment (PARFORCE) field campaign in September 1998 and June 1999. These measurements give indirect in situ information on the composition and state of mixing of the aerosol particles. The UF-TDMA was used for monitoring of hygroscopic diameter growth factors of aerosol particles with dry mobility diameters 8–20 nm when taken from dry state to a controlled humid environment (RH 90%). The CCN counter was used to study the activation of aerosol particles when exposed to supersaturated conditions (dry diameters of 15–150 nm). It was seen that in clean marine air masses during the observed particle formation events, the newly formed nucleation mode particles (8 and 10 nm) most often had low growth factors (between 1.0 and 1.1) resulting from low solubility. This indicates that the nucleation mode particles consist of nonsoluble or weakly soluble species, possible accompanied by a small soluble part; however, when nucleation mode particles were observed outside the event periods, the growth factors were higher (about 1.3–1.4). In contrast, the 20 nm particles usually clearly belonged to the Aitken mode (based on number size distribution measurements) and had hygroscopic properties similar to some common salts (growth factors 1.4–1.5).

### A general circulation model study of the global carbonaceous aerosol distribution

 Date added: 08/06/2002 Date modified: 07/27/2009 Filesize: 1.81 MB

Cooke, W. F., V. Ramaswamy, and P. Kasibhatla (2002), A general circulation model study of the global carbonaceous aerosol distribution, J. Geophys. Res., 107(D16), 4279, doi:10.1029/2001JD001274.

Abstract

Atmospheric distributions of carbonaceous aerosols are simulated using the Geophysical Fluid Dynamics Laboratory SKYHI general circulation model (GCM) (latitude-longitude resolution of ∼3° × 3.6°). A number of systematic analyses are conducted to investigate the seasonal and interannual variability of the concentrations at specific locations and to investigate the sensitivity of the distributions to various physical parameters. Comparisons are made with several observational data sets. At four specific sites (Mace Head, Mauna Loa, Sable Island, and Bondville) the monthly mean measurements of surface concentrations of black carbon made over several years reveal that the model simulation registers successes as well as failures. Comparisons are also made with averages of measurements made over varying time periods, segregated by geography and rural/remote locations. Generally, the mean measured remote surface concentrations exceed those simulated. Notwithstanding the large variability in measurements and model simulations, the simulations of both black and organic carbon tend to be within about a factor of 2 at a majority of the sites. There are major challenges in conducting comparisons with measurements due to inadequate sampling at some sites, the generally short length of the observational record, and different methods used for estimating the black and organic carbon amounts. The interannual variability in the model and in the few such measurements available points to the need for doing multiyear modeling and to the necessity of comparing with long-term measurements. There are very few altitude profile measurements; notwithstanding the large uncertainties, the present comparisons suggest an overestimation by the model in the free troposphere. The global column burdens of black and organic carbon in the present standard model integration are lower than in previous studies and thus could be regarded as approximately bracketing a lower end of the simulated anthropogenic burden due to these classes of aerosols, based on the current understanding of the carbonaceous aerosol cycle. Of the physical factors examined, the intensity and frequency of precipitation events are critical in governing the column burdens. Biases in the frequency of precipitation are likely the single biggest cause of discrepancies between simulation and observations. This parameter is available from very few sites and thus lacks a comprehensive global data set, unlike, say, monthly mean precipitation. Several multiyear GCM integrations have been performed to evaluate the sensitivity of the global mean black carbon distribution to the principal aerosol parameters, with due regard to variability and statistical significance. The most sensitive parameters, in order of importance, turn out to be the wet deposition, transformation from hydrophobic to hydrophilic state, and the partitioning of the emitted aerosol between the hydrophobic and hydrophilic varieties. From the sensitivity tests, it is estimated that the variations of the global mean column burden and lifetime of black carbon are within about a factor of 2 about their respective standard values. The studies also show that the column burdens over remote regions appear to be most sensitive to changes in each parameter, reiterating the importance of measurements in those locations for a proper evaluation of model simulation of these aerosols.

### Relative contribution of submicron and supermicron particles to aerosol light scattering...boun

 Date added: 08/06/2002 Date modified: 07/23/2009 Filesize: 399.76 kB

Kleefeld, C., C. D. O'Dowd, S. O'Reilly, S. G. Jennings, P. Aalto, E. Becker, G. Kunz, and G. de Leeuw (2002), Relative contribution of submicron and supermicron particles to aerosol light scattering in the marine boundary layer, J. Geophys. Res., 107(D19), 8103, doi:10.1029/2000JD000262.

Abstract

Measurements of the aerosol light scattering coefficient (σsp) at a wavelength of λ = 550 nm were conducted at a coastal atmospheric research station in the east Atlantic Ocean during June 1999. Size distribution measurements between diameters of 3 nm and 40 μm (at ambient humidity) were used to derive scattering coefficients from Mie theory. The calculated scattering coefficients were about a factor of 7.4 higher than the measured scattering coefficients. The discrepancy was explained by a reduced cutoff of the sampling system at particle diameters between 6 and 8 μm, dependent on wind speed. The calculated aerosol scattering was about 1 order of magnitude higher than previously reported measurements in the MBL and is attributed to supermicrometer particles at sizes d > 10 μm dominating aerosol scattering.

### Lidar observations of atmospheric boundary layer structure....Ireland (PARFORCE experiment)

 Date added: 08/06/2002 Date modified: 07/02/2009 Filesize: 798.06 kB
Kunz, G. J., G. de Leeuw, E. Becker, and C. D. O'Dowd (2002), Lidar observations of atmospheric boundary layer structure and sea spray aerosol plumes generation and transport at Mace Head, Ireland (PARFORCE experiment), J. Geophys. Res., 107(D19), 8106, doi:10.1029/2001JD001240.

Abstract

A scanning backscatter lidar was used to measure the depth and structure of the coastal atmospheric boundary layer and the evolution of primary aerosol (sea spray) plumes produced by breaking waves during the New Particle Formation and Fate in the Coastal Environment (PARFORCE) campaign at the Mace Head Atmospheric Research Station (Ireland) in September 1998 and in June 1999. The PBL structure was observed to vary from a single-layer well-mixed structure to multilayered structures. Comparison with in situ aircraft measurements of temperature and humidity exhibited good agreement. Using the lidar in the scanning mode allowed two-dimensional profiling over a spatial scale of 10 km, revealing significant primary aerosol plumes produced by breaking waves, particularly in the surf zone and at high wind speeds on the open sea. The initial plume heights were some tens of meters and evolved to hundreds of meters while transported over only a few kilometers from the source. The plumes were traceable to distances of more than 10 km down wind from the source.

### Condensation and coagulation sinks and formation of NMP in coastal and boreal forest BL

 Date added: 08/06/2002 Date modified: 07/21/2009 Filesize: 360.63 kB

Dal Maso, M., M. Kulmala, K. E. J. Lehtinen, J. M. Mäkelä, P. Aalto, and C. D. O'Dowd (2002), Condensation and coagulation sinks and formation of nucleation mode particles in coastal and boreal forest boundary layers, J. Geophys. Res., 107(D19), 8097, doi:10.1029/2001JD001053.

Abstract

The formation and growth of new particles has been evaluated using a revised version of a simple, but novel, theoretical tool. The concentration of condensable vapors and their source rates has been estimated using the aerosol condensation sink together with the measured particle growth rate. Also, by adding the coagulation sink and the measured formation rate of 3 nm particles, the formation rate of 1 nm particles and their concentration can be estimated. Condensation and coagulation sinks can be obtained from ambient aerosol size distribution data. The method has been applied to analyze the particle formation and growth rates observed during coastal and boreal forest nucleation events. The condensation sinks are typically 4-7 x 10-3 s-1 in the forest and 2 x 10-3 s-1 under coastal conditions, while the coagulation sinks for 1, 2, and 3 nm particles are typically smaller by factors 1.5-2, 5-7, and 11-15, respectively. The measured growth rates are 2-10 nm/h for the boreal forest and range from 15 to 180 nm/h at the coast, corresponding to a vapor concentration of 2-13 x 10 cm-3 and 108 cm-3 to 109 cm-3, respectively. The vapor source rate was 1-2 x 105 cm-3 s-1 in the boreal forest and 2-5 x 106 cm-3s-1 in the coastal environment. The estimated formation rate of 1 nm particles in the forest environment was 8-20 cm-3s-1 and 300-10,000 cm-3 s-1 at the coast. The concentration of 1 nm particles was estimated to be 2000-5000 and 4 × 104-7 × 106 particles cm-3 in forest and at coast, respectively.

### Atmospheric Particles from organic Vapours

 Date added: 08/06/2002 Date modified: 06/30/2009 Filesize: 99.71 kB

O'Dowd, Colin D.; Aalto, Pasi; Hmeri, Kaarle; Kulmala, Markku; Hoffmann, Thorsten, Aerosol formation: Atmospheric particles from organic vapours, Nature, Volume 416, Issue 6880, pp. 497-498 (2002)

Abstract

Aerosol particles produced over forested areas may affect climate by acting as nuclei for cloud condensation, but their composition (and hence the chemical species that drive their production) remains an open question. Here we show, to our knowledge for the first time, that these newly formed particles (3-5 nm in diameter) are composed primarily of organic species, such as cis-pinonic acid and pinic acid, produced by oxidation of terpenes in organic vapours released from the canopy.

### Potential for photochemical ozone formation in the troposphere over the North Atlantic as deriv

 Date added: 08/06/2002 Date modified: 07/23/2009 Filesize: 1.34 MB

Reeves, C. E., et al. (2002), Potential for photochemical ozone formation in the troposphere over the North Atlantic as derived from aircraft observations during ACSOE, J. Geophys. Res., 107(D23), 4707, doi:10.1029/2002JD002415.

Abstract

In this paper, ozone (O3), water vapor (H2O), carbon monoxide (CO), and peroxide concentrations and photolysis rates measured in the troposphere over the North Atlantic during two Atmospheric Chemistry Studies in the Oceanic Environment (ACSOE) aircraft field campaigns are used to calculate the concentration of nitric oxide (NO) required for net photochemical O3 production (nPO3) to be positive (NOcomp). NOcomp tended to show a decrease with altitude, although it was sometimes found to be low in the marine boundary layer (MBL) where H2O concentrations were high and O3 concentrations were low. nPO3 was calculated for the spring when NO data were available and was found to be mostly negative and generally increased from about −0.5 to −0.2 ppbv hr−1 in the MBL to +0.04 ppbv hr−1 at about 7–8 km altitude. The results suggest that much of the lower and middle troposphere over the eastern North Atlantic during spring is in a state of slow net photochemical O3 destruction. However, in the upper troposphere, the system changes to one of net photochemical production, which results from the drier environment and higher NO concentrations. Furthermore, examples of net O3 production were also observed in the lower and middle troposphere associated with either in situ sources of NO or long-range transport of pollution. The paper also illustrates the sensitivity of this O3 production/loss state to H2O and NO concentrations, photolysis rates, and temperatures.

### Potential for photochemical ozone formation in the troposphere over the North Atlantic as deriv

 Date added: 08/06/2002 Date modified: 09/11/2009 Filesize: 1.34 MB

Reeves, C. E., et al. (2002), Potential for photochemical ozone formation in the troposphere over the North Atlantic as derived from aircraft observations during ACSOE, J. Geophys. Res., 107(D23), 4707, doi:10.1029/2002JD002415.

Abstract

In this paper, ozone (O3), water vapor (H2O), carbon monoxide (CO), and peroxide concentrations and photolysis rates measured in the troposphere over the North Atlantic during two Atmospheric Chemistry Studies in the Oceanic Environment (ACSOE) aircraft field campaigns are used to calculate the concentration of nitric oxide (NO) required for net photochemical O3 production (nPO3) to be positive (NOcomp). NOcomp tended to show a decrease with altitude, although it was sometimes found to be low in the marine boundary layer (MBL) where H2O concentrations were high and O3 concentrations were low. nPO3 was calculated for the spring when NO data were available and was found to be mostly negative and generally increased from about −0.5 to −0.2 ppbv hr−1 in the MBL to +0.04 ppbv hr−1 at about 7–8 km altitude. The results suggest that much of the lower and middle troposphere over the eastern North Atlantic during spring is in a state of slow net photochemical O3 destruction. However, in the upper troposphere, the system changes to one of net photochemical production, which results from the drier environment and higher NO concentrations. Furthermore, examples of net O3 production were also observed in the lower and middle troposphere associated with either in situ sources of NO or long-range transport of pollution. The paper also illustrates the sensitivity of this O3 production/loss state to H2O and NO concentrations, photolysis rates, and temperatures.

### Eastern Atlantic Spring Experiment 1997 (EASE97)1. Measurements of OH and HO2 concentrations at

 Date added: 08/06/2002 Date modified: 07/01/2009 Filesize: 285.24 kB

Creasey, D. J., D. E. Heard, and J. D. Lee (2002), Eastern Atlantic Spring Experiment 1997 (EASE97) 1. Measurements of OH and HO2 concentrations at Mace Head, Ireland, J. Geophys. Res., 107(D10), 4091, doi:10.1029/2001JD000892.

Abstract

We report measurements of the hydroxyl (OH) and hydroperoxy (HO2) radicals, taken over 20 days, in the remote marine boundary layer at Mace Head, Ireland, during April and May 1997. OH was monitored directly by laser-induced fluorescence (LIF) spectroscopy at 308 nm, and HO2 was measured by chemical conversion to OH upon the addition of NO, with subsequent detection by LIF. The detection limit of the instrument at midday for OH was 6.0 × 105 molecule cm−3 (0.0024 parts per trillion by volume (pptv)) and for HO2 was 3.0 × 106 molecule cm−3 (0.12 pptv), as defined for a signal integration period of 2.5 min and a signal-to-noise ratio of 1. Midday OH and HO2 concentrations were between 2.0–6.0 × 106 molecule cm−3 (0.08–0.24 pptv) and 0.5–3.5 × 108 molecule cm−3 (2.5–14 pptv), respectively. OH concentrations correlated well with the rate of OH production from ozone photolysis for clean air from the Arctic containing low concentrations of both NOx and nonmethane hydrocarbons. A lower correlation was observed in more polluted air that originated from the United Kingdom and continental Europe. Measurements of OH and HO2 were made throughout two nights, and although no evidence was seen for OH above the detection limit, up to 2 pptv of HO2 was observed. The measured HO2/OH ratio was in good agreement with the predictions of a steady state expression for NO in the range 75–400 pptv.

### Eastern Atlantic Spring Experiment 1997 (EASE97) 2 Comparisions of model concentrations of OH...

 Date added: 08/06/2002 Date modified: 07/27/2009 Filesize: 640.01 kB

Carslaw,m N.; Creasey, D.J.; Heard, D.E.; Jacobs, P.; Lee, J.D.L.; Lewis, A.C.; McQuaid, J.B.; Pilling, M.J.; Bauguitte, S.; Penkett, S.A.; Monks, P.S.; Salisbury, G. (2002) Eastern Atlantic Spring Experiment 1997 (EASE97) - 2. Comparisons of model concentrations of OH, HO2, and RO2 with measurements, Journal of Geophysical Research, 107, pp.4190/ ACH5

Abstract

An observationally constrained box model has been used to investigate the chemistry of the marine boundary layer at the Mace Head Atmospheric Research Station, a remote site on the west coast of Ireland. The model aims to simulate concentrations of the hydroxyl (OH) and hydroperoxy (HO2) radicals measured by an in situ fluorescence assay by gas expansion instrument, and the sum of peroxy radicals ([HO2] + Σ[RO2]) as determined by a peroxy radical chemical amplification instrument. The model has been constructed based on observed concentrations of nonmethane hydrocarbons, measured in situ during the campaign by gas chromatography. The chemical mechanism for the model is a subset of a comprehensive master chemical mechanism. This paper details comparisons of the concentrations of modeled and measured radical species from a field campaign held at Mace Head during spring 1997. The air masses arriving at the site have been split into three categories depending on their origin and chemical characteristics and model-measurement comparisons carried out for each air mass. The average model-measurement ratios are 2.4 for [OH], 3.6 for [HO2], and 0.9 for ([HO2] + Σ[RO2]), respectively, between 1100 and 1500 hours: the level of agreement is better for all three sets of radicals in the cleanest air mass. Possible reasons for the observed discrepancies are discussed. In addition, a rate of production analysis is used to identify key OH and HO2 reactions in the three air masses. The rate of OH production from HO2 with NO exceeds that from ozone photolysis by factors of 2–6 in the polluted air masses studied. In cleaner air from the northern polar region, primary production from ozone photolysis exceeds that from HO2 + NO by a factor of 2.5. HO2 and CH3O2 dominate the peroxy radical composition in all air masses, but peroxy radicals derived from the oxidation of nonmethane hydrocarbons are more important in polluted air masses.

### In situ measurements of atmospheric methane at GAGE AGAGE sites during 1985–2000 and resulting source inferences

 Date added: 08/01/2002 Date modified: 07/24/2009 Filesize: 7.81 MB
Cunnold, D. M., et al. (2002), In situ measurements of atmospheric methane at GAGE/AGAGE sites during 1985–2000 and resulting source inferences, J. Geophys. Res., 107(D14), 4225, doi:10.1029/2001JD001226.

Abstract

Continuous measurements of methane since 1986 at the Global Atmospherics Gases Experiment/Advanced Global Atmospherics Gases Experiment (GAGE/AGAGE) surface sites are described. The precisions range from approximately 10 ppb at Mace Head, Ireland, during GAGE to better than 2 ppb at Cape Grim, Tasmania, during AGAGE (i.e., since 1993). The measurements exhibit good agreement with coincident measurements of air samples from the same locations analyzed by Climate Monitoring and Diagnostics Laboratory (CMDL) except for differences of approximately 5 ppb before 1989 (GAGE lower) and about 4 ppb from 1991 to 1995 (GAGE higher). These results are obtained before applying a factor of 1.0119 to the GAGE/AGAGE values to place them on the Tohoku University scale. The measurements combined with a 12-box atmospheric model and an assumed atmospheric lifetime of 9.1 years indicates net annual emissions (emissions minus soil sinks) of 545 Tg CH4 with a variability of only ±20 Tg from 1985 to 1997 but an increase in the emissions in 1998 of 37 ± 10 Tg. The effect of OH changes inferred by Prinn et al. [2001] is to increase the estimated methane emissions by approximately 20 Tg in the mid-1980s and to reduce them by 20 Tg in 1997 and by more thereafter. Using a two-dimensional (2-D), 12-box model with transport constrained by the GAGE/AGAGE chlorofluorocarbon measurements, we calculate that the proportion of the emissions coming from the Northern Hemisphere is between 73 and 81%, depending on the OH distribution used. However, this result includes an adjustment of 5% derived from a simulation of the 2-D estimation procedure using the 3-D MOZART model. This adjustment is needed because of the very different spatial emission distributions of the chlorofluorocarbons and methane which makes chlorofluorocarbons derived transport rates inaccurate for the 2-D simulation of methane. The 2-D model combined with the annual cycle in OH from Spivakovsky et al. [2000] provide an acceptable fit to the observed 12-month cycles in methane. The trend in the amplitude of the annual cycle of methane at Cape Grim is used to infer a trend in OH in 30°–90°S of 0 ± 5% per decade from 1985 to 2000, in qualitative agreement with Prinn et al. [2001] for the Southern Hemisphere.

### Atmospheric histories of halocarbons from analysis of Antarctic firn air Major Montreal Protocol species

 Date added: 08/01/2002 Date modified: 06/30/2009 Filesize: 832.27 kB
Sturrock, G. A., D. M. Etheridge, C. M. Trudinger, P. J. Fraser, and A. M. Smith (2002), Atmospheric histories of halocarbons from analysis of Antarctic firn air: Major Montreal Protocol species, J. Geophys. Res., 107(D24), 4765, doi:10.1029/2002JD002548.
Abstract

Air samples extracted from Antarctic firn at Law Dome have been analyzed for the suite of halocarbons that contribute most of the anthropogenic chlorine and about half the anthropogenic bromine presently released into the stratosphere. The species, all included in the Montreal Protocol, are the chlorofluorocarbons (CFCs -11, -12, -113, -114, -115), hydrochlorofluorocarbons (HCFCs -22, -141b, -142b), halons (H -1211, -1301), CH3CCl3 (methyl chloroform) and CCl4 (carbon tetrachloride). The measurements were used to reconstruct the atmospheric history of these species since the 1930s, providing a record considerably predating existing in situ records or other conventional air archives, encompassing virtually the entire history of anthropogenic emissions of CFCs, HCFCs, and halons and giving early 20th century levels for CH3CCl3 and CCl4. Significant features of this study are (1) the narrow age spread (spectral width 5 years) of the individual firn air samples, which reveals rapid atmospheric changes, (2) the use of inversion techniques to infer past atmospheric composition with associated uncertainties, and (3) the low analytical detection limit (<0.1 ppt), which, together with the narrow air age spread, detects early background levels and resolves the time that industrial emissions first appeared in the southern hemisphere atmosphere. Integrity of the data is demonstrated by successful intercomparison of data from independent firn sites on Law Dome with common time-series. An upper limit is given for the potential contribution to atmospheric levels of CH3CCl3 from nonindustrial sources. The atmospheric records produced from firn air are compared to calculations based on the history of their global emissions.

### A dedicated study of New Particle Formation and Fate in the Coastal Environment (PARFORCE): Overview

 Date added: 08/01/2002 Date modified: 07/21/2009 Filesize: 448.25 kB
O’Dowd, C. D., et al., A dedicated study of New Particle Formation and Fate in the Coastal Environment (PARFORCE):Overview of objectives and achievements, J. Geophys. Res., 107(D19), 8108, doi:10.1029/2001JD000555, 2002Overview of objectives and achievements, J. Geophys. Res., 107(D19), 8108, doi:10.1029/2001JD000555, 2002

Abstract

A dedicated study into the formation of new particles, New Particle Formation and Fate in the Coastal Environment (PARFORCE), was conducted over a period from 1998 to 1999 at the Mace Head Atmospheric Research Station on the western coast of Ireland. Continuous measurements of new particle formation were taken over the 2-year period while two intensive field campaigns were also conducted, one in September 1998 and the other in June 1999. New particle events were observed on ∼90% of days and occurred throughout the year and in all air mass types. These events lasted for, typically, a few hours, with some events lasting more than 8 hours, and occurred during daylight hours coinciding with the occurrence of low tide and exposed shorelines. During these events, peak aerosol concentrations often exceeded 106 cm-3 under clean air conditions, while measured formation rates of detectable particle sizes (i.e., d > 3 nm) were of the order of 104-105 cm-3 s-1. Nucleation rates of new particles were estimated to be, at least, of the Qrder of 105-106 cm-3 s-1and occurred for sulphuric acid concentrations above 2 x 106 molecules cm-3; however, no correlation existed between peak sulphuric acid concentrations, low tide occurrence, or nucleation events. Ternary nucleation theory of the H2SO4-H2O-NH3 system predicts that nucleation rates far in excess of 106 cm-3 s-1 can readily occur for the given sulphuric acid concentrations; however, aerosol growth modeling studies predict that there is insufficient sulphuric acid to grow new particles (of ∼1 nm in size) into detectable sizes of 3 nm. Hygroscopic growth factor analysis of recently formed 8-nm particles illustrate that these particles must comprise some species significantly less soluble than sulphate aerosol. The nucleation-mode hygroscopic data, combined with the lack of detectable VOC emissions from coastal biota, the strong emission of biogenic halocarbon species, and the fingerprinting of iodine in recently formed (7 nm) particles suggest that the most likely species resulting in the growth of new particles to detectable sizes is an iodine oxide as suggested by previous laboratory experiments. It remains an open question whether nucleation is driven by self nucleation of iodine species, a halocarbon derivative, or whether first, stable clusters are formed through ternary nucleation of sulphuric acid, ammonia, and water vapor, followed by condensation growth into detectable sizes by condensation of iodine species. Airborne measurements confirm that nucleation occurs all along the coastline and that the coastal biogenic aerosol plume can extend many hundreds of kilometers away from the source. During the evolution of the coastal plume, particle growth is observed up to radiatively active sizes of 100 nm. Modeling studies of the yield of cloud-condensation nuclei suggest that the cloud condensation nuclei population can increase by ∼100%. Given that the production of new particles from coastal biogenic sources occurs at least all along the western coast of Europe, and possibly many other coastlines, it is suggested that coastal aerosols contribute significantly to the natural background aerosol population.

### Small particle concentration fluctuations at a coastal site

 Date added: 08/01/2002 Date modified: 07/23/2009 Filesize: 877.43 kB
Vana, M., Jennings, S.G., Kleefeld, C., Mirme, A., and Tamm, E., 2002. Small particle concentration fluctuations at a coastal site, Atmos. Res., 63, pp. 247 – 269.

Abstract

Aerosol size spectra (d=10 nm–10 μm) were measured with an electrical aerosol spectrometer (EAS) at Mace Head on the west coast of Ireland. Several small aerosol particle (diameter 10–32 nm) concentration bursts were observed during the measurement period. Relationships between the events, air mass trajectories, tide height, and meteorological parameters are examined. Series of bursts were observed when a spectral transformation due to subsequent particle growth from 10 to 56–100 nm can be identified in an Eulerian experiment. Particle growth rates of between 1 and 3 nm/h were determined. These bursts appear in cold and comparatively clean arctic or polar air masses with temperature and relative humidity fluctuations, and do not correlate with low tide in some cases. These episodes, similar to those frequently found in the continental boundary layer, are thought to occur over a wide area and, for clear detection, require stable airflow for a few days. Elevated small-particle concentration events are more common during low tide or shortly after, and are typically associated with low wind speeds. Here, the increased shore exposure during low tide is thought to influence the nucleation and the subsequent growth of these aerosol particles. The occurrences of the bursts are found to depend on local wind direction. The highest d=10–32 nm particle concentrations appeared for wind sectors furthest from the tidal regions when the wind direction was 150–160°(south-easterly). Most of the events occurred during daytime when solar irradiation is most intense.

### Size-differentiated volatility analysis of internally mixed laboratory-generated aerosol,

 Date added: 08/01/2002 Date modified: 07/23/2009 Filesize: 348.8 kB
Brooks, B.J., M.H. Smith, M.K. Hill, and C.D. O'Dowd, Size-differenciated volatility analysis of internally mixed laboratory-generated aerosol, J. Aer. Sci.,33, 555-579, 2002.

Abstract

The increased application of volatility analysis to determine the composition and structure of sub-micron aerosol requires that the thermal behaviour of chemically complex aerosol be understood. Presented here is a volatility study, utilising a tandem volatility differential mobility analyser (TVDMA), of 30, 50, and 70nm radii, internally mixed, aerosol containing ionic-salts, acids, organics, and carbon. Evidence of some size-dependent behaviour was observed with several of the single component aerosol. Internally mixed aerosol displayed complex thermal behaviours that were dependent on both size and the volume mixing ratio of source solutions

### Relative contribution of submicron and supermicron particles

 Date added: 08/01/2002 Date modified: 07/23/2009 Filesize: 399.76 kB
Christoph Kleefeld, Colin O'Dowd, Sarah O'Reilly, S. Gerard Jennings, Pasi Alto, Edo, Becker, Gerard Kunz, Gerrit de Leeuw.The Relative Contribution of sub and super micron particles to aerosol light scattering in the marine boundary layer (MBL), J. Geophys. Res., 107, 10.1029/2000JD000262, 2002.

Abstract

Measurements of the aerosol light scattering coefficient (σsp) at a wavelength of λ = 550 nm were conducted at a coastal atmospheric research station in the east Atlantic Ocean during June 1999. Size distribution measurements between diameters of 3 nm and 40 μm (at ambient humidity) were used to derive scattering coefficients from Mie theory. The calculated scattering coefficients were about a factor of 7.4 higher than the measured scattering coefficients. The discrepancy was explained by a reduced cutoff of the sampling system at particle diameters between 6 and 8 μm, dependent on wind speed. The calculated aerosol scattering was about 1 order of magnitude higher than previously reported measurements in the MBL and is attributed to supermicrometer particles at sizes d > 10 μm dominating aerosol scattering.

### Quantification of carbon dioxide, methane, nitrous oxide and chloroform emissions over Ireland from atmospheric observations at Mace Head

 Date added: 08/01/2002 Date modified: 07/23/2009 Filesize: 738.69 kB

Biraud, S., Ciais, Philippe, Ramonet, Michel, Simmonds, Peter, Kazan, Victor, Monfray, Patrick, O’Doherty, Simon, Spain, Gerard, and Jennings, S. Gerard. 2002. Quantification of carbon dioxide, methane, nitrous oxide, and chloroform emissions over Ireland from atmospheric observations at Mace Head, Tellus, 54B, pp. 41-60.

Abstract

Flux estimates of CO2, CH4, N2O and CHCl3 over Ireland are inferred from continuous atmospheric records of these species. We use radon-222 (222Rn) as a reference compound to estimate unknown sources of other species. The correlation between each species and 222Rn is calculated for a suite of diurnal events that have been selected in the Mace Head record over the period 1995-1997 to represent air masses exposed to sources over Ireland. We established data selection criteria based on 222Rn and 212Pb concentrations. We estimated flux densities of 12 × 103 kg CH4 km-2 yr-1, 680 kg N2O km-2 yr-1 and 20 kg CHCl3 km-2 yr-1 for CH4, N2O and CHCl3, respectively. We also inferred flux densities of 250 x 103 kg C km-2 yr-1 for CO2 during wintertime, and of 760 x 103 kg C km-2 yr-1 for CO2 during summer night-time. Our CH4 inferred flux compare well with the CORINAIR90 and CORNAIR94 inventories for Ireland. The N2O emission flux we inferred is close to the inventory value by CORINAIR90, but twice the inventory value by CORINAIR94 and EDGAR 2.0. This discrepancy may have been caused by the use of the revised 1996 IPCC guidelines for national greenhouse gas inventories in 1994, which include a new methodology for N2O emissions from agriculture. We carried out the first estimation of CHCl3 emission fluxes over Ireland. This estimation is 4 times larger than the CHCl3 emission fluxes measured close to the Mace Head station over peatlands. Our CHCl3 emission fluxes estimate is consistent with the interpretation of the same data by Ryall (personal communication, 2000), who obtained, using a Lagrangian atmospheric transport model, CHCl3 fluxes of 24 ± 7 kg CHCl3 km-2 yr-1. Our estimates of CO2 emission fluxes during summer night-time and wintertime are close to those estimated from inventories and to one biogeochemical model of heterotrophic respiration.

### Particle size dependent response of aerosol counters

 Date added: 08/01/2002 Date modified: 07/03/2009 Filesize: 652.99 kB
Ankilov, A., A Baklanov, M. Colhoun, K-H. Enderle, J. Gras, Yu Jualanov, D. Kaller, A. Linder, A.A. Lushnikov, R. Mavliev, F. McGovern, T.C. O'Connor, J. Podzimek, O. Prining, G.P. Reischl, R. Rudolf, G.J. Sem, W.W. Szymanski, E. Tamm, A.E. Vrtala, P.E. Wagner, W. Winklmayr and V. Zagaynov, Particle size dependent response of aerosol particle counters, Atmos. Res., 62, 209-238, 2002.

Abstract

During an international workshop at the Institute for Experimental Physics of the University of Vienna, Austria, which was coordinated within the Committee on Nucleation and Atmospheric Aerosols (IAMAS-IUGG), 10 instruments for aerosol number concentration measurement were studied, covering a wide range of methods based on various different measuring principles. In order to investigate the detection limits of the instruments considered with respect to particle size, simultaneous number concentration measurements were performed for monodispersed aerosols with particle sizes ranging from 1.5 to 50 nm diameter and various compositions.

The instruments considered show quite different response characteristics, apparently related to the different vapors used in the various counters to enlarge the particles to an optically detectable size. A strong dependence of the 50% cutoff diameter on the particle composition in correlation with the type of vapor used in the specific instrument was found. An enhanced detection efficiency for ultrafine hygroscopic sodium chloride aerosols was observed with water operated systems, an analogous trend was found for n-butanol operated systems with nonhygroscopic silver and tungsten oxide particles.

### Particle deposition in ventilation duct onto three-dimensional roughness elements

 Date added: 08/01/2002 Date modified: 07/03/2009 Filesize: 133.69 kB
A.C.K. Lai, M.A. Byrne, A.J.H. Goddard, Particle deposition in ventilation duct onto three-dimensional roughness elements, Building and Environment, 37, No .10, 939-945, 2002.

Abstract

Gaining insights on particle deposition onto ventilation duct has many important applications. One key pathway by which outdoor polluted air enters the indoor environment is through mechanical ventilation ducts. An experimental system was designed for the study of particle deposition on regular arrays of uniform elements (in the form of discrete protrusions) in a turbulent ventilation duct flow using monodisperse tracer small particles, in the range 0.7–7.1 μm. The Reynolds number for the test conditions was 44,000 in the 150 mm square duct. Four different types of uniform roughness elements were tested. Compared to earlier measurements in the same duct system involving smooth or ribbed surfaces, a significant increase (up to 74 times) in deposition velocity onto the regular roughness elements is observed.

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