Numerical analysis of four-wave mixing between 2 ps mode-locked laser pulses in a tensile-strained bulk SOA

A numerical model of four-wave mixing between 2-ps pulses in a tensile-strained bulk semiconductor optical amplifier is presented. The model utilizes a modified Schrodinger equation to model the pulse propagation. The Schrodinger equation parameters such as the material gain first and second order dispersion, linewidth enhancement factors and optical loss coefficient are obtained using a previously developed steady-state model. The predicted four-wave mixing pulse characteristics show reasonably good agreement with experimental pulse characteristics obtained using frequency resolved optical gating

Developments in marine pCO2 measurement technology; towards sustained in situ observations

The oceanic uptake of anthropogenic CO2 causes pronounced changes to the marine carbonate system. High quality pCO2 measurements with good temporal and spatial coverage are required to monitor the oceanic uptake, identify regions with pronounced carbonate system changes, and observe the effectiveness of CO2 emission mitigation strategies. There are currently several instruments available, but many are unsuitable for autonomous deployments on in situ platforms such as gliders, moorings and Argo floats. We assess currently available technology on its suitability for in situ deployment, with a focus on optode technology developments. Optodes for pCO2 measurements provide a promising new technological approach, and were successfully calibrated over the range of 280–480 μatm applying modified time-domain dual lifetime referencing. A laboratory precision of 0.8 μatm (n = 10) and a response time (τ90) of 165 s were achieved, and with further development pCO2 optodes may become as widely used as their oxygen counterparts

Talc-dominated seafloor deposits reveal a new class of hydrothermal system

The Von Damm Vent Field (VDVF) is located on the flanks of the Mid-Cayman Spreading Centre, 13?km west of the axial rift, within a gabbro and peridotite basement. Unlike any other active vent field, hydrothermal precipitates at the VDVF comprise 85–90% by volume of the magnesium silicate mineral, talc. Hydrothermal fluids vent from a 3-m high, 1-m diameter chimney and other orifices at up to 215?°C with low metal concentrations, intermediate pH (5.8) and high concentrations (667?mmol?kg?1) of chloride relative to seawater. Here we show that the VDVF vent fluid is generated by interaction of seawater with a mafic and ultramafic basement which precipitates talc on mixing with seawater. The heat flux at the VDVF is measured at 487±101?MW, comparable to the most powerful magma-driven hydrothermal systems known, and may represent a significant mode of off-axis oceanic crustal cooling not previously recognized or accounted for in global models

Behaviour of chromium isotopes in the eastern sub-tropical Atlantic Oxygen Minimum Zone

Constraints on the variability of chromium (Cr) isotopic compositions in the modern ocean are required to validate the use of Cr isotopic signatures in ancient authigenic marine sediments for reconstructing past levels of atmospheric and ocean oxygenation. This study presents dissolved Cr concentrations (CrT, where CrT = Cr(VI) + Cr(III)) and Cr isotope data (δ53Cr) for shelf, slope and open ocean waters within the oxygen minimum zone (OMZ) of the eastern sub-tropical Atlantic Ocean. Although dissolved oxygen concentrations were as low as 44–90 μmol kg−1 in the core of the OMZ, there was no evidence for removal of Cr(VI). Nonetheless, there was significant variability in seawater δ53Cr, with values ranging from 1.08 to 1.72‰. Shelf CrT concentrations were slightly lower (2.21 ± 0.07 nmol kg−1) than in open ocean waters at the same water depth (between 0 and 160 m, 2.48 ± 0.07 nmol kg−1). The shelf waters also had higher δ53Cr values (1.41 ± 0.14‰ compared to 1.18 ± 0.05‰ for open ocean waters shallower than 160 m). This is consistent with partial reduction of Cr(VI) to Cr(III), with subsequent removal of isotopically light Cr(III) onto biogenic particles. We also provide evidence for input of relatively isotopically heavy Cr from sediments on the shelf. Intermediate and deep water masses (AAIW and NADW) show a rather limited range of δ53Cr values (1.19 ± 0.09‰) and inputs of Cr from remineralisation of organic material or re-oxidation of Cr(III) appear to be minimal. Authigenic marine precipitates deposited in deep water in the open ocean therefore have the potential to faithfully record seawater δ53Cr, whereas archives of seawater δ53Cr derived from shelf sediments must be interpreted with caution

Application of Stable Carbon Isotopes in a Subtropical North Atlantic MesocosmStudy: A New Approach to Assess CO2 Effects on the Marine Carbon Cycle

Stable isotope ratio analysis offers a unique opportunity to obtain information on ecosystem processes. The increase in atmospheric CO2 as a consequence of fossil fuel combustion and land-use change is altering the stable carbon isotope composition (δ13C) of the atmosphere and ocean. This work investigates the application of using δ13C measurements of seawater samples to explore the biogeochemical responses of marine ecosystems to anthropogenic CO2 perturbations. The combination of isotopic and non-isotopic measurements from a subtropical North-Atlantic mesocosm experiment provided a holistic view of the biogeochemical mechanisms that affect carbon dynamics under a gradient of pCO2 ranging from ~350 up to ~1,000 μatm during a phytoplankton succession. A clear CO2 response was detected in the isotopic datasets with 13C shifts of up to ~5%0, but increased CO2 levels only had a subtle effect on the concentrations of the dissolved and particulate organic carbon pools. Distinctive δ13C signatures of the particulate organic carbon pools in the water column and sediment traps were detectable for the different CO2 treatments after a nutrient stimulated phytoplankton bloom. These signatures were strongly correlated (p 0.05). Fractionation of carbon isotopes in phytoplankton was positively affected (9.6 < ε < 16.5%0) by high CO2 levels either because of the higher CO2 availability or because of a shift in phytoplankton community composition. Nevertheless, phytoplankton bloom intensity and development was independent of CO2 concentrations, and higher CO2 levels had no significant effect on inorganic nutrient uptake. Results from this mesocosm experiment showed that variations in the carbon isotopic signature of the carbon pools depend on both physical (air-sea exchange) and biological (community composition) drivers opening the door to new approaches for investigations of carbon cycling in marine ecosystems

Fluxes and fate of dissolved methane released at the seafloor at the landward limit of the gas hydrate stability zone offshore western Svalbard

Widespread seepage of methane from seafloor sediments offshore Svalbard close to the landward limit of the gas hydrate stability zone (GHSZ) may, in part, be driven by hydrate destabilization due to bottom water warming. To assess whether this methane reaches the atmosphere where it may contribute to further warming, we have undertaken comprehensive surveys of methane in seawater and air on the upper slope and shelf region. Near the GHSZ limit at ?400 m water depth, methane concentrations are highest close to the seabed, reaching 825 nM. A simple box model of dissolved methane removal from bottom waters by horizontal and vertical mixing and microbially mediated oxidation indicates that ?60% of methane released at the seafloor is oxidized at depth before it mixes with overlying surface waters. Deep waters are therefore not a significant source of methane to intermediate and surface waters; rather, relatively high methane concentrations in these waters (up to 50 nM) are attributed to isopycnal turbulent mixing with shelf waters. On the shelf, extensive seafloor seepage at &lt;100 m water depth produces methane concentrations of up to 615 nM. The diffusive flux of methane from sea to air in the vicinity of the landward limit of the GHSZ is ?4–20 ?mol m?2 d?1, which is small relative to other Arctic sources. In support of this, analyses of mole fractions and the carbon isotope signature of atmospheric methane above the seeps do not indicate a significant local contribution from the seafloor source

Evaluation of a ferrozine based autonomous in situ lab-on-chip analyzer for dissolved iron species in coastal waters

The trace metal iron (Fe) is an essential micronutrient for phytoplankton growth and limits, or co-limits primary production across much of the world's surface ocean. Iron is a redox sensitive element, with Fe(II) and Fe(III) co-existing in natural waters. Whilst Fe(II) is the most soluble form, it is also transient with rapid oxidation rates in oxic seawater. Measurements of Fe(II) are therefore preferably undertaken in situ. For this purpose an autonomous wet chemical analyzer based on lab-on-chip technology was developed for the in situ determination of the concentration of dissolved (<0.45 μm) Fe species (Fe(II) and labile Fe) suitable for deployments in a wide range of aquatic environments. The spectrophotometric approach utilizes a buffered ferrozine solution and a ferrozine/ascorbic acid mixture for Fe(II) and labile Fe(III) analyses, respectively. Diffusive mixing, color development and spectrophotometric detection take place in three separate flow cells with different lengths such that the analyzer can measure a broad concentration range from low nM to several μM of Fe, depending on the desired application. A detection limit of 1.9 nM Fe was found. The microfluidic analyzer was tested in situ for nine days in shallow waters in the Kiel Fjord (Germany) along with other sensors as a part of the SenseOCEAN EU-project. The analyzer's performance under natural conditions was assessed with discrete samples collected and processed according to GEOTRACES protocol [acidified to pH < 2 and analyzed via inductively coupled plasma mass spectrometry (ICP-MS)]. The mechanical performance of the analyzer over the nine day period was good (consistent high precision of Fe(II) and Fe(III) standards with a standard deviation of 2.7% (n = 214) and 1.9% (n = 217), respectively, and successful completion of every programmed data point). However, total dissolved Fe was consistently low compared to ICP-MS data. Recoveries between 16 and 75% were observed, indicating that the analyzer does not measure a significant fraction of natural dissolved Fe species in coastal seawater. It is suggested that an acidification step would be necessary in order to ensure that the analyzer derived total dissolved Fe concentration is reproducible and consistent with discrete values

Isotopic signature of dissolved iron delivered to the Southern Ocean from hydrothermal vents in the East Scotia Sea

It has recently been demonstrated that hydrothermal vents are an important source of dissolved Fe (dFe) to the Southern Ocean. The isotopic composition (?56Fe) of dFe in vent fluids appears to be distinct from other sources of dFe to the deep ocean, but the evolution of ?56Fe during mixing between vent fluids and seawater is poorly constrained. Here we present the evolution of ?56Fe for dFe in hydrothermal fluids and dispersing plumes from two sites in the East Scotia Sea. We show that ?56Fe values in the buoyant plume are distinctly lower (as low as ?1.19 ‰) than the hydrothermal fluids (?0.29 ‰), attributed to (i) precipitation of Fe-sulfides in the early stages of mixing, and (ii) partial oxidation of Fe(II) to Fe(III), > 55 % of which subsequently precipitates as Fe-oxyhydroxides. By contrast, the ?56Fe signature of stabilized dFe in the neutrally buoyant plume is ?0.3 to ?0.5 ‰. This cannot be explained by continued dilution of the buoyant plume with background seawater; rather, we suggest that isotope fractionation of dFe occurs during plume dilution due to Fe ligand complexation and exchange with labile particulate Fe. The ?56Fe signature of stabilized hydrothermal dFe in the East Scotia Sea is distinct from background seawater and may be used to quantify the hydrothermal dFe input to the ocean interior

Using a realist approach to evaluate smoking cessation interventions targeting pregnant women and young people

Background This paper describes a study protocol designed to evaluate a programme of smoking cessation interventions targeting pregnant women and young people living in urban and rural locations in Northeast Scotland. The study design was developed on so-called 'realist' evaluation principles, which are concerned with the implementation of interventions as well as their outcomes. Methods/design A two-phased study was designed based on the Theory of Change (TOC) using mixed methods to assess both process and outcome factors. The study was designed with input from the relevant stakeholders. The mixed-methods approach consists of semi-structured interviews with planners, service providers, service users and non-users. These qualitative interviews will be analysed using a thematic framework approach. The quantitative element of the study will include the analysis of routinely collected data and specific project monitoring data, such as data on service engagement, service use, quit rates and changes in smoking status. Discussion The process of involving key stakeholders was conducted using logic modelling and TOC tools. Engaging stakeholders, including those responsible for funding, developing and delivering, and those intended to benefit from interventions aimed at them, in their evaluation design, are considered by many to increase the validity and rigour of the subsequent evidence generated. This study is intended to determine not only the components and processes, but also the possible effectiveness of this set of health interventions, and contribute to the evidence base about smoking cessation interventions aimed at priority groups in Scotland. It is also anticipated that this study will contribute to the ongoing debate about the role and challenges of 'realist' evaluation approaches in general, and the utility of logic modelling and TOC approaches in particular, for evaluation of complex health interventions