Carbon In Atmospheric Aerosols Research Articles

Importance of organic and black carbon in atmospheric aerosols at Mace Head, on the West Coast of Ireland (53°19′N, 9°54′W)

The mass concentrations of total organic carbon (TC) and its chemical fractions, water-soluble organic carbon (WSOC), water-insoluble organic carbon (WISOC), and black carbon (BC), were determined in marine aerosols, which were collected during the period July 1998–September 1999 at the Mace Head Atmospheric Research Station on the west coast of Ireland. In addition, mass concentrations of major inorganic ions, like non-sea-salt (NSS) sulphate, and mass concentrations of dicarboxylic acids have been measured separately within the water-soluble aerosol fraction. The aerosol samples were classified into ‘clean marine aerosol samples’ and ‘modified marine aerosol samples’ according to the origin of air masses arriving at Mace Head, and using BC as a tracer for anthropogenic pollution. Following this classification, the data set was further divided into samples taken during summertime and wintertime. An average TC mass concentration of 591±75 ng m −3 was determined for all aerosol samples taken at Mace Head. WSOC was found to be the dominating fraction in ‘modified marine aerosol samples’, followed by WISOC and BC, whereas in ‘clean marine aerosol samples’ WISOC was the main fraction, followed by WSOC, and BC. A comparison of the mass concentration of the water-soluble organic matter to the main water-soluble inorganic component, NSS sulphate, gave an average ratio of 0.72±0.10, which increased to 1.59±0.23 when considering solely ‘clean marine aerosol samples’. The dominating dicarboxylic acid found in carbonaceous aerosols at Mace Head was oxalic acid, followed by malonic acid. Both diacids were responsible for about 14±2% of the WSOC (in terms of carbon).

A new approach for the fractionation of water-soluble organic carbon in atmospheric aerosols and cloud drops

A novel approach is described for the fractionation of water-soluble organic carbon (WSOC) in atmospheric aerosols and cloud drops. The method is based on the preliminary adsorption of the sample, acidified at pH 2, on a polymeric styrene-divinylbenzene resin (XAD-2) and subsequent elution with a series of solvents, which leads to the fractionation of the sample into three classes of compounds. The method was set up using synthetic mixtures of organic compounds and then applied to selected samples of atmospheric aerosols and cloud drops. All samples and collected fractions were analysed using size exclusion chromatography (SEC). This method proved particularly useful both in providing information on the organic content of the samples and for the characterisation of the macromolecular compounds (MMCs) in the samples. Synthetic samples were prepared using humic, fulvic and tannic acid to simulate naturally occurring MMCs. In the first fraction, eluted with HCl, only the most soluble organic compounds (oxalic acid, formic acid and acetic acid) were collected. In the second fraction, eluted with methanol, the major part of the organic material was collected together with the more hydrophilic constituents of the humic substances. In the third fraction, it was possible to separately recover the more hydrophobic component of the humic substances. A large number of atmospheric samples (fog, aerosol, cloud) were then analysed using SEC. Most of these samples evidenced a noteworthy chromatogram at 254 nm. Moreover, the chromatographic area evidenced a clear linear correlation with the total organic carbon (TOC) values. The fractionation method on XAD-2 was finally applied to selected atmospheric samples, yielding three classes of organic compounds. In each sample, a non-negligible amount of compounds with dimensional and chemical properties similar to humic substances were collected in the third fraction. The carbon content in this latter fraction was estimated both by TOC and by means of the correlation between TOC and SEC area.

Strong radiative heating due to the mixing state of black carbon in atmospheric aerosols.

Aerosols affect the Earth's temperature and climate by altering the radiative properties of the atmosphere. A large positive component of this radiative forcing from aerosols is due to black carbon--soot--that is released from the burning of fossil fuel and biomass, and, to a lesser extent, natural fires, but the exact forcing is affected by how black carbon is mixed with other aerosol constituents. From studies of aerosol radiative forcing, it is known that black carbon can exist in one of several possible mixing states; distinct from other aerosol particles (externally mixed) or incorporated within them (internally mixed), or a black-carbon core could be surrounded by a well mixed shell. But so far it has been assumed that aerosols exist predominantly as an external mixture. Here I simulate the evolution of the chemical composition of aerosols, finding that the mixing state and direct forcing of the black-carbon component approach those of an internal mixture, largely due to coagulation and growth of aerosol particles. This finding implies a higher positive forcing from black carbon than previously thought, suggesting that the warming effect from black carbon may nearly balance the net cooling effect of other anthropogenic aerosol constituents. The magnitude of the direct radiative forcing from black carbon itself exceeds that due to CH4, suggesting that black carbon may be the second most important component of global warming after CO2 in terms of direct forcing.

Volatility of elemental carbon

A volatility technique whereby aerosol particles are heated to the relatively high temperature of 860 °C is used to infer the presence of elemental carbon in polluted air masses in the vicinity of the west coast of Ireland. The volume of elemental carbon for submicrometre sized particles contained in the aerosol is estimated from the fall off in number concentration at a critical onset temperature of about 730–735 °C, as also obtained for laboratory carbon ink aerosol. The technique permits determination of the elemental carbon volume percentage of the total fine aerosol volume, and an estimation of the abundance of elemental carbon contained within the black carbon fraction of the atmospheric aerosol. Supplementary black carbon mass concentration measurements were obtained using a thermal method and an aethalometer absorption method. The work suggests that elemental carbon can be identified using the volatility technique and that it can yield size‐segregated information on the fraction of elemental carbon in atmospheric aerosol.

Determination of carbon in atmospheric aerosols by deuteron activation analysis

Nuclear reactions induced by 7.6-MeV deuterons are used to determine total carbon in atmospheric aerosols. The /sup 12/C-(d,n) /sup 13/N reaction produces the radionuclide /sup 13/N, a 10.0-min positron emitter, which is detected by its 0.511-MeV annihilation radiation. The detection system is a Ge(Li) ..gamma..-ray spectrometer. The method is nondestructive of the sample, permitting the sample to be studied by additional methods. Comparison of carbon found by deuteron activation analysis with that found by independent but destructive combustion methods shows a standard deviation of 10% for 15 samples analyzed over a wide range of carbon contents. The detection limit is estimated to be 0.5 ..mu..g/cm/sup 2/, corresponding to a carbon concentration of 0.2% in a sample of total thickness 250 ..mu..g/cm/sup 2/.

Determination of nitrogen in atmospheric aerosols by proton activation analysis

Nuclear reactions induced by 7.6-MeV deuterons are used to determine total carbon in atmospheric aerosols. The {sup 12}C(d,n){sup 13}N reaction produces the radionuclide {sup 13}N, a 10.0-min positron emitter, which is detected by its 0.511-MeV annihilation radiation. The detection system is a Ge(Li) {gamma}-ray spectrometer. The method is nondestructive of the sample, permitting the sample to be studied by additional methods. Comparison of carbon found by deuteron activation analysis with that found by independent but destructive combustion methods shows a standard deviation of 10% for 15 samples analyzed over a wide range of carbon contents. The detection limit is estimated to be 0.5 {micro}g/cm{sup 2}, corresponding to a carbon concentration of 0.2% in a sample of total thickness 250 {micro}g/cm{sup 2}.