Edward A. Boyle

Glacial/interglacial variations in atmospheric carbon dioxide.

Twenty years ago, measurements on ice cores showed that the concentration of carbon dioxide in the atmosphere was lower during ice ages than it is today. As yet, there is no broadly accepted explanation for this difference. Current investigations focus on the oceans ‘biological pump’, the sequestration of carbon in the ocean interior by the rain of organic carbon out of the surface ocean, and its effect on the burial of calcium carbonate in marine sediments. Some researchers surmise that the whole-ocean reservoir of algal nutrients was larger during glacial times, strengthening the biological pump at low latitudes, where these nutrients are currently limiting. Others propose that the biological pump was more efficient during glacial times because of more complete utilization of nutrients at high latitudes, where much of the nutrient supply currently goes unused. We present a version of the latter hypothesis that focuses on the open ocean surrounding Antarctica, involving both the biology and physics of that region.

On the Structure and Origin of Major Glaciation Cycles 1. Linear Responses to Milankovitch Forcing

Time series of ocean properties provide a measure of global ice volume and monitor key features of the wind-driven and density-driven circulations over the past 400,000 years. Cycles with periods near 23,000, 41,000, and 100,000 years dominate this climatic narrative. When the narrative is examined in a geographic array of time series, the phase of each climatic oscillation is seen to progress through the system in essentially the same geographic sequence in all three cycles. We argue that the 23,000- and 41,000-year cycles of glaciation are continuous, linear responses to orbitally driven changes in the Arctic radiation budget; and we use the phase progression in each climatic cycle to identify the main pathways along which the initial, local responses to radiation are propagated by the atmosphere and ocean. Early in this progression, deep waters of the Southern Ocean appear to act as a carbon trap. To stimulate new observations and modeling efforts, we offer a process model that gives a synoptic view of climate at the four end-member states needed to describe the systems evolution, and we propose a dynamic system model that explains the phase progression along causal pathways by specifying inertial constants in a chain of four subsystems. “Solutions to problems involving systems of such complexity are not born full grown like Athena from the head of Zeus. Rather they evolve slowly, in stages, each of which requires a pause to examine data at great lengths in order to guarantee a sure footing and to properly choose the next step.” —Victor P. Starr

On the structure and origin of major glaciation cycles 2. The 100,000‐year cycle

Climate over the past million years has been dominated by glaciation cycles with periods near 23,000, 41,000, and 100,000 years. In a linear version of the Milankovitch theory, the two shorter cycles can be explained as responses to insolation cycles driven by precession and obliquity. But the 100,000-year radiation cycle (arising from eccentricity variation) is much too small in amplitude and too late in phase to produce the corresponding climate cycle by direct forcing. We present phase observations showing that the geographic progression of local responses over the 100,000-year cycle is similar to the progression in the other two cycles, implying that a similar set of internal climatic mechanisms operates in all three. But the phase sequence in the 100,000-year cycle requires a source of climatic inertia having a time constant (similar to 15,000 years) much larger than the other cycles (similar to 5,000 years). Our conceptual model identifies massive northern hemisphere ice sheets as this larger inertial source. When these ice sheets, forced by precession and obliquity, exceed a critical size, they cease responding as linear Milankovitch slaves and drive atmospheric and oceanic responses that mimic the externally forced responses. In our model, the coupled system acts as a nonlinear amplifier that is particularly sensitive to eccentricity-driven modulations in the 23,000-year sea level cycle. During an interval when sea level is forced upward from a major low stand by a Milankovitch response acting either alone or in combination with an internally driven, higher-frequency process, ice sheets grounded on continental shelves become unstable, mass wasting accelerates, and the resulting deglaciation sets the phase of one wave in the train of 100,000-year oscillations. Whether a glacier or ice sheet influences the climate depends very much on the scale....The interesting aspect is that an effect on the local climate can still make an ice mass grow larger and larger, thereby gradually increasing its radius of influence.

Comparison of Atlantic and Pacific paleochemical records for the last 215,000 years: changes in deep ocean circulation and chemical inventories

Abstract Detailed Cd/Ca and δ 13 C data have been obtained for benthic foraminifera from western North Atlantic and Equatorial Pacific sediment cores. In the modern ocean, both tracers are closely linked to nutrient distributions. The sedimentary records for both tracers indicate that bottom waters overlying the Atlantic site have been nutrient-depleted relative to those at the Pacific site over the last 215,000 years. From this evidence it is reasonable to infer that there has been a continuous net flux of nutrient-depleted water from the western North Atlantic into the Pacific. This exchange has undergone significant fluctuations, with the export of nutrient-depleted Atlantic water diminishing by about a factor of two relative to the inflow from Southern Ocean sources. Over the last 215,000 years, carbon isotope fluctuations in both regions are dominated by variable storage of isotopically light carbon on continents with a lesser contribution from these deep ocean circulation changes. The cadmium signal in the North Atlantic is dominated by changes in deep ocean circulation patterns; cadmium shows less variability in the Pacific which may reflect changes in the global average cadmium content or minor changes in deep Pacific circulation patterns. Using these records to estimate global averages, it appears that glacial ocean water had 22% more Cd and 0.46‰ less 13 C than the modern ocean. These numbers are estimates which may be revised as more data become available, although they are not likely to be as much as 20% in error for Cd or 0.2‰ for 13 C. Relative North Atlantic Deep Water (NADW) formation rates are modulated with a significant 41 kyr periodicity linked to obliquity-induced variations in high latitude insolation; NADW lags 8 ± 2 kyr behind insolation, however.

The mechanism of iron removal in estuaries

Abstract A survey of U.S. east coast estuaries confirms that large-scale rapid removal of iron from river water is a general phenomenon during estuarine mixing. The river-borne ‘dissolved’ iron consists almost entirely of mixed iron oxide-organic matter colloids, of diameter less than 0.45 μm, stabilized by the dissolved organic matter. Precipitation occurs on mixing because the seawater cations neutralize the negatively charged iron-bearing colloids allowing flocculation. The process has been duplicated in laboratory experiments using both natural filtered and unfiltered river water and a synthetic colloidal goethite in 0.05 μm filtered water. The colloidal nature of the iron has been further confirmed by ultracentrifugation and ultrafiltration. A major consequence of the precipitation phenomena is to reduce the effective input of ‘dissolved’ iron to the ocean by about 90% of the primary river value, equivalent to a concentration of less than 1 μmol per liter of river water.

The removal of dissolved humic acids and iron during estuarine mixing

Abstract The estuarine chemistry of dissolved humic acids was determined by carrying out both field and laboratory studies. These approaches were combined in an investigation of the Amazon estuary while laboratory mixing experiments were performed using filtered (0.45−0.001 μm) river water fractions of the Water of Luce (Scotland). The results demonstrate that a small fraction of river dissolved organic matter is preferentially and rapidly flocculated during estuarine mixing. This fraction is the high molecular weight component of dissolved humic acids (0.45−0.1 μm filtered). Approximately 60–80% of the dissolved humic acid in these rivers flocculates during estuarine mixing. This represents a removal of only 3–6% of river dissolved organic matter and is responsible for the non-conservative behaviour of dissolved humic acid in the Amazon estuary even though total dissolved organic carbon appears conservative. The salinity dependence with which humic acid flocculates in estuaries is similar to that of iron. This implies that both constituents may be removed from river water by a common mechanism of colloid flocculation.

Deep Circulation of the North Atlantic over the Last 200,000 Years: Geochemical Evidence

Variations in the cadmium/calcium ratio of North Atlantic Deep Water are recorded in the fossil shells of benthic foraminifera. The oceanic distribution of cadmium is similar to that of the nutrients, hence the cadmium/calcium ratio in shells records temporal variations in nutrient distributions. Data from a North Atlantic sediment core show that over the past 200,000 years there has been a continuous supply of nutrient-depleted waters into the deep North Atlantic. The intensity of this source relative to nutrient-enriched southern waters diminished by about a factor of 2 during severe glaciations. This evidence combined with carbon isotope data indicates that the continental carbon inventory may have been less variable than previously suggested.

Temperature control on the incorporation of magnesium, strontium, fluorine, and cadmium into benthic foraminiferal shells from Little Bahama Bank: Prospects for thermocline paleoceanography

Surface sediments from Little Bahama Bank (LBB ), intersecting the subtropical thermocline, were used to assess the influence of temperature on the incorporation of Mg, Sr, F, and Cd into shells of benthic foraminifera. Samples were obtained from twelve ☐ cores along the southern slope of LBB, covering a temperature range of 18-4.5°C between 301 and 1585 m. We studied the composition of ten calcitic and one aragonitic species, which are often used in paleochemical reconstructions. Mg/Ca ratios decrease with increasing water depth in all benthic species, both with calcitic and aragonitic mineralogy, showing a strong correlation with water temperature. Similar decrease is seen in Sr/Ca but with no correlation with temperature. None of the benthic species studied here exhibits a depth or temperature related change in F/Ca. Similar trends are observed when using an ocean-wide dataset, which includes shallow and deep core tops (300–5000 m). We suggest that temperature is the primary control on the Mg content of benthic foraminifera. Based on inorganic precipitation experiments and thermodynamic considerations, presented here, a 30–40% decrease in the Mg distribution coefficient in calcite may be expected as a result of a temperature change from 25°C to 5°C, which is about half the observed change in LBB. A calibration curve applied to C. pachyderma data from core tops along the slope of Little Bahama Bank suggests that water temperature may be inferred from Mg/Ca ratios with an uncertainty of about ±0.8°C. Therefore, the Mg content of benthic foraminifera may provide a new, independent temperature proxy for studying shallow waters paleoceanography. The linear decrease in Sr/Ca with increasing depth is not correlated with temperature; the trend is constant from the ocean surface down to 5 km, suggesting that pressure related effects on the calcification process are a more likely explanation than post-depositional dissolution. Mg/Ca ratios in aragonitic shells of H. elegans covary with temperature, in accord with recent observations from corals. In contrast, the Sr and F chemistry of H. elegans is very different than that of corals and inorganically precipitated aragonites. The disparities between the elemental composition of biogenic and inorganic phases and the large intergeneric and interspecific differences observed both in planktonic and benthic foraminifera implicate temperature related physiological processes in regulating the coprecipitation of elements in foraminiferal shells. Our work demonstrates that Cd/Ca ratios of shallow calcitic species reflect the vertical distribution of nutrients; no significant influence of temperature on the partitioning of Cd into the shells was found. Our data extend the previous deep water calibration (Boyle, 1992), thereby allowing for the reconstruction of the nutrient chemistry of shallow thermocline waters.

On the chemical mass-balance in estuaries

Abstract A general model is presented for mixing processes between river and ocean water in which are established criteria for the identification of any non-conservative behavior of the dissolved constituents involved. A review of previous data shows that in no case has removal of silica been demonstrated unambiguously in estuarine regimes. New data for iron which show highly non-conservative behavior are used in an example of the application of the model.

Cadmium, zinc, copper, and barium in foraminifera tests

The concentrations of cadmium, zinc, copper and barium have been determined on 2-mg samples of single-species foraminifera populations. Cleaning techniques were tested using North Atlantic core tops, and followed by a detailed downcore study for the last 30,000 years in South Atlantic core V22-174. Raw foram tests cleaned by crushing followed by ultrasonic removal of fine-grained material, and dissolved in a pH 5.5 acetate buffer, contain appreciable amounts of trace elements associated with ferromanganese and alumino-silicate contaminants. A reductive/complexing cleaning treatment reduces ferromanganese contamination by 1–2 orders of magnitude. Acetate buffers at pH 5.5 complex iron and raise the solubility of ferromanganese oxides; these buffers are unsuitable for separating carbonate lattice-bound trace elements from the fraction associated with ferromanganese phases. Improved mechanical and ultrasonic reductive cleaning combined with a mild dissolution in distilled water under 1 atm.PCO2 reduces contaminant levels another order of magnitude. The Cd and Zn concentrations (order 10−8 mole Cd/mole Ca and 10−5 mole Zn/mole Ca) of species with low surface area show an increase with decreasing isotopic temperatures. This increase is consistent with the increasing concentrations of these metals from low values in surface waters to higher values at depth. The variance of Cd and Zn over the last 30,000 years in the central South Atlantic is consistent with the probable variability of the dissolved trace elements at the calcification levels of the species analyzed. Cu and Ba are irreproducible and probably sensitive to residual contaminant phases. The trace element content of the tests differs from levels observed in a recent coprecipitation study. Foraminifera may be a significant vector in zinc cycling in the ocean.