Mass Transfer And Hydraulic Testing Of The V-05 And V-10 Contactors With The Next Generation Solvent

The Modular Caustic Side Solvent Extraction (CSSX) Unit (MCU) facility is actively pursuing the transition from the current BOBCalixC6 based solvent to the Next Generation Solvent (NGS)-MCU solvent. To support this integration of NGS into the MCU facilities, Savannah River Remediation (SRR) requested that Savannah River National Laboratory (SRNL) perform testing of a blend of the NGS (MaxCalix based solvent) with the current solvent (BOBCalixC6 based solvent) for the removal of cesium (Cs) from the liquid salt waste stream. This testing differs from prior testing by utilizing a blend of BOBCalixC6 based solvent and the NGS with the full (0.05 M) concentration of the MaxCalix as well as a new suppressor, tris(3,7dimethyloctyl) guanidine. Single stage tests were conducted using the full size V-05 and V-10 centrifugal contactors installed at SRNL. These tests were designed to determine the mass transfer and hydraulic characteristics with the NGS solvent blended with the projected heel of the BOBCalixC6 based solvent that will exist in MCU at time of transition. The test program evaluated the amount of organic carryover and the droplet size of the organic carryover phases using several analytical methods. Stage efficiency and mass distribution ratios were determined by measuring Cs concentration in the aqueous and organic phases during single contactor testing. The nominal cesium distribution ratio, D(Cs) measured for extraction ranged from 37-60. The data showed greater than 96% stage efficiency for extraction. No significant differences were noted for operations at 4, 8 or 12 gpm aqueous salt simulant feed flow rates. The first scrub test (contact with weak caustic solution) yielded average scrub D(Cs) values of 3.3 to 5.2 and the second scrub test produced an average value of 1.8 to 2.3. For stripping behavior, the “first stage” D Cs) values ranged from 0.04 to 0.08. The efficiency of the low flow (0.27 gpm aqueous) was calculated to be 82.7%. The Spreadsheet Algorithm for Stagewise Solvent Extraction (SASSE) predicted equivalent DF for MCU from this testing is greater than 3,500 assuming 95% efficiency during extraction and 80% efficiency during scrub and strip. Hydraulically, the system performed very well in all tests. Target flows were easily obtained and stable throughout testing. Though some issues were encountered with plugging in the coalescer, they were not related to the solvent. No hydraulic upsets due to the solvent were experienced during any of the tests conducted. The first extraction coalescer element used in testing developed high pressure drop that made it difficult to maintain the target flow rates. Analysis showed an accumulation of sodium aluminosilicate solids. The coalescer was replaced with one from the same manufacturer’s lot and pressure drop was no longer an issue. Concentrations of Isopar™ L and Modifier were measured using semi-volatile organic analysis (SVOA) and high performance liquid chromatography (HPLC) to determine the amount of solvent carryover. For low-flow (0.27 gpm aqueous) conditions in stripping, SVOA measured the Isopar™ L post-contactor concentration to be 25 mg/L, HPLC measured 39 mg/L of Modifier. For moderate-flow (0.54 gpm aqueous) conditions, SVOA measured the Isopar™ L postcontactor to be ~69 mg/L, while the HPLC measured 56 mg/L for Modifier. For high-flow (0.8 gpm aqueous) conditions, SVOA measured the Isopar™ L post-contactor to be 39 mg/L. The post-coalescer (pre-decanter) measurements by SVOA for Isopar™ L were all less than the analysis detection limit of 10 mg/L. The HPLC measured 18, 22 and 20 mg/L Modifier for the low, medium, and high-low rates respectively. In extraction, the quantity of pre-coalescer Isopar™ L carryover measured by SVOA was ~280-410 mg/L at low flow (4 gpm aqueous), ~400-450 mg/L at moderate flow (8 gpm aqueous), and ~480 mg/L at high flow (12 gpm aqueous). The amount of post coalescer (pre-decanter) Isopar™ L carryover measured by SVOA was less than 45 mg/L for all flow rates. HPLC results for Modifier were 182, 217 and 222 mg/L for the post-contactor low, medium and high flow rates. The post-coalescer (pre-decanter) samples were measured to contain 12, 10 and 22 mg/L Modifier for the low, medium, and high flow rates. The carryover results and droplet size measurements were used to determine the decanter performance utilizing the decanter model developed by the ARES Corporation. Results show for the targeted salt flow rate of approximately 8 gpm, that over 93% of the solvent carryover from stripping is predicted to be recovered and over 96% solvent carryover from extraction is predicted to be recovered. This translates to a predicted solvent carryover of <3 ppm from stripping and <20 ppm solvent carryover from extraction. This projected performance at MCU is expected to be well within the operating limits and the historical performance for the baseline BOBCalixC6 based solvent. Droplet-size data obtained by MicroTrac™ S3400 analyzer consistently shows that the droplet size post-oalescer is significantly greater than the post-contactor or pre-coalescer samples. Increased flow rates did not show a consistent impact to the droplet size results. For the extraction testing, droplet size analysis showed that the post-contactor and pre-coalescer samples were essentially the same. The mean droplet sizes post-coalescer were less than the mean droplet sizes pre-coalescer with a very slight upward trend in the mean droplet size as the flow rate was increased. This result is probably due to the method of sampling. The larger post-coalescer drops immediately rise to the surface after leaving the coalescer element. The downstream sampling point was horizontally in-line with the element and therefore would only capture those organic droplets well mixed in the flowing aqueous stream

Entrainment of Solvent in Aqueous Stream from CINC V-5 Contactor

Personnel completed a rapid study of organic entrainment during operation of a CINC V-5 contactor under prototypical conditions covering the range of expected MCU operation. The study only considered the entrainment of organic into the strip acid effluent destined for the Defense Waste Processing Facility. Based on this work, the following observations are noted: (1) Concentrations of total organic from the contactor discharge, based upon modifier measurements, in the acid typically averaged 330 ppm{sub m}, for a range to 190-610 ppm{sub m}. (2) Entrained droplet sizes remained below 18 microns for samples collected at the decanter outlet and below 11 microns for samples taken from the contactor discharge. (3) Scouting tests showed that a vendor coalescer material promotes coalescence of smaller size droplets from the decanter effluent. (4) Personnel observed a previously unreported organic impurity in the solvent used for this study. Additional efforts are needed to ascertain the source of the impurity and its implication on the overall process. (5) Process throughputs and planned operating conditions result in very stable hydraulics, suggesting that the MCU stripping stages will have spare operating capacity. (6) The V-5 contactors show operated with relatively cool surfaces under the planned operating conditions. (7) If operating conditions result in an imbalance of the relative mixing and separation conditions within the contactor, a very stable emulsion may result. In this instance, the emulsion remained stable for weeks. The imbalance in this study resulted from use of improperly sized weir plates. (8) Personnel demonstrated an effective means of recovering emulsified solvent following a non-optimal equipment configuration. The protocols developed may offer benefit for MCU and SWPF operations. (9) This study developed and demonstrated the effectiveness of several analytical methods for support of the Caustic-Side Solvent Extraction process including infrared spectroscopy and droplet size measurement by a MicroTrac{trademark} S3000. Interfacial tension measurements also showed sensitivity to purity of the solvent suggesting that this technique may prove valuable for future process diagnostics. The study highlighted limitations of the current gas chromatography configuration for determination of modifier content of samples. Additional development of analytical methods for determining composition--and particularly modifier content--of organic and mixed aqueous-organic samples is warranted. Infrared spectroscopy shows particular promise. Additional full-scale studies are warranted to investigate the entrainment of organic in the aqueous effluent from the extraction operation. Since waste composition may differ appreciably for the process, this stream may exhibit much wider variance in hydraulic behavior, organic entrainment, and may pose a greater risk for poor hydraulics. Conducting contactor studies at SRNL allowed numerous personnel to view operations and facilitated the training of staff members. Members of the Design Authority, Engineering, and Training groups benefited from tours. Consideration should be given to procuring and installing a full-scale contactor at SRNL for future support and for assistance during commissioning of the MCU. Additional study of surface and interfacial tension is recommended. This tool may also offer economical and rapid process diagnostics for future operations

REMOVING SLUDGE HEELS FROM SAVANNAH RIVER SITE WASTE TANKS BY OXALIC ACID DISSOLUTION

The Savannah River Site (SRS) will remove sludge as part of waste tank closure operations. Typically the bulk sludge is removed by mixing it with supernate to produce a slurry, and transporting the slurry to a downstream tank for processing. Experience shows that a residual heel may remain in the tank that cannot be removed by this conventional technique. In the past, SRS used oxalic acid solutions to disperse or dissolve the sludge heel to complete the waste removal. To better understand the actual conditions of oxalic acid cleaning of waste from carbon steel tanks, the authors developed and conducted an experimental program to determine its effectiveness in dissolving sludge, the hydrogen generation rate, the generation rate of other gases, the carbon steel corrosion rate, the impact of mixing on chemical cleaning, the impact of temperature, and the types of precipitates formed during the neutralization process. The test samples included actual SRS sludge and simulated SRS sludge. The authors performed the simulated waste tests at 25, 50, and 75 C by adding 8 wt % oxalic acid to the sludge over seven days. They conducted the actual waste tests at 50 and 75 C by adding 8 wt % oxalic acid to the sludge as a single batch. Following the testing, SRS conducted chemical cleaning with oxalic acid in two waste tanks. In Tank 5F, the oxalic acid (8 wt %) addition occurred over seven days, followed by inhibited water to ensure the tank contained enough liquid to operate the mixer pumps. The tank temperature during oxalic acid addition and dissolution was approximately 45 C. The authors analyzed samples from the chemical cleaning process and compared it with test data. The conclusions from the work are: (1) Oxalic acid addition proved effective in dissolving sludge heels in the simulant demonstration, the actual waste demonstration, and in SRS Tank 5F. (2) The oxalic acid dissolved {approx} 100% of the uranium, {approx} 100% of the iron, and {approx} 40% of the manganese during a single contact in the simulant demonstration. (The iron dissolution may be high due to corrosion of carbon steel coupons.) (3) The oxalic acid dissolved {approx} 80% of the uranium, {approx} 70% of the iron, {approx} 50% of the manganese, and {approx} 90% of the aluminum in the actual waste demonstration for a single contact. (4) The oxalic acid dissolved {approx} 100% of the uranium, {approx} 15% of the iron, {approx} 40% of the manganese, and {approx} 80% of the aluminum in Tank 5F during the first contact cycle. Except for the iron, these results agree well with the demonstrations. The data suggest that a much larger fraction of the iron in the sludge dissolved, but it re-precipitated with the oxalate added to Tank 5F. (5) The demonstrations produced large volumes (i.e., 2-14 gallons of gas/gallon of oxalic acid) of gas (primarily carbon dioxide) by the reaction of oxalic acid with sludge and carbon steel. (6) The reaction of oxalic acid with carbon steel produced hydrogen in the simulant and actual waste demonstrations. The volume produced varied from 0.00002-0.00100 ft{sup 3} hydrogen/ft{sup 2} carbon steel. The hydrogen production proved higher in unmixed tanks than in mixed tanks

Microautophagy of the Nucleus Coincides with a Vacuolar Diffusion Barrier at Nuclear–Vacuolar Junctions

Nuclear-vacuolar (NV) junctions are organelle contact sites in yeast. They exclude nuclear pores from the organelle interface. On the vacuolar side, a lipid-dependent process excludes specific membrane proteins, such as V-ATPase, from the contact site. This suggests that NV junctions establish selective diffusion barriers

The impact of NHS based primary care complementary therapy services on health outcomes and NHS costs: a review of service audits and evaluations

<p>Abstract</p> <p>Background</p> <p>The aim of this study was to review evaluations and audits of primary care complementary therapy services to determine the impact of these services on improving health outcomes and reducing NHS costs. Our intention is to help service users, service providers, clinicians and NHS commissioners make informed decisions about the potential of NHS based complementary therapy services.</p> <p>Methods</p> <p>We searched for published and unpublished studies of NHS based primary care complementary therapy services located in England and Wales from November 2003 to April 2008. We identified the type of information included in each document and extracted comparable data on health outcomes and NHS costs (e.g. prescriptions and GP consultations).</p> <p>Results</p> <p>Twenty-one documents for 14 services met our inclusion criteria. Overall, the quality of the studies was poor, so few conclusions can be made. One controlled and eleven uncontrolled studies using SF36 or MYMOP indicated that primary care complementary therapy services had moderate to strong impact on health status scores. Data on the impact of primary care complementary therapy services on NHS costs were scarcer and inconclusive. One controlled study of a medical osteopathy service found that service users did not decrease their use of NHS resources.</p> <p>Conclusion</p> <p>To improve the quality of evaluations, we urge those evaluating complementary therapy services to use standardised health outcome tools, calculate confidence intervals and collect NHS cost data from GP medical records. Further discussion is needed on ways to standardise the collection and reporting of NHS cost data in primary care complementary therapy services evaluations.</p

TBK1: a new player in ALS linking autophagy and neuroinflammation.

Amyotrophic lateral sclerosis (ALS) is an adult-onset neurodegenerative disorder affecting motor neurons, resulting in progressive muscle weakness and death by respiratory failure. Protein and RNA aggregates are a hallmark of ALS pathology and are thought to contribute to ALS by impairing axonal transport. Mutations in several genes known to contribute to ALS result in deposition of their protein products as aggregates; these include TARDBP, C9ORF72, and SOD1. In motor neurons, this can disrupt transport of mitochondria to areas of metabolic need, resulting in damage to cells and can elicit a neuroinflammatory response leading to further neuronal damage. Recently, eight independent human genetics studies have uncovered a link between TANK-binding kinase 1 (TBK1) mutations and ALS. TBK1 belongs to the IKK-kinase family of kinases that are involved in innate immunity signaling pathways; specifically, TBK1 is an inducer of type-1 interferons. TBK1 also has a major role in autophagy and mitophagy, chiefly the phosphorylation of autophagy adaptors. Several other ALS genes are also involved in autophagy, including p62 and OPTN. TBK1 is required for efficient cargo recruitment in autophagy; mutations in TBK1 may result in impaired autophagy and contribute to the accumulation of protein aggregates and ALS pathology. In this review, we focus on the role of TBK1 in autophagy and the contributions of this process to the pathophysiology of ALS

Antagonism between DNA and H3K27 Methylation at the Imprinted Rasgrf1 Locus

At the imprinted Rasgrf1 locus in mouse, a cis-acting sequence controls DNA methylation at a differentially methylated domain (DMD). While characterizing epigenetic marks over the DMD, we observed that DNA and H3K27 trimethylation are mutually exclusive, with DNA and H3K27 methylation limited to the paternal and maternal sequences, respectively. The mutual exclusion arises because one mark prevents placement of the other. We demonstrated this in five ways: using 5-azacytidine treatments and mutations at the endogenous locus that disrupt DNA methylation; using a transgenic model in which the maternal DMD inappropriately acquired DNA methylation; and by analyzing materials from cells and embryos lacking SUZ12 and YY1. SUZ12 is part of the PRC2 complex, which is needed for placing H3K27me3, and YY1 recruits PRC2 to sites of action. Results from each experimental system consistently demonstrated antagonism between H3K27me3 and DNA methylation. When DNA methylation was lost, H3K27me3 encroached into sites where it had not been before; inappropriate acquisition of DNA methylation excluded normal placement of H3K27me3, and loss of factors needed for H3K27 methylation enabled DNA methylation to appear where it had been excluded. These data reveal the previously unknown antagonism between H3K27 and DNA methylation and identify a means by which epigenetic states may change during disease and development

Intercomparison of NO2, O4, O3 and HCHO slant column measurements by MAX-DOAS and zenith-sky UV¿visible spectrometers during CINDI-2

40 pags., 22 figs., 13 tabs.In September 2016, 36 spectrometers from 24 institutes measured a number of key atmospheric pollutants for a period of 17¿d during the Second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) that took place at Cabauw, the Netherlands (51.97¿¿N, 4.93¿¿E). We report on the outcome of the formal semi-blind intercomparison exercise, which was held under the umbrella of the Network for the Detection of Atmospheric Composition Change (NDACC) and the European Space Agency (ESA). The three major goals of CINDI-2 were (1) to characterise and better understand the differences between a large number of multi-axis differential optical absorption spectroscopy (MAX-DOAS) and zenith-sky DOAS instruments and analysis methods, (2) to define a robust methodology for performance assessment of all participating instruments, and (3) to contribute to a harmonisation of the measurement settings and retrieval methods. This, in turn, creates the capability to produce consistent high-quality ground-based data sets, which are an essential requirement to generate reliable long-term measurement time series suitable for trend analysis and satellite data validation. The data products investigated during the semi-blind intercomparison are slant columns of nitrogen dioxide (NO2), the oxygen collision complex (O4) and ozone (O3) measured in the UV and visible wavelength region, formaldehyde (HCHO) in the UV spectral region, and NO2 in an additional (smaller) wavelength range in the visible region. The campaign design and implementation processes are discussed in detail including the measurement protocol, calibration procedures and slant column retrieval settings. Strong emphasis was put on the careful alignment and synchronisation of the measurement systems, resulting in a unique set of measurements made under highly comparable air mass conditions. The CINDI-2 data sets were investigated using a regression analysis of the slant columns measured by each instrument and for each of the target data products. The slope and intercept of the regression analysis respectively quantify the mean systematic bias and offset of the individual data sets against the selected reference (which is obtained from the median of either all data sets or a subset), and the rms error provides an estimate of the measurement noise or dispersion. These three criteria are examined and for each of the parameters and each of the data products, performance thresholds are set and applied to all the measurements. The approach presented here has been developed based on heritage from previous intercomparison exercises. It introduces a quantitative assessment of the consistency between all the participating instruments for the MAX-DOAS and zenith-sky DOAS techniques.CINDI-2 received funding from the Netherlands Space Office (NSO). Funding for this study was provided by ESA through the CINDI-2 (ESA contract no. 4000118533/16/ISbo) and FRM4DOAS (ESA contract no. 4000118181/16/I-EF) projects and partly within the EU 7th Framework Programme QA4ECV project (grant agreement no. 607405). The BOKU MAX-DOAS instrument was funded and the participation of Stefan F. Schreier was supported by the Austrian Science Fund (FWF): I 2296-N29. The participation of the University of Toronto team was supported by the Canadian Space Agency (through the AVATARS project) and the Natural Sciences and Engineering Research Council (through the PAHA project). The instrument was primarily funded by the Canada Foundation for Innovation and is usually operated at the Polar Environment Atmospheric Research Laboratory (PEARL) by the Canadian Network for the Detection of Atmospheric Change (CANDAC). Funding for CISC was provided by the UVAS (“Ultraviolet and Visible Atmospheric Sounder”) projects SEOSAT/INGENIO, ESP2015-71299- R, MINECO-FEDER and UE. The activities of the IUP-Heidelberg were supported by the DFG project RAPSODI (grant no. PL 193/17-1). SAOZ and Mini-SAOZ instruments are supported by the Centre National de la Recherche Scientifique (CNRS) and the Centre National d’Etudes Spatiales (CNES). INTA recognises support from the National funding projects HELADO (CTM2013-41311-P) and AVATAR (CGL2014-55230-R). AMOIAP recognises support from the Russian Science Foundation (grant no. 16-17-10275) and the Russian Foundation for Basic Research (grant nos. 16-05- 01062 and 18-35-00682). Ka L. Chan received transnational access funding from ACTRIS-2 (H2020 grant agreement no. 654109). Rainer Volkamer recognises funding from NASA’s Atmospheric Composition Program (NASA-16-NUP2016-0001) and the US National Science Foundation (award AGS-1620530). Henning Finkenzeller is the recipient of a NASA graduate fellowship. Mihalis Vrekoussis recognises support from the University of Bremen and the DFG Research Center/Cluster of Excellence “The Ocean in the Earth System-MARUM”. Financial support through the University of Bremen Institutional Strategy in the framework of the DFG Excellence Initiative is gratefully appreciated for Anja Schönhardt. Pandora instrument deployment was supported by Luftblick through the ESA Pandonia Project and NASA Pandora Project at the Goddard Space Flight Center under NASA Headquarters’ Tropospheric Composition Program. The article processing charges for this open-access publication were covered by BK Scientific

Estimates of Particulate Organic Carbon Flowing from the Pelagic Environment to the Benthos through Sponge Assemblages

Despite the importance of trophic interactions between organisms, and the relationship between primary production and benthic diversity, there have been few studies that have quantified the carbon flow from pelagic to benthic environments as a result of the assemblage level activity of suspension-feeding organisms. In this study, we examine the feeding activity of seven common sponge species from the Taputeranga marine reserve on the south coast of Wellington in New Zealand. We analysed the diet composition, feeding efficiency, pumping rates, and the number of food particles (specifically picoplanktonic prokaryotic cells) retained by sponges. We used this information, combined with abundance estimates of the sponges and estimations of the total amount of food available to sponges in a known volume of water (89,821 m3), to estimate: (1) particulate organic carbon (POC) fluxes through sponges as a result of their suspension-feeding activities on picoplankton; and (2) the proportion of the available POC from picoplankton that sponges consume. The most POC acquired by the sponges was from non-photosynthetic bacterial cells (ranging from 0.09 to 4.69 g C d−1 with varying sponge percentage cover from 0.5 to 5%), followed by Prochlorococcus (0.07 to 3.47 g C d−1) and then Synechococcus (0.05 to 2.34 g C d−1) cells. Depending on sponge abundance, the amount of POC that sponges consumed as a proportion of the total POC available was 0.2–12.1% for Bac, 0.4–21.3% for Prochlo, and 0.3–15.8% for Synecho. The flux of POC for the whole sponge assemblage, based on the consumption of prokaryotic picoplankton, ranged from 0.07–3.50 g C m2 d−1. This study is the first to estimate the contribution of a sponge assemblage (rather than focusing on individual sponge species) to POC flow from three groups of picoplankton in a temperate rocky reef through the feeding activity of sponges and demonstrates the importance of sponges to energy flow in rocky reef environments