Nanogravimetric study of lead underpotential deposition on selenium thin films as a semiconductor alloy formation procedure

An electrochemical quartz crystal microbalance Au electrode modified with a Se thin film was used to investigate the electrochemical behavior of lead ad-atoms using underpotential deposition (UPD) conditions. A specific quasi-reversible process was observed during the reduction of Pb2+ on Se thin films in perchloric acid media. The charge density of Pb ad-atoms on Se thin film (46.86 mu C cm(-2)) suggests a recovery of 0.1 monolayers, which is in good agreement with EQCM data. The Se thin film can be successfully alloyed with Pb atoms that are deposited by chronoamperometry using time intervals large enough to allow for diffusion toward the inner Se phase. Linear sweep voltammetry combined with EQCM in perchloric acid was used to characterize the amount of Pb absorbed in the Se thin film. These findings offer a new strategy for alloy formation in semiconductor films using UPD as an effective tool to quantify the exact amount of the incorporated metal.

Structural and mechanical analysis for the optimization of PVD oxide coatings for protection against metal dusting

The evolution of the structure and properties of Cr/Cr oxide thin films deposited on HK40 steel substrates by reactive magnetron sputtering (RMS) was investigated and linked to their potential protective behavior against metal dusting. Deposition time, mode of oxygen feeding, and application of bias voltage were varied to assess their effect on the density, adhesion, and integrity of the films. All the films showed a very fine columnar microstructure and the presence of amorphous Cr oxide. Both, an increasing time and a constant oxygen flow during deposition led to the development of relatively low density films and mud-like cracking patterns. A graded oxygen flow resulted in films with fewer cracks, but a careful control of the oxygen flow is required to obtain films with a truly graded structure. The effect of the bias voltage was much more significant and beneficial. An increasing negative bias voltage resulted in the development of denser films with a transition to an almost crack-free structure and better adhesion. The amorphous oxide resulted in low values of hardness and Young's modulus. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Synthesis and characterization of metal-chalcogenide MQ 2-Nanoparticles (M = Mo, W, Zr; Q = S, O)

Here, we present the adaptation and optimization of (i) the solvothermal and (ii) the metal-organic chemical vapor deposition (MOCVD) approach as simple methods for the high-yield synthesis of MQ2 (M=Mo, W, Zr; Q = O, S) nanoparticles. Extensive characterization was carried out using X-ray diffraction (XRD), scanning and transmission electron micros¬copy (SEM/TEM) combined with energy dispersive X-ray analysis (EDXA), Raman spectroscopy, thermal analyses (DTA/TG), small angle X-ray scattering (SAXS) and BET measurements. After a general introduction to the state of the art, a simple route to nanostructured MoS2 based on the decomposition of the cluster-based precursor (NH4)2Mo3S13∙xH2O under solvothermal conditions (toluene, 653 K) is presented. Solvothermal decomposition results in nanostructured material that is distinct from the material obtained by decomposition of the same precursor in sealed quartz tubes at the same temperature. When carried out in the presence of the surfactant cetyltrimethyl¬ammonium bromide (CTAB), the decomposition product exhibits highly disordered MoS2 lamellae with high surface areas. The synthesis of WS2 onion-like nanoparticles by means of a single-step MOCVD process is discussed. Furthermore, the results of the successful transfer of the two-step MO¬CVD based synthesis of MoQ2 nanoparticles (Q = S, Se), comprising the formation of amorphous precursor particles and followed by the formation of fullerene-like particles in a subsequent annealing step to the W-S system, are presented. Based on a study of the temperature dependence of the reactions a set of conditions for the formation of onion-like structures in a one-step reaction could be derived. The MOCVD approach allows a selective synthesis of open and filled fullerene-like chalcogenide nanoparticles. An in situ heating stage transmission electron microscopy (TEM) study was employed to comparatively investigate the growth mechanism of MoS2 and WS2 nanoparticles obtained from MOCVD upon annealing. Round, mainly amorphous particles in the pristine sample trans¬form to hollow onion-like particles upon annealing. A significant difference between both compounds could be demonstrated in their crystallization conduct. Finally, the results of the in situ hea¬ting experiments are compared to those obtained from an ex situ annealing process under Ar. Eventually, a low temperature synthesis of monodisperse ZrO2 nanoparticles with diameters of ~ 8 nm is introduced. Whereas the solvent could be omitted, the synthesis in an autoclave is crucial for gaining nano-sized (n) ZrO2 by thermal decomposition of Zr(C2O4)2. The n-ZrO2 particles exhibits high specific surface areas (up to 385 m2/g) which make them promising candidates as catalysts and catalyst supports. Co-existence of m- and t-ZrO2 nano-particles of 6-9 nm in diameter, i.e. above the critical particle size of 6 nm, demonstrates that the particle size is not the only factor for stabilization of the t-ZrO2 modification at room temperature. In conclusion, synthesis within an autoclave (with and without solvent) and the MOCVD process could be successfully adapted to the synthesis of MoS2, WS2 and ZrO2 nanoparticles. A comparative in situ heating stage TEM study elucidated the growth mechanism of MoS2 and WS2 fullerene-like particles. As the general processes are similar, a transfer of this synthesis approach to other layered transition metal chalcogenide systems is to be expected. Application of the obtained nanomaterials as lubricants (MoS2, WS2) or as dental filling materials (ZrO2) is currently under investigation.

Noble-metal nanoparticles produced with colloidal lithography: fabrication, optical properties and applications

In this work, metal nanoparticles produced by nanosphere lithography were studied in terms of their optical properties (in connection to their plasmon resonances), their potential application in sensing platforms - for thin layer sensing and bio-recognition events -, and for a particular case (the nanocrescents), for enhanced spectroscopy studies. The general preparation procedures introduced early in 2005 by Shumaker-Parry et al. to produce metallic nanocrescents were extended to give rise to more complex (isolated) structures, and also, by combining colloidal monolayer fabrication and plasma etching techniques, to arrays of them. The fabrication methods presented in this work were extended not only to new shapes or arrangements of particles, but included also a targeted surface tailoring of the substrates and the structures, using different thiol and silane compounds as linkers for further attachment of, i.e. polyelectrolyte layers, which allow for a controlled tailoring of their nanoenvironment. The optical properties of the nanocrescents were studied with conventional transmission spectroscopy; a simple multipole model was adapted to explain their behaviour qualitatively. In terms of applications, the results on thin film sensing using these particles show that the crescents present an interesting mode-dependent sensitivity and spatial extension. Parallel to this, the penetrations depths were modeled with two simplified schemes, obtaining good agreement with theory. The multiple modes of the particles with their characteristic decay lengths and sensitivities represent a major improvement for particle-sensing platforms compared to previous single resonance systems. The nanocrescents were also used to alter the emission properties of fluorophores placed close to them. In this work, green emitting dyes were placed at controlled distances from the structures and excited using a pulsed laser emitting in the near infrared. The fluorescence signal obtained in this manner should be connected to a two-photon processes triggered by these structures; obtaining first insight into plasmon-mediated enhancement phenomena. An even simpler and faster approach to produce plasmonic structures than that for the crescents was tested. Metallic nanodiscs and nanoellipses were produced by means of nanosphere lithography, extending a procedure reported in the literature to new shapes and optical properties. The optical properties of these particles were characterized by extinction spectroscopy and compared to results from the literature. Their major advantage is that they present a polarization-dependent response, like the nanocrescents, but are much simpler to fabricate, and the resonances can be tailored in the visible with relative ease. The sensing capabilities of the metallic nanodiscs were explored in the same manner as for the nanocrescents, meaning their response to thin layers and to bio-recognition events on their surface. The sensitivity of these nanostructures to thin films proved to be lower than that of the crescents, though in the same order of magnitude. Experimental information about the near field extension for the Au nanodiscs of different sizes was also extracted from these measurements. Further resonance-tailoring approaches based on electrochemical deposition of metals on the nanodiscs were explored, as a means of modifying plasmon resonances by changing surface properties of the nanoparticles. First results on these experiments would indicate that the deposition of Ag on Au on a submonolayer coverage level can lead to important blue-shifts in the resonances, which would open a simple way to tailor resonances by changing material properties in a local manner.

Impact of metal and metal oxide engineered nanoparticles in soil and plant systems

Nanotechnology promises huge benefits for society and capital invested in this new technology is steadily increasing, therefore there is a growing number of nanotechnology products on the market and inevitably engineered nanomaterials will be released in the atmosphere with potential risks to humans and environment. This study set out to extend the comprehension of the impact of metal (Ag, Co, Ni) and metal oxide (CeO2, Fe3O4, SnO2, TiO2) nanoparticles (NPs) on one of the most important environmental compartments potentially contaminated by NPs, the soil system, through the use of chemical and biological tools. For this purpose experiments were carried out to simulate realistic environmental conditions of wet and dry deposition of NPs, considering ecologically relevant endpoints. In detail, this thesis involved the study of three model systems and the evaluation of related issues: (i) NPs and bare soil, to assess the influence of NPs on the functions of soil microbial communities; (ii) NPs and plants, to evaluate the chronic toxicity and accumulation of NPs in edible tissues; (iii) NPs and invertebrates, to verify the effects of NPs on earthworms and the damaging of their functionality. The study highlighted that NP toxicity is generally influenced by NP core elements and the impact of NPs on organisms is specie-specific; moreover experiments conducted in media closer to real conditions showed a decrease in toxicity with respect to in vitro test or hydroponic tests. However, only a multidisciplinary approach, involving physical, chemical and biological skills, together with the use of advanced techniques, such as X-ray absorption fine structure spectroscopy, could pave the way to draw the right conclusions and accomplish a deeper comprehension of the effects of NPs on soil and soil inhabitants.

Characterization of legacy organic carbon in a culturally eutrophic lake : the role of the historic carbon deposition in the time course and extent of lake recovery

The time course of lake recovery after a reduction in external loading of nutrients is often controlled by conditions in the sediment. Remediation of eutrophication is hindered by the presence of legacy organic carbon deposits, that exert a demand on the terminal electron acceptors of the lake and contribute to problems such as internal nutrient recycling, absence of sediment macrofauna, and flux of toxic metal species into the water column. Being able to quantify the timing of a lake’s response requires determination of the magnitude and lability, i.e., the susceptibility to biodegradation, of the organic carbon within the legacy deposit. This characterization is problematic for organic carbon in sediments because of the presence of different fractions of carbon, which vary from highly labile to refractory. The lability of carbon under varied conditions was tested with a bioassay approach. It was found that the majority of the organic material found in the sediments is conditionally-labile, where mineralization potential is dependent on prevailing conditions. High labilities were noted under oxygenated conditions and a favorable temperature of 30 °C. Lability decreased when oxygen was removed, and was further reduced when the temperature was dropped to the hypolimnetic average of 8° C . These results indicate that reversible preservation mechanisms exist in the sediment, and are able to protect otherwise labile material from being mineralized under in situ conditions. The concept of an active sediment layer, a region in the sediments in which diagenetic reactions occur (with nothing occurring below it), was examined through three lines of evidence. Initially, porewater profiles of oxygen, nitrate, sulfate/total sulfide, ETSA (Electron Transport System Activity- the activity of oxygen, nitrate, iron/manganese, and sulfate), and methane were considered. It was found through examination of the porewater profiles that the edge of diagenesis occurred around 15-20 cm. Secondly, historical and contemporary TOC profiles were compared to find the point at which the profiles were coincident, indicating the depth at which no change has occurred over the (13 year) interval between core collections. This analysis suggested that no diagenesis has occurred in Onondaga Lake sediment below a depth of 15 cm. Finally, the time to 99% mineralization, the t99, was viewed by using a literature estimate of the kinetic rate constant for diagenesis. A t99 of 34 years, or approximately 30 cm of sediment depth, resulted for the slowly decaying carbon fraction. Based on these three lines of evidence , an active sediment layer of 15-20 cm is proposed for Onondaga Lake, corresponding to a time since deposition of 15-20 years. While a large legacy deposit of conditionally-labile organic material remains in the sediments of Onondaga Lake, it becomes clear that preservation, mechanisms that act to shield labile organic carbon from being degraded, protects this material from being mineralized and exerting a demand on the terminal electron acceptors of the lake. This has major implications for management of the lake, as it defines the time course of lake recovery following a reduction in nutrient loading.

Fabrication of nanoparticles by short-distance sputter deposition

During the past decades, tremendous research interests have been attracted to investigate nanoparticles due to their promising catalytic, magnetic, and optical properties. In this thesis, two novel methods of nanoparticle fabrication were introduced and the basic formation mechanisms were studied. Metal nanoparticles and polyurethane nanoparticles were separately fabricated by a short-distance sputter deposition technique and a reactive ion etching process. First, a sputter deposition method with a very short target-substrate distance is found to be able to generate metal nanoparticles on the glass substrate inside a RIE chamber. The distribution and morphology of nanoparticles are affected by the distance, the ion concentration and the process time. Densely-distributed nanoparticles of various compositions are deposited on the substrate surface when the target-substrate distance is smaller than 130mm. It is much less than the atoms’ mean free path, which is the threshold in previous research for nanoparticles’ formation. Island structures are formed when the distance is increased to 510mm, indicating the tendency to form continuous thin film. The trend is different from previously-reported sputtering method for nanoparticle fabrication, where longer distance between the target and the substrate facilitates the formation of nanoparticle. A mechanism based on the seeding effect of the substrate is proposed to interpret the experimental results. Secondly, in polyurethane nanoparticles’ fabrication, a mechanism is put forward based on the microphase separation phenomenon in block copolymer thin film. The synthesized polymers have formed dispersed and continuous phases because of the different properties between segments. With harder mechanical property, the dispersed phase is remained after RIE process while the continuous phase is etched away, leading to the formation of nanoparticles on the substrate. The nanoparticles distribution is found to be affected by the heating effect, the process time and the plasma power. Superhydrophilic property is found on samples with these two types of nanoparticles. The relationship between the nanostructure and the hydrophilicity is studied for further potential applications.

Trace metal content in Pliocene to Pleistocene sediments of ODP Leg 127 holes

Quaternary sedimentation within the Japan Sea was controlled by the configuration of peripheral sills, seasonal and long-term climatic variability, and the resultant fluctuations in sea level (Tamaki, 1988). Prior to drilling in the area, piston cores recovered from its basins contained Pleistocene sediments having distinctive color and fabric variation. Sedimentological and geochemical studies conducted on those facies indicated that the variability in fabric was the result of fluctuating marine and/or terrigenous influx to the deep-water basins of the Japan Sea (see, for example, Chough, 1984; Matoba, 1984). The sequences recovered during Leg 127 at Sites 794, 795, and 797 contain long, virtually undisturbed sequences (92.3, 123, and 119.9 mbsf [Hole 797B], respectively) of upper Miocene, upper Pliocene, and Pleistocene/Holocene sediments. The majority of these sequences consists of dark-colored (dark brown, green, and black) silty-clays, many of which are enriched in biogenic components (majority silicious, some carbonate) and/or organic matter, some containing pyrite and/or ash. These facies alternate with light-colored silty-clays, some containing ash and some showing signs of bioturbation (for example, Tamaki, Pisciotto, Allan, et al., 1990, p. 425-433). The dark-to-light sequences are present throughout the section, although they are especially dominant throughout the Pleistocene (for a more detailed lithology of Quaternary sequences recovered at Sites 794, 795, and 797, see Follmi et al. 1992 and Tada et al., 1992). This data report provides trace metal information on Pliocene-Pleistocene-Holocene samples at Sites 794,795, and 797. These data can be used (1) to provide information related to the depositional environments of the Japan Sea during the Quaternary period, (2) to permit comparisons between the dark organic-rich sediments recovered from this semi-enclosed basin and those reported for other silled basins (for example, the Mediterranean and Black seas), and (3) to permit comparisons between these sediments and contemporary equivalents found, for instance, beneath areas of high biogenic productivity. By providing such data, one should be able (1) to determine more precisely the processes governing the deposition of sediments with various levels of organic matter within enclosed basins, (2) to compare individual basin-wide processes, (3) to look for and compare the signatures present as a result of climatic fluctuation, and (4) to attempt to identify the presence and/or absence of cyclicity within such sequences.

Measurements of trace metal abundances and isotopes in carbonate sediments, Exuma, Bahamas

In order to validate the use of 238U/235U as a paleoredox proxy in carbonates, we examined the incorporation and early diagenetic evolution of U isotopes in shallow Bahamian carbonate sediments. Our sample set consists of a variety of primary precipitates that represent a range of carbonate producing organisms and components that were important in the past (scleractinian corals, calcareous green and red algae, ooids, and mollusks). In addition, four short push cores were taken in different depositional environments to assess the impact of early diagenesis and pore water chemistry on the U isotopic composition of bulk carbonates. We find that U concentrations are much higher in bulk carbonate sediments (avg. 4.1 ppm) than in primary precipitates (avg. 1.5 ppm). In almost all cases, the lowest bulk sediment U concentrations were as high as or higher than the highest concentrations found in primary precipitates. This is consistent with authigenic accumulation of reduced U(IV) during early diagenesis. The extent of this process appears sensitive to pore water H2S, and thus indirectly to organic matter content. d238/235U values were very close to seawater values in all of the primary precipitates, suggesting that these carbonate components could be used to reconstruct changes in seawater U geochemistry. However, d238/235U of bulk sediments from the push cores was 0.2-0.4 per mil heavier than seawater (and primary precipitates). These results indicate that authigenic accumulation of U under open-system sulfidic pore water conditions commonly found in carbonate sediments strongly affects the bulk U concentrations and 238U/235U ratios. We also report the occurrence of dolomite in a tidal pond core which contains low 234U/238U and 238U/235U ratios and discuss the possibility that the dolomitization process may result in sediments depleted in 238U. From this initial exploration, it is clear that 238U/235U variations in ancient carbonate sediments could be driven by changes in global average seawater, by spatial and temporal variations in the local deposition environment, or subsequent diagenesis. To cope with such effects, proxies for syndepositional pore water redox conditions (e.g., organic matter content, iron speciation, and trace metal distributions) and careful consideration of possible post-deposition alteration will be required to avoid spurious interpretation of 238U/235U data from ancient carbonate sediments.

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.

Self-organized colloidal quantum dots and metal nanoparticles for plasmon-enhanced intermediate-band solar cells

A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude. In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance. The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

Low metal content Co and Ni alumina supported catalysts for the CO2 reforming of methane

Low metal content Co and Ni alumina supported catalysts (4.0, 2.5 and 1.0 wt% nominal metal content) have been prepared, characterized (by ICP-OES, TEM, TPR-H2 and TPO) and tested for the CO2 reforming of methane. The objective is to optimize the metal loading in order to have a more efficient system. The selected reaction temperature is 973 K, although some tests at higher reaction temperature have been also performed. The results show that the amount of deposited carbon is noticeably lower than that obtained with the Co and Ni reference catalysts (9 wt%), but the CH4 and CO2 conversions are also lower. Among the catalysts tested, the Co(1) catalyst (the value in brackets corresponds to the nominal wt% loading) is deactivated during the first minutes of reaction because CoAl2O4 is formed, while Ni(1) and Co(2.5) catalysts show a high specific activity for methane conversion, a high stability and a very low carbon deposition.

(Table 2) Trace metal concentrations in ODP Hole 169-1033B

We measured the concentrations of redox-sensitive trace metals (Mn, V, Mo, U, Cd and Re) in sediments from ODP Leg 169S Hole 1033B in Saanich Inlet, British Columbia, to determine changes in redox conditions associated with the onset of laminated sediments at ~12.5 kyr. The most striking result is a large peak in authigenic Re along with detrital levels of Mo at the glacial terrigenous clay-diatomaceous sediment transition. In contrast, the underlying glacial terrigenous clay, which extends throughout the bottom section of the core, is chemically similar to detrital concentrations, either Cowichan River particulates or average shale values. These data suggest a period of oxic bottom waters but reducing pore-waters. This could be due to the dramatic transformation of Saanich Inlet during the late deglaciation from an open bay to an inlet, which restricted circulation and slowed bottom water oxygen renewal. A peak and gradual increase in authigenic Mn in younger sediments subsequent to the Re peak suggests that increasingly oxic conditions followed the authigenic enrichment in Re. These conditions could be connected to the Younger Dryas cooling period, which was coincident with an increase in well oxygenated upwelled waters on the west coast of North America that form the bottom waters of Saanich Inlet. Metal concentrations in a gray clay bed (~11 kyr) are similar to their concentrations in the glacial terrigenous clay, implying that they have a common source. Authigenic enrichments of Re with little authigenic Mo and Cd suggest that before the deposition of this bed, bottom waters were oxic and pore-water oxygen was consumed in the top centimeter or less. Laminations above the clay layer suggest anoxic conditions, which are also indicated by higher authigenic Mo and Cd and slightly lower Re/Mo ratios in these sediments. The basin remained mostly anoxic after the gray clay was emplaced, as seen by continuous authigenic enrichment of the redox-sensitive trace metals. These results are consistent with increased stratification of the water column, brought about by an influx of fresh water to the basin by a large flood.

Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).