Regulatory Off-Gas Analysis from the Evaporation of Hanford Simulated Waste Spiked with Organic Compounds

Abstract

After strontium/transuranics removal by precipitation followed by cesium/technetium removal by ion exchange, the remaining low-activity waste in the Hanford River Protection Project Waste Treatment Plant is to be concentrated by evaporation before being mixed with glass formers and vitrified. To provide a technical basis to permit the waste treatment facility, a relatively organic-rich Hanford Tank 241-AN-107 waste simulant was spiked with 14 target volatile, semi-volatile, and pesticide compounds and evaporated under vacuum in a bench-scale natural circulation evaporator fitted with an industrial stack off-gas sampler at the Savannah River National Laboratory. An evaporator material balance for the target organics was calculated by combining liquid stream mass and analytical data with off-gas emissions estimates obtained using U.S. Environmental Protection Agency (EPA) SW-846 Methods. Volatile and light semi-volatile organic compounds (<220 °C BP, >1 mm Hg vapor pressure) in the waste simulant were found to largely exit through the condenser vent, while heavier semi-volatiles and pesticides generally remain in the evaporator concentrate. An OLI Environmental Simulation Program (licensed by OLI Systems, Inc.) evaporator model successfully predicted operating conditions and the experimental distribution of the fed target organics exiting in the concentrate, condensate, and off-gas streams, with the exception of a few semi-volatile and pesticide compounds. Comparison with Henry's Law predictions suggests the OLI Environmental Simulation Program model is constrained by available literature data.     

Simultaneous determination of seven anticoagulant rodenticides in agricultural products by gel permeation chromatography and liquid chromatography–tandem mass spectrometry

A sensitive and reliable method for the simultaneous determination of hydroxycoumarin-type (brodifacoum, bromadiolone, coumatetralyl, and warfarin) and indandione-type (chlorophacinone, diphacinone, and pindone) rodenticides in agricultural products by gel permeation chromatography (GPC) and liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed. The procedure involved extraction of the rodenticides from samples with acetone, followed by liquid–liquid partitioning with hexane/ethyl acetate (1:1, v/v) and 10% sodium chloride aqueous solution, then cleanup using GPC, and finally, analysis using LC–MS/MS. High recoveries from the GPC column were obtained for all rodenticides tested using a mobile phase of acetone/cyclohexane/triethylamine (400:1600:1, v/v/v). An ODS column, which contains low levels of metal impurities, gave satisfactory peak shapes for both hydroxycoumarin- and indandione-type rodenticides in the LC–MS/MS separation. The average recoveries of rodenticides from eight agricultural foods (apple, eggplant, cabbage, orange, potato, tomato, brown rice, and soybean) fortified at 0.0005–0.001 mg/kg ranged from 76 to 116%, except for bromadiolone in orange (53%) and diphacinone in soybean (54%), and the relative standard deviations ranged from 1 to 16%. The proposed method effectively removed interfering components, such as pigments and lipids, and showed high selectivity. In addition, the matrix effects were negligible for most of the rodenticide/food combinations. The results suggest that the proposed method is reliable and suitable for determining hydroxycoumarin- and indandione-type rodenticides in agricultural products.     

Blood levels of PCDDs,PCDFs, and coplanar PCBs in Yusho mothers and their descendants: Association with fetal Yusho disease

Maternal exposure to polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) may result in adverse health effects in their children. In Japan in 1968, an accidental human exposure to rice oil contaminated with PCDDs, PCDFs, and PCBs, led to the development of Yusho disease. Yusho mothers delivered descendants with low birth weights and hyperpigmented skin and mucosa, which are characteristic of fetal Yusho disease (FYD). The Yusho cohort was used to evaluate the effect of maternal exposure to PCDDs, PCDFs, and PCBs on the development of FYD. Blood samples, obtained from 64 Yusho mothers (117 descendants: 10 with FYD and 107 without FYD), were analyzed for congeners of seven PCDDs, 10 PCDFs, and four coplanar PCBs. We investigated the association between the maternal estimated blood levels of dioxins at delivery and the risk of fetal Yusho disease. We also studied the differences in dioxin blood levels in 24 mother–descendant pairs (5 with FYD and 19 without FYD). The estimated levels of total PCDD TEQ, total PCDF TEQ, total coplanar PCB TEQ, and total TEQ in the maternal blood at delivery were associated with significantly increased risk of FYD. The odds ratios, which present the risk of FYD for a 10-fold increase in blood dioxin, were largest for 1,2,3,6,7,8-HexaCDD (odds ratio = 28.6, 95% confidence interval = 1.67–489.9, p = 0.02). The levels of 1,2,3,6,7,8-HexaCDD in both the Yusho mothers and their descendants with FYD were higher than the levels in those without FYD. These findings suggest that 1,2,3,6,7,8-HexaCDD is the most important causative congener for the development of FYD.     

Analysis method for PCBs in reclaimed oil using a fast-GC triple stage quadrupole mass spectrometer with the 13-component quantitation method

It is necessary for companies supplying reclaimed oil to analyze polychlorinated biphenyls (PCBs), because there is a possibility of the presence of contaminants due to trace-level PCBs in the reclaimed oil. However, common analysis methods of PCBs are time-consuming and complicated. Fast-GC triple stage quadrupole mass spectrometer with the 13-component quantitation method is an official method for analyzing PCBs in insulating oil in Japan. This method is extremely fast and simplified. The purpose of this study involves an investigation of the aforementioned fast and simple method for potential use in the analysis of reclaimed oil. Furthermore, it was attempted to combine the method with sample preparation involving only hexane dilution. The effect of sample dilutions corresponding to 100, 300, and 500 times was evaluated for reducing the matrix effect. The matrix effect was suppressed at a dilution ratio equal to or exceeding 300 times. Calibration curves of four points, namely 0.01, 0.05, 0.1, and 0.5 ng/mL, (ignored origin) by using an internal standard method were prepared for the 13 components. The square of regression coefficient (R²) values of all calibration curves exceeded 0.997. This method was adopted for the analysis of reclaimed oil containing 0.5 μg/mL PCBs, which corresponds to the judgment criteria, and accurate quantitation (accuracy value, 94.0–102%) and good repeatability (%RSD, 3.6%) were obtained. Furthermore, the required sensitivity was maintained even when 800 samples were analyzed without a cleaning ion source and an exchanging analysis column.     

Regional and seasonal characteristics of emission sources of fine airborne particulate matter collected in the center and suburbs of Tokyo, Japan as determined by multielement analysis and source receptor models

Airborne particulate matter, suspected to induce adverse effects on human health, have been one of the most important concerns regarding recent air pollution issues in Japan. To characterize regional and seasonal variations in emission sources of fine airborne particulate matter (d < 2 microm), monthly samples (n = 36 for each site) were collected at urban (Tokyo), suburban (Maebashi), and mountainous (Akagi) sites in Japan from April 2003 to March 2006. Multielement analysis of chemical species (Na, Al, K, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Sb, and Pb) was performed by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry. The combined source receptor model, which consists of positive matrix factorization and chemical mass balance, determined the contributions of nine emission sources (local and continental soils, road dust, coal and oil combustion, waste incineration, steel industry, brake wear, and diesel exhaust) to the observed elemental concentrations. Large regional differences were identified in the source contributions among the observational sites. Diesel exhaust was identified as the most significant source (70% of identified contributions) at the urban site. Local and continental soils, coal combustion, and diesel exhaust were intricately assigned (20-30% each) to the suburban site. Continental soil was the predominant source (65%) at the mountainous site. Respective significant source contributions dominated the seasonal variations of total elemental concentrations at each site. These results suggest that a better understanding of the regional and seasonal characteristics of impacting emission sources will be important for improving regional environments.     

Evaluation of operational parameters in thermophilic acid fermentation of kitchen waste

In this study, the effect of operational parameters, such as solids retention time (SRT), pH, and substrate total solids (TS) concentration, on acid fermentation efficiency was investigated. From batch tests, it was shown that the appropriate pH range for thermophilic acidogens was around 6–7 and that the optimum pH condition was 6. From the continuous experiment, pH and SRT were shown to be the most important operational parameters for solubilization and organic acid production. In contrast, TS concentration did not show any obvious effect on chromium chemical oxygen demand (CODcr) solubilization when TS was in the range 3.5%–10%. The optimum operational conditions for thermophilic acid fermentation were an SRT of 2 days and a pH of 6. This research was carried as a part of the CREST project of Japan Science and Technology Agency.     

Decolorization and estrogenic activity of colored livestock wastewater after electrolysis treatment

Livestock wastewater is treated by activated sludge treatment. Untreated livestock wastewater has high estrogen activity because animal excreta contains estrogen. When activated sludge treatment is applied, the estrogen activity declines or is lost. However, the color of treated livestock wastewater is deep brownish-red because of the decomposition of organic compounds or the synthesis of metabolites. Discharging colored wastewater to the environment could cause some problems, so it is necessary to decolorize colored wastewater before it is discharged. It has been suggested that electrolysis decolorization technology is suitable for treating colored wastewater; however, the process produces volatile organic compounds (VOCs). In fact, little research has been conducted with reference to estrogen activity in wastewater that has undergone electrolysis, especially on the contribution of the electrolysis decolorization process to estrogen activity, i.e., the possibility of resynthesis of some substance with estrogen activity due to resolved and metabolized colored components. In this study, the concentration of VOC was measured for various electrolysis conditions, and estrogen activity was examined using a yeast two-hybrid assay. From the results, decolorization of colored livestock wastewater by electrolysis was possible, and the VOC generation during electrolysis could be controlled depending on the electrolysis conditions. Estrogen activity in colored livestock wastewater disappeared on electrolysis decolorization.     

Optimization of separation and logistics for recycling materials from wallpaper hanging sites

It is of huge importance for sustainability to find a pragmatic solution for recycling of a variety of wastes emitted in small mass such as the case of wallpaper replacements. A combination of two-step sorting scheme and transportation of the wastes in collaboration with the wholesalers was proposed to enhance the efficiency of recycling. The two-step sorting consists of the first sorting at the wallpaper hanging sites to separate and group wastes in a way to avoid heavy additional burden on the hanging job. Secondary sorting is conducted at a Sorting Center to re-group wastes to send to an intermediate processing company for recycling. To minimize the costs for transportation, the grouped wastes emitted at the hanging sites are brought back by the hangers and kept temporally and then moved to the wholesaler(s) on the way to receive new materials. When the wastes at the wholesaler(s) become sufficiently large for economic transportation, a truck is arranged to collect the wastes to transport them to the Sorting Center. A feasibility study to test the practicality of the method confirmed that it could be operable and the cost would be comparable or lower than that currently incurred for disposal of the wastes.     

Preliminary estimations of energy and cost for CO2 recovery by a membrane flash process utilizing waste thermal energy

The membrane flash process utilizing waste thermal energy was developed to achieve an energy-saving technology and to substitute it for a conventional regenerator. The operating conditions of the membrane flash at high temperature were studied. The petroleum refining process and iron manufacturing process were proposed for candidate processes that actually had waste energy sources. The DEA concentration and the flashing pressure had optimum values to improve the performance and reduce the energy consumption for CO₂ recovery. Energy consumptions and costs for CO₂ recovery in the membrane flash and chemical absorption were estimated by a process simulator and discussed under the same conditions. The membrane flash can achieve lower energy capture than the chemical absorption for the above industrial processes. The membrane flash is suitable for the CO₂ emission sources that had high CO₂ concentration independently of the plant scale. The chemical absorption can be applied if the plant scale is large and also the CO₂ concentration is low.     

Migration of C in the paddy soil-to-rice plant system after C-acetic acid breakdown by microorganisms below the plow layer

Migration of ¹⁴C derived from ¹⁴C-acetic acid was examined by using soils sampled from paddies in four administrative areas in Japan (Aomori, Yamanashi, Ehime and Okinawa) and rice plant in a tracer experiment to understand the fate of ¹⁴C in the paddy soil-to-rice plant system. The loss of ¹⁴C radioactivity levels derived from ¹⁴C-acetic acid was caused by soil microorganism breakdown. A part of the ¹⁴C fixation to soil was caused by microbial assimilation into the fatty acid fraction. ¹⁴C moved upward via two different types of ¹⁴C dynamics in soil: quick movement upward; and constant but slow movement upward. ¹⁴C was highly assimilated into the plant panicle and that was caused by the root-uptake and the transfer of ¹⁴C. Migration of ¹⁴C derived from ¹⁴C-acetic acid relied heavily upon changes of chemical forms and characteristics of ¹⁴C-compound as caused by microorganisms in soil.