Patterns of phosphorus, nitrogen and δ15N along a peat development gradient in a coastal mire, Panama

Differentiation of limiting nutrients within small spatial scales has been observed in coastal mangrove forests, but research on other tropical peatlands suggests it is a more widespread phenomenon. In the Changuinola mire of coastal Panama, oligotrophy was hypothesized to increase along a gradient of peat development (peat doming). Nutrient and carbon concentration of leaf tissue, soil, and soil porewater were characterised over a successive sequence of plant communities along the gradient. Soil phosphorus (P) and nitrogen (N) concentrations decreased from 1200 μg P g−1 and 27 mg N g−1 to 377 μg P g−1 and 22 mg N g−1 within 2.7 km into the mire interior. These changes coincided with an increase in soil and average leaf N:P molar ratios from 52–128 and 24–41, respectively. Soil P was strongly related to leaf P and soil N:P to foliar N:P. There was a wide range in δ15N values for canopy (4.0 to −9.4‰), Campnosperma panamense (4.0 to −7.8‰) and understorey (4.8 to −3.1‰) species. Foliar δ15N values of canopy species were strongly related to soil N:P, soil P and leaf P. The depleted foliar δ15N values appeared to be an effect of both the N atmospheric source and P limitation. Here, P limitation is likely associated with ombrotrophic conditions that developed as hydrologic inputs became dominated by precipitation.

Evaluation of the evidential value of the elemental composition of glass, ink and paper by laser-based microspectrochemical methods

Elemental analysis can become an important piece of evidence to assist the solution of a case. The work presented in this dissertation aims to evaluate the evidential value of the elemental composition of three particular matrices: ink, paper and glass. In the first part of this study, the analytical performance of LIBS and LA-ICP-MS methods was evaluated for paper, writing inks and printing inks. A total of 350 ink specimens were examined including black and blue gel inks, ballpoint inks, inkjets and toners originating from several manufacturing sources and/or batches. The paper collection set consisted of over 200 paper specimens originating from 20 different paper sources produced by 10 different plants. Micro-homogeneity studies show smaller variation of elemental compositions within a single source (i.e., sheet, pen or cartridge) than the observed variation between different sources (i.e., brands, types, batches). Significant and detectable differences in the elemental profile of the inks and paper were observed between samples originating from different sources (discrimination of 87–100% of samples, depending on the sample set under investigation and the method applied). These results support the use of elemental analysis, using LA-ICP-MS and LIBS, for the examination of documents and provide additional discrimination to the currently used techniques in document examination. In the second part of this study, a direct comparison between four analytical methods (µ-XRF, solution-ICP-MS, LA-ICP-MS and LIBS) was conducted for glass analyses using interlaboratory studies. The data provided by 21 participants were used to assess the performance of the analytical methods in associating glass samples from the same source and differentiating different sources, as well as the use of different match criteria (confidence interval (±6s, ±5s, ±4s, ±3s, ±2s), modified confidence interval, t-test (sequential univariate, p=0.05 and p=0.01), t-test with Bonferroni correction (for multivariate comparisons), range overlap, and Hotelling's T2 tests. Error rates (Type 1 and Type 2) are reported for the use of each of these match criteria and depend on the heterogeneity of the glass sources, the repeatability between analytical measurements, and the number of elements that were measured. The study provided recommendations for analytical performance-based parameters for µ-XRF and LA-ICP-MS as well as the best performing match criteria for both analytical techniques, which can be applied now by forensic glass examiners.

Sediment Accretion and Organic Carbon Burial Relative to Sea-Level Rise and Storm Events in Two Mangrove Forests in Everglades National Park

The goal of this investigation was to examine how sediment accretion and organic carbon (OC) burial rates in mangrove forests respond to climate change. Specifically, will the accretion rates keep pace with sea-level rise, and what is the source and fate of OC in the system? Mass accumulation, accretion and OC burial rates were determined via 210Pb dating (i.e. 100 year time scale) on sediment cores collected from two mangrove forest sites within Everglades National Park, Florida (USA). Enhanced mass accumulation, accretion and OC burial rates were found in an upper layer that corresponded to a well-documented storm surge deposit. Accretion rates were 5.9 and 6.5 mm yr− 1 within the storm deposit compared to overall rates of 2.5 and 3.6 mm yr− 1. These rates were found to be matching or exceeding average sea-level rise reported for Key West, Florida. Organic carbon burial rates were 260 and 393 g m− 2 yr− 1 within the storm deposit compared to 151 and 168 g m− 2 yr− 1 overall burial rates. The overall rates are similar to global estimates for OC burial in marine wetlands. With tropical storms being a frequent occurrence in this region the resulting storm surge deposits are an important mechanism for maintaining both overall accretion and OC burial rates. Enhanced OC burial rates within the storm deposit could be due to an increase in productivity created from higher concentrations of phosphorus within storm-delivered sediments and/or from the deposition of allochthonous OC. Climate change-amplified storms and sea-level rise could damage mangrove forests, exposing previously buried OC to oxidation and contribute to increasing atmospheric CO2 concentrations. However, the processes described here provide a mechanism whereby oxidation of OC would be limited and the overall OC reservoir maintained within the mangrove forest sediments.

Data compilation on the biological response to ocean acidification: environmental and experimental context of data sets and related literature

The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

Advanced thermal analysis of microelectronics using spreading resistance models

Thermal analysis of electronic devices is one of the most important steps for designing of modern devices. Precise thermal analysis is essential for designing an effective thermal management system of modern electronic devices such as batteries, LEDs, microelectronics, ICs, circuit boards, semiconductors and heat spreaders. For having a precise thermal analysis, the temperature profile and thermal spreading resistance of the device should be calculated by considering the geometry, property and boundary conditions. Thermal spreading resistance occurs when heat enters through a portion of a surface and flows by conduction. It is the primary source of thermal resistance when heat flows from a tiny heat source to a thin and wide heat spreader. In this thesis, analytical models for modeling the temperature behavior and thermal resistance in some common geometries of microelectronic devices such as heat channels and heat tubes are investigated. Different boundary conditions for the system are considered. Along the source plane, a combination of discretely specified heat flux, specified temperatures and adiabatic condition are studied. Along the walls of the system, adiabatic or convective cooling boundary conditions are assumed. Along the sink plane, convective cooling with constant or variable heat transfer coefficient are considered. Also, the effect of orthotropic properties is discussed. This thesis contains nine chapters. Chapter one is the introduction and shows the concepts of thermal spreading resistance besides the originality and importance of the work. Chapter two reviews the literatures on the thermal spreading resistance in the past fifty years with a focus on the recent advances. In chapters three and four, thermal resistance of a twodimensional flux channel with non-uniform convection coefficient in the heat sink plane is studied. The non-uniform convection is modeled by using two functions than can simulate a wide variety of different heat sink configurations. In chapter five, a non-symmetrical flux channel with different heat transfer coefficient along the right and left edges and sink plane is analytically modeled. Due to the edge cooling and non-symmetry, the eigenvalues of the system are defined using the heat transfer coefficient on both edges and for satisfying the orthogonality condition, a normalized function is calculated. In chapter six, thermal behavior of two-dimensional rectangular flux channel with arbitrary boundary conditions on the source plane is presented. The boundary condition along the source plane can be a combination of the first kind boundary condition (Dirichlet or prescribed temperature) and the second kind boundary condition (Neumann or prescribed heat flux). The proposed solution can be used for modeling the flux channels with numerous different source plane boundary conditions without any limitations in the number and position of heat sources. In chapter seven, temperature profile of a circular flux tube with discretely specified boundary conditions along the source plane is presented. Also, the effect of orthotropic properties are discussed. In chapter 8, a three-dimensional rectangular flux channel with a non-uniform heat convection along the heat sink plane is analytically modeled. In chapter nine, a summary of the achievements is presented and some systems are proposed for the future studies. It is worth mentioning that all the models and case studies in the thesis are compared with the Finite Element Method (FEM).

IRAS 00183-7111: ALMA and X-ray view of an ultra luminous infrared galaxy

The aim of this Thesis work is to study the multi-frequency properties of the Ultra Luminous Infrared Galaxy (ULIRG) IRAS 00183-7111 (I00183) at z = 0.327, connecting ALMA sub-mm/mm observations with those at high energies in order to place constraints on the properties of its central power source and verify whether the gas traced by the CO may be responsible for the obscuration observed in X-rays. I00183 was selected from the so-called Spoon diagnostic diagram (Spoon et al. 2007) for mid-infrared spectra of infrared galaxies based on the equivalent width of the 6.2 μm Polycyclic Aromatic Hydrocarbon (PAH) emission feature versus the 9.7 μm silicate strength. Such features are a powerful tool to investigate the contribution of star formation and AGN activity in this class of objects. I00183 was selected from the top-left region of the plot where the most obscured sources, characterized by a strong Si absorption feature, are located. To link the sub-mm/mm to the X-ray properties of I00183, ALMA archival Cycle 0 data in Band 3 (87 GHz) and Band 6 (270 GHz) have been calibrated and analyzed, using CASA software. ALMA Cycle 0 was the Early Science program for which data reprocessing is strongly suggested. The main work of this Thesis consisted in reprocessing raw data to provide an improvement with respect to the available archival products and results, which were obtained using standard procedures. The high-energy data consists of Chandra, XMM-Newton and NuSTAR observations which provide a broad coverage of the spectrum in the energy range 0.5 − 30 keV. Chandra and XMM archival data were used, with an exposure time of 22 and 22.2 ks, respectively; their reduction was carried out using CIAO and SAS software. The 100 ks NuSTAR are still private and the spectra were obtained by courtesy of the PI (K. Iwasawa). A detailed spectral analysis was done using XSPEC software; the spectral shape was reproduced starting from simple phenomenological models, and then more physical models were introduced to account for the complex mechanisms that involve this source. In Chapter 1, an overview of the scientific background is discussed, with a focus on the target, I00183, and the Spoon diagnostic diagram, from which it was originally selected. In Chapter 2, the basic principles of interferometry are briefly introduced, with a description of the calibration theory applied to interferometric observations. In Chapter 3, ALMA and its capabilities, both current and future, are shown, explaining also the complex structure of the ALMA archive. In Chapter 4, the calibration of ALMA data is presented and discussed, showing also the obtained imaging products. In Chapter 5, the analysis and discussion of the main results obtained from ALMA data is presented. In Chapter 6, the X-ray observations, data reduction and spectral analysis are reported, with a brief introduction to the basic principle of X-ray astronomy and the instruments from which the observations were carried out. Finally, the overall work is summarized, with particular emphasis on the main obtained results and the possible future perspectives.

Total mercury and total methylmercury during the POLARSTERN cruise ARK-XXVI/3 (TransArc)

Methylmercury (MeHg) is a neurotoxic compound that threatens wildlife and human health across the Arctic region. Though much is known about the source and dynamics of its inorganic mercury (Hg) precursor, the exact origin of the high MeHg concentrations in Arctic biota remains uncertain. Arctic coastal sediments, coastal marine waters and surface snow are known sites for MeHg production. Observations on marine Hg dynamics, however, have been restricted to the Canadian Archipelago and the Beaufort Sea (<79°N). Here we present the first central Arctic Ocean (79-90°N) profiles for total mercury (tHg) and MeHg. We find elevated tHg and MeHg concentrations in the marginal sea ice zone (81-85°N). Similar to other open ocean basins, Arctic MeHg concentration maxima also occur in the pycnocline waters, but at much shallower depths (150-200 m). The shallow MeHg maxima just below the productive surface layer possibly result in enhanced biological uptake at the base of the Arctic marine food web and may explain the elevated MeHg concentrations in Arctic biota. We suggest that Arctic warming, through thinning sea ice, extension of the seasonal sea ice zone, intensified surface ocean stratification and shifts in plankton ecodynamics, will likely lead to higher marine MeHg production.

Chlorofluorocarbons, helium, and neon measured on water bottle samples during POLARSTERN cruise ANT-XXII/2 (ISPOL)

During Ice Station POLarstern (ISPOL; R.V. Polarstern cruise ANT XXII/2, November 2004-January 2005), hydrographic and tracer observations were obtained in the western Weddell Sea while drifting closely in front of the Larsen Ice Shelf. These observations indicate recently formed Weddell Sea Bottom Water, which contains significant contributions of glacial melt water in its upper part, and High-Salinity Shelf Water in its lower layer. The formation of this bottom water cannot be related to the known sources in the south, the Filchner-Ronne Ice Shelf. We show that this bottom water is formed in the western Weddell Sea, most likely in interaction with the Larsen C Ice Shelf. By applying an Optimum Multiparameter Analysis (OMP) using temperature, salinity, and noble gas observations (helium isotopes and neon), we obtained mean glacial melt-water fractions of about 0.1% in the bottom water. On sections across the Weddell Gyre farther north, melt-water fractions are still on the order of 0.04%. Using chlorofluorocarbons (CFCs) as age tracers, we deduced a mean transit time between the western source and the bottom water found on the slope toward the north (9±3 years). This transit time is larger and the inferred transport rate is small in comparison to previous findings. But accounting for a loss of the initially formed bottom water volume due to mixing and renewal of Weddell Sea Deep Water, a formation rate of 1.1±0.5 Sv in the western Weddell Sea is plausible. This implies a basal melt rate of 35±19 Gt/year or 0.35±0.19 m/year at the Larsen Ice Shelf. This bottom water is shallow enough that it could leave the Weddell Basin through the gaps in the South Scotia Ridge to supply Antarctic Bottom Water. These findings emphasize the role of the western Weddell Sea in deep- and bottom-water formation, particularly in view of changing environmental conditions due to climate variability, which might induce enhanced melting or even decay of ice shelves.

Design, Fabrication, and Characterization of Carbon Nanotube Field Emission Devices for Advanced Applications

Carbon nanotubes (CNTs) have recently emerged as promising candidates for electron field emission (FE) cathodes in integrated FE devices. These nanostructured carbon materials possess exceptional properties and their synthesis can be thoroughly controlled. Their integration into advanced electronic devices, including not only FE cathodes, but sensors, energy storage devices, and circuit components, has seen rapid growth in recent years. The results of the studies presented here demonstrate that the CNT field emitter is an excellent candidate for next generation vacuum microelectronics and related electron emission devices in several advanced applications.

The work presented in this study addresses determining factors that currently confine the performance and application of CNT-FE devices. Characterization studies and improvements to the FE properties of CNTs, along with Micro-Electro-Mechanical Systems (MEMS) design and fabrication, were utilized in achieving these goals. Important performance limiting parameters, including emitter lifetime and failure from poor substrate adhesion, are examined. The compatibility and integration of CNT emitters with the governing MEMS substrate (i.e., polycrystalline silicon), and its impact on these performance limiting parameters, are reported. CNT growth mechanisms and kinetics were investigated and compared to silicon (100) to improve the design of CNT emitter integrated MEMS based electronic devices, specifically in vacuum microelectronic device (VMD) applications.

Improved growth allowed for design and development of novel cold-cathode FE devices utilizing CNT field emitters. A chemical ionization (CI) source based on a CNT-FE electron source was developed and evaluated in a commercial desktop mass spectrometer for explosives trace detection. This work demonstrated the first reported use of a CNT-based ion source capable of collecting CI mass spectra. The CNT-FE source demonstrated low power requirements, pulsing capabilities, and average lifetimes of over 320 hours when operated in constant emission mode under elevated pressures, without sacrificing performance. Additionally, a novel packaged ion source for miniature mass spectrometer applications using CNT emitters, a MEMS based Nier-type geometry, and a Low Temperature Cofired Ceramic (LTCC) 3D scaffold with integrated ion optics were developed and characterized. While previous research has shown other devices capable of collecting ion currents on chip, this LTCC packaged MEMS micro-ion source demonstrated improvements in energy and angular dispersion as well as the ability to direct the ions out of the packaged source and towards a mass analyzer. Simulations and experimental design, fabrication, and characterization were used to make these improvements.

Finally, novel CNT-FE devices were developed to investigate their potential to perform as active circuit elements in VMD circuits. Difficulty integrating devices at micron-scales has hindered the use of vacuum electronic devices in integrated circuits, despite the unique advantages they offer in select applications. Using a combination of particle trajectory simulation and experimental characterization, device performance in an integrated platform was investigated. Solutions to the difficulties in operating multiple devices in close proximity and enhancing electron transmission (i.e., reducing grid loss) are explored in detail. A systematic and iterative process was used to develop isolation structures that reduced crosstalk between neighboring devices from 15% on average, to nearly zero. Innovative geometries and a new operational mode reduced grid loss by nearly threefold, thereby improving transmission of the emitted cathode current to the anode from 25% in initial designs to 70% on average. These performance enhancements are important enablers for larger scale integration and for the realization of complex vacuum microelectronic circuits.

Organic functionalisation, doping and characterisation of semiconductor surfaces for future CMOS device applications

Organic Functionalisation, Doping and Characterisation of Semiconductor Surfaces for Future CMOS Device Applications Semiconductor materials have long been the driving force for the advancement of technology since their inception in the mid-20th century. Traditionally, micro-electronic devices based upon these materials have scaled down in size and doubled in transistor density in accordance with the well-known Moore’s law, enabling consumer products with outstanding computational power at lower costs and with smaller footprints. According to the International Technology Roadmap for Semiconductors (ITRS), the scaling of metal-oxide-semiconductor field-effect transistors (MOSFETs) is proceeding at a rapid pace and will reach sub-10 nm dimensions in the coming years. This scaling presents many challenges, not only in terms of metrology but also in terms of the material preparation especially with respect to doping, leading to the moniker “More-than-Moore”. Current transistor technologies are based on the use of semiconductor junctions formed by the introduction of dopant atoms into the material using various methodologies and at device sizes below 10 nm, high concentration gradients become a necessity. Doping, the controlled and purposeful addition of impurities to a semiconductor, is one of the most important steps in the material preparation with uniform and confined doping to form ultra-shallow junctions at source and drain extension regions being one of the key enablers for the continued scaling of devices. Monolayer doping has shown promise to satisfy the need to conformally dope at such small feature sizes. Monolayer doping (MLD) has been shown to satisfy the requirements for extended defect-free, conformal and controllable doping on many materials ranging from the traditional silicon and germanium devices to emerging replacement materials such as III-V compounds This thesis aims to investigate the potential of monolayer doping to complement or replace conventional doping technologies currently in use in CMOS fabrication facilities across the world.

Geochemistry of carbon at DSDP Legs 58 and 59 Holes

I obtained 68 quarter sections of cores from the JOIDES Organic Geochemistry Panel for studying type, distribution, and stages of organic diagenesis of sedimentary organic matter in the West Philippine and Parece Vela basins and Mariana Trough area (Figure 1). The present chapter compares (1) 11 geochemical parameters used to determine organic source and its stage of genesis within the 9 site locations in this study area and (2) compares these 11 with the same parameters reported from Leg 56, outer trench slope of the Japan Trench, and Leg 60, Mariana Trough and Trench (Schorno, in press a, b). Even though these sediments are considered pelagic, the organic content in most of the core sections appears to be hemipelagic. The sedimentary organic matter in these cores is believed to be in an early stage of diagenesis. Both conclusions are based primarily on the fl-alkane distribution within the organic matter. This particular parameter, I note later, has a major weakness. As Hunt (Hunt, 1979) and I (in press b) observed, marine organisms synthesize /z-alkanes with distributions containing neither odd nor even preferences. Thus those sediments that did contain w-alkane distributions with OEP near 1, suggesting a late stage of catagenesis, may in actuality be immature marine sediments.

Strontium and neodymium concentrations and isotopic compositions of Arctic marine sediments

Sr and Nd isotopic compositions of Arctic marine sediments characterize changes of sediment source regions and trace shelf-ocean particle pathways during glacial-interglacial transitions in the eastern Arctic Ocean. In the 140-ka sedimentary record of a marine core from Yermak Plateau, north of Svalbard, 87Sr/86Sr ratios and epsion-Nd values vary between 0.717 and 0.740 and 39.3 and 314.9, respectively. Sr and Nd isotopic composition both change characteristically during glacial-interglacial cycles and are correlated with the extension of the Svalbard/Barents Sea ice sheet (SBIS). The downcore variation in Sr and Nd isotopic composition indicates climatically induced changes in sediment provenance from two isotopically distinct end-members: (1) Eurasian shelf sediments as a distal source; and (2) Svalbard bedrock as a proximal source that coincide with a change in transport mechanism from sea ice to glacial ice. During glacier advance from Svalbard and intensified glacial bedrock erosion, epsion-Nd values decrease gradually to a minimum value of 314.9 due to increased input of crystalline Svalbard bedrock material. During glacial maxima, the SBIS covered the entire Barents Sea shelf and supplied increasing amounts of Eurasian shelf material to the Arctic Ocean as ice rafted detritus (IRD). Epsion-Nd values in glacial sediments reach maximum values that are comparable to the average value of modern Eurasian shelf and sea ice sediments (epsion-Nd = 310.3). This confirms ice rafting as a major sediment transport mechanism for Eurasian shelf sediments into the Arctic Ocean and trace a sediment origin from the Kara Sea/Laptev Sea shelf area. After the decay of the shelf-based SBIS, the glacial shelf sediment spikes during glacial terminations I (epsion-Nd = 310.6) and II (epsion-Nd = 310.1) epsion-Nd values rapidly decrease to values of 312.5 typical for interglacial averages. The downcore Sr isotopic composition is anticorrelated to the Nd isotopic composition, but may be also influenced by grain-size effects. In contrast, the Nd isotopic composition in clay- to silt-size fractions of one bulk sediment sample is similar to within 0.3-0.8 epsion-Nd units and seems to be a grain-size independent provenance tracer.

(Table DR1) Argon isotope data and dating for individual >63 µm amphibole grains from Labrador Sea sediments, ODP Hole 105-647A

Variations of global and regional silicate weathering rates and paleo-ocean circulation patterns are estimated by using radiogenic isotope records, but the effects of changes in provenance are generally ignored. Here sediment provenance has been constrained through the use of Ar-Ar ages for individual detrital minerals from the Labrador Sea, which can be compared directly to the radiogenic isotope compositions from the same core material. Dramatic changes in the radiogenic isotope composition of North Atlantic Deep Water through the Quaternary Period are shown to reflect discrete changes in both sources and weathering processes accompanying Northern Hemisphere glaciation. Changes in the different radiogenic isotope systems reflect the influence of source, physical weathering, and chemical weathering, and not simply changes in the underlying weathering rate or ocean circulation patterns that are typically inferred.

Nitrite consumption and associated isotope changes during a river flood event in the Elbe river

In oceans, estuaries, and rivers, nitrification is an important nitrate source, and stable isotopes of nitrate are often used to investigate recycling processes (e.g. remineralisation, nitrification) in the water column. Nitrification is a two-step process, where ammonia is oxidised via nitrite to nitrate. Nitrite usually does not accumulate in natural environments, which makes it difficult to study the single isotope effect of ammonia oxidation or nitrite oxidation in natural systems. However, during an exceptional flood in the Elbe River in June 2013, we found a unique co-occurrence of ammonium, nitrite, and nitrate in the water column, returning towards normal summer conditions within 1 week. Over the course of the flood, we analysed the evolution of d15N-[NH4]+ and d15N-[NO2]- in the Elbe River. In concert with changes in suspended particulate matter (SPM) and d15N SPM, as well as nitrate concentration, d15N-NO3 - and d18O-[NO3] -, we calculated apparent isotope effects during net nitrite and nitrate consumption. During the flood event, > 97 % of total reactive nitrogen was nitrate, which was leached from the catchment area and appeared to be subject to assimilation. Ammonium and nitrite concentrations increased to 3.4 and 4.4 µmol/l, respectively, likely due to remineralisation, nitrification, and denitrification in the water column. d15N-[NH4]+ values increased up to 12 per mil, and d15N-[NO2]- ranged from -8.0 to -14.2 per mil. Based on this, we calculated an apparent isotope effect 15-epsilon of -10.0 ± 0.1 per mil during net nitrite consumption, as well as an isotope effect 15-epsilon of -4.0 ± 0.1 per mil and 18-epsilon of -5.3 ± 0.1 per mil during net nitrate consumption. On the basis of the observed nitrite isotope changes, we evaluated different nitrite uptake processes in a simple box model. We found that a regime of combined riparian denitrification and 22 to 36 % nitrification fits best with measured data for the nitrite concentration decrease and isotope increase.

(Table 1) Bulk Fe isotope values and pyrite framboids sizes of Cenomanian-Turonian samples

Organic carbon-rich shales from localities in England, Italy, and Morocco, which formed during the Cenomanian-Turonian oceanic anoxic event (OAE), have been examined for their total organic carbon (TOC) values together with their carbon, nitrogen, and iron isotope ratios. Carbon isotope stratigraphy (d13Corg and d13Ccarb) allows accurate recognition of the strata that record the oceanic anoxic event, in some cases allowing characterization of isotopic species before, during, and after the OAE. Within the black shales formed during the OAE, relatively heavy nitrogen isotope ratios, which correlate positively with TOC, suggest nitrate reduction (leading ultimately to denitrification and/or anaerobic ammonium oxidation). Black shales deposited before the onset of the OAE in Italy have unusually low bulk d57Fe values, unlike those found in the black shale (Livello Bonarelli) deposited during the oceanic anoxic event itself: These latter conform to the Phanerozoic norm for organic-rich sediments. Pyrite formation in the pre-OAE black shales has apparently taken place via dissimilatory iron reduction (DIR), within the sediment, a suboxic process that causes an approximately -2 per mil fractionation between a lithogenic Fe(III)oxide source and Fe(II)aq. In contrast, bacterial sulfate reduction (BSR), at least partly in the water column, characterized the OAE itself and was accompanied by only minor iron isotope fractionation. This change in the manner of pyrite formation is reflected in a decrease in the average pyrite framboid diameter from ~10 to ~7 µm. The gradual, albeit irregular increase in Fe isotope values during the OAE, as recorded in the Italian section, is taken to demonstrate limited isotopic evolution of the dissolved iron pool, consequent upon ongoing water column precipitation of pyrite under euxinic conditions. Given that evidence exists for both nitrate and sulfate reduction during the OAE, it is evident that redox conditions in the water column were highly variable, in both time and space.