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At least 685 records · Page 38

Nitric-glycolic flowsheet evaluation with the slurry-fed melt rate furnace

The Savannah River National Laboratory (SRNL) was tasked to support validation of the Defense Waste Processing Facility (DWPF) melter offgas flammability model for the nitric-glycolic (NG) flowsheet. The work supports Deliverable 4 of the DWPF & Saltstone Facility Engineering Technical Task Request (TTR)1 and is supplemental to the Cold Cap Evaluation Furnace (CEF) testing conducted in 2014.2 The Slurry-fed Melt Rate Furnace (SMRF) was selected for the supplemental testing as it requires significantly less resources than the CEF and could provide a tool for more rapid analysis of melter feeds in the future. The SMRF platform has been used previously to evaluate melt rate behavior of DWPF glasses, but was modified to accommodate analysis of the offgas stream. Additionally, the Melt Rate Furnace (MRF) and Quartz Melt Rate Furnace (QMRF) were utilized for evaluations. MRF data was used exclusively for melt behavior observations and REDuction/OXidation (REDOX) prediction comparisons and will be briefly discussed in conjunction with its support of the SMRF testing. The QMRF was operated similarly to the SMRF for the same TTR task, but will be discussed in a separate future report. The overall objectives of the SMRF testing were to; 1) Evaluate the efficacy of the SMRF as a platform for steady state melter testing with continuous feeding and offgas analysis; and 2) Generate supplemental melter offgas flammability data to support the melter offgas flammability modelling effort for DWPF implementation of the NG flowsheet.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

EVALUATION OF REQUIREMENTS FOR THE DWPF HIGHER CAPACITY CANISTER

The Defense Waste Processing Facility (DWPF) is considering the option to increase canister glass capacity by reducing the wall thickness of the current production canister. This design has been designated as the DWPF Higher Capacity Canister (HCC). A significant decrease in the number of canisters processed during the life of the facility would be achieved if the HCC were implemented leading to a reduced overall reduction in life cycle costs. Prior to implementation of the change, Savannah River National Laboratory (SRNL) was requested to conduct an evaluation of the potential impacts. The specific areas of interest included loading and deformation of the canister during the filling process. Additionally, the effect of the reduced wall thickness on corrosion and material compatibility needed to be addressed. Finally the integrity of the canister during decontamination and other handling steps needed to be determined. The initial request regarding canister fabrication was later addressed in an alternate study. A preliminary review of canister requirements and previous testing was conducted prior to determining the testing approach. Thermal and stress models were developed to predict the forces on the canister during the pouring and cooling process. The thermal model shows the HCC increasing and decreasing in temperature at a slightly faster rate than the original. The HCC is shown to have a 3°F ΔT between the internal and outer surfaces versus a 5°F ΔT for the original design. The stress model indicates strain values ranging from 1.9% to 2.9% for the standard canister and 2.5% to 3.1% for the HCC. These values are dependent on the glass level relative to the thickness transition between the top head and the canister wall. This information, along with field readings, was used to set up environmental test conditions for corrosion studies. Small 304-L canisters were filled with glass and subjected to accelerated environmental testing for 3 months. No evidence of stress corrosion cracking was indicated on either the canisters or U-bend coupons. Calculations and finite element modeling were used to determine forces over a range of handling conditions along with possible forces during decontamination. While expected reductions in some physical characteristics were found in the HCC, none were found to be significant when compared to the required values necessary to perform its intended function. Based on this study and a review of successful testing of thinner canisters at West Valley Demonstration Project (WVDP), the mechanical properties obtained with the thinner wall do not significantly undermine the ability of the canister to perform its intended function.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DWPF Melter Off-Gas Chemistry Model for the Nitric-Glycolic Acid Flowsheet

The Defense Waste Processing Facility (DWPF) melter off-gas flammability model for the current nitricformic acid (NFA) flowsheet was revised in Revision 0 to reflect the upcoming reductant change from formic to glycolic acid. The necessary data for the model revision was obtained during Phase 2 of the Coldcap Evaluation Furnace (CEF) test, which was completed on March 21, 2014 after 24 days of round-theclock feeding and pouring, including a total downtime of ~20 hours due to equipment failures. Specifically, the CEF was run to generate steady state melter off-gas data during the first 10 days using two nitricglycolic acid (NGA) flowsheet feeds prepared at 100% and 125% acid stoichiometry from the same Sludge Batch 6 (SB6) simulant used during the Phase 1 CEF test in 2013. Each feed was fed under both bubbled and non-bubbled conditions, while maintaining the CEF vapor space temperature constant for at least two hours approximately at 700, 600, 500, 400, 350, and <300 °C for a total of 26 steady state runs. During the next 8 days, the CEF was run at the nominal vapor space temperature of 700 °C to generate the off-gas surge data using the 100% acid-stoichiometry feed under bubbled and non-bubbled conditions. The remaining days were spent on producing additional data using the 100% acid-stoichiometry feed spiked with excess antifoam as well as re-running some of the earlier steady state runs.

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Submersible Blend Pump Mixing Evaluation

Savannah River Remediation (SRR) requested Savannah River National Laboratory (SRNL) to perform an engineering analysis to investigate the mixing behavior in feed blend tanks for the Salt Waste Processing Facility (SWPF). The baseline for mixing the feed blend tanks is a U 0 D of 5.1 ft 2 /s, a pump nozzle elevation of 165.86 inches above the sludge layer and 174 inches above the tank bottom, a liquid level 174.28 inches above the pump nozzle, and a blend time of 10.63 hours. The current Salt Batch Plan identifies Tanks 21, 26, 41, and 42 as the designated blend tanks. This supplemental study only addresses Type IIIA tanks (i.e., Tanks 26, 41, and 42). Using the Tank 41 current configuration as the baseline, the analysis considers the impact on blending if: 1) the distance between the pump discharge nozzle and the liquid surface increases above the baseline, 2) the distance between the pump discharge nozzle and the liquid surface decreases below the baseline, 3) the distance between the pump discharge nozzle and the sludge layer at the bottom of the tank increases above the baseline, or 4) the distance between the pump discharge nozzle and the sludge layer at the bottom of the tank decreases below the baseline, each while maintaining the minimum U 0 D of 5.1 ft 2 /s. Per subsequent direction from SRR, the minimum distance between the pump discharge nozzle and the sludge will be 165.86 inches. Hence, distances less than 165.86 inches between the pump discharge nozzle and the sludge were not included in the analysis. In addition, SRR requested SRNL to evaluate the impact of the abandoned in place, failed slurry pumps in Tank 42 on liquid blending.

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Analysis Of 2h-Evaporator Scale Wall [HTF-13-82] And Pot Bottom [HTF-13-77] Samples

Savannah River Remediation (SRR) is planning to remove a buildup of sodium aluminosilicate scale from the 2H-evaporator pot by loading and soaking the pot with heated 1.5 M nitric acid solution. Sampling and analysis of the scale material has been performed so that uranium and plutonium isotopic analysis can be input into a Nuclear Criticality Safety Assessment (NCSA) for scale removal by chemical cleaning. Historically, since the operation of the Defense Waste Processing Facility (DWPF), silicon in the DWPF recycle stream combines with aluminum in the typical tank farm supernate to form sodium aluminosilicate scale mineral deposits in the 2Hevaporator pot and gravity drain line. The 2H-evaporator scale samples analyzed by Savannah River National Laboratory (SRNL) came from the bottom cone sections of the 2H-evaporator pot [Sample HTF-13-77] and the wall 2H-evaporator [sample HTF-13-82]. X-ray diffraction analysis (XRD) confirmed that both the 2H-evaporator pot scale and the wall samples consist of nitrated cancrinite (a crystalline sodium aluminosilicate solid) and clarkeite (a uranium oxy-hydroxide mineral). On “as received” basis, the bottom pot section scale sample contained an average of 2.59E+00 ± 1.40E-01 wt % total uranium with a U-235 enrichment of 6.12E-01 ± 1.48E-02 %, while the wall sample contained an average of 4.03E+00 ± 9.79E-01 wt % total uranium with a U-235 enrichment of 6.03E-01% ± 1.66E-02 wt %. The bottom pot section scale sample analyses results for Pu-238, Pu-239, and Pu-241 are 3.16E- 05 ± 5.40E-06 wt %, 3.28E-04 ± 1.45E-05 wt %, and <8.80E-07 wt %, respectively. The evaporator wall scale samples analysis values for Pu-238, Pu-239, and Pu-241 averages 3.74E-05 ± 6.01E-06 wt %, 4.38E-04 ± 5.08E-05 wt %, and <1.38E-06 wt %, respectively. The Pu-241 analyses results, as presented, are upper limit values. These results are provided so that SRR can calculate the equivalent uranium-235 concentrations for the NCSA. Results confirm that the uranium contained in the scale remains depleted with respect to natural uranium. SRNL did not calculate an equivalent U-235 enrichment, which takes into account other fissionable isotopes U-233, Pu-239 and Pu-241. The applicable method for calculation of equivalent U-235 will be determined in the NCSA.

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Tank 40 final sludge batch 9 chemical and fissile radionuclide characterization results

A sample of Sludge Batch (SB) 9 was pulled from Tank 40 in order to obtain radionuclide inventory analyses necessary for compliance with the Waste Acceptance Product Specifications (WAPS)i. The SB9 WAPS sample was also analyzed for chemical composition, including noble metals, and fissile constituents, and these results are reported here. These analyses along with the WAPS radionuclide analyses will help define the composition of the sludge in Tank 40 that is fed to the Defense Waste Processing Facility (DWPF) as SB9. At the Savannah River National Laboratory (SRNL), the 3-L Tank 40 SB9 sample was transferred from the shipping container into a 4-L high density polyethylene bottle and solids were allowed to settle. Supernate was then siphoned off and circulated through the shipping container to complete the transfer of the sample. Following thorough mixing of the 3-L sample, a 547 g sub-sample was removed. This sub-sample was then utilized for all subsequent slurry sample preparations. Eight separate aliquots of the slurry were digested, four with HNO3/HCl (aqua regiaii) in sealed Teflon® vessels and four with NaOH/Na2O2 (alkali or peroxide fusioniii) using Zr crucibles. Three Analytical Reference Glass – 1iv (ARG-1) standards were digested along with a blank for each preparation. Each aqua regia digestion and blank was diluted to 1:100 with deionized water and submitted to Analytical Development (AD) for inductively coupled plasma – atomic emission spectroscopy (ICP-AES) analysis, inductively coupled plasma – mass spectrometry (ICP-MS) analysis, atomic absorption spectroscopy (AA) for As and Se, and cold vapor atomic absorption spectroscopy (CV-AA) for Hg. Equivalent dilutions of the alkali fusion digestions and blank were submitted to AD for ICP-AES analysis. Tank 40 SB9 supernate was collected from a mixed slurry sample in the SRNL Shielded Cells and submitted to AD for ICP-AES, ion chromatography (IC), total base/free OH-/other base, total inorganic carbon/total organic carbon (TIC/TOC) analyses. Weighted dilutions of slurry were submitted for IC, TIC/TOC, and total base/free OH-/other base analyses. Activities for U-233, U-235, and Pu-239 were determined from the ICP-MS data for the aqua regia digestions of the SB9 WAPS slurry using the specific activity of each isotope. The Pu-241 value was determined from a Pu-238/-241 method developed by SRNL AD and previously described.v

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chemical Composition and PCT Data for the Initial Set of Hanford Enhanced Waste Loading Glasses

In this report, the Savannah River National Laboratory provides chemical analyses and Product Consistency Test results for 20 simulated high level waste glasses fabricated by the Pacific Northwest National Laboratory. The results of these analyses will be used as part of efforts to revise or extend the validation ranges of the current Hanford Waste Treatment and Immobilization Plant glass property models to cover a broader span of waste compositions. The measured chemical composition data are reported and compared with the targeted values for each component for each glass. Two components of the study glasses, fluorine and silver, were not measured since each of these species would have required the use of an additional preparation method and their measured values were likely to be near or below analytical detection limits. Some of the glasses were difficult to prepare for chemical analysis. A sodium peroxide fusion dissolution method was successful in completely dissolving the glasses. Components present in the glasses in minor concentrations can be difficult to measure using this dissolution method due to dilution requirements. The use of a lithium metaborate preparation method for the minor components (planned for use since it is typically successful in digesting Defense Waste Processing Facility HLW glasses) resulted in an unacceptable amount of undissolved solids remaining in the sample solutions. An acid dissolution method was used instead, which provided more thorough dissolution of the glasses, although a small amount of undissolved material remained for some of the study glasses. The undissolved material was analyzed to determine those components of the glasses that did not fully dissolve. These components (e.g., calcium and chromium) were present in sufficient quantities to be reported from the measurements resulting from the sodium peroxide fusion preparation method, which did not leave undissolved material. Overall, the analyses resulted in sums of oxides that ranged from about 98 to 101.5 wt % for the study glasses, indicating excellent recovery of all the components in the chemical composition analyses. Comparisons of the targeted and measured chemical compositions indicated that, in general, the measured values for the glasses met the targeted concentrations. Exceptions were Cr 2 O 3 , MgO, and P 2 O 5 . The measured values for Cr 2 O 3 were somewhat low when compared to the targeted values for all of the study glasses targeting Cr 2 O 3 concentrations above 0.5 wt %. Many of the measured MgO and P 2 O 5 values were below the targeted values for those glasses that contained these components. Two of the study glasses exhibited differences from the targeted compositions that may indicate a batching error. Glasses EWG-HAI-Centroid-2 and EWG-OL-1672 had measured values for Al 2 O 3 and SiO 2 that were lower than the targeted values, and measured values for B 2 O 3 that were higher than the targeted values. Glass EWG-HAI-Centroid-2 also had a measured value for Fe 2 O 3 that was lower than the targeted value. A review of the PCT data, including standards and blanks, revealed no issues with the performance of the tests. The PCT results were normalized to both the targeted and measured compositions of the study glasses. Comparisons of the normalized PCT results for both the quenched and Canister Centerline Cooled versions of the study glasses are made with the Environmental Assessment benchmark glass for reference.

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Literature Review on Next Generation Solvent Isopar ® L Vapor Pressure Curve and the Partitioning of its Modifier and Extractant

The Next Generation Solvent (NGS) is set to replace the Original Caustic Side Solvent Extractant (CSSX) at the Salt Waste Processing Facility (SWPF). The Savannah River National Laboratory (SRNL) was requested by Savannah River Mission Completion (SRMC), formerly Savannah River Remediation (SRR), to perform a literature review on the following topics to address flammability concerns with the current solvent: Isopar ® L vapor pressure curve for NGS, partitioning ratio for the extractant MaxCalix and the modifier Cs-7SB, and high cesium concentration impacts on NGS radiolysis and potential solvent degradation rates in high cesium concentrations. The following conclusions and recommendations are made based on previous experimental work and literature: (1) Current SWPF flammable gas generation calculations use an Isopar ® L vapor pressure curve based on experimental testing with the Original CSSX solvent. No such testing to date has been performed with NGS. It is suggested that the decrease in Cs-7SB concentration for NGS compared to the Original CSSX solvent would lead to a slightly higher vapor pressure at all temperatures in SWPF vessels. A bounding NGS vapor pressure curve has been provided; it is recommended to see if these values would challenge current flammability controls and to perform testing if needed.(2) The partitioning ratio for Cs-7SB is known in the Original CSSX solvent with dilute nitric acid and caustic solutions. No tests could be found for the partitioning of Cs-7SB to dilute boric acid solutions; however, a similar partitioning ratio is expected. Due to the lipophilic alkyl chains on MaxCalix, it is expected to be even less soluble than BOBCalixC6 in the aqueous phase and should not be considered a significant contributor to the f organic term. Additionally, the reaction rate of N,N’,N’’-Tris(3,7-dimethyloctyl)guanidine (TiDG) or its degradation products with a hydrogen radical should be estimated/determined if they are found to be significant contributors to the f organic term. (3) NGS is expected to see much higher Cs concentrations at SWPF in comparison to its use at the Modular CSSX Unit (MCU). These higher Cs concentrations could influence radiolytic degradation rates of the solvent. NGS appears to be fairly stable to radiolytic degradation based on previous testing and its use at MCU. However, there has not been radiolytic flammable gas generation testing with NGS to date. There is a risk that the continued use of G-values obtained for flammable gases produced from the irradiation of the Original CSSX solvent is not bounding for NGS, but this is considered a very low risk due to the similarities in the composition of the solvents, as well as the conservatisms in the experimental design of the Original CSSX testing.

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Assessment of Cold Spraying Mild-Steel Powder onto Mild-Steel Substrate for Development of Waste Tank Repair System - 20515

Infrastructure for nuclear waste storage and processing (e.g., waste tanks, transfer pipelines, evaporators) at the U.S. Department of Energy (DOE) Hanford Site has been in service well beyond its original design life. Past corrosion control methods at Hanford for waste tanks have not been fully successful, as evidenced by leaks forming in tank AY-102, the first double-shell tank (DST) constructed, and significant degradation detected in the primary tanks of AP-102 and AY-101. Failure of infrastructure components can pose a significant risk to the environment, worker safety, and project schedules. Therefore, remotely deployable methods for repairing and extending the service life of the existing tank waste infrastructure are needed. Cold spray has been identified as a potential technique for performing in situ repairs and material buildup for life extension of waste storage and processing infrastructure. Cold-spray repair methods and technology are well-established and are used extensively by industry and the military for making repairs using dissimilar materials. Pacific Northwest National Laboratory is evaluating the process of making repairs using mild-steel powder applied to a mild-steel substrate to minimize the galvanic corrosion potential. This paper presents the initial results for a feasibility ('go/no-go') assessment as to whether low-density deposits with sound metallurgic bonds, to build-back steel plate material, can be achieved using existing commercial cold-spray equipment. An assessment of steel-on-steel deposit is necessary to determine if cold spray is a viable candidate for DST carbon steel plate restoration/repair and thus DST service life extension. Powder properties and preparation requirements have been investigated and operating conditions and parameters for depositing a cold-spray buildup of mild steel on a mild-steel substrate have been determined. Soundness of metallurgic bonding as a function of the operating parameters exercised and results from applying cold spray to lay a deposit over simulated small-diameter flaws in 1/2-inch mild-steel plate are presented. Application of in situ cold-spray repair to the DOE complex has the potential to reduce cost and schedule impacts associated with component failures and the need to procure and construct replacement infrastructure. (authors)

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Assessing I 2 S-LWR economic competitiveness using systematic differential capital cost evaluation methodology

One of the major factors impeding nuclear power plant (NPP) construction is their economics. In this study, a systematic differential economics evaluation approach was developed through the use of the Code of Accounts guidelines to assess the costs of nuclear power plants. The methodology, entirely based on publicly available data, may serve as a template to evaluate direct costs for reactors of any size and design at any stage of developments. In particular, this approach was used to assess the costs of the Integral Inherently Safe Light Water Reactor (I 2 S-LWR). The I 2 S-LWR is a design concept of a large (~1000 MWe) light water reactor. One of its key design features promoting inherent safety is implementation of an integral primary circuit configuration, which however necessitates a compact design of the core and primary circuit components. Through the methodology here presented, a representative loop PWR design was taken as a reference and the differential cost was estimated for each individual account based on the design difference, or similarity. Cost scaling techniques were applied to the accounts representing systems that differ from the ones of the reference PWR. Cost estimating techniques were used to evaluate cost of innovative components that are not part of standard PWR designs. By evaluating the cost difference of the I 2 S-LWR from the standard PWR, rather than the absolute cost, the uncertainty in the estimate is reduced. A similar approach was used by ORNL to estimate the cost of a Fluoride-salt High-temperature Reactor (FHR). A traditional four-loop PWR plant with a core thermal power of 3417 MWth (1144 MWe) was selected as the reference. Costs for that plant were prepared in 1978 by the Department of Energy (DOE) Energy Economics Data Base (EEDB), averaging actual cost incurred in the construction of several nuclear power plants (NPP), itemized with a great level of detail according to the Code of Accounts. This best estimate costs are denoted PWR12-BE. For each account, the cost of equipment, site labor and site material is provided. Industry experts at Westinghouse Electric Company performed a “sanity check” of the cost items, adjusting the cost of several items to match the current market and supply chain data. The detailed cost assessment of I 2 S-LWR was performed, systematically analyzing cost for each account, and applying the differential economics approach. First, Relative importance of each account, i.e., its contribution to the total cost was established, to help focus analysis on the most significant contributors. Moreover, the accounts describing components that are different than that of the PWR12-BE were identified. The integral configuration of the reactor has important implications on the cost of the reactor plant equipment (accounts 22x). Turbine generator equipment (Accounts 23x) is not believed to be much different than that of the reference design. I 2 S-LWR structures (Accounts 21x) mainly differ from that of a standard LWR as several buildings (containment building, shield building, annex building, waste processing building, fuel storage building) are integrated into a single building (nuclear island). Yardwork has a higher cost for the I 2 S-LWR, as the NI is partially below grade. On the other hand, due to its compact Nuclear Island footprint, I 2 S-LWR facilitates (and includes in its reference version) the use of seismic isolators, which contribute to reducing the direct cost. The total capital investment cost (TCIC), on the $/kW basis, of I 2 S-LWR is 5.84% lower than that of PWR12-BE, in spite of the lower power output of I 2 S-LWR. However, for the Western US (0.7 g), benefits of the seismic isolation are more pronounced, and the I 2 S-LWR total capital investment cost is 13.02% lower than that of PWR12-BE. If the I 2 S-LWR is compared to a PWR10-BE (traditional loop design, but scaled to the same power level as I 2 S-LWR), the savings are even higher, in the range 11.12%–17.89%. The analysis indicates that I 2 S-LWR has potential to offer an economically attractive design, with TCIC lower than that of a nuclear power plant based on a traditional loop PWR design. In other words, I 2 S-LWR design offers significantly enhanced safety, while at the same time improving economics. The differential economics approach developed in this paper can be used in identifying changes in cost of key components in order to improve the economics of a nuclear reactor design. The method can also help compare the economics of advanced Generation IV reactors and innovative water-cooled SMR (Small Modular Reactors) with respect to standard LWR technologies. In summary, the differential economics approach and can be used as a tool capable of helping stakeholder decisions.

Economic↗

Approach on environmental risk assessment of nanosilver released from textiles

Based on the increased utilization of nanosilver (silver nanomaterials=AgNM) as antibacterial agent, there is the strong need to assess the potential environmental implication associated with its new application areas. In this study an exemplary environmental risk assessment (ERA) of AgNM applied in textiles was performed. Environmental exposure scenarios (via municipal sewage treatment plant (STP)) with wastewater supply from domestic homes) were developed for three different types of textiles equipped with AgNM. Based on these scenarios predicted environmental concentrations (PECs) were deduced for STPs and for the environmental compartments surface water, sediment as well as soil. These PECs were related to PNECs (predicted no effect concentrations). PNECs were deduced from results of ecotoxicity tests of a selected AgNM (NM-300K). Data on ecotoxicology were derived from various tests with activated sludge, cyanobacteria, algae, daphnids, fish, duckweed, macrophytes, chironomids, earthworms, terrestrial plants as well as soil microorganisms. Emission data for the AgNM NM-300K from textiles were derived from washing experiments. The performed ERA was based on the specifications defined in the ECHA Guidances on information requirements and chemical safety assessment. Based on the chosen scenarios and preconditions, no environmental risk of the AgNM NM-300K released from textiles was detected. Under conservative assumptions a risk quotient for surface water close to 1 indicated that the aquatic compartment may be affected by an increased emission of AgNM to the environment due to the high sensitivity of aquatic organisms to silver. Based on the successful retention of AgNM in the sewage sludge and the still ongoing continual application of sewage sludge on farmland it is recommended to introduce a threshold for total silver content in sewage sludge into the respective regulations. Regarding potential risk mitigation measures, it is emphasized to preferably directly introduce AgNM into the textile fiber since this will strongly minimize the release of AgNM during washing. If this is not possible due to technical limitations or other reasons, the introduction of a threshold level controlling the release of AgNM from textiles is suggested. It has to be noted that this study is a case study which is only valid for the investigated NM-300K and its potential application in textiles. - Highlights: • Washing: release rates of AgNM depend on furnishing in textiles. • Calculated PNECs for the aquatic compartment were low. • For the chosen scenarios no environmental risk of AgNM from textiles was observed. • AgNM is retained in sewage sludge. • In WWTP most of the silver adsorbs to sewage sludge and thus, may reach farmland.

54 ENVIRONMENTAL SCIENCES↗

The relative viscosity of NaNO 3 and NaNO 2 aqueous solutions

In aqueous solution, both nitrate and nitrite are planar, monovalent, and have the same elements but different sizes and charge densities. Comparing the viscosity of NaNO 2 and NaNO 3 aqueous solutions provides an opportunity to determine the relative importance of anion size versus strength of anion interaction with water. The viscosity of aqueous NaNO 2 and NaNO 3 were measured over a temperature and concentration range relevant to nuclear waste processing. The viscosity of NaNO 2 solutions was consistently larger than NaNO 3 under all conditions, even though nitrate is larger than nitrite. This was interpreted in terms of quantum mechanical charge field molecular dynamics calculations that indicate that nitrite forms more and stronger hydrogen bonds with water per oxygen atom than nitrate. Furthermore, these hydrogen bonds inhibit rotational motion required for fluid flow, thus increasing the nitrite solution viscosity relative to that of an equivalent nitrate solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Municipal wastewater affects adipose deposition in male mice and increases 3T3-L1 cell differentiation

Trace concentration of EDs (endocrine disrupting compounds) in water bodies caused by wastewater treatment plant effluents is a recognized problem for the health of aquatic organisms and their potential to affect human health. In this paper we show that continuous exposure of male mice from early development to the adult life (140 days) to unrestricted drinking of wastewater collected from a municipal sewage treatment plant, is associated with an increased adipose deposition and weight gain during adulthood because of altered body homeostasis. In parallel, bisphenol A (BPA) at the administration dose of 5 μg/kg/body weight, shows an increasing effect on total body weight and fat mass. In vitro, a solid phase extract (SPE) of the wastewater (eTW), caused stimulation of 3T3-L1 adipocyte differentiation at dilutions of 0.4 and 1 % in the final culture medium which contained a concentration of BPA of 40 nM and 90 nM respectively. Pure BPA also promoted adipocytes differentiation at the concentration of 50 and 80 μM. BPA effect in 3T3-L1 cells was associated to the specific activation of the estrogen receptor alpha (ERα) in undifferentiated cells and the estrogen receptor beta (ERβ) in differentiated cells. BPA also activated the Peroxisome Proliferator Activated Receptor gamma (PPARγ) upregulating a minimal 3XPPARE luciferase reporter and the PPARγ-target promoter of the aP2 gene in adipose cells, while it was not effective in preadipocytes. The pure estrogen receptor agonist diethylstilbestrol (DES) played an opposite action to that of BPA inhibiting PPARγ activity in adipocytes, preventing cell differentiation, activating ERα in preadipocytes and inhibiting ERα and ERβ regulation in adipocytes. The results of this work show that the drinking of chemically-contaminated wastewater promotes fat deposition in male mice and that EDs present in sewage are likely responsible for this effect through a nuclear receptor-mediated mechanism. - Highlights: • Sewage watewaters (TW) sampled from a Municipal Treatment Sewage Plant are biologically active in mice and in vitro. • In male mice TW promotes an increase in adipose mass deposition following exposure from foetal to adult life. A similar effect is produced by BPA. • The expression of key genes of the adipose metabolism is increased in epidydimal fat both by TW and BPA. • An extract from the TW which concentrated the contained chemicals by a factor of 1000, is able to stimulate 3T3-L1 adipocyte differentiation. • The major chemicals contained in the TW, bisphenol A and nonylphenol, are able to promote adipocyte differentiation at the low environmentally relevant doses as are found in the TW.

60 APPLIED LIFE SCIENCES↗

WEEE and portable batteries in residual household waste: Quantification and characterisation of misplaced waste

Highlights: • We analyse 26.1 Mg of residual waste from 3129 Danish households. • We quantify and characterise misplaced WEEE and portable batteries. • We compare misplaced WEEE and batteries to collection through dedicated schemes. • Characterisation showed that primarily small WEEE and light sources are misplaced. • Significant amounts of misplaced batteries were discarded as built-in WEEE. - Abstract: A total of 26.1 Mg of residual waste from 3129 households in 12 Danish municipalities was analysed and revealed that 89.6 kg of Waste Electrical and Electronic Equipment (WEEE), 11 kg of batteries, 2.2 kg of toners and 16 kg of cables had been wrongfully discarded. This corresponds to a Danish household discarding 29 g of WEEE (7 items per year), 4 g of batteries (9 batteries per year), 1 g of toners and 7 g of unidentifiable cables on average per week, constituting 0.34% (w/w), 0.04% (w/w), 0.01% (w/w) and 0.09% (w/w), respectively, of residual waste. The study also found that misplaced WEEE and batteries in the residual waste constituted 16% and 39%, respectively, of what is being collected properly through the dedicated special waste collection schemes. This shows that a large amount of batteries are being discarded with the residual waste, whereas WEEE seems to be collected relatively successfully through the dedicated special waste collection schemes. Characterisation of the misplaced batteries showed that 20% (w/w) of the discarded batteries were discarded as part of WEEE (built-in). Primarily alkaline batteries, carbon zinc batteries and alkaline button cell batteries were found to be discarded with the residual household waste. Characterisation of WEEE showed that primarily small WEEE (WEEE directive categories 2, 5a, 6, 7 and 9) and light sources (WEEE directive category 5b) were misplaced. Electric tooth brushes, watches, clocks, headphones, flashlights, bicycle lights, and cables were items most frequently found. It is recommended that these findings are taken into account when designing new or improving existing special waste collection schemes. Improving the collection of WEEE is also recommended as one way to also improve the collection of batteries due to the large fraction of batteries found as built-in. The findings in this study were comparable to other western European studies, suggesting that the recommendations made in this study could apply to other western European countries as well.

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Financial sustainability in municipal solid waste management – Costs and revenues in Bahir Dar, Ethiopia

Highlights: • Cost-revenue analysis over 2 years revealed insufficient cost-recovery. • Expenses for motorized secondary collection increased by 82% over two years. • Low fee collection rate and reliance on only one revenue stream are problematic. • Different options for cost reduction and enhanced revenue streams are recommended. • Good public–private alliance is crucial to plan and implement improvement measures. - Abstract: Providing good solid waste management (SWM) services while also ensuring financial sustainability of the system continues to be a major challenge in cities of developing countries. Bahir Dar in northwestern Ethiopia outsourced municipal waste services to a private waste company in 2008. While this institutional change has led to substantial improvement in the cleanliness of the city, its financial sustainability remains unclear. Is the private company able to generate sufficient revenues from their activities to offset the costs and generate some profit? This paper presents a cost-revenue analysis, based on data from July 2009 to June 2011. The analysis reveals that overall costs in Bahir Dar’s SWM system increased significantly during this period, mainly due to rising costs related to waste transportation. On the other hand, there is only one major revenue stream in place: the waste collection fee from households, commercial enterprises and institutions. As the efficiency of fee collection from households is only around 50%, the total amount of revenues are not sufficient to cover the running costs. This results in a substantial yearly deficit. The results of the research therefore show that a more detailed cost structure and cost-revenue analysis of this waste management service is important with appropriate measures, either by the privates sector itself or with the support of the local authorities, in order to enhance cost efficiency and balance the cost-revenues towards cost recovery. Delays in mitigating the evident financial deficit could else endanger the public-private partnership (PPP) and lead to failure of this setup in the medium to long term, thus also endangering the now existing improved and currently reliable service. We present four options on how financial sustainability of the SWM system in Bahir Dar might be enhanced: (i) improved fee collection efficiency by linking the fees of solid waste collection to water supply; (ii) increasing the value chain by sales of organic waste recycling products; (iii) diversifying revenue streams and financing mechanisms (polluter-pays-, cross-subsidy- and business-principles); and (iv) cost reduction and improved cost-effectiveness. We argue that in a PPP setup such as in Bahir Dar, a strong alliance between the municipality and private enterprise is important so that appropriate solutions for improved financial sustainability of a SWM system can be sought and implemented.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Anaerobic co-digestion of food waste and landfill leachate in single-phase batch reactors

Highlights: • Anaerobic co-digestion strategy for food waste treatment at OLR 41.8 g VS/L. • A certain amount of raw leachate effectively relieved acidic inhibition. • The study showed that food waste was completely degraded. - Abstract: In order to investigate the effect of raw leachate on anaerobic digestion of food waste, co-digestions of food waste with raw leachate were carried out. A series of single-phase batch mesophilic (35 ± 1 °C) anaerobic digestions were performed at a food waste concentration of 41.8 g VS/L. The results showed that inhibition of biogas production by volatile fatty acids (VFA) occurred without raw leachate addition. A certain amount of raw leachate in the reactors effectively relieved acidic inhibition caused by VFA accumulation, and the system maintained stable with methane yield of 369–466 mL/g VS. Total ammonia nitrogen introduced into the digestion systems with initial 2000–3000 mgNH{sub 4}–N/L not only replenished nitrogen for bacterial growth, but also formed a buffer system with VFA to maintain a delicate biochemical balance between the acidogenic and methanogenic microorganisms. UV spectroscopy and fluorescence excitation–emission matrix spectroscopy data showed that food waste was completely degraded. We concluded that using raw leachate for supplement water addition and pH modifier on anaerobic digestion of food waste was effective. An appropriate fraction of leachate could stimulate methanogenic activity and enhance biogas production.

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Impact of different catalysis supported by oyster shells on the pyrolysis of tyre wastes in a single and a double fixed bed reactor

Highlights: • An innovative way in the disposal of tyre wastes with energy recovery by pyrolysis is proposed. • Performance of catalysts is improved by spreading them over layers of oyster shells. • One or two levels of supported catalytic beds may favor the quantity and/or the calorific value of the pyrolysis by-products. - Abstract: The treatment and disposal of tyres from vehicles has long been of considerable environmental importance. Studies have been undertaken to reduce their environmental impact. In this study, an alternative gas was produced from automobile tyre wastes by the means of a controlled pyrolysis. To do so, a novel catalytic system was designed with the aim of increasing the rate of conversion and improving the quality of the pyrolysis products. This work aimed also to reduce the severity of the overall reactions, by using powder catalysts (MgO, Al{sub 2}O{sub 3}, CaCO{sub 3}, and zeolite ZSM-5) uniformly distributed on two layers of oyster shells (OS) particles. The catalyst/tyres mass ratio was kept for all the tests at 1/30. The pyrolysis reactor was maintained at 500 °C and the influence of each catalyst and of the number of shell beds (0, 1 or 2), on the yield and composition of the derived products, was examined. The gas yields could contribute by 1.2% of total consumption in Tunisia. Furthermore, some combinations could upgrade the derived gas and made it possible to use it as such or with the minimum of post-treatment. It was found that, with the use of supported catalyst, the gas produced is 45% greater compared to classical thermal pyrolysis. The Heating value of the produced gas was also improved by the use of supported catalysts; it was found 16% greater with the use of Al{sub 2}O{sub 3}/OS compared to non-catalytic pyrolysis. When compared to the gas obtained from only one catalytic supported bed, the sulfur content was reduced by 80% with the use of CaCO{sub 3}/OS on two catalytic beds.

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Computational Investigation of Technetium(IV) Incorporation into Inverse Spinels: Magnetite (Fe 3 O 4 ) and Trevorite (NiFe 2 O 4 )

Iron oxides and oxyhydroxides play an important role in minimizing the mobility of redox-sensitive elements in engineered and natural environments. For the radionuclide technetium-99 (Tc), these phases hold promise as primary hosts for increasing Tc loading into glass waste form matrices, or as secondary sinks during the long-term storage of nuclear materials. Recent experiments show that the inverse spinel, magnetite [Fe(II)Fe(III)2O4], can incorporate Tc(IV) into its octahedral sub-lattice, and in that same class of materials, trevorite [Ni(II)Fe(III)2O4] is also being investigated for its ability to host Tc(IV). However, questions remain regarding the most energetically favorable charge-compensation mechanism for Tc(IV) incorporation in each structure, which will affect Tc behavior under changing waste processing or storage conditions. Here, quantum-mechanical methods were used to evaluate incorporation energies and optimized lattice bonding environments for three different, charge-balanced Tc(IV) incorporation mechanisms in magnetite and trevorite. In both cases, the removal of two octahedral Fe(II) or Ni(II) ions upon the addition of Tc(IV) to an octahedral site is the most stable mechanism, relative to the creation of octahedral Fe(III) defects or increasing octahedral Fe(II) content. Following hydration-energy corrections, Tc(IV) incorporation into magnetite is energetically favorable while an energy barrier exists for trevorite.

Environmental Molecular Sciences Laboratory↗