Nitrous concentration of water samples from the Northeast Atlantic (Table 1)

Data on the N2O contents of marine sea water from the Northeast Atlantic Ocean are presented. The N2O content of marine air is rather constant. The data are in accordance with earlier measurements. The sea water down to depth greater tha 1000 meters is considerably aupersaturated with N2O with respect to air. Supersaturation values obtain from surface water allow the conclusion that part of the North Atlantic acts as a net cource of atmospheric N2O.

Underway measurements of dissolved gases along POLARSTERN cruise track ANT-XXVII/2

We present measurements of pCO2, O2 concentration, biological oxygen saturation (Delta O2/Ar) and N2 saturation (Delta N2) in Southern Ocean surface waters during austral summer, 2010-2011. Phytoplankton biomass varied strongly across distinct hydrographic zones, with high chlorophyll a (Chla) concentrations in regions of frontal mixing and sea-ice melt. pCO2 and Delta O2 /Ar exhibited large spatial gradients (range 90 to 450 µatm and -10 to 60%, respectively) and co-varied strongly with Chla. However, the ratio of biological O2 accumulation to dissolved inorganic carbon (DIC) drawdown was significantly lower than expected from photosynthetic stoichiometry, reflecting the differential time-scales of O2 and CO2 air-sea equilibration. We measured significant oceanic CO2 uptake, with a mean air-sea flux (~ -20 mmol m-2 d-1) that significantly exceeded regional climatological values. N2 was mostly supersaturated in surface waters (mean Delta N2 of +2.5 %), while physical processes resulted in both supersaturation and undersaturation of mixed layer O2 (mean Delta O2phys = 2.1 %). Box model calculations were able to reproduce much of the spatial variability of Delta N2 and Delta O2phys along the cruise track, demonstrating significant effects of air-sea exchange processes (e.g. atmospheric pressure changes and bubble injection) and mixed layer entrainment on surface gas disequilibria. Net community production (NCP) derived from entrainment-corrected surface Delta O2 /Ar data, ranged from ~ -40 to > 300 mmol O2 m-2 d-1 and showed good coherence with independent NCP estimates based on seasonal mixed layer DIC deficits. Elevated NCP was observed in hydrographic frontal zones and regions of sea-ice melt with shallow mixed layer depths, reflecting the importance of mixing in controlling surface water light and nutrient availability.

Evidence for methane production by the marine algae Emiliania huxleyi

Methane (CH4), an important greenhouse gas that affects radiation balance and consequently the earth's climate, still has uncertainties in its sinks and sources. The world's oceans are considered to be a source of CH4 to the atmosphere, although the biogeochemical processes involved in its formation are not fully understood. Several recent studies provided strong evidence of CH4 production in oxic marine and freshwaters, but its source is still a topic of debate. Studies of CH4 dynamics in surface waters of oceans and large lakes have concluded that pelagic CH4 supersaturation cannot be sustained either by lateral inputs from littoral or benthic inputs alone. However, regional and temporal oversaturation of surface waters occurs frequently. This comprises the observation of a CH4 oversaturating state within the surface mixed layer, sometimes also termed the "oceanic methane paradox". In this study we considered marine algae as a possible direct source of CH4. Therefore, the coccolithophore Emiliania huxleyi was grown under controlled laboratory conditions and supplemented with two 13C-labeled carbon substrates, namely bicarbonate and a position-specific 13C-labeled methionine (R-S-13CH3). The CH4 production was 0.7 µg particular organic carbon (POC) g−1 d−1, or 30 ng g−1 POC h−1. After supplementation of the cultures with the 13C-labeled substrate, the isotope label was observed in headspace CH4. Moreover, the absence of methanogenic archaea within the algal culture and the oxic conditions during CH4 formation suggest that the widespread marine algae Emiliania huxleyi might contribute to the observed spatially and temporally restricted CH4 oversaturation in ocean surface waters.

Evidence for methane production by the marine algae Emiliania huxleyi

Methane (CH4), an important greenhouse gas that affects radiation balance and consequently the earth's climate, still has uncertainties in its sinks and sources. The world's oceans are considered to be a source of CH4 to the atmosphere, although the biogeochemical processes involved in its formation are not fully understood. Several recent studies provided strong evidence of CH4 production in oxic marine and freshwaters, but its source is still a topic of debate. Studies of CH4 dynamics in surface waters of oceans and large lakes have concluded that pelagic CH4 supersaturation cannot be sustained either by lateral inputs from littoral or benthic inputs alone. However, regional and temporal oversaturation of surface waters occurs frequently. This comprises the observation of a CH4 oversaturating state within the surface mixed layer, sometimes also termed the "oceanic methane paradox". In this study we considered marine algae as a possible direct source of CH4. Therefore, the coccolithophore Emiliania huxleyi was grown under controlled laboratory conditions and supplemented with two 13C-labeled carbon substrates, namely bicarbonate and a position-specific 13C-labeled methionine (R-S-13CH3). The CH4 production was 0.7 µg particular organic carbon (POC) g−1 d−1, or 30 ng g−1 POC h−1. After supplementation of the cultures with the 13C-labeled substrate, the isotope label was observed in headspace CH4. Moreover, the absence of methanogenic archaea within the algal culture and the oxic conditions during CH4 formation suggest that the widespread marine algae Emiliania huxleyi might contribute to the observed spatially and temporally restricted CH4 oversaturation in ocean surface waters.

Downstream processing of reverse osmosis brine: Characterisation of potential scaling compounds

Reverse osmosis (RO) brine produced at a full-scale coal seam gas (CSG) water treatment facility was characterized with spectroscopic and other analytical techniques. A number of potential scalants including silica, calcium, magnesium, sulphates and carbonates, all of which were present in dissolved and non-dissolved forms, were characterized. The presence of spherical particles with a size range of 10-1000nm and aggregates of 1-10 microns was confirmed by transmission electron microscopy (TEM). Those particulates contained the following metals in decreasing order: K, Si, Sr, Ca, B, Ba, Mg, P, and S. Characterization showed that nearly one-third of the total silicon in the brine was present in the particulates. Further, analysis of the RO brine suggested supersaturation and precipitation of metal carbonates and sulphates during the RO process should take place and could be responsible for subsequently capturing silica in the solid phase. However, the precipitation of crystalline carbonates and sulphates are complex. X-ray diffraction analysis did not confirm the presence of common calcium carbonates or sulphates but instead showed the presence of a suite of complex minerals, to which amorphous silica and/or silica rich compounds could have adhered. A filtration study showed that majority of the siliceous particles were less than 220nm in size, but could still be potentially captured using a low molecular weight ultrafiltration membrane. © 2015 Elsevier Ltd.

Modular continuous crystallizer: operation, experimental arrangement and identification of process parameters

Crystallization is employed in different industrial processes. The method and operation can differ depending on the nature of the substances involved. The aim of this study is to examine the effect of various operating conditions on the crystal properties in a chemical engineering design window with a focus on ultrasound assisted cooling crystallization. Batch to batch variations, minimal manufacturing steps and faster production times are factors which continuous crystallization seeks to resolve. Continuous processes scale-up is considered straightforward compared to batch processes owing to increase of processing time in the specific reactor. In cooling crystallization process, ultrasound can be used to control the crystal properties. Different model compounds were used to define the suitable process parameters for the modular crystallizer using equal operating conditions in each module. A final temperature of 20oC was employed in all experiments while the operating conditions differed. The studied process parameters and configuration of the crystallizer were manipulated to achieve a continuous operation without crystal clogging along the crystallization path. The results from the continuous experiment were compared with the batch crystallization results and analysed using the Malvern Morphologi G3 instrument to determine the crystal morphology and CSD. The modular crystallizer was operated successfully with three different residence times. At optimal process conditions, a longer residence time gives smaller crystals and narrower CSD. Based on the findings, at a constant initial solution concentration, the residence time had clear influence on crystal properties. The equal supersaturation criterion in each module offered better results compared to other cooling profiles. The combination of continuous crystallization and ultrasound has large potential to overcome clogging, obtain reproducible and narrow CSD, specific crystal morphologies and uniform particle sizes, and exclusion of milling stages in comparison to batch processes.

The use of mo and cu monochromatic radiations for quantitative phase analysis: study of the accuracy

Cement hydration is a very complex process in which crystalline phases are dissolving in water and after supersaturation hydrated crystalline and amorphous phases precipitate. Great efforts are being made to develop analytical tools to accurately quantify these processes and X-ray Powder Diffraction (XRPD) combined with Rietveld methodology is a suitable tool to quantify these complex mixtures and their time evolutions. However, some problems/drawbacks should be overcome to fully apply it to cement pastes characterization in order to get accurate phase analyses. In order to tackle this issue, a comparison of the Rietveld quantitative phase analyses (RQPA) obtained using Cu-Kα1, Mo-Kα1, and synchrotron strictly monochromatic radiations of three set of mixtures with increasing amounts of a given phase (spiking-method) is presented. The main aim is to test a simple hypothesis: high energy Mo-radiation, combined with high resolution laboratory X-ray powder diffraction optics, could yield more accurate RQPA, for challenging samples, than well-established Cu-radiation procedure(s). Firstly, a series of crystalline inorganic phase mixtures with increasing amounts of an analyte was studied in order to determine if Mo-Kα1 methodology is as robust as the well-established Cu-Kα1 one. Secondly, a series of crystalline organic phase mixtures with increasing amounts of an organic compound was analyzed. This type of mixture can result in transparency problems in reflection and inhomogeneous loading in narrow capillaries for transmission studies. Finally, a third series with variable amorphous content was studied. Limit of detection in Cu-patterns, ~0.2 wt%, are slightly lower than those derived from Mo-patterns, ~0.3 wt%, for similar recording times and limit of quantification for a well crystallized inorganic phase using laboratory powder diffraction was established ~0.10 wt%. From the obtained results it is inferred that RQPA from Mo-Kα1 radiation have slightly better accuracies than those obtained from Cu-Kα1. The results obtained in the previous comparison have been taken into account to obtain accurate RQPA, including the amorphous component with internal standard methodology, of hydrating cement pastes. The final goal of this second study was understanding the early-stage hydration mechanisms of a variety of cementing systems (Ordinary Portland Cement or Belite Alite Ye’elimite cement) as a function of water content, superplasticizer additives and type and content of sulfate source. In order to do so, X-ray powder diffraction data were taken in-situ with the humidity chamber coupled to the Mo-Kα1 powder diffractometer. Some results of this ongoing investigation will be reported and discussed.

Nano-precipitation : preparation and application in the field of pharmacy

Over the last 30 years, nanoparticle-based medicine has received tremendous attention due to its advances with smart therapeutics and less toxicity. Few nanomedicine products have been approved for commercial use in the clinic (such as Doxil®, Ambraxane®…). Nanomedicine research is still at its early stage and the preparation of nanoparticles must be carefully considered. Systems involving further increased supersaturation, either via solvent evaporation, temperature reduction or anti-solvent mixture, were suggested to be capable of inducing nanoprecipitation (NPT). Since this technique is straight-forward, fast and easy to duplicate in practice, it is highly preferred and recommended. In this review, the process of NTP was described and discussed in detail. Factors that affect the encapsulation efficiency, the nanoparticle size, the morphology and the stability of nanoparticles prepared by NTP were described. This process is one of the most preferable processes for preparing solid nano-protein due to their elegant techniques that preserve the bioactivity of proteins. Although the production of nanoparticles by this process has not been applied in the pharmaceutical industry due to the organic solvent issue, the production equipment for large-scale has been marketed.

EBSD and AFM observations of the microstructural changes induced by low temperature plasma carburising on AISI 316

Low temperature plasma carburising (LTPC) has been increasingly accepted as a hardening process for austenitic stainless steels because it produces a good combination of tribological and corrosion properties. The hardening mechanism is based on the supersaturation of the austenitic structure with carbon, which greatly hardens the material, significantly expands the fcc unit cell, produces high levels of compressive residual stresses and, ultimately, leads to the occurrence of deformation bands and rotation of the crystal lattice. The microstructural changes introduced during plasma carburising have a significant impact on the mechanical, tribological and corrosion performance and, for this reason, the microstructure of expanded austenite or S-phase has been extensively studied. However, modern surface characterisation techniques could provide new insights into the formation mechanism of S-phase layers. In this work, backscattered electron diffraction and atomic force microscopy were used to characterise the surface layers of expanded austenite produced by LTPC in an active screen furnace. Based on the experimental results, the plastic deformation, its dependence on crystallographic orientation, the evolution of grain boundaries, and their effects on mechanical, tribological and corrosion properties are discussed. © 2011 Elsevier B.V. All rights reserved.