Daniel C. McCorkle

Marine calcifiers exhibit mixed responses to CO2-induced ocean acidification

Anthropogenic elevation of atmospheric carbon dioxide ( p CO2) is making the oceans more acidic, thereby reducing their degree of saturation with respect to calcium carbonate (CaCO3). There is mounting concern over the impact that future CO2-induced reductions in the CaCO3 saturation state of seawater will have on marine organisms that construct their shells and skeletons from this mineral. Here, we present the results of 60 d laboratory experiments in which we investigated the effects of CO2-induced ocean acidification on calcification in 18 benthic marine organisms. Species were selected to span a broad taxonomic range (crustacea, cnidaria, echinoidea, rhodophyta, chlorophyta, gastropoda, bivalvia, annelida) and included organisms producing aragonite, low-Mg calcite, and high-Mg calcite forms of CaCO3. We show that 10 of the 18 species studied exhibited reduced rates of net calcification and, in some cases, net dissolution under elevated p CO2. However, in seven species, net calcification increased under the intermediate and/or highest levels of p CO2, and one species showed no response at all. These varied responses may reflect differences amongst organisms in their ability to regulate pH at the site of calcification, in the extent to which their outer shell layer is protected by an organic covering, in the solubility of their shell or skeletal mineral, and in the extent to which they utilize photosynthesis. Whatever the specific mechanism(s) involved, our results suggest that the impact of elevated atmospheric p CO2 on marine calcification is more varied than previously thought.

Natural abundance-level measurement of the nitrogen isotopic composition of oceanic nitrate: an adaptation of the ammonia diffusion method

We have adapted the “ammonia diffusion” method of nitrate extraction for natural-abundance level nitrogen isotopic measurement of oceanic nitrate. The method involves: (1) sample concentration (by boiling or evaporation); (2) conversion of nitrate to ammonia using Devardas alloy; and (3) the gas-phase diffusion of ammonia onto an acidified glass fiber disk which is sandwiched between two porous Teflon membranes. We have investigated the conditions necessary to effect complete ammonia recovery from natural seawater samples and the use of Devardas alloy under these conditions. In addition, we have characterized the blanks in this method and designed a protocol to minimize them. Here, we report our protocol for nitrate extraction from seawater and provide an explanation of the protocol based on our method development work. To demonstrate the performance of the method, we present nitrate nitrogen isotopic data from nitrate standard additions to Sargasso Sea surface water and from several Southern Ocean depth profiles. The nitrate extraction method gives highly reproducible, complete recovery of nitrate and a standard deviation for isotopic analysis of < 0.2%c down to 5 μM nitrate (or lower). Replicate extractions of a nitrate standard added to Sargasso Sea surface water demonstrate agreement between the isotopic composition of the added and recovered N, with the extraction blank causing a ≤ 0.3%. discrepancy for 5 μM nitrate. The blanks inherent in the extraction procedure are from Devardas alloy and seawater dissolved organic nitrogen (“DON”). The N blank of the Devardas alloy reagent depends on brand and lot number. The Devardas alloy which we are currently using results in a blank of ~ 0.4 nmol N per 100 ml of seawater (effectively 0.4 μM). An isotopic correction is made for this blank. For standard incubation conditions, stored Woods Hole seawater (with ~ 10 μM DON) gives a ~ 0.6 μM DON blank, while stored Sargasso Sea (with ~ 6 μm DON) surface water gives a DON blank of 0.3–0.5 μM. The DON blank appears to cause the ≤ 0.3%. difference between the measured and actual isotopic composition of nitrate added to Sargasso Sea surface water at the 5 μM nitrate level. We discuss several ways to lower the DON blank for samples in which the DON concentration is high relative to the nitrate concentration. The nitrogen isotopic data from several Southern Ocean profiles, in conjunction with the other results presented in this paper, demonstrate the consistency of the data produced by the ammonia diffusion method. The ammonia diffusion-based protocol is more reliable and allows for better precision than the nitrate reduction/ammonia distillation method (Cline and Kaplan, 1975) in our hands. While the samples have an incubation time of 4 days or longer, we find that the diffusion method allows for higher throughput than the distillation method because samples can be run conveniently in large batches.

The δ15N of nitrate in the southern ocean: Consumption of nitrate in surface waters

We report nitrogen isotope data for nitrate from transects of hydrocast and surface samples collected in the eastern Indian and Pacific sectors of the Southern Ocean, focusing here on the data from the upper water column to study the effect of nitrate consumption by phytoplankton. The δ15N of nitrate increases by 1–2‰ from deep water into the Antarctic summertime surface layer, due to kinetic isotopic fractionation during nitrate uptake. Estimation of the nitrate uptake isotope effect from Antarctic depth profiles yields values in the range of 5–6‰ in east Indian sector and 4–5‰ in the east Pacific sector. Surface transect data from the Pacific sector also yield values of 4–5‰. The major uncertainty in the profile-based estimation of the isotope effect involves the δ15N of nitrate from the temperature minimum layer below the summertime Antarctic surface layer, which deviates significantly from the predictions of simple models of isotope fractionation. For the Subantarctic surface, it is possible to distinguish between nitrate supplied laterally from the surface Antarctic and nitrate supplied vertically from the Subantarctic thermocline because of the distinctive relationships between the δ15N and concentration of nitrate in these two potential sources. Our Subantarctic samples, collected during the summer and fall, indicate that nitrate is supplied to the Subantarctic surface largely by northward transport of Antarctic surface water. Isotopic data from the Pacific sector of the Subantarctic suggest an isotope effect of 4.5‰, indistinguishable from the Antarctic estimates in this sector.

Geochemistry of barium in marine sediments : Implications for its use as a paleoproxy

Abstract Variations in the accumulation rate of barium in marine sediments are thought to be indicative of variations in marine biological productivity through time. However, the use of Ba as a proxy for paleoproductivity is partly dependent upon its being preserved in the sediment record in a predictable or consistent fashion. Arguments in favor of high Ba preservation are partly based on the assumption that sediment porewaters are generally at saturation with respect to pure barite. The idea is that because nondetrital sedimentary Ba predominantly exists as barite, porewater saturation would promote burial. We present sediment porewater, sediment solid phase, and benthic incubation chamber data suggesting that solid-phase Ba preservation may be compromised in some geochemical settings. We propose that under suboxic diagenetic conditions, characterized by low bottom water oxygen and high organic carbon respiration rates, Ba preservation may be reduced. Independent of the mechanism, if this assertion is true, then it becomes important to know when the Ba record is unreliable. We present evidence demonstrating that the sedimentary accumulation of authigenic U may serve as a proxy for when the Ba record is unreliable. We then provide an example from the Southern Ocean during the last glacial period where high authigenic U concentrations coincide with high Pa:Th ratios and high accumulation rates of biogenic opal, but we find low accumulation rates of sedimentary Ba. Thus, for the study sites presented here during the last glacial, we conclude that Ba is an unreliable productivity proxy.

Carbon fluxes and burial rates over the continental slope and rise off Central California with implications for the global carbon cycle

The present invention relates to brown cigarette paper having reduced gas phase constituents during pyrolysis wherein the paper which has been stained with humic acid or salts thereof is further treated by washing with water in an amount effective to reduce the amount of water-soluble alkali metal salts present in the paper.

Ocean warming slows coral growth in the central Red Sea.

Red Sea Coral Decline Large, rapid sea surface temperature rises of 1°C or greater typically cause bleaching of corals. Cantin et al. (p. 322) show that smaller temperature increases also have detrimental effects on corals, dramatically reducing their rates of calcification and skeletal extension. Corals in the Red Sea, where water temperatures have risen by 0.4 to 1°C since the mid-1970s, have declined in skeletal extension by about 30%, and decreased in calcification rates by around 18% since 1998. This finding suggests that we may see an end to coral growth in the Red Sea this century. Rising summertime sea surface temperatures are slowing the rate of growth of healthy corals in the Red Sea. Sea surface temperature (SST) across much of the tropics has increased by 0.4° to 1°C since the mid-1970s. A parallel increase in the frequency and extent of coral bleaching and mortality has fueled concern that climate change poses a major threat to the survival of coral reef ecosystems worldwide. Here we show that steadily rising SSTs, not ocean acidification, are already driving dramatic changes in the growth of an important reef-building coral in the central Red Sea. Three-dimensional computed tomography analyses of the massive coral Diploastrea heliopora reveal that skeletal growth of apparently healthy colonies has declined by 30% since 1998. The same corals responded to a short-lived warm event in 1941/1942, but recovered within 3 years as the ocean cooled. Combining our data with climate model simulations by the Intergovernmental Panel on Climate Change, we predict that should the current warming trend continue, this coral could cease growing altogether by 2070.

The isotopic composition of diatom‐bound nitrogen in Southern Ocean sediments

Treatment of diatom microfossils from Southern Ocean sediments with hot perchloric acid leaves a “diatom-bound” N fraction which is 0–4‰ lower in δ15N than the bulk sediment, typically 3‰ lower in recent Antarctic diatom ooze. Results from Southern Ocean surface sediments indicate that early diagenetic changes in bulk sediment N content and δ15N are not reflected in diatom-bound N, suggesting that diatom-bound N is physically protected from early diagenesis by the microfossil matrix. A meridional transect of multicores from the Indian sector of the Southern Ocean shows a northward increase in the δ15N of diatom-bound N, suggesting that diatom-bound δ15N, like bulk sedimentary δ15N, varies with nitrate utilization in the overlying surface waters. The δ15N of diatom-bound N is 3–4‰ higher in glacial age Antarctic sediments than in Holocene sediments, supporting the hypothesis, previously based on bulk sediment δ15N, that nitrate utilization in the surface Antarctic was higher during the last ice age. While there are important uncertainties, the inferred range of utilization changes could potentially explain the entire ∼80 ppm amplitude of observed glacial/interglacial variations in atmospheric CO2.

The δ15N of nitrate in the Southern Ocean: Nitrogen cycling and circulation in the ocean interior

We report analyses of the nitrogen isotopic composition of nitrate in the eastern Indian and Pacific sectors of the Southern Ocean. In this paper, we focus on the subsurface data as well as data from the deep waters of other ocean basins. Nitrate δ15N is relatively invariant in much of the abyssal ocean (i.e., below 2.5 km), with a value of 4.8±0.2‰ observed in Lower Circumpolar Deep Water, North Atlantic Deep Water, and central Pacific deep water. The isotopic invariance of deep ocean nitrate stems fundamentally from the completeness of nitrate utilization in most of the global surface ocean, the Southern Ocean surface being an important exception. In the Subantarctic Zone (north of the Polar Frontal Zone) the nitrate δ15N of Upper Circumpolar Deep Water is ∼0.7‰ greater than that of Lower Circumpolar Deep Water. This isotopic enrichment appears to result from denitrification in the low-latitude water masses with which Upper Circumpolar Deep Water communicates. The isotopic enrichment of Upper Circumpolar Deep Water is diminished in the Antarctic, probably because of the remineralization of sinking organic N, which has a low δ15N in the Antarctic. Relative to the other water masses of the Southern Ocean, the Subantarctic thermocline has a very low nitrate δ15N for its nitrate concentration because of exchange with the low-latitude thermocline, where this isotopic signature appears to originate. This signature of the low-latitude thermocline has two probable causes: (1) mixing with low-nitrate surface water and (2) the oxidation of newly fixed N.

Evidence of a dissolution effect on benthic foraminiferal shell chemistry: δ13C, Cd/Ca, Ba/Ca, and Sr/Ca results from the Ontong Java Plateau

Core-top benthic foraminifera (Cibicidoides wuellerstorfi) from a depth transect of Soutar box cores from the Ontong-Java Plateau (1.6–4.4 km) were analyzed for cadmium, barium, and strontium (Cd/Ca, Ba/Ca, and Sr/Ca) and for their stable isotopic composition (δ13C and δ18O). We also measured bottom water δ13C, Cd, and Ba at these sites. Foraminiferal δ13C values remain roughly constant over the entire depth range while bottom water δ13C values increase slightly, such that the δ13C difference between C. wuellerstorfi and bottom water ranges from about +0.2 ‰ in cores above 2.5 km to about −0.2 ‰ in cores below 4 km. This apparent depth dependence has not been previously reported, but this range in Δδ13C values is comparable to the uncertainty in published δ13C calibration studies. We observe strong decreases in foraminiferal Cd/Ca, Ba/Ca, and Sr/Ca ratios (50, 25, and 15 percent, respectively) at water depths greater than about 2.5 km. These decreases are substantially larger than the corresponding changes in bottom water trace element concentrations, and they are not correlated with variations in pore water Cd and Ba concentrations at these sites. Together, the foraminiferal and bottom water Cd/Ca, Ba/Ca, and Sr/Ca data yield decreases in the apparent distribution coefficients for these metals into calcite with increasing water depth, again a pattern which has not been previously reported. These results when combined with the data from published core-top calibration studies suggest that a preferential loss of Cd, Ba, and Sr occurs during the dissolution of benthic foraminiferal calcite on the sea floor and raise the possibility of a dissolution-driven decrease in benthic foraminiferal δ13C values.

Changes in the δ13C of surface water particulate organic matter across the subtropical convergence in the SW Indian Ocean

We have measured the carbon isotopic composition of particulate organic matter suspended in surface waters (POM) between 59°S and 30°S in the SW Indian Ocean during the austral summer. In an attempt to further document the pattern and causes of covariance between POC-δ13C and [CO2aq], we concurrently measured surface water pCO2, temperature, salinity, nitrate concentration, POM concentration, chlorophyll a and the δ13C of total dissolved inorganic carbon. While we found the previously reported general negative correlation between POC-δ13C and [CO2aq], we also observed a prominent maximum in POC-δ13C in the region immediately north of the Subtropical Convergence, coinciding with a maximum in [POM] and chlorophyll a, and with a minimum in pCO2. The increase in POC-δ13C between 59°S and the Subtropical Convergence is consistent with the trend expected if [CO2aq] were the main factor controlling the isotopic composition of POM. In contrast, data from the region north of the Subtropical Convergence clearly illustrate that POC-δ13C can also vary independently of [CO2aq] as a 5 per mil decrease in POC-δ13C was found in a region characterized by nearly constant [CO2aq]. We review several physiological factors which may account for these observations and discuss their implications for paleoceanographic reconstruction of [CO2aq] from the carbon isotopic composition of sedimentary organic matter.