Universal Treatment Standards Research Articles

Stabilization and solidification of arsenic and iron contaminated canola meal biochar using chemically modified phosphate binders

Adsorption is a widely used process for removal of heavy metals, but the management of spent adsorbent containing concentrated amounts of heavy metals is a problem due to potential risk of groundwater contamination from leaching of heavy metals. Generally, cementitious binder and additives are used for stabilization and solidification treatment, however heavy metals tend to leach from such matrices. Therefore, this research investigated the effectiveness of chemically modified phosphate biochar (CMPB) composite for the simultaneous solidification and stabilization of arsenic (As) and iron (Fe) contaminated canola meal biochar. Results showed that the performance of spent biochar added CMPB composites was significantly better than the pure composites (without biochar) due to filling of inter-aggregate pores using biochar and availability of sufficient amount of MgKPO4 for binding of biochar particles. Moreover, leaching test and risk assessment studies indicated that there is no potential adverse effect as the concentrations of As and Fe in TCLP leachate were well below the Universal Treatment Standard (UTS) in optimized CMPB composites. In conclusion, chemically modified phosphate binders were found effective in stabilization and solidification of As and Fe contaminated biochar into thermodynamically stable material with high immobilization capacity and low leachability.

A simultaneous stabilization and solidification of the top five most toxic heavy metals (Hg, Pb, As, Cr, and Cd)

A novel chemically bonded phosphate ceramic (CBPC) binder was developed for the simultaneous treatment of the top five most toxic heavy metals (Hg, Pb, As, Cr, and Cd). Various CBPC binders were synthesized and tested, and their toxicity characteristic leaching procedure (TCLP) values were obtained. A magnesium/calcium-potassium phosphate ceramic binder with FeCl2 (M/C-KP-FeCl2) simultaneously stabilized multiple heavy metals. The TCLP value of the final product for industrial waste (IW) treatment using the M/C-KP-FeCl2 technology was well below the Universal Treatment Standard (UTS). Additionally, the compressive strength of the final product was below the US Nuclear Regulatory Commission Standard.

Potential of Bayesian networks for adaptive management in water recycling

Water recycling is an important solution to increasing water scarcity. However, universal wastewater treatment standards deter uptake of recycling schemes. Lack of data also impedes fit-for-purpose water recycling and water managers are challenged by decision making under uncertain conditions. Bayesian networks (BNs) are increasingly recognised as a valuable tool for decision making under uncertainty. In this study BNs are used to model health risks associated with wastewater irrigation of a public open space. Three BNs based on quantitative microbial risk assessment model risk reduction potential along a treatment chain and at the site of reuse. The BNs simulate multiple exposure profiles and scenarios, providing conditional probability of infection or illness, comparable with health-based targets. Study findings highlight the significant impact of post treatment risk mitigation, despite challenging conditions. BNs provide a transparent, defensible evidence base for mapping and quantifying risk pathways, comparing decision options and predicting outcomes of management policies.

Assessment of ferrous chloride and Portland cement for the remediation of chromite ore processing residue

Chromite Ore Processing Residue (COPR) is an industrial waste containing up to 7% chromium (Cr) including up to 5% hexavalent chromium [Cr(VI)]. The remediation of COPR has been challenging due to the slow release of Cr(VI) from a clinker like material and thereby the incomplete detoxification of Cr(VI) by chemical reagents. The use of sulfur based reagents such as ferrous sulfate and calcium polysulfide to detoxify Cr(VI) has exasperated the swell potential of COPR upon treatment. This study investigated the use of ferrous chloride alone and in combination with Portland cement to address the detoxification of Cr(VI) in COPR and the potential swell of COPR. Chromium regulatory tests, X-ray powder diffraction (XRPD) analyses and X-ray absorption near edge structure (XANES) analyses were used to assess the treatment results. The treatment results indicated that Cr(VI) concentrations for the acid pretreated micronized COPR as measured by XANES analyses were below the New Jersey Department of Environmental Protection (NJDEP) standard of 20mgkg−1. The Toxicity characteristic leaching procedure (TCLP) Cr concentrations for all acid pretreated samples also were reduced below the TCLP regulatory limit of 5mgL−1. Moreover, the TCLP Cr concentration for the acid pretreated COPR with particle size ⩽0.010mm were less than the universal treatment standard (UTS) of 0.6mgL−1. The treatment appears to have destabilized all COPR potential swell causing minerals. The unconfined compressive strength (UCS) for the treated samples increased significantly upon treatment with Portland cement.

Stabilization/solidification of mercury-contaminated waste ash using calcium sodium phosphate (CNP) and magnesium potassium phosphate (MKP) processes

This study examined the stabilization and solidification (S/S) of mercury (Hg)-contaminated waste ash generated from an industrial waste incinerator using chemically bonded phosphate ceramic (CBPC) technology. A magnesium potassium phosphate (MKP; MgKPO4·6H2O) ceramic, fabricated from MgO and KH2PO4, and a calcium sodium phosphate (CNP; CaNaPO4) ceramic, fabricated from CaO and Na2HPO4, were used as solidification binders in the CBPC process, and Na2S or FeS was added to each solidification binder to stabilize the Hg-contaminated waste ash. The S/S processes were conducted under various operating conditions (based on the solidification binder and stabilization reagent, stabilization reagent dosage, and waste loading ratio), and the performance characteristics of the S/S sample under each operating condition were compared, including the Hg leaching value and compressive strength. The Hg leaching value of untreated Hg-contaminated waste ash was 231.3μg/L, whereas the S/S samples treated using the MKP and CNP processes exhibited Hg leaching values below the universal treatment standard (UTS) limit (25μg/L). Although the compressive strengths of the S/S samples decreased as the sulfide dosage and waste loading ratio were increased, most of the S/S samples fabricated by the MKP and CNP processes exhibited good mechanical properties.

Development of iron phosphate ceramic waste form to immobilize radioactive waste solution

The objective of this research was to develop an iron phosphate ceramic (IPC) waste form using converter slag obtained as a by-product of the steel industry as a source of iron instead of conventional iron oxide. Both synthetic off-gas scrubber solution containing technetium-99 (or Re as a surrogate) and LiCl–KCl eutectic salt, a final waste solution from pyrochemical processing of spent nuclear fuel, were used as radioactive waste streams. The IPC waste form was characterized for compressive strength, reduction capacity, chemical durability, and contaminant leachability. Compressive strengths of the IPC waste form prepared with different types of waste solutions were 16MPa and 19MPa for LiCl–KCl eutectic salt and the off-gas scrubber simulant, respectively, which meet the minimum compressive strength of 3.45MPa (500psi) for waste forms to be accepted into the radioactive waste repository. The reduction capacity of converter slag, a main dry ingredient used to prepare the IPC waste form, was 4136meq/kg by the Ce(IV) method, which is much higher than those of the conventional Fe oxides used for the IPC waste form and the blast furnace slag materials. Average leachability indexes of Tc, Li, and K for the IPC waste form were higher than 6.0, and the IPC waste form demonstrated stable durability even after 63-day leaching. In addition, the Toxicity Characteristic Leach Procedure measurements of converter slag and the IPC waste form with LiCl–KCl eutectic salt met the universal treatment standard of the leachability limit for metals regulated by the Resource Conservation and Recovery Act. This study confirms the possibility of development of the IPC waste form using converter slag, showing its immobilization capability for radionuclides in both LiCl–KCl eutectic salt and off-gas scrubber solutions with significant cost savings.

An assessment of Portland cement, cement kiln dust and Class C fly ash for the immobilization of Zn in contaminated soils

Zn-contaminated soils obtained from a steel company in the Republic of Korea were stabilized using Portland cement (PC), cement kiln dust (CKD) and Class C fly ash (FA). The effectiveness of the treatment was evaluated by the United States Environmental Protection Agency toxicity characteristic leaching procedure (TCLP) and the Universal Treatment Standard (UTS) of 4.3 mg/L. X-ray powder diffraction (XRPD) analyses were performed to investigate the crystalline phases associated with Zn immobilization. Scanning electron microscopy (SEM)–energy dispersive X-ray (EDX) analyses were utilized to support the XRPD results. The treatment results showed that the TCLP-Zn concentrations obtained from the 10 wt% PC and 15 wt% CKD treated samples were less than the UTS, after 7 days curing. However, the FA treatment (up to 30 wt%) was not effective in meeting the UTS even after 28 days curing. All PC–CKD treatment combinations were effective in reducing the TCLP-Zn concentrations below the UTS criteria. Moreover, a 20 wt% dose of a PC-FA treatment combination (75/25 PC-FA) was successful in reducing the TCLP-Zn concentrations below 4.3 mg/L after 1 day. The XRPD results showed that ettringite and Zn6Al2(OH)16CO3·4H2O were the possible phases associated with Zn immobilization upon PC and CKD treatment. The SEM–EDX results confirmed the presence of ettringite, while Zn6Al2(OH)16CO3·4H2O was not identified.

Evaluation of the treatment of chromite ore processing residue by ferrous sulfate and asphalt

The effectiveness of the treatment of chromite ore processing residue (COPR) with ferrous sulfate and encapsulation into asphalt were explored separately and in combination. The asphalt treatment was conducted by mixing COPR or ferrous sulfate pretreated COPR with varying amounts of asphalt. To assess the efficacy of the treatment, the leachability of toxicity characteristic leaching procedure (TCLP) total chromium (Cr) from all treated samples was determined for curing periods up to 16 months. X-ray absorption near edge structure (XANES) analyses were also performed to evaluate the Cr 6+ concentration in the selected samples. The combination treatment of ferrous sulfate and the encapsulation of the treated COPR into asphalt reduced the TCLP total Cr concentration to lower than the regulatory limit of 5 mg/L for Cr contaminated soils, after 16 months. However, the Cr concentrations were still higher than the universal treatment standards (UTS) of 0.6 mg/L for hazardous waste. On the other hand, treatment with ferrous sulfate alone or the encapsulation of the COPR in asphalt failed to meet the TCLP total Cr concentration of 5 mg/L, after 16 months. XANES analyses results showed that more than 75% Cr 6+ reduction was achieved upon pretreatment with ferrous sulfate.

Laboratory stabilization/solidification of tank sludges: GAAT, OHF, and combined tank sets

Highly radioactive, mixed-waste sludges that have been collected at Oak Ridge over several decades are being combined for treatment and disposal. Stabilization of the sludges in the different tank sets was tested prior to the proposed combination and treatment. This paper, which follows a previous article on the Melton Valley Storage Tank/Bethel Valley Evaporator Storage Tank set, documents the testing of the Gunite and Associated Tank and Old Hydrofracture Facility tank sets, as well as the combined sludges of all the Oak Ridge National Laboratory tank sets; the third paper on this subject will discuss efforts to maximize the sludge loading. The grout formulations were tested in the laboratory with surrogates. A wet-sludge loading of 60 wt% resulted in strong wasteforms with no free water and gave a volume increase of about 30–40 vol%. The Resource Conservation and Recovery Act metals included in the surrogate testing were silver, cadmium, chromium, lead, selenium, thallium, zinc, and mercury. The grout formulations stabilized these metals within the Universal Treatment Standards limits. In addition, a grout leachability index of about 10.0–12.0 was measured for both 85Sr and 137Cs, meeting the recommended requirement of >6.0.

Laboratory stabilizations/solidification of tank sludges: MVST/BVEST

Oak Ridge tank sludges that have been collected over several decades are being combined for treatment and disposal. Stabilization of the highly radioactive, mixed-waste sludges in the different tank sets has been evaluated prior to the proposed combination and treatment. This paper documents the testing of a Melton Valley Storage Tank (MVST)/Bethel Valley Evaporator Storage Tank set. Subsequent papers will discuss continued work on other tank sets and efforts to maximize the sludge loading. Grout formulations were tested in the laboratory both with a surrogate and with a sample of an actual mixed waste tank sludge from MVST W-25. Wet-sludge loadings of 50–60 wt% resulted in strong wasteforms with no free water and gave a volume increase of about 40–50 vol%. Resource Conservation and Recovery Act (RCRA) metals included in the surrogate testing were cadmium, chromium, lead, selenium, thallium, and mercury. The actual sludge sample was only characteristically hazardous for mercury by the Toxic Characteristic Leaching Procedure but exceeded the Universal Treatment Standard (UTS) limit for chromium. The grout formulations stabilized these two RCRA metals within UTS limits. In addition, a grout leachability index of about 9.0–10.0 was measured for both 85Sr and 137Cs, meeting the recommended requirement of >6.0.

Tank‐based bioremediation of petroleum waste sludges

AbstractPetroleum waste sludges are treated in a continuous flow multistage slurry bioreactor system that operates at relatively short residence times with minimal loss of volatile constituents. The paper presents data for both pilot‐ and commercial‐scale versions of the process applied to the treatment of petroleum industry wastes of the classifications primary separation sludge (F037), API separator sludge (K051), dissolved gas flotation float (K048), and slop‐oil emulsion solids (K049). The process is shown to meet the EPA Universal Treatment Standards (UTS). The pilot‐scale system treated petrochemical‐based tarry wastes that contained volatile and semi‐volatile petroleum hydrocarbons in combination with a variety of chlorinated compounds, including polychlorinated biphenyls.The commercial‐scale system included centrifugation to recover recyclable oil and reduce sludge volume; slurry‐phase biotreatment to degrade hazardous organic constituents and convert these to carbon dioxide, water, and less toxic intermediates; and, finally, dewatering of the residual, biotreated sludge before off‐site disposal. These petroleum waste sludges are initially treated to recover oil and generate solid cake at approximately 50 wt % moisture. The solids are slurried with active cultures of facultative anaerobic bacteria, and treated in tank‐based slurry bioreactors before being disposed of in a hazardous waste landfill.The process is shown to meet UTS criteria for volatile organics (i.e., benzene through xylenes); polycyclic aromatic hydrocarbons (PAHs), including naphthalene through benzo(a)pyrene; and phenolics. The most challenging treatment targets were the PAHs, which were present at concentrations significantly above the regulatory criteria. The higher molecular weight PAHs, including the four‐ring compounds of pyrene, benzo(a)anthracene, and chrysene, were effectively treated at destruction efficiencies greater than 90%.

NON-COMBUSTIBLE WASTE VITRIFICATION WITH PLASMA TORCH MELTER

Non-combustible radioactive wastes generated from Nuclear Power Plants (NPPs) are composed of concrete, glass, asbestos, metal, sand, soil, spent filters, etc. The melting tests for concrete, glass, sand, and spent filters were carried out using a 60 kW plasma torch system. The surrogate wastes were prepared for the tests. Non-radioactive Co and Cs were added to the surrogates in order to simulate the radioactive waste. Several kinds of surrogate prepared by their own mixture or by single waste were melted with the plasma torch system to produce glassy waste forms. The characteristics of glassy waste forms were examined for the volume reduction factor (VRF) and the leach rate. The VRFs were estimated through the density measurement of the surrogates and the glassy waste forms, and were turned out to be 1.2–2.4. The EPA (Environmental Protection Agency) Toxicity Characteristic Leaching Procedure (TCLP) was used to determine the leach resistance for As, Ba, Hg, Pb, Cd, Cr, Se, Co, and Cs. The leaching index was calculated using the total content of each element in both the waste forms and the leachant. The TCLP tests resulted in that the leach rates for all elements except Co and Cs were lower than those of the Universal Treatment Standard (UTS) limits. There were no UTS limits for Co and Cs, and their leach rate & index from the experiments were resulted in around 10 times higher than those of other elements.

Laboratory stabilization/solidification of surrogate and actual mixed-waste sludge in glass and grout

Grout and glass formulations were developed for the stabilization of highly radioactive tank sludges. These formulations were tested in the laboratory with a surrogate and with a sample of an actual mixed waste tank sludge. The grout formulation was tested at wet-sludge loadings of 50–60 wt%, giving a volume increase of about 40–50 vol%. Dried sludge was vitrified into glass at waste oxide loadings of 40–50 wt%, giving a volume decrease of about 50–60 vol%. The Resource Conservation and Recovery Act (RCRA) metals included in surrogate testing were Ag, Ba, Cd, Cr, Ni, Pb, Se, Tl and Hg. Since vitrification would volatilize, not stabilize mercury, it was not included in the surrogates vitrified. The actual sludge sample was only characteristically hazardous for mercury by the toxic characteristic leaching procedure (TCLP) but exceeded the Universal Treatment Standard (UTS) limit for chromium. The grout and glass formulations stabilized these RCRA metals within UTS limits. In addition, a grout leachability index of about 9–10 was measured for both 85Sr and 137Cs, meeting the recommended requirement of >6. The glass leachability index was estimated to be >18 for cold cesium and strontium.

Vitrification of an incinerator blowdown waste containing both chloride salts and carbon

Abstract A low‐level, mixed‐waste simulant, derived from incinerator blowdown residue, has been vitrified in a series of crucible tests. Major components of this waste simulant included carbon, sodium chloride, silica, and alumina. Hazardous and surrogate radioactive metal complexes were also included. Two different formulations of additives were combined with the waste to facilitate glass formation. These glass formulations included NaNO3 to serve as a flux and to assist in the oxidation of the carbon. During vitrification, a chloride salt layer was observed on the melt surface which volatilized during the course of heating. Furthermore, significant concentrations of As, Cd, Cs, Ni, Pb, Sb, Se, Tl, and Zn had volatilized during vitrification. It is postulated that this was due, in part, to the formation of volatile metal chlorides. Upon quenching, small metal nuggets, containing Pb, Sb, Ag, and Ni separated from the glasses. This reduction of the metal oxides was caused by the presence of carbon in the simulant. The chemical durability was evaluated by both the Toxicity Characteristic Leaching Procedure (TCLP) and the Product Consistency Test (PCT). The TCLP results were below the limits for the toxicity characteristic for a hazardous waste and also met the Universal Treatment Standards for listed wastes such as F006. The PCT elemental release rates were considerably below the waste acceptance criteria for high level waste glass, which is also indicative of highly leach resistant glasses. Even though the glass products themselves were chemically durable, the formation of secondary waste streams, due to the presence of the chloride and carbon, may pose difficult challenges for the vitrification of incinerator wastes.

Ceramic Waste Form for Residues from Molten Salt Oxidation of Mixed Wastes

AbstractA ceramic waste form based on Synroc-D is under development for the incorporation of the mineral residues from molten salt oxidation treatment of mixed low-level wastes. Samples containing as many as 32 chemical elements have been fabricated, characterized, and leach-tested. Universal Treatment Standards have been satisfied for all regulated elements except two (lead and vanadium). Efforts are underway to further improve chemical durability.