Iodine containing species in the remote marine boundary layer: A link to oceanic phytoplankton

[1] Iodine containing species have been measured in the particle phase (PM2.5) and the gas phase during a ship campaign between January and February 2007 in the South Atlantic marine boundary layer (MBL). Methyl iodide (CH3I) in the gas phase and soluble iodine species, i.e. iodide, iodate and an unidentified organic iodine species (UOI), in PM2.5 were measured. Temporal variations of gaseous and particulate iodine species were investigated. The exposure of the sampled air masses to phytoplankton along the back-trajectories was studied using a lagrangian transport model and satellite observations of oceanic chlorophyll-a concentration. Significant correlations were found between the concent…

Iodine speciation in marine aerosols along a 30,000 km round-trip cruise path from Shanghai, China to Prydz Bay, Antarctica

[1] Total suspended particle (TSP) samples were collected onboard a round-trip cruise from Shanghai, China to Prydz Bay, Antarctica from November 2005 to March 2006. Water soluble iodine species were measured using ion chromatography coupled to Inductively Coupled Plasma-Mass Spectrometry (IC-ICP-MS). The results reveal that soluble organic iodine (SOI) is the most abundant fraction, accounting for approximately 70 % of total soluble iodine (TSI) on average. One unidentified organic iodine (UOI) signal was present in almost all of the samples and was responsible for up to 38.3% of TSI. The abundance of inorganic iodine species, iodate and iodide, was less than 30% of TSI. Iodide was signifi…

Iodine speciation in rain, snow and aerosols

Iodine oxides, such as iodate, should be the only thermodynamically stable sink species for iodine in the troposphere. However, field observations have increasingly found very little iodate and significant amounts of iodide and soluble organically bound iodine (SOI) in precipitation and aerosols. The aim of this study was to investigate iodine speciation, including the organic fraction, in rain, snow, and aerosols in an attempt to further clarify aqueous phase iodine chemistry. Diurnal aerosol samples were taken with a 5 stage cascade impactor and a virtual impactor (PM<sub>2.5</sub>) from the Mace Head research station, Ireland, during summer 2006. Rain was collected from Austr…

Gel Electrophoresis Coupled to Inductively Coupled Plasma−Mass Spectrometry Using Species-Specific Isotope Dilution for Iodide and Iodate Determination in Aerosols

In this paper, we present an online coupling of gel electrophoresis (GE) and inductively coupled plasma-mass spectrometry (ICP-MS) for the determination of iodine species (iodide and iodate) in liquid (seawater) and aerosol samples. For the first time, this approach is applied to the analysis of small molecules, and initial systematic investigations revealed that the migration behavior as well as the detection sensitivity strongly depends on the matrix (e.g., high concentrations of chloride). These effects could consequently affect the accuracy of analytical results, so that they need to be considered for the analysis of real samples. The technique used for quantification is species-specifi…

Atmospheric protein chemistry influenced by anthropogenic air pollutants: nitration and oligomerization upon exposure to ozone and nitrogen dioxide

The allergenic potential of airborne proteins may be enhanced via post-translational modification induced by air pollutants like ozone (O3) and nitrogen dioxide (NO2). The molecular mechanisms and kinetics of the chemical modifications that enhance the allergenicity of proteins, however, are still not fully understood. Here, protein tyrosine nitration and oligomerization upon simultaneous exposure of O3 and NO2 were studied in coated-wall flow-tube and bulk solution experiments under varying atmospherically relevant conditions (5–200 ppb O3, 5–200 ppb NO2, 45–96% RH), using bovine serum albumin as a model protein. Generally, more tyrosine residues were found to react via the nitration pathw…

Metaproteomic analysis of atmospheric aerosol samples.

Metaproteomic analysis of air particulate matter provides information about the abundance and properties of bioaerosols in the atmosphere and their influence on climate and public health. We developed and applied efficient methods for the extraction and analysis of proteins from glass fiber filter samples of total, coarse, and fine particulate matter. Size exclusion chromatography was applied to remove matrix components, and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was applied for protein fractionation according to molecular size, followed by in-gel digestion and LC-MS/MS analysis of peptides using a hybrid Quadrupole-Orbitrap MS. Maxquant software and the Swiss-…

Iodine speciation in atmospheric aerosols in the marine boundary layer

Iodine Speciation in Marine Boundary Layer

Release of free amino acids upon oxidation of peptides and proteins by hydroxyl radicals

Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl ra…