A comprehensive estimate for loss of atmospheric carbon tetrachloride (CCl₄) to the ocean

Abstract. Extensive undersaturations of carbon tetrachloride (CCl₄) in Pacific, Atlantic, and Southern Ocean surface waters indicate that atmospheric CCl₄ is consumed in large amounts by the ocean. Observations made on 16 research cruises between 1987 and 2010, ranging in latitude from 60° N to 77° S, show that negative saturations extend over most of the surface ocean. Corrected for physical effects associated with radiative heat flux, mixing, and air injection, these anomalies were commonly on the order of −5 to −10 %, with no clear relationship to temperature, productivity, or other gross surface water characteristics other than being more negative in association with upwelling. The atmospheric flux required to sustain these undersaturations is 12.4 (9.4–15.4) Gg yr⁻¹, a loss rate implying a partial atmospheric lifetime with respect to the oceanic loss of 183 (147–241) yr and that  ∼  18 (14–22)  % of atmospheric CCl₄ is lost to the ocean. Although CCl₄ hydrolyzes in seawater, published hydrolysis rates for this gas are too slow to support such large undersaturations, given our current understanding of air–sea gas exchange rates. The even larger undersaturations in intermediate depth waters associated with reduced oxygen levels, observed in this study and by other investigators, strongly suggest that CCl₄ is ubiquitously consumed at mid-depth, presumably by microbiota. Although this subsurface sink creates a gradient that drives a downward flux of CCl₄, the gradient alone is not sufficient to explain the observed surface undersaturations. Since known chemical losses are likewise insufficient to sustain the observed undersaturations, this suggests a possible biological sink for CCl₄ in surface or near-surface waters of the ocean. The total atmospheric lifetime for CCl₄, based on these results and the most recent studies of soil uptake and loss in the stratosphere is now 32 (26–43) yr.