Sensitivity of antioxidant-deficient yeast to hypochlorite and chlorite

Sodium hypochlorite and sodium chlorite are commonly used as disinfectants, and understanding the mechanisms of microbial resistance to these compounds is of considerable importance. In this study, the role of oxidative stress and antioxidant enzymes in the sensitivity of the yeast Saccharomyces cerevisiae to hypochlorite and chlorite was studied. Yeast mutants lacking Cu-Zn superoxide dismutase, but not mutants deficient in cytoplasmic and peroxisomal catalase, were hypersensitive to the action of both hypochlorite and chlorite. Both compounds depleted cellular glutathione, induced the production of reactive oxygen species and decreased the viability of the cells. The toxicity of hypochlorite and chlorite was abolished by hypoxic and anoxic conditions and ameliorated by thiol antioxidants and ascorbate. The results demonstrated that the action of hypochlorite and chlorite involves the formation of superoxide and peroxide and that SOD1 is protective, probably by limiting the formation of hydroxyl radicals and damage to proteins.

Ammonite biostratigraphy, lithofacies variations, and paleoceanographic implications for Barremian-Aptian sequences of northeastern Mexico

Two Barremian-Aptian sequences studied in Durango and Nuevo Leon States, northeastern Mexico include three lithic units which have been described as the Cupido Formation of Barremian-early Early Aptian age, its lateral equivalent, the Lower Tamaulipas Formation, and the La Peña Formation extending through the early Albian. ^ The present work improves the existing ammonite Aptian biozonation by considering constraints associated with a discontinuous spatial and temporal record of the different taxa within the La Peña Formation. ^ Four ammonite biozones are established: (1) The Dufrenoyia justinae Zone for the late Early Aptian, (2) The Burckhardtites nazasensis/Rhytidoplites robertsi Zone for the middle Aptian, (3) The Cheloniceras inconstans Zone for the early Late Aptian, and (4) The Hypacanthoplites cf. leanzae Zone for the late late Aptian. ^ Also, a detailed sedimentological analysis of the sections shed further light on the possible causes that controlled intermittent occurrences of the ammonites in relation to the prevailing paleoceanographic and paleoecologic conditions in northeastern Mexico during the late Barremian-Aptian. ^ Microfacies analyses show that the upper part of the Cupido facies are represented by biocalcirudite with rudists, biocalcarenites with oolites and algae, and rich benthonic foraminifera assemblages with ostracods. These facies are related to paleoceanographic conditions of sedimentation within a shallow-marine carbonate platform. Its lateral equivalent, deep-water facies extended to the southeast and it is represented by the Lower Tamaulipas Formation, which includes planktonic foraminifera, ostracods, and mollusk and echinoid fragments. The beginning of deposition of the La Peña Formation in the late Early Aptian is characterized by an increase in terrigenous materials and significant decrease in the abundance of benthic fauna. The La Peña Formation is recognized by an alternation of marls and shale limestones containing ammonites, planktonic foraminifera, ostracods, and radiolaria toward the top. Accumulation of the La Peña continued throughout the end of the Aptian and records changes in conditions of sedimentation and productivity in the water column, which abruptly terminated the carbonate deposition in the Cupido Platform. ^ Results of carbon/carbonate content analyses show that changes from the Cupido to the La Peña facies are also characterized by an increase of organic carbon, which indicate the onset of enhanced dysoxic/anoxic conditions in the lower water column. ^

High-resolution cyclostratigraphy of the Cenomanian-Turonian interval: Paleoceanographic implications, a comparison between deep sea drilling project site 386 and 144

The purpose of this study was to determine the extent to which oceanic anoxic events (OAE's) are recorded in deep-water deposits of the former western Tethyan Sea, by investigating the Cenomanian-Turonian time interval characterized by the worldwide OAE 2 event. The study improved our knowledge of the possible controlling mechanisms that triggered this event at these sites, and furthered our understanding of this global phenomenon. This was examined by high-resolution, multi-proxy analyses of sediments at DSDP Sites 386 and 144, including sedimentology, scanning electron microscopy, stable isotopes, bulk and clay mineralogy, major and trace element geochemistry, biomarkers, and paleontological data. ^ The results provide a better stratigraphic resolution for the Cenomanian-Turonian, which allowed for more precise determination of chronologic boundaries, sedimentation rates at DSDP Site 386, and a more accurate calculation of the frequency of the cycles recorded in the sequence, which fall predominantly within the precession (∼23 kyr) and short eccentricity (∼100 kyr) ranges. The combined proxies allow assessment of the correlation of δ13Corg, and major and trace elements with the predominance of cyanobacteria. These organisms were the main producers of the organic matter during the dysoxic and euxinic conditions of OAE 2 at DSDP Site 386. A huge amount of microcrystalline quartz of eolian origin is also associated with OAE 2. The geochemical proxies further provide evidence that OAE 2 was linked to increased volcanism outside the deep water of the proto-Atlantic Ocean. The clays in the Turonian sediments are terrigenous and derived predominantly from eolian transport. Comparing DSDP Site 386 and 144 with stratotype sections, the δ13C org and TOC data indicate that OAE 2 seems diachronous throughout the proto-Atlantic Ocean. ^ This study concludes that the development of anoxic conditions in the deep water of the Atlantic during the latest Cenomanian-Turonian resulted from a combination of factors related to local oceanic setting and mitigated by global tectonism and climate. The data provide a more comprehensive view of the interacting factors that led to sustained high productivity of the cyanobacteria and photosynthetic protists that produced organic-carbon-rich deposits in the world's oceans. ^

Paleoenvironmental implications of the Indidura Formation (Cenomanian/Turonian), northeastern Mexico: A high resolution stratigraphic study

High-resolution lithostratigraphic data from rock sequences known as the Indidura Formation near Parras de La Fuente, Coahuila, NE Mexico, led to achieve a significant improvement of our knowledge of that Formation. The results of this study indicate for the first time that the sequence at Parras de La Fuente developed from the deposition of calcareous cyanobacterial microspheroids that accumulated under perennial blooms during the Late Cenomanian through the Middle Turonian. Multi-proxy analyses included sedimentological, petrographical, scanning electron microscopy, stable isotope, trace element geochemistry, and paleontological data. The combined results allowed the correlation of δ13C and anomalies in Mo, V, and Cr with the abundance and predominance of calcareous cyanobacterial microspheroids, which were the main suppliers of the carbonate components and the organic matter throughout deposition of the Indidura Formation in the Parras de la Fuente area, under dysoxic/anoxic conditions. Conspicuous interbeds of dark and light-gray laminated marly calcilutites, and dark-gray marlstones that characterize the stratigraphic sequence formed in response to external forcing climatic factors of millennial-scale Milankovitch cycles (ca. 20 ka precession). At the microscopic level, the prominent dark and light-gray laminae were formed during cycles similar to the 10 to 15 years solar irradiance maximum, and represent alternating periods of high and low calcareous cyanobacterial microspheroids productivity.

Paleoenvironments and geochemical signals from the late Barremian to the middle Aptian in a Tethyan marginal basin, northeast Spain: Implications for carbon sequestration in restricted basins

The hallmark of oceanic anoxic event 1a (OAE1a) (early Aptian ~125 Ma) corresponds to worldwide deposition of black shales with total organic carbon (TOC) content > 2% and a δ13C positive excursion up to ~5‰. OAE1a has been related to large igneous province volcanism and dissociation of methane hydrates during the Lower Cretaceous. However, the occurrence of atypical, coeval and diachronous organic-rich deposits associated with OAE1a, which are also characterized by positive spikes of the δ 13C in epicontinental to restricted marine environments of the Tethys Ocean, indicates localized responses decoupled from complex global forcing factors. ^ The present research is a high-resolution, multiproxy approach to assess the paleoenvironmental conditions that led to enhanced carbon sequestration from the late Barremian to the middle Aptian in a restricted, Tethyan marginal basin prior to and during OAE1a. I studied the lower 240 m of the El Pui section, Organyà Basin, Spanish Pyrenees. The basin developed as the result of extensional tectonism linked to the opening of the Atlantic Ocean. At the field scale the section consists of a sequence of alternating beds of cm – m-scale, medium-gray to grayish-black limestones and marlstones with TOC up to ~4%. ^ The results indicate that the lowest 85 m of the section, from latest Barremian -earliest Aptian, characterize a deepening phase of the basin concomitant with sustained riverine flux and intensified primary productivity. These changes induced a shift in the sedimentation pattern and decreased the oxygen levels in the water column through organic matter respiration and limited ventilation of the basin. ^ The upper 155 m comprising the earliest – late-early Aptian document the occurrence of OAE1a and its associated geochemical signatures (TOC up to 3% and a positive shift in δ13C of ~5‰). However, a low enrichment of redox-sensitive trace elements indicates that the basin did not achieve anoxic conditions. The results also suggest that a shallower-phase of the basin, coeval with platform progradation, may have increased ventilation of the basin at the same time that heightened sedimentation rates and additional input of organic matter from terrestrial sources increased the burial and preservation rate of TOC in the sediment.^

Paleoenvironmental Implications of the Indidura Formation (Cenomanian/Turonian), Northeastern Mexico: a High Resolution Stratigraphic Study

High-resolution lithostratigraphic data from rock sequences known as the Indidura Formation near Parras de La Fuente, Coahuila, NE Mexico, led to achieve a significant improvement of our knowledge of that Formation. The results of this study indicate for the first time that the sequence at Parras de La Fuente developed from the deposition of calcareous cyanobacterial microspheroids that accumulated under perennial blooms during the Late Cenomanian through the Middle Turonian. Multi-proxy analyses included sedimentological, petrographical, scanning electron microscopy, stable isotope, trace element geochemistry, and paleontological data. The combined results allowed the correlation of δ13C and anomalies in Mo, V, and Cr with the abundance and predominance of calcareous cyanobacterial microspheroids, which were the main suppliers of the carbonate components and the organic matter throughout deposition of the Indidura Formation in the Parras de la Fuente area, under dysoxic/anoxic conditions. Conspicuous interbeds of dark and light-gray laminated marly calcilutites, and dark-gray marlstones that characterize the stratigraphic sequence formed in response to external forcing climatic factors of millennial-scale Milankovitch cycles (ca. 20 ka precession). At the microscopic level, the prominent dark and light-gray laminae were formed during cycles similar to the 10 to 15 years solar irradiance maximum, and represent alternating periods of high and low calcareous cyanobacterial microspheroids productivity.

Ammonite biostratigraphy, lithofacies variations, and paleoceanographic implications for barremian-aptian sequences of northeastern Mexico

Two Barremian-Aptian sequences studied in Durango and Nuevo Leon States, northeastern Mexico include three lithic units which have been described as the Cupido Formation of Barremian-early Early Aptian age, its lateral equivalent, the Lower Tamaulipas Formation, and the La Pena Formation extending through the early Albian. The present work improves the existing ammonite Aptian biozonation by considering constraints associated with a discontinuous spatial and temporal record of the different taxa within the La Pena Formation. Four ammonite biozones are established: 1) The Dufrenoyia justinae Zone for the late Early Aptian, 2) The Burckhardtites nazasensis/Rhytidoplites robertsi Zone for the middle Aptian, 3) The Cheloniceras inconstans Zone for the early Late Aptian, and 4) The Hypacanthoplites cf. leanzae Zone for the late late Aptian. Also, a detailed sedimentological analysis of the sections shed further light on the possible causes that controlled intermittent occurrences of the ammonites in relation to the prevailing paleoceanographic and paleoecologic conditions in northeastern Mexico during the late Barremian-Aptian. Microfacies analyses show that the upper part of the Cupido facies are represented by biocalcirudite with rudists, biocalcarenites with oolites and algae, and rich benthonic foraminifera assemblages with ostracods. These facies are related to paleoceanographic conditions of sedimentation within a shallow-marine carbonate platform. Its lateral equivalent, deep-water facies extended to the southeast and it is represented by the Lower Tamaulipas Formation, which includes planktonic foraminifera, ostracods, and mollusk and echinoid fragments. The beginning of deposition of the La Pena Formation in the late Early Aptian is characterized by an increase in terrigenous materials and significant decrease in the abundance of benthic fauna. The La Pena Formation is recognized by an alternation of marls and shale limestones containing ammonites, planktonic foraminifera, ostracods, and radiolaria toward the top. Accumulation of the La Pena continued throughout the end of the Aptian and records changes in conditions of sedimentation and productivity in the water column, which abruptly terminated the carbonate deposition in the Cupido Platform. Results of carbon/carbonate content analyses show that changes from the Cupido to the La Pena facies are also characterized by an increase of organic carbon, which indicate the onset of enhanced dysoxic/anoxic conditions in the lower water column.

Distribution of neodymium isotopes and concentrations during M77/3 and M77/4

The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 11400N and 161S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (eNd=-2). Surface waters in the northernmost part of the study area are even more radiogenic (eNd = +3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (141S) are clearly controlled by advection of water masses with less radiogenic signatures (eNd=- 7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to eNd=-2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000-6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40-60 pmol/kg), which suggests enhanced removal of Nd in the EEP.

(Table 2) Hydrogen sulphide and methane content, and loss on ignition in sediments obtained in the Gotland Deep, Baltic Sea

The distribution of methane and hydrogen sulfide concentrations in sediments of various basins of the Baltic Sea was investigated during 4 cruises in 1995 and 1996. Significant differences in the concentrations of both compounds were recorded between the basins and also between different areas within the Gotland Deep. High-methane sediments with distinctly increasing concentrations from the surface to deeper layers were distinguished from low-methane sediments without a clear gradient. Methane concentrations exhibited a fair correlation with the sediment accumulation rate, determined by measuring the total thickness of the post-Ancylus Holocene sequence on echosounding profiles in the Gotland Deep. Only weak correlations were observed with the content of organic matter in the surface layers of the sediments. Hydrogen sulfide concentrations in the sediments showed a positive correlation with methane concentrations, but, in contrast to methane concentrations, were strongly influenced by the transition from oxic to anoxic conditions in the water column between 1995 and 1996. Sediments in the deepest part of the Gotland Basin (>237 m water depth), covering an area of approximately 35 km**2, were characterized by especially high accumulation rates (>70 cm/ka) and high methane and hydrogen sulfide contents. Concentrations of these compounds decreased rapidly towards the slope of the basin.

Sea-surface temperature reconstruction of sediment cores from the Skagerrak

We attempt a reconstruction of salinity levels of the central Baltic Sea based on diatom assemblages, the isotopic composition of organic matter and sedimentological expression of anoxia over the last 10 000 years. We use the data to investigate the dependence of salinity levels on climate evolution and isostasy. Changes in salinity of surface and deep waters were most pronounced from 8400 to approximately 5000 cal. BP. Density stratification between salty deep and fresher surface waters caused the frequent development of anoxic conditions and deposition of laminated sediments on large parts of the sea floor in the central Baltic Sea, and dramatic changes in organic carbon-accumulation rates. From 5000 to 3100 cal. BP, the salinity of the basin decreased, oxygenation of deep sea floors was improved, and fertility of the sea surface was significantly reduced. This is reflected by low accumulation rates of organic carbon in bioturbated sediments. Since 2800 cal. BP, salinity rose again and anoxic periods were more common. Even though the major steps in environmental evolution in the Baltic Sea coincide with known patterns of climatic change of the North Atlantic realm over the last 10 000 years, we find no conclusive evidence for synchronous changes or linear responses on submillennial timescales. However, we note that major variations in our salinity records agree with temporal patterns of reconstructed summer warmth and winter precipitation in southern Scandinavia. Both types of record suggest that climate in the mid-Holocene was far from stable. Our data also confirm that climate evolution over the late Holocene had significant impact on environmental conditions in the Baltic Sea.

Chemistry of eastern tropical Atlantic porewater

Distributions of pore water O2, NO-2, NO-3, NH+4, Si(OH)4, PO[3-]4, Mn[2+], F-, and T.A. were determined at 15 stations in the eastern equatorial Atlantic. While overall profile characteristics are consistent with previous models of organic matter diagenesis, profile shapes suggest that a deep reaction layer, rich in organic C, is also present at many sites. While it is unlikely that the oxidation of organic C in this layer has had a major effect on the ocean C cycle, pore water profile shapes are significantly altered. Despite exposure to seawater SO[2-]4 concentrations for > 1000 years, decomposition of the organic matter in the layer appears to be restricted to oxic and suboxic processes. These results suggest major differences in organic carbon decomposition and preservation under oxic/suboxic and anoxic conditions. Present-day benthic fluxes are largest adjacent to the eastern boundary coastal upwelling region and similar in magnitude to values reported for the eastern Pacific. Preliminary estimates suggest that the benthic respiration in the eastern 1/3 of the North Atlantic south of 20°N may alone account for >20% of the total deep North Atlantic respiration. Combining these results with estimates of organic C burial and deep water-column decomposition suggests that this region is a major location of organic C input into the deep sea.

(Figure 1 and 2) Phosphorus pools in the investigated sediments quantified by SEDEX sequential extraction and distribution of recovered 33P spike between sedimentary P pools after incubation

Phosphorus is an essential nutrient for life. In the ocean, phosphorus burial regulates marine primary production**1, 2. Phosphorus is removed from the ocean by sedimentation of organic matter, and the subsequent conversion of organic phosphorus to phosphate minerals such as apatite, and ultimately phosphorite deposits**3, 4. Bacteria are thought to mediate these processes**5, but the mechanism of sequestration has remained unclear. Here, we present results from laboratory incubations in which we labelled organic-rich sediments from the Benguela upwelling system, Namibia, with a 33P-radiotracer, and tracked the fate of the phosphorus. We show that under both anoxic and oxic conditions, large sulphide-oxidizing bacteria accumulate 33P in their cells, and catalyse the nearly instantaneous conversion of phosphate to apatite. Apatite formation was greatest under anoxic conditions. Nutrient analyses of Namibian upwelling waters and sediments suggest that the rate of phosphate-to-apatite conversion beneath anoxic bottom waters exceeds the rate of phosphorus release during organic matter mineralization in the upper sediment layers. We suggest that bacterial apatite formation is a significant phosphorus sink under anoxic bottom-water conditions. Expanding oxygen minimum zones are projected in simulations of future climate change**6, potentially increasing sequestration of marine phosphate, and restricting marine productivity.

(Table S1) Geochemistry for sediment core MD02-2515

A high-resolution, 55-kyr long record of chalcophile and redox-sensitive trace element accumulation (Ag, Cd, Re, Mo) from MD02-2515, western Guaymas Basin, is investigated in conjunction with patterns in stratigraphy and productivity. High opal concentrations (~58 wt. %), representing increased diatom production, coincide with laminated sediments, and dilute the concentrations of organic carbon (Corg) and metals. A similarity between opal and normalized Corg, Ag and Cd concentrations suggests delivery to the sediments by diatom export production, while patterns in normalized Re and Mo accumulation suggest a different emplacement mechanism. Although Mo enrichment in organic-rich, laminated sediments typically represents anoxic conditions at other locations, Mo (and Re) in Guaymas Basin is enriched in nonlaminated and bioturbated sediments that are representative of oxygenated conditions. Adsorption onto Fe- and/or Mn-oxyhydroxide surfaces during oxygenation inadequately explains both the Re and Mo enrichments. Thus, recently published mechanisms invoking direct Re and Mo removal from the water column and bioturbation-assisted irrigation of Re into the sediments are used to explain the counterintuitive observations in Guaymas Basin. The MD02-2515 stratigraphic and proxy records are also different from other records in the northeast Pacific in that there is little correspondence with Greenland Dansgaard-Oeschger interstadials. There is some correlation with Heinrich events, suggesting that ventilation of intermediate waters and/or reduced productivity may be important in controlling stratigraphy and trace element accumulation. The results question whether MD02-2515 records can be compared to northeast Pacific open-margin records, especially before 17 kyr BP.

Bulk geochemical and Rock-Eval data of sediment core IKU-7430/10-U-01 (Table 1)

The late Volgian (early "Boreal" Berriasian) sapropels of the Hekkingen Formation of the central Barents Sea show total organic carbon (TOC) contents from 3 to 36 wt%. The relationship between TOC content and sedimentation rate (SR), and the high Mo/Al ratios indicate deposition under oxygen-free bottom-water conditions, and suggest that preservation under anoxic conditions has largely contributed to the high accumulation of organic carbon. Hydrogen index values obtained from Rock-Eval pyrolysis are exceptionally high, and the organic matter is characterized by well-preserved type II kerogen. However, the occurrence of spores, freshwater algae, coal fragments, and charred land-plant remains strongly suggests proximity to land. Short-term oscillations, probably reflecting Milankovitch-type cyclicity, are superimposed on the long-term trend of constantly changing depositional conditions during most of the late Volgian. Progressively smaller amounts of terrestrial organic matter and larger amounts of marine organic matter upwards in the core section may have been caused by a continuous sea-level rise.

(Table 1) Geochemistry of Sapropels of the Mediterranean Sea

Sapropels -organic-matter rich layers- are common in Neogene sediments of the eastern Mediterranean Sea. The formation of these layers has been attributed to climate-related increases in organic-matter production (Calvert et al., 1992, doi:10.1038/359223a0; Rossignol-Strick et al., 1982, doi:10.1038/295105a0; Rohling, 1994, doi:10.1016/0025-3227(94)90202-X) and increased organic-matter preservation due to oxygen depletion in more stagnant bottom waters (Rossignol-Strick et al., 1982, doi:10.1038/295105a0; Rohling, 1994, doi:10.1016/0025-3227(94)90202-X). Here we report that eastern Mediterranean Pliocene sapropels (Emeis et al., 1996, doi:10.2973/odp.proc.ir.160.102.1996) contain molecular fossils of a compound (isorenieratene) known to be synthesized by photosynthetic green sulphur bacteria, suggesting that sulphidic (euxinic) -and therefore anoxic- conditions prevailed in the photic zone of the water column. These sapropels also have a high trace-metal content, which is probably due to the efficient scavenging of these metals by precipitating sulphides in a euxinic water column. The abundance and sulphur-isotope composition of pyrite are consistent with iron sulphide formation in the water column. We conclude that basin-wide water-column euxinia occurred over substantial periods during Pliocene sapropel formation in the eastern Mediterranean Sea, and that the ultimate degradation of the increased organic-matter production was strongly influential in generating and sustaining the euxinic conditions.