Volcanic aerosol phosphorus, chlorine, and sulfur at Kilauea, Hawaii

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Abstract
Aerosol concentrations of P, Cl, S, and major soil‐derived elements were measured sequentially at the Hawaiian Volcano Observatory (HVO) from March to September 1979, with 3.7‐hour time resolution using a Nuclepore‐filter sampler. The filters were analyzed by particle‐induced X ray emission (PIXE). Comparison with diurnal variations in the air flow inferred from major soil elements, e.g., Fe, as well as measurements made previously at fumaroles near HVO, indicate that the P, Cl, and S may be attributed mainly to volcanic emissions from Kilauea. From April 23 to June 30, P was found with concentrations up to 1000 ng m−3, but before and after those dates, P was generally below the detection limit of 50–80 ng m−3. Cl and S were frequently found over the entire sampling period, also with concentrations up to 1000 ng m−3. However, when P was found, Cl was almost never detected simultaneously. The mutually exclusive occurrences of P and Cl suggest volatility release of HCl from aerosol particles by reaction with strong acid associated with P. If strong acidity is due to H2SO4, it is not well predicted by S, which may also include other sulfates or sulfur, since aerosol S concentrations are not well correlated with P or Cl. The behavior of these three elements suggests that the volcanic sources of P are more localized than those of Cl or S. It is significant that concentrations of aerosol P can be as high as aerosol Cl and S, all apparently of primary volcanic origin, indicating that volcanism may be an important, but hitherto unrecognized, process in the atmospheric geochemical cycling of phosphorus.