Iron isotope and trace metal record of Cenomanian-Turonian sediments

he global carbon cycle during the mid-Cretaceous (~125-88 million years ago, Ma) experienced numerous major perturbations linked to increased organic carbon burial under widespread, possibly basin-scale oxygen deficiency and episodes of euxinia (anoxic and H2S-containing). The largest of these episodes, the Cenomanian-Turonian boundary event (ca. 93.5 Ma), or oceanic anoxic event (OAE) 2, was marked by pervasive deposition of organic-rich, laminated black shales in deep waters and in some cases across continental shelves. This deposition is recorded in a pronounced positive carbon isotope excursion seen ubiquitously in carbonates and organic matter. Enrichments of redox-sensitive, often bioessential trace metals, including Fe and Mo, indicate major shifts in their biogeochemical cycles under reducing conditions that may be linked to changes in primary production. Iron enrichments and bulk Fe isotope compositions track the sources and sinks of Fe in the proto-North Atlantic at seven localities marked by diverse depositional conditions. Included are an ancestral mid-ocean ridge and euxinic, intermittently euxinic, and oxic settings across varying paleodepths throughout the basin. These data yield evidence for a reactive Fe shuttle that likely delivered Fe from the shallow shelf to the deep ocean basin, as well as (1) hydrothermal sources enhanced by accelerated seafloor spreading or emplacement of large igneous province(s) and (2) local-scale Fe remobilization within the sediment column. This study, the first to explore Fe cycling and enrichment patterns on an ocean scale using iron isotope data, demonstrates the complex processes operating on this scale that can mask simple source-sink relationships. The data imply that the proto-North Atlantic received elevated Fe inputs from several sources (e.g., hydrothermal, shuttle and detrital inputs) and that the redox state of the basin was not exclusively euxinic, suggesting previously unknown heterogeneity in depositional conditions and biogeochemical cycling within those settings during OAE-2.

Concentrations of PCBs, DDT and thyroid hormones in gray (Halichoerus grypus) and ringed (Phoca hispida) seals

The high levels of polychlorinated biphenyls (PCBs) and DDT in gray seal (Halichoerus grypus) and ringed seal (Phoca hispida botnica) in the Baltic Sea have been associated with pathological disruptions, including bone lesions and reproductive failures. The underlying environmental and toxicological mechanisms leading to these pathological changes are not yet fully understood. The present study investigated the relationship between the individual contaminant load and bone- and thyroid-related effects in adult gray seals (n = 30) and ringed seals (n = 46) in the highly contaminated Baltic Sea and in reference areas (Sable Island, Canada, and Svalbard, Norway). In the gray seals, multivariate and correlation analyses revealed a clear relationship between circulating 1,25-dihydroxyvitamin D3 (1,25(OH)2D), calcium, phosphate, and thyroid hormone (TH) levels and hepatic PCB and DDT load, which suggests contaminant-mediated disruption of the bone and thyroid homeostasis. Contaminants may depress 1,25(OH)2D levels or lead to hyperthyroidism, which may cause bone resorption. In the ringed seals, associations between circulating 1,25(OH)2D, THs, and hepatic contaminants were less prominent. These results suggest that bone lesions observed in the Baltic gray seals may be associated with contaminant-mediated vitamin D and thyroid disruption.

Seawater carbonate chemistry and biological processes during experiments with calcifiing organisms, 2009

Anthropogenic elevation of atmospheric carbon dioxide (pCO2) 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 pCO2. However, in seven species, net calcification increased under the intermediate and/or highest levels of pCO2, 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 whether they utilize photosynthesis. Whatever the specific mechanism(s) involved, our results suggest that the impact of elevated atmospheric pCO2 on marine calcification is more varied than previously thought.

(Table 1) Organic carbon contents and vitrinite reflection in sediments from DSDP Holes 63-467, 63-471, and 64-481A

A number of C25 and C30 highly branched isoprenoid (HBI) sulphur compounds (E.G., thiolanes, 1-oxo-thiolanes, thiophenes, and benzo[b]thiophenes) with 2,6,10,14-tetramethyl-7-(3-methylpentyl)pentadecane and 2,6,10,14,18-pentamethyl-7-(3-methylpentyl)nonadecane carbon skeletons were identified in sediments, ranging from Holocene to Upper Cretaceous. These identifications are based on mass spectral characterisation, desulphurisation, and, in some cases, by comparison of mass spectral and relative retention time data with those of authentic standards. The presence of unsaturated C25 and C30 HBI thiolanes in a Recent sediment from the Black Sea (age 3-6 ka) strongly supports their formation during early diagenesis. The co-occurrence of HBI polyenes (C25 and C30) and unsaturated HBI thiolanes (C25 and C30) possessing two double bonds less than the corresponding HBI polyenes, in this Recent sediment, testifies to the formation of unsaturated HBI thiolanes by a reaction of inorganic sulphur species with double bonds of the HBI polyenes. Furthermore, a diagenetic scheme for HBI sulphur compounds is proposed based on the identification of HBI sulphur compounds in sediment samples with different maturity levels.

(Table 1) Neutral and phenolic organohalogen compounds in blubber samples of ringed seals (Pusa hispida) from East Greenland

We report on the comparative bioaccumulation, biotransformation and/or biomagnification from East Greenland ringed seal (Pusa hispida) blubber to polar bear (Ursus maritimus) tissues (adipose, liver and brain) of various classes and congeners of persistent chlorinated and brominated contaminants and metabolic by-products: polychlorinated biphenyls (PCBs), chlordanes (CHLs), hydroxyl (OH-) and methylsulfonyl (MeSO2-) PCBs, polybrominated biphenyls (PBBs), OH-PBBs, polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants and OH- and methoxyl (MeO-) PBDEs, 2,2-dichloro-bis(4-chlorophenyl)ethene (p,p'-DDE), 3-MeSO2-p,p'-DDE, pentachlorophenol (PCP) and 4-OH-heptachlorostyrene (4-OH-HpCS). We detected all of the investigated contaminants in ringed seal blubber with high frequency, the main diet of East Greenland bears, with the exception of OH-PCBs and 4-OH-HpCS, which indicated that these phenolic contaminants were likely of metabolic origin and formed in the bears from accumulated PCBs and octachlorostyrene (OCS), respectively, rather than being bioaccumulated from a seal blubber diet. For all of the detectable sum of classes or individual organohalogens, in general, the ringed seal to polar bear mean BMFs for SumPCBs, p,p'-DDE, SumCHLs, SumMeSO2-PCBs, 3-MeSO2-p,p'-DDE, PCP, SumPBDEs, total-(alpha)-HBCD, SumOH-PBDEs, SumMeO-PBDEs and SumOH-PBBs indicated that these organohalogens bioaccumulate, and in some cases there was tissue-specific biomagnification, e.g., BMFs for bear adipose and liver ranged from 2 to 570. The blood-brain barrier appeared to be effective in minimizing brain accumulation as BMFs were <= 1 in the brain, with the exception of SumOH-PBBs (mean BMF = 93±54). Unlike OH-PCB metabolites, OH-PBDEs in the bear tissues appeared to be mainly accumulated from the seal blubber rather than being metabolic formed from PBDEs in the bears. In vitro PBDE depletion assays using polar bear hepatic microsomes, wherein the rate of oxidative metabolism of PBDE congeners was very slow, supported the probability that accumulation from seals is the main source of OH-PBDEs in the bear tissues. Our findings demonstrated from ringed seal to polar bears that organohalogen biotransformation, bioaccumulation and/or biomagnification varied widely and depended on the contaminant in question. Our results show the increasing complexity of bioaccumulated and in some cases biomagnified, chlorinated and brominated contaminants and/or metabolites from the diet may be a contributing stress factor in the health of East Greenland polar bears.

(Table 1) Grain size, sedimentation rates and accumulation rates of ODP Hole 152-919A coarse-sand ice-rafted debris

At mid- to high-latitude marine sites, ice-rafted debris (IRD) is commonly recognized as anomalously coarse-grained terrigenous material contained within a fine-grained hemipelagic or pelagic matrix (e.g., Conolly and Ewing, 1970; Ruddiman, 1977, doi:10.1130/0016-7606(1977)88<1813:LQDOIS>2.0.CO;2; Krissek, 1989, doi:10.2973/odp.proc.sr.104.114.1989; Jansen et al., 1990; Bond et al., doi:10.1038/360245a0, 1992; Krissek, 1995, doi:10.2973/odp.proc.sr.145.118.1995). The presence of such ice-rafted material is a valuable indicator of the presence of glacial ice at sea level on an adjacent continent, whereas the composition of the IRD can often be used to identify the location of the source area (e.g., Goldschmidt, 1995, doi:10.1016/0025-3227(95)00098-J). Because the amount of core recovered during Leg 163 was very limited, this shore-based, postcruise study focuses on materials recovered at a nearby site during Leg 152. In particular, this study examines sediments recovered at Site 919; these sediments were described as containing a significant ice-rafted component in the Leg 152 Initial Reports volume (Larsen, Saunders, Clift, et al., 1994, doi:10.2973/odp.proc.ir.152.1994). In this study, the sedimentary section from Site 919 has been examined with the goal of providing a detailed history of glaciations on Greenland and other landmasses adjacent to the Norwegian-Greenland Sea; this history ultimately will be calibrated using an oxygen isotope stratigraphy (Flower, 1998, doi:10.2973/odp.proc.sr.152.219.1998), although that calibration has not been completed at this time. Because ice-core studies of the Greenland Ice Sheet (GIS) have shown that the GIS changed dramatically, and in some cases extremely rapidly, during at least the last interglacial stage (GRIP Members, 1993, doi:10.1038/364203a0), a detailed IRD record from the Southeast Greenland margin should provide insight into the longer term behavior of this sensitive component of the Northern Hemisphere climate system.

Micropaleontology and stable isotope record of ODP Hole 178-1098C

Detailed study of four Holocene sediment intervals from Ocean Drilling Program Site 1098 (Palmer Deep, Antarctic Peninsula) reveals that in situ dissolution of calcareous foraminifers in the core repository has significantly altered and in some cases eliminated calcareous foraminifers. Despite dissolution, the foraminifer and supporting diatom data show that the most open-ocean and reduced sea-ice conditions occurred in the early Holocene. The influence of Circumpolar Deep Water was greatest during the early Holocene but continued to be important throughout the Holocene. An increase in sea-ice proximal diatoms at 3500 cal. BP documents an expansion in the amount of persistent sea ice. The inferred increase in sea ice corresponds with an overall increase in magnetic susceptibility values. Benthic foraminifers are present in all samples from the Palmer Deep, including the middle Holocene pervasively laminated sediments with low magnetic susceptibility values. The consistent presence of mobile epifaunal benthic foraminifers in the laminated sediments demonstrates that the laminations do not represent anoxic conditions. The uniform composition of the agglutinated foraminifer fauna throughout the late Holocene suggests that the Palmer Deep did not experience bottom-water-mass changes associated with the alternating deposition of bioturbated or laminated sediments.

Stable carbon and oxygen isotope ratios of benthic and planktonic foraminifera of ODP Hole 171-1049C

Ocean anoxic events were periods of high carbon burial that led to drawdown of atmospheric carbon dioxide, lowering of bottom-water oxygen concentrations and, in many cases, significant biological extinction (Arthur et al., 1990; Erbacher et al., 1996, doi:10.1130/0091-7613(1996)024<0499:EPORAO>2.3.CO;2; Kuypers et al., 1999, doi:10.1038/20659; Jenkyns, 1997; Hochuli et al., 1999, doi:10.1130/0091-7613(1999)027<0657:EOHPAC>2.3.CO;2). Most ocean anoxic events are thought to be caused by high productivity and export of carbon from surface waters which is then preserved in organic-rich sediments, known as black shales. But the factors that triggered some of these events remain uncertain. Here we present stable isotope data from a mid-Cretaceous ocean anoxic event that occurred 112 Myr ago, and that point to increased thermohaline stratification as the probable cause. Ocean anoxic event 1b is associated with an increase in surface-water temperatures and runoff that led to decreased bottom-water formation and elevated carbon burial in the restricted basins of the western Tethys and North Atlantic. This event is in many ways similar to that which led to the more recent Plio-Pleistocene Mediterranean sapropels, but the greater geographical extent and longer duration (~46 kyr) of ocean anoxic event 1b suggest that processes leading to such ocean anoxic events in the North Atlantic and western Tethys were able to act over a much larger region, and sequester far more carbon, than any of the Quaternary sapropels.

Gas, water and volume characteristics during controlled degassing experiments on ODP Leg 164 PCS cores

A pressurized core with CH4 hydrate or dissolved CH4 should evolve gas volumes in a predictable manner as pressure is released over time at isothermal conditions. Incremental gas volumes were collected as pressure was released over time from 29 pressure core sampler (PCS) cores from Sites 994, 995, 996, and 997 on the Blake Ridge. Most of these cores were kept at or near 0ºC with an ice bath, and many of these cores yielded substantial quantities of CH4. Volume-pressure plots were constructed for 20 of these cores. Only five plots conform to expected volume and pressure changes for sediment cores with CH4 hydrate under initial pressure and temperature conditions. However, other evidence suggests that sediment in these five and at least five other PCS cores contained CH4 hydrate before core recovery and gas release. Detection of CH4 hydrate in a pressurized sediment core through volume-pressure relationships is complicated by two factors. First, significant quantities of CH4-poor borehole water fill the PCS and come into contact with the core. This leads to dilution of CH4 concentration in interstitial water and, in many cases, decomposition of CH4 hydrate before a degassing experiment begins. Second, degassing experiments were conducted after the PCS had equilibrated in an ice-water bath (0ºC). This temperature is significantly lower than in situ values in the sediment formation before core recovery. Our results and interpretations for PCS cores collected on Leg 164 imply that pressurized containers formerly used by the Deep Sea Drilling Project (DSDP) and currently used by ODP are not appropriately designed for direct detection of gas hydrate in sediment at in situ conditions through volume-pressure relationships.

Seawater carbonate chemistry and community calcification during Reunion Island coral reef community study, 2007

To assess the contribution of soft-bottoms to the carbon cycle in coral reefs, the net community production (p) was measured in winter at 3 stations on La Saline inner reef flat (Reunion Island). Changes in pH and total alkalinity at different irradiances (I) were assessed using benthic chambers (0.2 m2) during a 1-h incubation. Mean grain size, the silt and clay load and chlorophyll a content of the sediments were analysed in each chamber. Daily community production (P), gross community production (Pg) and community respiration (R) were estimated from p-I curves and daily irradiance variations (PAR, 400-700 nm). Sediment characteristics and chlorophyll a contents did not differ between the three sites, except for the silt and clay fraction at one station. R being higher than Pg (84.88 ± 7.36 and -62.29 ± 3.34 mmolC m-2 d-1 respectively), P value reached 22.59 ± 5.66 mmolC m-2 d-1. The sediments were therefore heterotrophic with a mean Pg/R lower than 1 (0.74 ± 0.05) and appear to be a carbon source. Our data suggested the importance of the degradation process in the functioning of near-reef sediments.