David W. Hastings

Foraminiferal magnesium in Globeriginoides sacculifer as a paleotemperature proxy

Foraminiferal magnesium shows increasing promise as a paleothermometer, but the accuracy and precision are limited by biases introduced by partial dissolution, salinity variations, Mg-rich gametogenic calcite, and contaminant phases. We improved cleaning methods and reduced errors introduced by partial dissolution by sampling from well-preserved cores in the equatorial Atlantic and the Caribbean Sea with different dissolution histories. All cores reveal a synchronous 25% increase in Mg/Ca from the stage 2/3 boundary to the Holocene core top, indicating that dissolution is not a controlling factor. Modern temperatures estimated from core top Mg/Ca are 24.5°–25.0°C, equal to mean annual water temperatures at 50–100 m. We estimate that sea surface temperature increased by 2.6°C (±1.3) from the last glacial maximum to the Holocene. Holocene values were comparable to those during isotope stage 5e. Our data indicate that biases from contaminant phases and partial dissolution can be reduced. This paleothermometer holds promise if uncertainties introduced by salinity variations and gametogenic calcite can be constrained.

Phasing of deglacial warming and Laurentide Ice Sheet meltwater in the Gulf of Mexico

Evidence is emerging that the tropical climate system played a major role in global climate change during the last deglaciation. However, existing studies show that deglacial warming was asyn- chronous across the tropical band, complicating the identification of causal mechanisms. The Orca Basin in the northern Gulf of Mexico is ideally located to record subtropical Atlantic sea-surface temperature (SST) warming in relation to meltwater input from the Laurentide Ice Sheet. Paired d 18 O and Mg/Ca data on the planktonic foraminifer Globigerinoides ruber from core EN32-PC6 are used to separate deglacial changes in SST and d 18 O of sea- water. SST as calculated from Mg/Ca data increased by .3 8C from ca. 17.2 to 15.5 ka in association with Heinrich event 1 and was not in phase with Greenland air temperature. Subtracting tem- perature effects from d 18 O values in G. ruber reveals two excur- sions representing Laurentide meltwater input to the Gulf of Mex- ico, one of .1.5‰ from ca. 16.1 to 15.6 ka and a second major spike of .2.5‰ from ca. 15.2 to 13.0 ka that encompassed melt- water pulse 1A and peaked ca. 13.8 ka during the Bolling-Allerod. Conversion to salinity through the use of a Laurentide meltwater end member of 225‰ indicates that near-surface salinity de- creased by 2‰-4‰ during these spikes. These results suggest that Gulf of Mexico SST warming preceded peak Laurentide Ice Sheet decay and the Bolling-Allerod interval by .2 k.y. and that heat was retained in the subtropical Atlantic during Heinrich event 1, consistent with modulation of deglacial climate by thermohaline circulation.

Interlaboratory comparison study of calibration standards for foraminiferal Mg/Ca thermometry

An interlaboratory study of Mg/Ca and Sr/Ca ratios in three commercially available carbonate reference materials (BAM RS3, CMSI 1767, and ECRM 752-1) was performed with the participation of 25 laboratories that determine foraminiferal Mg/Ca ratios worldwide. These reference materials containing Mg/Ca in the range of foraminiferal calcite (0.8 mmol/mol to 6 mmol/mol) were circulated with a dissolution protocol for analysis. Participants were asked to make replicate dissolutions of the powdered samples and to analyze them using the instruments and calibration standards routinely used in their laboratories. Statistical analysis was performed in accordance with the International Standardization Organization standard 5725, which is based on the analysis of variance (ANOVA) technique. Repeatability (RSDr%), an indicator of intralaboratory precision, for Mg/Ca determinations in solutions after centrifuging increased with decreasing Mg/Ca, ranging from 0.78% at Mg/Ca = 5.56 mmol/mol to 1.15% at Mg/Ca = 0.79 mmol/mol. Reproducibility (RSDR%), an indicator of the interlaboratory method precision, for Mg/Ca determinations in centrifuged solutions was noticeably worse than repeatability, ranging from 4.5% at Mg/Ca = 5.56 mmol/mol to 8.7% at Mg/Ca = 0.79 mmol/mol. Results of this study show that interlaboratory variability is dominated by inconsistencies among instrument calibrations and highlight the need to improve interlaboratory compatibility. Additionally, the study confirmed the suitability of these solid standards as reference materials for foraminiferal Mg/Ca (and Sr/Ca) determinations, provided that appropriate procedures are adopted to minimize and to monitor possible contamination from silicate mineral phases.

Oxidation of manganese by spores of a marine bacillus: Kinetic and thermodynamic considerations☆

Abstract The catalytic properties of spores of a marine Bacillus known to oxidize divalent manganese were used to perform laboratory Mn(II) oxidation experiments at environmental conditions of pH and Mn(II) concentration. We found that at pH 7.8 the initial kinetics of Mn(II) oxidation facilitated by the spores was four orders of magnitude greater than that which would be expected for abiotic autocatalysis on a colloidal MnO 2 surface. The rate progressively decreased as the spores became coated with manganese oxide, eventually becoming very near that predicted for abiotic surface catalysis. Transmission electron microscopic observations and oxidation state measurements of solids precipitated at pH 7.5 and [Mn(II)] 3 O 4 or MnO x where x = 1.33) which aged to more highly oxidized MnO 2 ( x = 1.9) in the time scale of weeks. By utilizing spores to catalyze the oxidation rate, we were able to maintain our experimental system within the seawater range of pH and Mn(II) where highly oxidized manganese oxide precipitates are thermodynamically stable. In doing so we obtained, for the first time, laboratory precipitates with oxidation states similar to that found in marine particulate material. These results suggest that the concentration of manganese in seawater and the oxidation state of marine manganese oxides are controlled by the rapid precipitation of Mn 3 O 4 , which can be microbially mediated, followed by the disproportionation to MnO 2 .

A century-scale record of the preservation of chlorophyll and its transformation products in anoxic sediments

Abstract We have determined the chlorophyll pigment composition by liquid chromatography (LC) and LC/MS/MS in a 1.45-m long freeze core, representing 157 years of annually varved sedimentation, from Saanich Inlet, B.C, Canada. We investigated the very early diagenetic processes of chlorophyll a alteration in these anoxic sediments and the possible implications for palaeoproductivity studies. Excellent preservation of pigments is indicated by high total pigment concentrations, and the presence of labile compounds such as chlorophyllide a. The lack of systematic down core changes in both the total pigment concentration and the chlorin composition indicates that no detectable alteration of the pigment composition has occurred during the past 157 years. The sedimentary pigment composition is the result of processes occurring in the water column, or within few months after deposition. Chlorophyll derivatives corresponding to different diagenetic processes have distinct down core profiles. Profiles of compounds related to grazing activity steryl pyrophaeophorbide esters (SPE) and pyrophaeophytin a, are very similar. In contrast, dephytylated compounds (chlorophyllide a and phaeophorbide a), which are related to chlorophyllase activity during the degradation of ungrazed diatom cells, show an independent pattern. Quantifying pigment composition in Saanich Inlet sediments can help constrain processes regarding the transport of algal pigments to the sediments.

Vanadium in foraminiferal calcite: Evaluation of a method to determine paleo-seawater vanadium concentrations

We assess the potential of using foraminiferal calcite as a paleoceanographic indicator of seawater V concentrations. Laboratory culture experiments show that living benthic and planktonic foraminifera incorporate V into their test in direct proportion to seawater concentrations. Distribution coefficients relative to the culture solution are D = 2.1 × 10−3 and 2.8 × 10−3 for G. calida and A. lobifera, respectively. We use a cleaning procedure that effectively removes most V-rich contaminant phases from foraminiferal calcite preserved in the fossil record including organic matter and MnFe oxyhydroxides. MnCO3 overgrowths cannot be eliminated. Since V is conservative in the ocean, foraminiferal calcite recently accreted and found in surface sediment samples should have the same V content if this tracer accurately reflects seawater concentrations. V /Ca values for the same species of foraminifera are constant for core-top samples collected above the foraminiferal lysocline in different ocean basins. The mean distribution coefficients relative to seawater are D = 5.8 (± 1.0) × 10−3, 10.3 (±0.7) × 10−3 and 32 (+2.5) X 10−3 for G. sacculifer, G. tumida, and C. wuellerstorfi, respectively. These differences suggest that V incorporation is species dependent. Core-top analyses along two submarine rises in the Equatorial Atlantic and Pacific oceans indicate significant dissolution effects. With increasing depth of deposition, and thus more extensive partial dissolution of the test, VCa decreases by a factor of three in G. tumida, increases by up to a factor of four in G. sacculifer, and increases by a factor of two in C. wuellerstorfi. No exchange between foraminiferal V and detrital V in sediments is observed over an interval of 200 kyr.

Hydrocarbons in Deep-Sea Sediments following the 2010 Deepwater Horizon Blowout in the Northeast Gulf of Mexico

The Deepwater Horizon (DWH) spill released 4.9 million barrels of oil into the Gulf of Mexico (GoM) over 87 days. Sediment and water sampling efforts were concentrated SW of the DWH and in coastal areas. Here we present geochemistry data from sediment cores collected in the aftermath of the DWH event from 1000 – 1500 m water depth in the DeSoto Canyon, NE of the DWH wellhead. Cores were analyzed at high-resolution (at 2 mm and 5 mm intervals) in order to evaluate the concentration, composition and input of hydrocarbons to the seafloor. Specifically, we analyzed total organic carbon (TOC), aliphatic, polycyclic aromatic hydrocarbon (PAHs), and biomarker (hopanes, steranes, diasteranes) compounds to elucidate possible sources and transport pathways for deposition of hydrocarbons. Results showed higher hydrocarbon concentrations during 2010-2011 compared to years prior to 2010. Hydrocarbon inputs in 2010-2011 were composed of a mixture of sources including terrestrial, planktonic, and weathered oil. Our results suggest that after the DWH event, both soluble and highly insoluble hydrocarbons were deposited at enhanced rates in the deep-sea. We proposed two distinct transport pathways of hydrocarbon deposition: 1) sinking of oil-particle aggregates (hydrocarbon-contaminated marine snow and/or suspended particulate material), and 2) advective transport and direct contact of the deep plume with the continental slope surface sediments between 1000-1200 m. Our findings underline the complexity of the depositional event observed in the aftermath of the DWH event in terms of multiple sources, variable concentrations, and spatial (depth-related) variability in the DeSoto Canyon, NE of the DWH wellhead.

Sedimentation Pulse in the NE Gulf of Mexico following the 2010 DWH Blowout

The objective of this study was to investigate the impacts of the Deepwater Horizon (DWH) oil discharge at the seafloor as recorded in bottom sediments of the DeSoto Canyon region in the northeastern Gulf of Mexico. Through a close coupling of sedimentological, geochemical, and biological approaches, multiple independent lines of evidence from 11 sites sampled in November/December 2010 revealed that the upper ~1 cm depth interval is distinct from underlying sediments and results indicate that particles originated at the sea surface. Consistent dissimilarities in grain size over the surficial ~1 cm of sediments correspond to excess 234Th depths, which indicates a lack of vertical mixing (bioturbation), suggesting the entire layer was deposited within a 4–5 month period. Further, a time series from four deep-sea sites sampled up to three additional times over the following two years revealed that excess 234Th depths, accumulation rates, and 234Th inventories decreased rapidly, within a few to several months after initial coring. The interpretation of a rapid sedimentation pulse is corroborated by stratification in solid phase Mn, which is linked to diagenesis and redox change, and the dramatic decrease in benthic formanifera density that was recorded in surficial sediments. Results are consistent with a brief depositional pulse that was also reported in previous studies of sediments, and marine snow formation in surface waters closer to the wellhead during the summer and fall of 2010. Although sediment input from the Mississippi River and advective transport may influence sedimentation on the seafloor in the DeSoto Canyon region, we conclude based on multidisciplinary evidence that the sedimentation pulse in late 2010 is the product of marine snow formation and is likely linked to the DWH discharge.

High precision glacial–interglacial benthic foraminiferal Sr/Ca records from the eastern equatorial Atlantic Ocean and Caribbean Sea

Abstract Glacial–interglacial variation in the marine Sr/Ca ratio has important implications for coral Sr thermometry [J.W. Beck et al., Science 257 (1992) 644–647]. A possible variation of 1–3% was proposed based on ocean models [H.M. Stoll and D.P. Schrag, Geochim. Cosmochim. Acta 62 (1998) 1107–1118]. Subsequently, studies have used fossil foraminifera to test this prediction [P.A. Martin et al., Geochem. Geophys. Geosyst. 1 (1999); H.M. Stoll et al., Geochim. Cosmochim. Acta 63 (1999) 3535–3547; H. Elderfield et al., Geochem. Geophys. Geosyst. 1 (2000)]. But whether some component of foraminiferal Sr/Ca variation can be uniquely ascribed to seawater Sr variation is still not clear. To address this question, we developed cleaning and analysis techniques and measured Sr/Ca ratios on individual shells of the modern benthic foraminifer Cibicidoides wuellerstorfi. We showed that different size shells have different Sr/Ca ratios; however, samples with shell sizes of 355–500 μm appear to have normally distributed Sr/Ca ratios (1σ=1.8%). For multi-shell measurements (with estimated errors of 0.12–0.39%), the ratio varied by as much as 7.2±0.5% during the last glaciation for two Caribbean records at the same site and by 3.7±0.5% over the past 40,000 yr for one record from the Sierra Leone Rise in the eastern equatorial Atlantic. The two Caribbean records are very similar indicating that the behavior of shell Sr uptake was identical locally and that the shell Sr/Ca ratio faithfully reflects the local environment. The Atlantic record differs from the Caribbean records by as much as several percent. Thus, the foraminiferal Sr/Ca changes cannot be solely due to changes in seawater Sr/Ca unless the glacial deep ocean had spatial variation in Sr/Ca well in excess of the modern ocean. Certain similarities between the three records do exist. Notably, the rate of change of Sr/Ca is similar between 9 and 0 ka (−0.25%/kyr) and between 25 and 16 ka (+0.16%/kyr). This suggests that during these intervals, benthic foraminiferal Sr/Ca was affected by similar large-scale variables. One of these variables may be the average marine Sr/Ca ratio; however, comparison with model predictions [H.M. Stoll and D.P. Schrag, Geochim. Cosmochim. Acta 62 (1998) 1107–1118] suggests other factors must also be considered. The discrepancies between the two sites may be related to the different water mass histories for the Caribbean and eastern Atlantic. Our results suggest that variation of the seawater Sr budget only partially contributed to C. wuellerstorfi Sr/Ca records, while other significant factors still need to be quantified. At present we cannot confidently determine past seawater Sr/Ca variation from our foraminiferal records.

Correction: A Decline in Benthic Foraminifera following the Deepwater Horizon Event in the Northeastern Gulf of Mexico

Sediment cores were collected from three sites (1000–1200 m water depth) in the northeastern Gulf of Mexico from December 2010 to June 2011 to assess changes in benthic foraminiferal density related to the Deepwater Horizon (DWH) event (April-July 2010, 1500 m water depth). Short-lived radioisotope geochronologies (210Pb, 234Th), organic geochemical assessments, and redox metal concentrations were determined to relate changes in sediment accumulation rate, contamination, and redox conditions with benthic foraminiferal density. Cores collected in December 2010 indicated a decline in density (80–93%). This decline was characterized by a decrease in benthic foraminiferal density and benthic foraminiferal accumulation rate (BFAR) in the surface 10 mm relative to the down-core mean in all benthic foraminifera, including the dominant genera (Bulimina spp., Uvigerina spp., and Cibicidoides spp.). Cores collected in February 2011 documented a site-specific response. There was evidence of a recovery in the benthic foraminiferal density and BFAR at the site closest to the wellhead (45 NM, NE). However, the site farther afield (60 NM, NE) recorded a continued decline in benthic foraminiferal density and BFAR down to near-zero values. This decline in benthic foraminiferal density occurred simultaneously with abrupt increases in sedimentary accumulation rates, polycyclic aromatic hydrocarbon (PAH) concentrations, and changes in redox conditions. Persistent reducing conditions (as many as 10 months after the event) in the surface of these core records were a possible cause of the decline. Another possible cause was the increase (2–3 times background) in PAH’s, which are known to cause benthic foraminifera mortality and inhibit reproduction. Records of benthic foraminiferal density coupled with short-lived radionuclide geochronology and organic geochemistry were effective in quantifying the benthic response and will continue to be a valuable tool in determining the long-term effects of the DWH event on a larger spatial scale.