Naturally occurring radioactive materials in offshore infrastructure: Understanding formation and characteristics of baryte scale during decommissioning planning.

Contaminants, including naturally occurring radioactive material (NORM) of the 238-uranium and 232-thorium decay series, have been recognized as a global research priority to inform offshore petroleum infrastructure decommissioning decisions. This study aimed to characterize pipeline scale retrieved from a decommissioned subsea well tubular pipe through high-resolution elemental mapping and isotopic analysis. This was achieved by utilizing transmission electron microscopy, Synchrotron x-ray fluorescence, photostimulated luminescence autoradiography and Isotope Ratio Mass Spectrometry. The scale was identified as baryte (BaSO4) forming a dense crystalline matrix, with heterogenous texture and elongated crystals. The changing chemical and physical microenvironment within the pipe influenced the gradual growth rate of baryte over the production life of this infrastructure. A distinct compositional banding of baryte and celestine (SrSO4) bands was observed. Radioactivity attributed by the presence of radionuclides (226Ra, 228Ra) throughout the scale was strongly correlated with baryte. From the detailed scale characterization, we can infer the baryte scale gradually formed within the internals of the tubular well pipe along the duration of production (i.e., 17 years). This new knowledge and insight into the characteristics and formation of petroleum waste products will assist with decommissioning planning to mitigate potential radiological risks to marine ecosystems.

Total scattering measurements at the Australian Synchrotron Powder Diffraction beamline: capabilities and limitations.

This study describes the capabilities and limitations of carrying out total scattering experiments on the Powder Diffraction (PD) beamline at the Australian Synchrotron, ANSTO. A maximum instrument momentum transfer of 19 Å-1 can be achieved if the data are collected at 21 keV. The results detail how the pair distribution function (PDF) is affected by Qmax, absorption and counting time duration at the PD beamline, and refined structural parameters exemplify how the PDF is affected by these parameters. There are considerations when performing total scattering experiments at the PD beamline, including (1) samples need to be stable during data collection, (2) highly absorbing samples with a µR > 1 always require dilution and (3) only correlation length differences >0.35 Šmay be resolved. A case study comparing the PDF atom-atom correlation lengths with EXAFS-derived radial distances of Ni and Pt nanocrystals is also presented, which shows good agreement between the two techniques. The results here can be used as a guide for researchers considering total scattering experiments at the PD beamline or similarly setup beamlines.

Porous titania beads for remediation of arsenic contamination from acid mine drainage.

Hierarchically porous titania beads with and without amine functionalisation have been developed and tested as adsorbents for removal of highly toxic As(V) from environments affected by acid mine drainage (AMD). The unique acid stability of the titania framework enables these adsorbents to function in highly acidified environments and their granular form facilitates practical deployment under continuous flow conditions. Herein, both non-functionalised and amine-functionalised titania beads have been demonstrated to selectively remove As(V) from simulated and real AMD solutions at pH 2.6. Novel selectivity for As(V) over Na(I), Mg(II), Al(III), Si(VI), Ca(II), Co(II), Cu(II), Zn(II), Nd(III) and Ho(III) was achieved, with competing element concentrations similar to or up to an order of magnitude greater than that of As(V). Although Fe(III) and some Fe(II) were also adsorbed by the titania beads, Fe adsorption did not inhibit As(V) adsorption, indicating different adsorption mechanisms for these two elements. The As(V) adsorption capacity of the titania beads decreased from ∼20 mg/g from pure As(V) solution to ∼10 mg/g from real AMD solution, demonstrating the importance of adsorbent testing under applied conditions. Amine functionalisation increased the kinetics of adsorption, but the non-functionalised titania beads showed greater selectivity for As(V) over Fe(II) and Fe(III) and hence were considered preferable for As remediation applications. Nevertheless, the functionalisation ability of the porous titania beads makes them a promising, flexible technology for remediation of a wide range of AMD affected environments.

The effect of thermal pasteurization, freeze-drying, and gamma irradiation on donor human milk.

The availability of donor human milk (DHM) is currently limited by the volumes that can be thermally pasteurized and kept in long-term cold storage. This study assesses the application of freeze-drying followed by low-dose gamma irradiation of DHM for simplified, safe long-term storage. Solid-phase microextraction (SPME) GC-MS, SDS and native PAGE gel electrophoresis demonstrated that the overall changes in volatile and protein profiles in Holder pasteurized and freeze-dried DHM was negligible compared to the natural variations in DHM. Freeze-dried DHM samples (moisture < 2.2 %) processed with 2 kGy gamma irradiation did not show any significant lipid oxidation end-products and variation in protein profile. Therefore, freeze-drying followed by in-packaging gamma irradiation could be a safe method for pasteurization, convenient storage and delivery of DHM at ambient temperature. These methods may generate a means to create a reserve stock of DHM for emergencies and humanitarian aid.

Insight Into Disorder, Stress and Strain of Radiation Damaged Pyrochlores: A Possible Mechanism for the Appearance of Defect Fluorite.

We have examined the irradiation response of a titanate and zirconate pyrochlore-both of which are well studied in the literature individually-in an attempt to define the appearance of defect fluorite in zirconate pyrochlores. To our knowledge this study is unique in that it attempts to discover the mechanism of formation by a comparison of the different systems exposed to the same conditions and then examined via a range of techniques that cover a wide length scale. The conditions of approximately 1 displacement per atom via He2+ ions were used to simulate long term waste storage conditions as outlined by previous results from Ewing in a large enough sample volume to allow for neutron diffraction, as not attempted previously. The titanate sample, used as a baseline comparison since it readily becomes amorphous under these conditions behaved as expected. In contrast, the zirconate sample accumulates tensile stress in the absence of detectable strain. We propose this is analogous to the lanthanide zirconate pyrochlores examined by Simeone et al. where they reported the appearance of defect fluorite diffraction patterns due to a reduction in grain size. Radiation damage and stress results in the grains breaking into even smaller crystallites, thus creating even smaller coherent diffraction domains. An (ErNd)2(ZrTi)2O7 pyrochlore was synthesized to examine which mechanism might dominate, amorphization or stress/strain build up. Although strain was detected in the pristine sample via Synchrotron X-ray diffraction it was not of sufficient quality to perform a full analysis on.

Hydrothermal Syntheses of Uranium Oxide Hydrate Materials with Sm(III) Ions: pH-Driven Diversities in Structures and Morphologies and Sm-Doped Porous Uranium Oxides Derived from Their Thermal Decompositions.

We report the hydrothermal syntheses of three uranyl oxide hydroxy-hydrate (UOH) materials containing Sm(III) ions (UOH-Sm) by controlling the solution pH and a new way to make Sm-doped porous uranium oxides with different U-to-Sm atomic ratios via their thermal decompositions. While layer-structured UOH-Sm phases with U-to-Sm atomic ratios of 1 (UOH-Sm1) and 4 (UOH-Sm2) were obtained from the reaction of schoepite and samarium nitrate with final solution pH values of over 4, similar reactions without pH adjustment with final solution pH values of less than 4 led to the formation of a uranyl oxide framework (UOF-Sm) with a U-to-Sm atomic ratio of 5.5. The crystal structure of compound UOF-Sm was revealed with synchrotron single-crystal X-ray diffraction and confirmed with transmission electron microscopy. The two-dimensional uranyl oxide hydroxide layers, similar to that for ß-U3O8, are linked by double pentagonal uranyl polyhedra to form a three-dimensional framework with Sm(III) ions in the channels. Scanning electron microscopy characterization revealed nanoplate crystal morphologies for the two UOH-Sm phases, in contrast to the needle morphology for UOF-Sm. Subsequent thermal treatments led to the formation of Sm-doped uranium oxides, maintaining the original crystal shapes and U-to-Sm ratios but with nanopores. This work demonstrated that the hydrothermal synthesis conditions, especially fine-tuning of the solution pH, have a significant impact on the uranium hydrolysis, thus leading to well-defined products. This will facilitate the targeted syntheses of UOH phases with lanthanide (Ln) ions and explore the subsequent applications of these materials and Ln-doped porous uranium oxides as potential nuclear or functional materials.

Charge tunable thin-film composite membranes by gamma-ray triggered surface polymerization.

Thin-film composite poly(amide) (PA) membranes have greatly diversified water supplies and food products. However, users would benefit from a control of the electrostatic interactions between the liquid and the net surface charge interface in order to benefit wider application. The ionic selectivity of the 100 nm PA semi-permeable layer is significantly affected by the pH of the solution. In this work, for the first time, a convenient route is presented to configure the surface charge of PA membranes by gamma ray induced surface grafting. This rapid and up-scalable method offers a versatile route for surface grafting by adjusting the irradiation total dose and the monomer concentration. Specifically, thin coatings obtained at low irradiation doses between 1 and 10 kGy and at low monomer concentration of 1 v/v% in methanol/water (1:1) solutions, dramatically altered the net surface charge of the pristine membranes from -25 mV to +45 mV, whilst the isoelectric point of the materials shifted from pH 3 to pH 7. This modification resulted in an improved water flux by over 55%, from 45.9 to up 70 L.m-2.h-1, whilst NaCl rejection was found to drop by only 1% compared to pristine membranes.