Wally's quest to understand the ocean's CaCO3 cycle.

Aspects of the production and dissolution of CaCO3 hard parts dominate the literature regarding contemporary marine chemistry and paleoceanography. During my long career I have contributed more than 200 papers related to this subject. In this prefatory article in the first volume of the Annual Review of Marine Science, I recount what I consider to be the highlights of my attempts to understand the cycle of CaCO3 in today's ocean and in oceans of the past. These studies began in the Bahamas in the early 1960s and then quickly graduated to the world ocean. Although much of my research has involved stable and radioisotopes contained in shells and coral directed toward reconstruction of the late Quaternary operation of the earth system, in this review I concentrate on carbonate chemistry and, in particular, the compensation in the deep sea for the overproduction of CaCO3 by marine organisms.

Does the trigger for abrupt climate change reside in the ocean or in the atmosphere?

Two hypotheses have been put forward to explain the large and abrupt climate changes that punctuated glacial time. One attributes such changes to reorganizations of the ocean's thermohaline circulation and the other to changes in tropical atmosphere-ocean dynamics. In an attempt to distinguish between these hypotheses, two lines of evidence are examined. The first involves the timing of the freshwater injections to the northern Atlantic that have been suggested as triggers for the global impacts associated with the Younger Dryas and Heinrich events. The second has to do with evidence for precursory events associated with the Heinrich ice-rafted debris layers in the northern Atlantic and with the abrupt Dansgaard-Oeschger warmings recorded in the Santa Barbara Basin.

Glacial-to-Holocene redistribution of carbonate ion in the deep sea.

We have reconstructed the glacial-age distribution of carbonate ion concentration in the deep waters of the equatorial ocean on the basis of differences in weight between glacial and Holocene foraminifera shells picked from a series of cores spanning a range of water depth on the western Atlantic's Ceara Rise and the western Pacific's Ontong Java Plateau. The results suggest that unlike today's ocean, sizable vertical gradients in the carbonate ion concentration existed in the glacial-age deep ocean. In the equatorial Pacific, the concentration increased with depth, and in the Atlantic, it decreased with depth. In addition, the contrast between the carbonate ion concentration in deep waters produced in the northern Atlantic and deep water in the Pacific appears to have been larger than in today's ocean.

Cooling of Tropical Brazil (5{degrees}C) During the Last Glacial Maximum.

A 30,000-year paleotemperature record derived from noble gases dissolved in carbon-14-dated ground water indicates that the climate in lowland Brazil (Piaui Province, 7 degrees S, 41.5 degrees W; altitude, 400 meters) was 5.4 degrees +/- 0.6 degrees C cooler during the last glacial maximum than today. This result suggests a rather uniform cooling of the Americas between 40 degrees S and 40 degrees N. A 5.4 degrees C cooling of tropical South America is consistent with pollen records, snow line reconstructions, and strontium/calcium ratios and delta(18)O coral records but is inconsistent with the sea-surface temperature reconstruction of CLIMAP (Climate: Long-Range Investigation, Mapping and Prediction). On the basis of these results, it appears that the tropical Americas are characterized by a temperature sensitivity comparable to that found in higher latitudes.

The effect of changing land use on soil radiocarbon.

Most carbon budgets require greening of the terrestrial biosphere as a sink for some of the excess carbon dioxide produced by fossil fuel burning and deforestation. Much of this storage is thought to occur in soils, but running counter to this conclusion is the observation that cultivation has reduced the agricultural reservoir of soil humus. Radiocarbon measurements in agricultural soils lend support to this browning of agricultural lands. Moreover, the loss is from the fast cycling portion of the humus.

Paleotemperatures in the southwestern United States derived from noble gases in ground water.

A paleotemperature record based on measurements of atmospheric noble gases dissolved in ground water of the Carrizo aquifer (Texas) shows that the annual mean temperature in the southwestern United States during the last glacial maximum was about 5 degrees C lower than the present-day value. In combination with evidence for fluctuations in mountain snow lines, this cooling indicates that the glacial lapse rate was approximately the same as it is today. In contrast, measurements on deep-sea sediments indicate that surface temperatures in the ocean basins adjacent to our study area decreased by only about 2 degrees C. This difference between continental and oceanic records poses questions concerning our current understanding of paleoclimate and climate-controlling processes.

Carbon-14 in methane sources and in atmospheric methane: the contribution from fossil carbon.

Measurements of carbon-14 in small samples of methane from major biogenic sources, from biomass burning, and in "clean air" samples from both the Northern and Southern hemispheres reveal that methane from ruminants contains contemporary carbon, whereas that from wetlands, pat bogs, rice fields, and tundra is somewhat, depleted in carbon-14. Atmospheric (14)GH(4) seems to have increased from 1986 to 1987, and levels at the end of 1987 were 123.3 +/- 0.8 percent modern carbon (pMC) in the Northern Hemisphere and 120.0 +/- 0.7 pMC in the Southern Hemisphere. Model calculations of source partitioning based on the carbon-14 data, CH(4) concentrations, and delta(13)C in CH(4) indicate that 21 +/- 3% of atmospheric CH(4) was derived from fossil carbon at the end of 1987. The data also indicate that pressurized water reactors are an increasingly important source of (14)CH(4).

Gas exchange-wind speed relation measured with sulfur hexafluoride on a lake.

Gas-exchange processes control the uptake and release of various gases in natural systems such as oceans, rivers, and lakes. Not much is known about the effect of wind speed on gas exchange in such systems. In the experiment described here, sulfur hexafluoride was dissolved in lake water, and the rate of escape of the gas with wind speed (at wind speeds up to 6 meters per second) was determined over a 1-month period. A sharp change in the wind speed dependence of the gas-exchange coefficient was found at wind speeds of about 2.4 meters per second, in agreement with the results of wind-tunnel studies. However, the gas-exchange coefficients at wind speeds above 3 meters per second were smaller than those observed in wind tunnels and are in agreement with earlier lake and ocean results.

A Climatic Freshening of the Deep Atlantic North of 50{degrees}N over the Past 20 Years.

Observations made in summer 1981 show a significant and widespread decrease in salinity, averaging 0.02 per mil, in deep waters of the subpolar North Atlantic over the past two decades. This implies a relatively rapid response of deep water formation to climatic perturbation.

Fate of fossil fuel carbon dioxide and the global carbon budget.

The fate of fossil fuel carbon dioxide released into the atmosphere depends on the exchange rates of carbon between the atmosphere and three major carbon reservoirs, namely, the oceans, shallow-water sediments, and the terrestrial biosphere. Various assumptions and models used to estimate the global carbon budget for the last 20 years are reviewed and evaluated. Several versions of recent atmosphere-ocean models appear to give reliable and mutually consistent estimates for carbon dioxide uptake by the oceans. On the other hand, there is no compelling evidence which establishes that the terrestrial biomass has decreased at a rate comparable to that of fossil fuel combustion over the last two decades, as has been recently claimed.

Climatic change: are we on the brink of a pronounced global warming?

If man-made dust is unimportant as a major cause of climatic change, then a strong case can be made that the present cooling trend will, within a decade or so, give way to a pronounced warming induced by carbon dioxide. By analogy with similar events in the past, the natural climatic cooling which, since 1940, has more than compensated for the carbon dioxide effect, will soon bottom out. Once this happens, the exponential rise in the atmospheric carbon dioxide content will tend to become a significant factor and by early in the next century will have driven the mean planetary temperature beyond the limits experienced during the last 1000 years.

Floating glacial ice caps in the arctic ocean.

Two arguments are presented, one in favor of the existence of thicker ice in the Arctic Ocean during glacial time, and the other in favor of a full-fledged Arctic ice cap. The first is based on the Greenland air temperature record obtained from isotopic studies of the Camp Century ice core. The second is based on the oxygen isotope record of benthic foraminifera from a deep Pacific Ocean core.

Atmospheric carbon dioxide: its role in maintaining phytoplankton standing crops.

The rate of invasion of carbon dioxide into an artificially eutrophic Canadian Shield lake with insufficient internal sources of carbon was determined by two methods: measuring the carbon : nitrogen : phosphorus ratios of seston after weekly additions of nitrogen and phosphorus, and measuring the loss of radon-222 tracer from the epilimnion. Both methods gave an invasion rate of about 0.2 gram of carbon per square meter per day. The results demonstrate that invasion of atmospheric carbon dioxide may be sufficient to permit eutrophication of any body of water receiving an adequate supply of phosphorus and nitrogen.