Adsorption kinetics, thermodynamics, and isotherm studies for functionalized lanthanide-chelating resins.

Conventional ion exchange resins are widely utilized to remove metals from aqueous solutions, but their limited selectivity precludes dilute ion extraction. This research investigated the adsorption performance of ligand-functionalized resins towards rare earth elements (REE). Functionalized resin particles were synthesized by grafting different ligands (diethylenetriaminepentaacetic dianhydride (DTPADA), phosphonoacetic acid (PAA), or N,N-bis(phosphonomethyl)glycine (BPG)) onto pre-aminated polymeric adsorbents (diameter ∼ 0.6 mm). Lanthanide uptake trends were evaluated for the functionalized resins using batch adsorption experiments with a mixture of three REEs (Nd, Gd, and Ho at 0.1-1000 mg/L each). Resin physical-chemical properties were determined by measuring their surface area, ligand concentrations, and acidity constants. The aminated supports contained 4.0 mmol/g primary amines, and ligand densities for the functionalized resins were 0.33 mmol/g (PAA), 0.22 mmol/g (BPG), and 0.42 mmol/g (DTPADA). Kinetic studies revealed that the functionalized resins followed pseudo-second order binding kinetics with rates limited by intraparticle diffusion. Capacity estimates for total REE adsorption based on Langmuir qMax were 0.12 mg/g (amine; ≈ 0.77 µmol/g), 5.0 mg/g (PAA; ≈ 32.16 µmol/g), 3.0 mg/g (BPG; ≈ 19.30 µmol/g), and 2.9 mg/g (DTPADA; ≈ 18.65 µmol/g). Attaching ligands to the aminated resins greatly improved their REE binding strength and adsorption efficiency.

Measurement and Modeling of Setschenow Constants for Selected Hydrophilic Compounds in NaCl and CaCl2 Simulated Carbon Storage Brines.

Carbon capture, utilization, and storage (CCUS), a climate change mitigation strategy, along with unconventional oil and gas extraction, generates enormous volumes of produced water containing high salt concentrations and a litany of organic compounds. Understanding the aqueous solubility of organic compounds related to these operations is important for water treatment and reuse alternatives, as well as risk assessment purposes. The well-established Setschenow equation can be used to determine the effect of salts on aqueous solubility. However, there is a lack of reported Setschenow constants, especially for polar organic compounds. In this study, the Setschenow constants for selected hydrophilic organic compounds were experimentally determined, and linear free energy models for predicting the Setschenow constant of organic chemicals in concentrated brines were developed. Solid phase microextraction was employed to measure the salting-out behavior of six selected hydrophilic compounds up to 5 M NaCl and 2 M CaCl2 and in Na-Ca-Cl brines. All compounds, which include phenol, p-cresol, hydroquinone, pyrrole, hexanoic acid, and 9-hydroxyfluorene, exhibited log-linear behavior up to these concentrations, meaning Setschenow constants previously measured at low salt concentrations can be extrapolated up to high salt concentrations for hydrophilic compounds. Setschenow constants measured in NaCl and CaCl2 brines are additive for the compounds measured here; meaning Setschenow constants measured in single salt solutions can be used in multiple salt solutions. The hydrophilic compounds in this study were selected to elucidate differences in salting-out behavior based on their chemical structure. Using data from this study, as well as literature data, linear free energy relationships (LFERs) for prediction of NaCl, CaCl2, LiCl, and NaBr Setschenow constants were developed and validated. Two LFERs were improved. One LFER uses the Abraham solvation parameters, which include the index of refraction of the organic compound, organic compound's polarizability, hydrogen bonding acidity and basicity of the organic compound, and the molar volume of the compound. The other uses an octanol-water partitioning coefficient to predict NaCl Setschenow constants. Improved models from this study now include organic compounds that are structurally and chemically more diverse than the previous models. The CaCl2, LiCl, and NaBr single parameter LFERs use concepts from the Hofmeister series to predict new, respective Setschenow constants from NaCl Setschenow constants. The Setschenow constants determined here, as well as the LFERs developed, can be incorporated into CCUS reactive transport models to predict aqueous solubility and partitioning coefficients of organic compounds. This work also has implications for beneficial reuse of water from CCUS; this can aide in determining treatment technologies for produced waters.

New Linear Partitioning Models Based on Experimental Water: Supercritical CO2 Partitioning Data of Selected Organic Compounds.

Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch-reactor system with dual spectroscopic detectors: a near-infrared spectrometer for measuring the organic analyte in the CO2 phase and a UV detector for quantifying the analyte in the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly parameter linear free-energy relationship and to develop five new linear free-energy relationships for predicting water-sc-CO2 partitioning coefficients. A total of four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than does the model built for the entire data set.

Measurement of Setschenow constants for six hydrophobic compounds in simulated brines and use in predictive modeling for oil and gas systems.

Treatment and reuse of brines, produced from energy extraction activities, requires aqueous solubility data for organic compounds in saline solutions. The presence of salts decreases the aqueous solubility of organic compounds (i.e. salting-out effect) and can be modeled using the Setschenow Equation, the validity of which has not been assessed in high salt concentrations. In this study, we used solid-phase microextraction to determine Setschenow constants for selected organic compounds in aqueous solutions up to 2-5 M NaCl, 1.5-2 M CaCl2, and in Na-Ca binary electrolyte solutions to assess additivity of the constants. These compounds exhibited log-linear behavior up to these high NaCl concentrations. Log-linear decreases in solubility with increasing salt concentration were observed up to 1.5-2 M CaCl2 for all compounds, and added to a sparse database of CaCl2 Setschenow constants. Setschenow constants were additive in binary electrolyte mixtures. New models to predict CaCl2 and KCl Setschenow constants from NaCl Setschenow constants were developed, which successfully predicted the solubility of the compounds measured in this study. Overall, data show that the Setschenow Equation is valid for a wide range of salinity conditions typically found in energy-related technologies.

Matrix effect of sodium compounds on the determination of metal ions in aqueous solutions by underwater laser-induced breakdown spectroscopy.

A significant portion of the carbon sequestration research being performed in the United States involves the risk assessment of injecting large quantities of carbon dioxide into deep saline aquifers. Leakage of CO2 has the potential to affect the quality of groundwater supplies in case contaminants migrate through underlying conduits. New remote sensing and near-surface monitoring technologies are needed to ensure that injection, abandoned, and monitoring wells are structurally sound, and that CO2 remains within the geologic storage reservoir. In this paper, we propose underwater laser-induced breakdown spectroscopy (underwater LIBS) as an analytical method for monitoring naturally occurring elements that can act as tracers to detect a CO2 leak from storage sites. Laboratory-scale experiments were conducted to measure Sr2+, Ca2+, K(+), and Li(+) in bulk solutions to ascertain the analytical performance of underwater LIBS. We compared the effect of NaCl, Na2CO3, and Na2SO4 on the analytes calibration curves to determine underwater LIBS' ability to analyze samples of sodium compounds. In all cases, the calibration curves showed a good linearity within 2 orders of magnitude. The limit of detections (LODs) obtained for K(+) (30±1 ppb) and Li(+) (60±2 ppb) were in ppb range, while higher LODs were observed for Ca(2+) (0.94±0.14 ppm) and Sr(2+) (2.89±0.11 ppm). Evaluation of the calibration curves for the analytes in mixed solutions showed dependence of the lines' intensity with the sodium compounds. The intensities increased respectively in the presence of dissolved NaCl and Na2SO4, whereas the intensities slightly decreased in the presence of Na2CO3. Finally, the capabilities of underwater LIBS to detect certain elements in the ppb or in the low ppm range make it particularly appealing for in situ monitoring of a CO2 leak.

Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale.

In this work, the geochemistry of the rare earth elements (REE) was studied in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In these samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.

Determination of Rare Earth Elements in Hypersaline Solutions Using Low-Volume, Liquid-Liquid Extraction.

Complex, hypersaline brines-including those coproduced with oil and gas, rejected from desalination technologies, or used as working fluids for geothermal electricity generation-could contain critical materials such as the rare earth elements (REE) in valuable concentrations. Accurate quantitation of these analytes in complex, aqueous matrices is necessary for evaluation and implementation of systems aimed at recovering those critical materials. However, most analytical methods for measuring trace metals have not been validated for highly saline and/or chemically complex brines. Here we modified and optimized previously published liquid-liquid extraction (LLE) techniques using bis(2-ethylhexyl) phosphate as the extractant in a heptane diluent, and studied its efficacy for REE recovery as a function of three primary variables: background salinity (as NaCl), concentration of a competing species (here Fe), and concentration of dissolved organic carbon (DOC). Results showed that the modified LLE was robust to a range of salinity, Fe, and DOC concentrations studied as well as constant, elevated Ba concentrations. With proper characterization of the natural samples of interest, this method could be deployed for accurate analysis of REE in small volumes of hyper-saline and chemically complex brines.

A method for preparation and cleaning of uniformly sized arsenopyrite particles.

BACKGROUND: The oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 150-250 µm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from the surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM-EDS). RESULTS: Results indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface. CONCLUSIONS: Although sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.

Laser-induced breakdown spectroscopy (LIBS) of a high-pressure CO2-water mixture: application to carbon sequestration.

Geologic carbon storage in deep saline aquifers is considered a feasible and possible approach of mitigating the problem of increasing greenhouse gas emissions. However, there are latent risks in which carbon dioxide (CO2) could migrate from the deep saline formations to shallower aquifers. In the event of a significant CO2 leakage to an underground source of drinking water, CO2 will dissolve in the water, thereby increasing its acidity, which could potentially enhance the solubility of various aquifer constituents, including hazardous compounds, subsequently compromising groundwater quality due to increased concentration of aqueous metals. In this paper we explore the possibility of detecting such leakage by the use of laser-induced breakdown spectroscopy (LIBS). The experiments were conducted in calcium chloride solution at three pressures of 10, 50, and 120 bar. To evaluate the direct effect of elevated CO2 on the intensity of calcium emission lines (422.67 and 393.37 nm), we also performed experiments with pure nitrogen (N2) gas, offering large water solubility contrast. We found that when performed in presence of CO2, LIBS showed only a modest decrease in Ca emission intensity from 10 to 120 bar compared to N2. These results indicate that LIBS is a viable tool for measuring brine/water contents in high-pressure CO2 environment and can be applied for monitoring CO2 leakage and displaced brine migration.

Rare earth element distributions and trends in natural waters with a focus on groundwater.

Systematically varying properties and reactivities have led to focused research of the environmental forensic capabilities of rare earth elements (REE). Increasing anthropogenic inputs to natural systems may permanently alter the natural signatures of REE, motivating characterization of natural REE variability. We compiled and analyzed reported dissolved REE concentration data over a wide range of natural water types (ground-, ocean, river, and lake water) and groundwater chemistries (e.g., fresh, brine, and acidic) with the goal of quantifying the extent of natural REE variability, especially for groundwater systems. Quantitative challenges presented by censored data were addressed with nonparametric distributions and regressions. Reported measurements of REE in natural waters range over nearly 10 orders of magnitude, though the majority of measurements are within 2-4 orders of magnitude, and are highly correlated with one another. Few global correlations exist among dissolved abundance and bulk solution properties in groundwater, indicating the complex nature of source-sink terms and the need for care when comparing results between studies. This collection, homogenization, and analysis of a disparate literature facilitates interstudy comparison and provides insight into the wide range of variables that influence REE geochemistry.

Effect of sodium chloride concentration on elemental analysis of brines by laser-induced breakdown spectroscopy (LIBS).

Leakage of injected carbon dioxide (CO2) or resident fluids, such as brine, is a major concern associated with the injection of large volumes of CO2 into deep saline formations. Migration of brine could contaminate drinking water resources by increasing their salinity or endanger vegetation and animal life as well as human health. The main objective of this study was to investigate the effect of sodium chloride (NaCl) concentration on the detection of calcium and potassium in brine samples using laser-induced breakdown spectroscopy (LIBS). The ultimate goals were to determine the suitability of the LIBS technique for in situ measurements of metal ion concentrations in NaCl-rich solution and to develop a chemical sensor that can provide the early detection of brine intrusion into formations used for domestic or agricultural water production. Several brine samples of NaCl-CaCl2 and NaCl-KCl were prepared at NaCl concentrations between 0.0 and 3.0 M. The effect of NaCl concentration on the signal-to-background ratio (SBR) and signal-to-noise ratio (SNR) for calcium (422.67 nm) and potassium (769.49 nm) emission lines was evaluated. Results show that, for a delay time of 300 ns and a gate width of 3 µs, the presence of and changes in NaCl concentration significantly affect the SBR and SNR for both emission lines. An increase in NaCl concentration from 0.0 to 3.0 M produced an increase in the SNR, whereas the SBR dropped continuously. The detection limits obtained for both elements were in the milligrams per liter range, suggesting that a NaCl-rich solution does not severely limit the ability of LIBS to detect trace amount of metal ions.

Multimodel predictive system for carbon dioxide solubility in saline formation waters.

The prediction of carbon dioxide solubility in brine at conditions relevant to carbon sequestration (i.e., high temperature, pressure, and salt concentration (T-P-X)) is crucial when this technology is applied. Eleven mathematical models for predicting CO(2) solubility in brine are compared and considered for inclusion in a multimodel predictive system. Model goodness of fit is evaluated over the temperature range 304-433 K, pressure range 74-500 bar, and salt concentration range 0-7 m (NaCl equivalent), using 173 published CO(2) solubility measurements, particularly selected for those conditions. The performance of each model is assessed using various statistical methods, including the Akaike Information Criterion (AIC) and the Bayesian Information Criterion (BIC). Different models emerge as best fits for different subranges of the input conditions. A classification tree is generated using machine learning methods to predict the best-performing model under different T-P-X subranges, allowing development of a multimodel predictive system (MMoPS) that selects and applies the model expected to yield the most accurate CO(2) solubility prediction. Statistical analysis of the MMoPS predictions, including a stratified 5-fold cross validation, shows that MMoPS outperforms each individual model and increases the overall accuracy of CO(2) solubility prediction across the range of T-P-X conditions likely to be encountered in carbon sequestration applications.

Partitioning behavior of organic contaminants in carbon storage environments: a critical review.

Carbon capture and storage is a promising strategy for mitigating the CO(2) contribution to global climate change. The large scale implementation of the technology mandates better understanding of the risks associated with CO(2) injection into geologic formations and the subsequent interactions with groundwater resources. The injected supercritical CO(2) (sc-CO(2)) is a nonpolar solvent that can potentially mobilize organic compounds that exist at residual saturation in the formation. Here, we review the partitioning behavior of selected organic compounds typically found in depleted oil reservoirs in the residual oil-brine-sc-CO(2) system under carbon storage conditions. The solubility of pure phase organic compounds in sc-CO(2) and partitioning of organic compounds between water and sc-CO(2) follow trends predicted based on thermodynamics. Compounds with high volatility and low aqueous solubility have the highest potential to partition to sc-CO(2). The partitioning of low volatility compounds to sc-CO(2) can be enhanced by cosolvency due to the presence of higher volatility compounds in the sc-CO(2). The effect of temperature, pressure, salinity, pH, and dissolution of water molecules into sc-CO(2) on the partitioning behavior of organic compounds in the residual oil-brine-sc-CO(2) system is discussed. Data gaps and research needs for models to predict the partitioning of organic compounds in brines and from complex mixtures of oils are presented. Models need to be able to better incorporate the effect of salinity and cosolvency, which will require more experimental data from key classes of organic compounds.

Trace metal source terms in carbon sequestration environments.

Carbon dioxide sequestration in deep saline and depleted oil geologic formations is feasible and promising; however, possible CO(2) or CO(2)-saturated brine leakage to overlying aquifers may pose environmental and health impacts. The purpose of this study was to experimentally define a range of concentrations that can be used as the trace element source term for reservoirs and leakage pathways in risk simulations. Storage source terms for trace metals are needed to evaluate the impact of brines leaking into overlying drinking water aquifers. The trace metal release was measured from cements and sandstones, shales, carbonates, evaporites, and basalts from the Frio, In Salah, Illinois Basin, Decatur, Lower Tuscaloosa, Weyburn-Midale, Bass Islands, and Grand Ronde carbon sequestration geologic formations. Trace metal dissolution was tracked by measuring solution concentrations over time under conditions (e.g., pressures, temperatures, and initial brine compositions) specific to the sequestration projects. Existing metrics for maximum contaminant levels (MCLs) for drinking water as defined by the U.S. Environmental Protection Agency (U.S. EPA) were used to categorize the relative significance of metal concentration changes in storage environments because of the presence of CO(2). Results indicate that Cr and Pb released from sandstone reservoir and shale cap rocks exceed the MCLs by an order of magnitude, while Cd and Cu were at or below drinking water thresholds. In carbonate reservoirs As exceeds the MCLs by an order of magnitude, while Cd, Cu, and Pb were at or below drinking water standards. Results from this study can be used as a reasonable estimate of the trace element source term for reservoirs and leakage pathways in risk simulations to further evaluate the impact of leakage on groundwater quality.

Anion leaching from refinery oily sludge and ash from incineration of oily sludge stabilized/solidified with cement. Part I. Experimental results.

This paper presents the leaching behavior of anions (SO4(2-) and CrO4(2-)) from refinery oily sludge and ash produced by incineration of oily sludge, stabilized/solidified (s/s) with two types of cement, 142.5 and 1142.5. Anion leaching was examined using a 5-step sequential toxicity characteristic leaching procedure (TCLP) test. A single TCLP extraction resulted in limited sulfate release (<50 mg/L) for s/s ash and significant sulfate release (<850 mg/L) for s/s oily sludge. Chromate release was <1 mg/L for s/s ash and nondetectable for s/s oily sludge. The sequential TCLP tests resulted in increased leaching for both sulfate and chromate. In general,the increase of liquid-to-solid ratio (TCLP leachant-to-waste ratio) resulted in increased leaching of sulfate from solidified samples compared to untreated oily sludge, ash and cement. In contrast, chromate leaching decreased by s/s process. A qualitatively similar leaching behavior for SO4(2-), even for radically different wastes such as oily sludge and ash, solidified with two different types of cement was observed.

Anion leaching from refinery oily sludge and ash from incineration of oily sludge stabilized/solidified with cement. Part II. Modeling.

This paper presents the modeling of anion leaching (SO4(2-) and CrO4(2-)) from refinery oily sludge and ash produced by incineration of oily sludge, stabilized/solidified (s/s) with two types of cement, 142.5 and 1142.5. Anion leaching was examined using a sequential toxicity characteristic leaching procedure (TCLP) test. To elucidate the mechanisms of sulfate and chromate leaching, we employed Visual MINTEQ, incorporating a multiple-problem setup. Specifically, 10-14 different problems, depending on the pH range of the leachates, were connected together in the same run. Each problem corresponded to one pH value of the leachate and the model run covered the pH range of the five sequential TCLP extractions. This modeling approach was tested using chemical equilibrium with or without sorption onto ferrihydrite. Good agreement between experimental and modeling results was obtained for sulfate leaching from solidified oily sludge and ash, considering surface complexation onto ferrihydrite on top of chemical equilibrium controlled by gypsum at pH <11 and ettringite at pH >11. Chromate leaching was described by chemical equilibrium, controlled by CaCrO4(s) (at pH <11) and Cr(VI)ettringite (at pH >11).

Characterization of stabilized/solidified refinery oily sludge and incinerated refinery sludge with cement using XRD, SEM and EXAFS.

Solidification/stabilization (S/S) of refinery oily sludge and incinerated oily sludge (ash) with cement type I42.5 and II42.5 was investigated using, X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) combined with Energy Dispersive Spectroscopy (EDS) and Extended X-ray Absorption Fine Structure (EXAFS). The results showed that delayed ettringite formation (DEF) and major cement hydration reactions occurred. XRD analysis of S/S oily sludge samples revealed cement-bearing solid phases, such as portlandite, calcite, C(3)S, C(2)S and C(4)AF. SEM analysis, confirmed ettringite at solidified oily sludge samples. Solidified ash samples contained ettringite substituted by chromates. However, solid phases found in solidified ash samples with I42.5 cement showed minor variation in type and structure compared to those observed in solidified ash samples with II42.5 cement. Fe K edge EXAFS analysis revealed the presence of iron oxides in both S/S wastes. The comparison between spectra of the S/S resulting materials and the ones of their original components, showed that the first sphere Fe-O distances were longer than in the pure iron oxide thereby providing evidence that the resulting materials were not simple mixtures, but products of a reaction that modified the local environment of iron.

Cement-based stabilization/solidification of oil refinery sludge: Leaching behavior of alkanes and PAHs.

Stabilization/solidification is a process widely applied for the immobilization of inorganic constituents of hazardous wastes, especially for metals. Cement is usually one of the most common binders for that purpose. However, limited results have been presented on immobilization of hydrocarbons in cement-based stabilized/solidified petroleum solid waste. In this study, real oil refinery sludge samples were stabilized and solidified with various additions of I42.5 and II42.5 cement (Portland and blended cement, respectively) and subject to leaching. The target analytes were total petroleum hydrocarbons, alkanes and 16 polycyclic aromatic hydrocarbons of the EPA priority pollutant list. The experiments showed that the waste was confined in the cement matrix by macroencapsulation. The rapture of the cement structure led to the increase of leachability for most of the hydrocarbons. Leaching of n-alkanes from II42.5 cement-solidified samples was lower than that from I42.5 solidified samples. Leaching of alkanes in the range of n-C(10) to n-C(27) was lower than that of long chain alkanes (>n-C(27)), regardless the amount of cement addition. Generally, increasing the cement content in the solidified waste samples, increased individual alkane leachability. This indicated that cement addition resulted in destabilization of the waste. Addition of I42.5 cement favored immobilization of anthracene, benzo[a]anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene, benzo[a]pyrene and dibenzo[a,h]anthracene. However, addition of II42.5 favored 5 out of 16, i.e., naphthalene, anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene and dibenzo[a,h]anthracene.

Release of Zn, Ni, Cu, SO4(2-) and CrO4(2-) as a function of pH from cement-based stabilized/solidified refinery oily sludge and ash from incineration of oily sludge.

A framework for the evaluation of leaching behavior of inorganic constituents from stabilized/solidified refinery oily sludge and ash produced from incineration of oily sludge with cement was employed. Metal and anion release as a function of pH was investigated. The leaching test consisted of multiple parallel extractions at pH range from 2 to 12. Remarkably good immobilization >98% was observed for metals of solidified ash at pH>6 and >93% of solidified oily sludge at pH>7. Sulfate leaching was high at pH range 2-12. The leaching behavior of metals and anions was simulated by VMINTEQ. The calculations showed that leaching behavior of Zn, Ni and Cu was controlled by chemical equilibrium and surface complexation onto ferrihydrite, at the pH range 2-12. The dominant solid phases that controlled metal leachability were metal hydroxides. The dominant mechanism that described sulfate leaching was found to be chemical equilibrium. Sulfate and also chromate leachability was controlled by Ettringite and Cr(VI)Ettringite as the major minerals affecting their release.

Application of stabilization/solidification technology on oil refinery sludge contaminated by heavy metals.

The oily sludge produced by petroleum refineries is classified as a solid hazardous waste, according to European regulations. The objective of this work was to investigate whether stabilization/solidification can be used as a management method for the oily sludge. The sludge samples used originated from a petroleum-storing tank and a centrifuge unit of two Greek refineries. The experiments were designed to study the leachability of the heavy metals Pb, Cr, Cd, Ni, and Cu, which are contained in the sludge, using the Toxicity Characteristic Leaching Procedure (TCLP). Despite the fact that the metals were immobilized in a cement-based environment in the presence of organic load, leaching tests have shown a low metal leachability, less than 5%. Acid Neutralizing Capacity (ANC) tests were employed in order to estimate the acid resistance of the stabilized/solidified waste. In addition to ANC, a sequential TCLP test was employed in order to understand how the pH affects the leachability of Ni from the stabilized/solidified specimen.