|dc.description.abstract||Vapor phase stripping and solid adsorbent trapping were applied to seawater and related samples to concentrate volatile organic compounds. The concentrates were subsequently analyzed by glass capillary gas chromatography and combined gas chromatography-mass spectrometry. The
compound identities and the spatial and temporal distributions of their concentrations were used to determine some sources, transformations, and transport mechanisms of organic matter in the sea.
Volatile organic compounds were determined in seawater samples from the Sargasso Sea, the western Equatorial Atlantic, and the upwelling region off Peru. Pentadecane was present in all three areas in surface samples at 10-40ng/kg and decreased to 1-2 ng/kg in the deep water.
A source related to the transformation of the algal fatty acid, hexadecaugic acid, by zooplankton is proposed since anthropogenic and direct phytoplankton sources are unlikely. C2-alkylated benzenes were found in the upwelled water off Peru at about 4 ng/kg in the surface (5 and 20m), 3 ng/kg below the thermocline (100m), and 2 ng/kg or less in deeper water.
A surface or atmospheric source is required to produce this distribution.
C6-C10 aldehydes were also found in seawater from off Peru. The direct correlation of their concentrations with chlorophyll a and with oxygen indicated that they are derived from chemical oxidation of algal metabolites, for example, unsaturated fatty acids. Total volatiles in the oligotrophic Sargasso Sea were about 10-30 ng/kg while the biologically productive
upwelling region off Peru contained up to 100 ng/kg.
The temporal variations of volatile organic compound concentrations
were investigated in coastal seawater from Vineyard Sound, Massachusetts.
Pentadecane and heptadecane showed large summertime concentration increases
which were ascribed to benthic algal sources. Laboratory incubations of
benthic algal samples supported this conclusion. The saturated hydrocarbons,
from C13-C17, and alkylated benzenes and naphthalenes were all
abundant after an oil spill several miles from the sampling site. C2- and C3-
benzenes were the most persistently abundant volatile compounds and their
concentrations were observed to be 2-10 times higher than average immediately
after summer weekends, peak periods of tourist and recreational
activities on Cape Cod. Naphthalene and its homologues were more abundant
in the winter than in the summer. C6-C10 aldehydes were observed year-round,
but showed a concentration maximum at the time of the late-winter
phytoplankton bloom. C12-C15 aldehydes were also found in abundance at
that time. Oxidation of algal matter by zooplankton or photochemically-produced
oxidizing agents may produce the aldehydes, since laboratory
cultures of phytoplankton did not produce these oxygenated volatiles. An
alkene, structurally similar to the known benthic algal gamone, fucoserraten, was also found in Vineyard Sound seawater and in the upwelling
region off Peru. Its appearance in Vineyard Sound samples coincided with
the period of expected algal reproductive activity in February and March.
Dimethyl polysulfides were found in coastal seawater. They may be
produced within the water from precursors such as methyl mercaptan or other
known polysulfide metabolites. Total volatile concentrations in Vineyard
Sound seawater varied between 2OO and 500 ng/kg for the period from
January to June. Maximum concentrations occurred during the late-winter
phytoplankton bloom and again in the spring from anthropogenic inputs of
The highest concentrations of C2- and C3-benzenes found in Vineyard Sound
seawater coincided with motorboat use in the immediate vicinity of the
sampling station. The average year-round isomer distribution most closely
resembled distributions from gasoline and auto exhaust dissolved in seawater,
consistent with an inboard or inboard/outboard motorboat source.
Atmospheric and runoff delivery of C2- and C3-benzenes to Vineyard Sound
seawater during the period from spring through fall was concluded to be
of lesser importance. The atmosphere may serve as a buffer for seawater
concentrations of the aromatic compounds, supporting low concentrations in
the winter and limiting high concentrations in the summer.||en||