Applying chemical oxidation technologies at NAPL‐impacted sites to facilitate risk‐based closure

In situ chemical oxidation (ISCO) has found widespread remedial application at sites that lack nonaqueous‐phase liquid (NAPL) or have a relatively small amount of contaminant mass. Historically, its use has been limited at sites with large amounts of NAPL, primarily because of cost considerations. Proper application of ISCO can expand its use at sites with substantial amounts of NAPL—particularly where it is being used to selectively remediate higher toxicity fractions or reduce the mobility of the NAPL itself through artificial weathering. Alone or in conjunction with conventional technologies, chemical oxidation provides a means for reducing the risk associated with NAPL and potentially closing impacted sites without completely removing NAPL. © 2010 Wiley Periodicals, Inc.     

In‐Situ Plasma Remediation of Contaminated Soils

Plasma‐torch technology has excellent potential for cost‐effective treatment of contaminated soils and other types of buried waste material. This article describes the evolution and basic features of this technology, with emphasis on the non‐transferred plasma arc torch. In addition, selected results from both laboratory experiments and field demonstrations will show how this technology can successfully destroy hazardous/toxic materials and/or stabilize contaminants in situ so they are no longer a threat to human health and the environment. © 2001 John Wiley & Sons, Inc.     

强酸性硫化砷废渣的稳定固化

采用污泥、石灰、氧化镁和水泥等药剂稳定固化强酸性硫化砷废渣(简称砷渣)。以浸出液中砷的质量浓度为考核指标,采用正交实验考察了稳定化药剂加入量对废渣浸出毒性的影响。实验结果表明:污泥加入量是影响废渣浸出毒性的最主要因素;在m(污泥):m(砷渣)=2.0、m(石灰):m(砷渣)=1.0、m(氧化镁):m(砷渣)=0.10、m(水泥):m(砷渣)=0.3的最佳实验条件下,砷的浸出质量浓度由1780.00 mg/L降至1.37 mg/L,低于GB 18598—2001《危险废物填埋污染控制标准》中砷浸出质量浓度为2.5 mg/L的填埋限值;处理后废渣中其他金属的浸出质量浓度也低于标准限值。     

In‐Situ and Ex‐Situ Bioremediation Options for Treating Perchlorate in Groundwater

Perchlorate has been identified as a water contaminant in 14 states, including California, Nevada, New Mexico, Arizona, Utah, and Texas, and current estimates suggest that the compound may affect the drinking water of as many as 15 million people. Biological treatment represents the most‐favorable technology for the effective and economical removal of perchlorate from water. Biological fluidized bed reactors (FBRs) have been tested successfully at the pilot scale for perchlorate treatment at several sites, and two full‐scale FBR systems are currently treating perchlorate‐contaminated groundwater in California and Texas. A third full‐scale treatment system is scheduled for start‐up in early 2002. The in‐situ treatment of perchlorate through addition of specific electron donors to groundwater also appears to hold promise as a bioremediation technology. Recent studies suggest that perchlorate‐reducing bacteria are widely occurring in nature, including in groundwater aquifers, and that these organisms can be stimulated to degrade perchlorate to below the current analytical reporting limit (< 4 μg/l) in many instances. In this article, in‐situ and ex‐situ options for biological treatment of perchlorate‐contaminated groundwater are discussed and results from laboratory and field experiments are presented. © 2002 Wiley Periodicals, Inc.     

Remedial Process Optimization and Ozone Sparging for Petroleum Hydrocarbon‐Impacted Groundwater

A former natural gas processing station is impacted with total petroleum hydrocarbons (TPH) and benzene. Remedial process optimization (RPO) was conducted to evaluate the effectiveness of the historical air sparging/soil vapor extraction (AS/SVE) system and the current groundwater extraction and treatment system. The RPO indicated that both remedial activities offered no further benefit in meeting remediation goals. Instead, an in situ chemical oxidation (ISCO) system was recommended. Ozone was selected, and the results of a bench test indicated that the ozone demand was 8 to 12 mg ozone/mg TPH and that secondary by‐products would include hexavalent chromium and bromate. A capture zone analysis was conducted through groundwater flow modeling (MODFLOW) to ensure containment of the injected oxidant using the existing groundwater extraction system. Results of a pilot study indicated that the optimum frequency of ozone sparging is 60 minutes in order to reach a maximum radius of influence of 20 feet. TPH concentrations within the treatment zone decreased by 97 percent over two months of ozone sparging. Concentrations of hexavalent chromium and bromate increased from nondetect to 44 and 110 mg/L, respectively, during the ozone sparging but attenuated to nondetectable concentrations within three months of system shut down. ©2016 Wiley Periodicals, Inc.     

The ART In‐Well Technology test at a chlorinated solvent site in central Iowa

An Accelerated Remediation Technologies (ART) In‐Well Technology pilot test was performed to evaluate the removal of chlorinated volatile organic compounds (VOCs) from groundwater. The ART In‐Well Technology was installed in one well located in the source area where dense nonaqueous‐phase liquid has been identified and VOC concentrations exceed 140,000 μg/L. Monitoring wells at the site were positioned between 10 and 170 feet from the ART test well. Overall, VOC concentrations from samples collected from the groundwater monitoring wells and in the vapors extracted for discharge from the ART treatment well were analyzed over the testing period. Monitoring results showed that concentrations of perchloroethylene were reduced in the closest monitoring well to nondetectable concentrations within 90 days. The cumulative removal of chlorinated VOCs from the ART test well over the six‐month pilot test period exceeded 9,500 pounds based on air monitoring data. The ART technology proved effective and cost‐efficient in reducing contaminant concentrations and removing a large mass of contamination from the subsurface in a short period of time. The radius of influence of the ART technology at the site was estimated to range between 65 and 170 feet. © 2007 Wiley Periodicals, Inc.     

In‐well sediment incubators to evaluate microbial community stability and dynamics following bioimmobilization of uranium

An in‐well sediment incubator (ISI) was developed to investigate the stability and dynamics of sediment‐associated microbial communities to prevailing subsurface oxidizing or reducing conditions. Herein we describe the use of these devices at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site. During a seven‐month period in which oxidized Rifle Aquifer background sediment (RABS) were deployed in previously biostimulated wells under iron‐reducing conditions, cell densities of known iron‐reducing bacteria, including Geobacteraceae, increased significantly, showing the microbial community response to local subsurface conditions. Phospholipid fatty acid (PLFA) profiles of RABS following in situ deployment were strikingly similar to those of adjacent sediment cores, suggesting ISI results could be extrapolated to the native material of the test plots. Results for ISI deployment with laboratory‐reduced sediments showed only slight changes in community composition and pointed toward the ability of the ISI to monitor microbial community stability and response to subsurface conditions. © 2009 Wiley Periodicals, Inc.     

Evaluation of a Slag and Portland Cement Mix to Simulate Treatment of Acidic Waste via Solidification/Stabilization in a Deep Soil Mix Application

Site investigations at an oil and gas facility identified a highly acidic waste referred to as residual acid tar that resulted in the transport of dissolved nickel toward the point of compliance at concentrations that exceeded site environmental screening levels. Solidification/stabilization (S/S) via deep soil mixing was selected as the remedial approach and a mixture of ground granulated blast furnace slag cement and Portland cement was subjected to treatability testing to evaluate the reagent mix's ability to achieve treatment objectives. Results from the treatability test showed a cement mix dose of 21 percent was sufficient to raise the pH above the target of 6.0 and reduce dissolved nickel concentrations to below site screening levels in leachate from treated samples of residual acid tar and material impacted by residual acid tar. Cement mix doses of 21 percent or greater were sufficient to achieve target strengths in the unimpacted shallow overburden. However, none of the doses tested were able to achieve target strengths in the residual acid tar or peaty material impacted by the residual acid tar. Results showed soil strengths increased significantly when the pH in leachate from the treated samples approached 12, suggesting the presence of organic acids related to the peaty soils may interfere with the cement set. Recommendations from the study include additional treatability testing to evaluate pre‐treatment with hydrated lime to satisfy acid neutralization requirements prior to dosing with the cement mix. ©2016 Wiley Periodicals, Inc.     

Solidification/stabilization of ash from medical waste incineration into geopolymers

In the present work, bottom and fly ash, generated from incinerated medical waste, was used as a raw material for the production of geopolymers. The stabilization (S/S) process studied in this paper has been evaluated by means of the leaching and mechanical properties of the S/S solids obtained. Hospital waste ash, sodium hydroxide, sodium silicate solution and metakaolin were mixed. Geopolymers were cured at 50 °C for 24 h. After a certain aging time of 7 and 28 days, the strength of the geopolymer specimens, the leachability of heavy metals and the mineralogical phase of the produced geopolymers were studied. The effects of the additions of fly ash and calcium compounds were also investigated. The results showed that hospital waste ash can be utilized as source material for the production of geopolymers. The addition of fly ash and calcium compounds considerably improves the strength of the geopolymer specimens (2–8 MPa). Finally, the solidified matrices indicated that geopolymerization process is able to reduce the amount of the heavy metals found in the leachate of the hospital waste ash.     

Solidification/stabilization of landfill leachate concentrate using different aggregate materials

The application of reverse osmosis for the treatment of landfill leachate is becoming widespread in Turkey as well as in Europe. A major drawback of this process is the production of concentrate, which could be as much as 30% of the feed stream, and high concentrations of salts and contaminants. The reverse osmosis concentrate is disposed of by using several methods including re-infiltration, drying, incineration and solidification/stabilization. In this study, solidification/stabilization (S/S) technology was studied for the treatment of reverse osmosis concentrate produced from landfill leachate. In order to benefit from its capability to absorb heavy metals, ammonia and some other pollutants, zeolite and different aggregate materials were used in solidification experiments. Main pollutants in the leachate concentrate, TOC, DOC, TDS and ammonia were successfully solidified and approximately 1% of TOC, DOC, TDS and ammonia remained in the eluate water. The results indicated that the landfill disposal limits could be attained by solidification/stabilization process.     

In Situ Solidification (ISS) of River Sediments: Pilot Demonstration and Discussion of ISS as a Remedial Alternative to Dredging and Capping

In situ solidification (ISS) is a proven technology for remediation of upland site soils, but has not been thoroughly demonstrated for use in impacted underwater sediments. This article describes the first successful use of ISS techniques to solidify underwater sediments containing manufactured gas plant non‐aqueous‐phase liquid (NAPL). The techniques consisted of mixing cementitious grout with the sediments in situ to create a monolith that immobilized the contaminants, significantly decreased the hydraulic conductivity, and also vastly decreased contaminant leaching potential of the sediments. The success of this pilot demonstration project suggests that ISS may be a viable alternative for: sites requiring deep dredging; large volume projects on urban waterways where staging and amending areas are limited; sites with NAPL impacts that cannot be controlled during dredging; and sites where eventual NAPL breakthrough is anticipated if reactive caps are employed. The potential economic, environmental, and operational benefits of this technology will be discussed. This article focuses on the primary objectives of the pilot demonstration: to meet quantitative performance criteria for strength and hydraulic conductivity; to assess the leach performance of the solidified sediments; and to satisfy water quality parameters for turbidity, pH, and sheen. Approach/activities: The pilot study utilized a customized marine platform (modular floats, tug boats, etc.) and full‐scale ISS equipment (auger rig, silos, etc.) and varied operational parameters to provide a range of data to assist in evaluating the feasibility and efficacy of the technology for use in similar environments and in planning future ISS projects on the water. Water quality controls and monitoring were implemented during the operation, and the study documented and evaluated the environmental disruption (short‐term impacts) and costs of the application of the ISS process to contaminated aquatic sediments. ©2016 Wiley Periodicals, Inc.     

Cement‐based solidification/stabilization of phenol‐contaminated soil by bentonite and organophilic clay

The performance of ordinary and organophilic clays in the solidification and stabilization process was investigated with respect to the unconfined compressive strength (UCS) and leaching of phenol‐contaminated soil. The samples contained 2,000 mg/kg of phenol. White cement (15 and 30 percent by weight [wt%]) was used as binder, while ordinary and organophilic clays (8, 15, and 30 wt%) were applied as additives for reducing the harmful effects of phenol interference in cement hydration with a 28‐day curing time. The results revealed that the UCS is reduced by increasing the amount of clays. The values of UCS of all samples met the minimum standards specified for disposal in sanitary landfills determined by developed countries. The leaching test demonstrated that the degree of leaching diminished with increased clay content in all samples of both clay types. This reduction was observed to be greater in samples containing organophilic clay than in bentonite clay samples. Furthermore, the best composition of the materials tested was determined to be 30 wt% white cement plus 13.3 wt% organophilic clay with a compressive strength of 3,839 kPa, phenol removal percentage of 80 percent, and a cost of $67 per ton of contaminated soil.     

Remediating TCE‐contaminated groundwater in low‐permeability media using hydraulic fracturing to emplace zero‐valent iron/organic carbon amendment

A field pilot test in which hydraulic fracturing was used to emplace granular remediation amendment (a mixture of zero‐valent iron [ZVI] and organic carbon) into fine‐grained sandstone to remediate dissolved trichloroethene (TCE)‐contaminated groundwater was performed at a former intercontinental ballistic missile site in Colorado. Hydraulic fracturing was used to enhance the permeability of the aquifer with concurrent emplacement of amendment that facilitates TCE degradation. Geophysical monitoring and inverse modeling show that the network of amendment‐filled fractures extends throughout the aquifer volume targeted in the pilot test zone. Two years of subsequent groundwater monitoring demonstrate that amendment addition resulted in development of geochemical conditions favorable to both abiotic and biological TCE degradation, that TCE concentrations were substantially reduced (i.e., greater than 90 percent reduction in TCE mass), and that the primary degradation processes are likely abiotic. The pilot‐test data aided in re‐evaluating the conceptual site model and in designing the full‐scale remedy to address a larger portion of the TCE‐contaminated groundwater plume. © 2012 Wiley Periodicals, Inc.     

Unreliability of co‐occurrence‐based sediment quality guidelines for contaminated sediment evaluations at Superfund/hazardous chemical sites

Many Superfund/hazardous chemical sites include waterbodies whose sediments contain hazardous chemicals. With the need to assess, rank, and remediate contaminated sediments at such sites, as well as in other waterways, regulators seek a simple, quantitative assessment approach that feeds easily into a decision‐making scheme. Numeric, co‐occurrence‐based “sediment quality guidelines” have emerged with the appearance of administrative simplicity. However, the very foundation of the co‐occurrence approach, based on the total concentrations of a chemical(s) in sediment, is technically invalid; its application relies on additional technically invalid presumptions. Use of technically invalid evaluation approaches renders any assessment of the significance of sediment contamination unreliable. This article reviews the technical roots and assumptions of the co‐occurrence‐based SQGs, the fundamental flaws in the rationale behind their development and application, and their misapplication for sediment quality evaluation. It also reviews concepts and approaches for the more reliable evaluation, ranking, and cleanup assessment of contaminated sediments at Superfund sites and elsewhere. © 2005 Wiley Periodicals, Inc.     

Solidification/stabilisation of arsenic bearing fly ash from the metallurgical industry. Immobilisation mechanism of arsenic

When a fly ash waste material from a copper refining process containing large amounts of As2O3 is solidified using cement and lime, the arsenic concentration in the leachate can be lowered to ca. 5 mg/l in a saturated solution of Ca(OH)2. It is shown that the decrease of the concentration in the leachate, mainly of As(III), is due to the formation of insoluble CaHAsO3 in the leachate in the presence of Ca(OH)2. This method is compared with a method whereby use is made of oxidation of the waste before solidification to oxidise As(III) to As(V) using H2O2. The arsenic concentration in the leachate of the extraction test of an oxidised S/S sample was lowered to ca. 0.5 mg/l, a factor of 10 below the one for a non-oxidised sample. It is shown that the decrease of the concentration in the leachate mainly of As(V) is due to the formation of insoluble Ca3(AsO4)2 in the presence of Ca(OH)2. Extensive use was made of the speciation program MINTEQA2, to clarify the immobilisation of arsenic.     

Stabilization/solidification of ashes in clays used in the manufacturing of ceramic bricks.

This paper presents the results of the lixiviation of metals from different mixtures of fly and bottom ashes that have been stabilized and solidified in clays used in the manufacture of bricks. The ashes used for this study were obtained from a Hoffmann-type brick furnace adapted for the incineration of municipal solid waste during the manufacturing of ceramic bricks. The ashes were stabilized in clay in different proportions of clay:ash mix (99:1, 95:5, 90:10, 80:20 and 60:40). Such mixes were used to manufacture bricks that were calcined at a temperature ranging from 50 to 1100 degrees C. The clay, ashes and manufactured bricks were characterized using X-ray diffraction, fluorescent X-ray, thermogravimetry, differential thermal analysis, atomic absorption spectroscopy and scanning electronic microscopy. In addition, toxicity characteristic leaching procedure lixiviation tests were performed according to the EPA 1311 method for the determination of heavy metals. The results showed an affinity between clay and ash, and also that the bricks manufactured with these mixtures present low lixiviation levels. The tests also showed the highest decrease in the concentration of arsenic, nickel, chromium, zinc and silver for 99:1 mixtures. The 95:5 mixture was found to be the most favourable for the stabilization (greater concentration decrease) of lead and cadmium. Selenium was the metal with the lowest concentration change whereas arsenic, nickel, chromium, zinc and cadmium showed the greatest concentration change in all mixtures, with the exception of cadmium in the mixture 99:1.     

Solidification/stabilisation of air pollution control residues using Portland cement: Physical properties and chloride leaching

Portland cement (CEMI) was used to solidify air pollution control (APC) residues from an energy-from-waste plant burning municipal solid waste. APC residue/CEMI mixes were prepared with CEMI additions ranging from 0 to 50 weight% (wt%) of total dry mass and water/solids ratios between 0.40 and 0.80. Isothermal conduction calorimetry was used to assess the effect of APC residues on the hydration of CEMI. Although up to 30wt% additions of APC residues accelerated CEMI hydration, the total heat of hydration during the initial 98h was significantly reduced. Higher levels of APC residues severely inhibited CEMI hydration. The consistence, setting time, compressive strength, porosity and chloride leaching characteristics of the solidified products were determined. As might be expected, increasing the CEMI addition and reducing the water content resulted in increased compressive strengths. All mixes achieved compressive strengths greater than 1MPa at 7 and 28days but only 50wt% samples did not show significant strength reduction when tested after immersion in water. Monolithic leaching tests indicated low physical immobilisation of chloride in the CEMI solidified APC residues, with chloride leaching in excess of relevant UK landfill waste acceptance criteria (WAC). The results of this study show that greater than 50% CEMI additions would be required to effectively treat APC residues to meet current WAC limits.     

Abiotic/biotic degradation and mineralization of N‐nitrosodimethylamine in aquifer sediments

The N‐nitrosodimethylamine (NDMA) degradation rate and mineralization rate were measured in two aquifer sediments that received treatments to create oxic, reducing, and sequential reducing/oxic environments. Chemically reduced sediments rapidly abiotically degraded NDMA to nontoxic dimethylamine to parts per trillion levels, then degraded to further products. NDMA was partially mineralized in reduced sediments (6 to 28 percent) at a slow rate (half‐life 3,460 h) by an unknown abiotic/biotic pathway. In contrast, NDMA was mineralized more rapidly (half‐life 342 h) and to a greater extent (30 to 81 percent) in oxic sediments with propane addition, likely by a propane monooxygenase pathway. NDMA mineralization in sequential reduced sediment followed by oxic sediment treatment did result in slightly more rapid mineralization and a greater mineralization extent relative to reduced systems. These increases were minor, so aerobic NDMA mineralization with oxygen and propane addition was the most viable in situ NDMA mineralization strategy. © 2008 Wiley Periodicals, Inc.     

Stable Isotope Probing to Confirm Field‐Scale Co‐Metabolic Biodegradation of 1,4‐Dioxane

1,4‐Dioxane, a common co‐contaminant with chlorinated solvents, is present in groundwater at Site 24 at Vandenberg Air Force Base in California. Historical use of chlorinated solvents resulted in concentrations of 1,4‐dioxane in groundwater up to approximately 2,000 μg/L. Starting in 2013, an in situ propane biosparge system operation demonstrated reductions in 1,4‐dioxane concentrations in groundwater. The work detailed herein extends the efforts of the first field demonstration to a second phase and confirms the biodegradation mechanism via use of stable isotope probing (SIP). After two months of operation, 1,4‐dioxane concentrations decreased approximately 45 to 83 percent at monitoring locations in the test area. The results of the SIP confirmed ¹³C‐enriched 1,4‐dioxane was transformed into dissolved inorganic carbon (suggesting mineralization to carbon dioxide) and incorporated into microbial biomass (likely attributed to metabolic uptake of biotransformation intermediates or of carbon dioxide).  ©2016 Wiley Periodicals, Inc.