Laboratory and field evaluation of a pretreatment system for removing organics from produced water.

Co-produced water from the oil and gas industry accounts for a significant waste stream in the United States. This "produced water" is characterized by saline water containing a variety of pollutants, including water soluble and immiscible organics and many inorganic species. To reuse produced water, removal of both the inorganic dissolved solids and organic compounds is necessary. In this research, the effectiveness of a pretreatment system consisting of surfactant modified zeolite (SMZ) adsorption followed by a membrane bioreactor (MBR) was evaluated for simultaneous removal of carboxylates and hazardous substances, such as benzene, toluene, ethylbenzene, and xylenes (BTEX) from saline-produced water. A laboratory-scale MBR, operated at a 9.6-hour hydraulic residence time, degraded 92% of the carboxylates present in synthetic produced water. When BTEX was introduced simultaneously to the MBR system with the carboxylates, the system achieved 80 to 95% removal of BTEX via biodegradation. These results suggest that simultaneous biodegradation of both BTEX and carboxylate constituents found in produced water is possible. A field test conducted at a produced water disposal facility in Farmington, New Mexico confirmed the laboratory-scale results for the MBR and demonstrated enhanced removal of BTEX using a treatment train consisting of SMZ columns followed by the MBR. While most of the BTEX constituents of the produced water adsorbed onto the SMZ adsorption system, approximately 95% of the BTEX that penetrated the SMZ and entered the MBR was biodegraded in the MBR. Removal rates of acetate (influent concentrations of 120 to 170 mg/L) ranged from 91 to 100%, and total organic carbon (influent concentrations as high as 580 mg/L) ranged from 74 to 92%, respectively. Organic removal in the MBR was accomplished at a low biomass concentration of 1 g/L throughout the field trial. While the transmembrane pressure during the laboratory-scale tests was well-controlled, it rose substantially during the field test, where no pH control was implemented. The results suggest that pretreatment with an SMZ/MBR system can provide substantial removal of organic compounds present in produced water, a necessary first step for many water-reuse applications.

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets.

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.

Removal of perchlorate from contaminated waters using surfactant-modified zeolite.

We investigated the potential of using surfactant (hexadecyltrimethylammonium)-modified zeolite (SMZ) as an inexpensive sorbent for removing perchlorate (ClO(4)(-)) from contaminated waters in the presence of competing anions. In batch systems, the presence of 10 mM OH(-) (i.e., pH 12), CO(3)(2-), Cl(-), or SO(4)(2-) had little effect on the sorption of ClO(4)(-) by SMZ, indicating that the sorption of ClO(4)(-) by SMZ was very selective. The presence of 10 mM NO(3)(-), however, reduced the sorption of ClO(4)(-) at low initial concentrations. The maximum sorption capacity for ClO(4)(-) by the SMZ remained relatively constant (40-47 mmol kg(-1)), in the absence or presence of the competing ions. In flow-through systems, ClO(4)(-) broke through the SMZ columns much later than other anions present in an artificial ground water. The affinity of the anions for SMZ followed the sequence of ClO(4)(-) > > NO(3)(-) > SO(4)(2-) > Cl(-). Perchlorate loading under dynamic flow-through conditions was 34 mmol kg(-1), somewhat less than the maximum loading of 40 to 47 mmol kg(-1) determined by the batch method. Less than 1% of previously sorbed ClO(4)(-) was leached out by ultra-pure water, by extraction fluid #1 of the standard toxicity characteristic leaching procedure (TCLP), or by a solution of 0.28 M Na(2)CO(3)/0.5 M NaOH. About 40% of the previously sorbed ClO(4)(-) was leached out from SMZ by a 0.5 M NO(3)(-) solution. The exchange of ClO(4)(-) with NO(3)(-) corroborated results of the batch tests where NO(3)(-) was shown to compete with ClO(4)(-) sorption.

A shift in pathway of iron-mediated perchloroethylene reduction in the presence of sorbed surfactant--a column study.

Surface modification of zero-valent iron (ZVI) to enhance its reduction rates for chlorinated ethanes and ethenes has recently attracted great attention. In this research, the enhancement of perchloroethylene (PCE) reduction by ZVI in the presence of sorbed micelles of the cationic surfactant hexadecyltrimethylammonium (HDTMA) was examined in a series of laboratory column tests with varying flow rates and input PCE concentrations. Model simulations using HYDRUS-1D showed that the overall pseudo first-order rate constants for PCE reduction by ZVI increased by a factor of four in the presence of sorbed HDTMA admicelles. The increase in reduction rate was attributed to a higher distribution coefficient (K(d)) for contaminant sorption on surfactant-modified ZVI (SM-ZVI) compared to untreated ZVI. Modeling results also showed that in the presence of HDTMA admicelles 58-100% of PCE reduction occurred via hydrogenolysis. In contrast, only 12-25% PCE underwent hydrogenolysis when HDTMA was absent. The significant increase in TCE production during PCE reduction by SM-ZVI verified a shift in reaction pathway previously observed in batch studies, most likely from beta-elimination to hydrogenolysis. Although this shift in reaction pathway resulted in a higher accumulation of TCE, the combined concentrations of chlorinated hydrocarbons in the effluent were 1.5-5 times lower when SM-ZVI rather than unmodified ZVI was used.

Adsorption of chromate by clinoptilolite exchanged with various metal cations.

Unmodified zeolite surfaces show no affinity for anions, due to the fact that zeolites are negatively charged. Thus, adsorption of anions by zeolites has not been given much attention. In this work, after modification of clinoptilolite by different cations, the mineral was found to adsorb a considerable amount of the divalent anion chromate. Chromate adsorption was proportional to the K(sp) of the chromate precipitate and the amount of the exchangeable cation. The amount of chromate adsorbed was maximized when the Pb-exchanged form was used. Chromate desorption in deionized water indicated that between 2.50% and 18.60% of the adsorbed chromate was released depending upon the exchangeable cation. Some of the exchanged forms are candidate materials for adsorption and immobilization of chromate.

Partitioning of hydrophobic organic chemicals (HOC) into anionic and cationic surfactant-modified sorbents.

Surfactant-modified sorbents have been proposed for the removal of organic compounds from aqueous solution. In the present study, one cationic (HDTMA) and three anionic (DOWFAX-8390, STEOL-CS330, and Aerosol-OT) surfactants were tested for their sorptive behavior onto different sorbents (alumina, zeolite, and Canadian River Alluvium). These surfactant-modified materials were then used to sorb a range of hydrophobic organic chemicals (HOCs) of varying properties (benzene, toluene, ethylbenzene, 1,2-dichlorobenzene, naphthalene, and phenanthrene), and their sorption capacity and affinity (organic-carbon-normalized sorption coefficient, K(oc)) were quantified. The HDTMA-zeolite system proved to be the most stable surfactant-modified sorbent studied because of the limited surfactant desorption. Both anionic and cationic surfactants resulted in modified sorbents with higher sorption capacity and affinity than the unmodified Canadian River Alluvium containing only natural organic matter. The affinities of the surfactant-modified sorbents (K(oc)) for most HOCs are lower than octanol/water partition coefficient (K(ow)) normalized to the organic carbon content (f(oc)) and the density of octanol (K(oc) octanol); naphthalene and phenanthrene are the exceptions to this rule.

Sorption of arsenic from soil-washing leachate by surfactant-modified zeolite.

Post-treatment of leachate from soil-washing remedial actions may be necessary depending on the amounts of dissolved contaminants present. Uptake of arsenic species by surfactant-modified zeolite (SMZ) from a synthetic soil leachate (pH of approximately 12 [NaOH]) was measured as a test of SMZ as a post-treatment sorbent. Batch sorption isotherms were prepared using leachate to SMZ ratios from 40:1 to 4:1, and temperatures of 25 and 15 degrees C. Equilibrium levels of dissolved and total solution arsenic were similar. At each temperature, sorption appeared to reach a plateau or maximum, then decreased at the highest solution concentration, corresponding to the lowest amount of zeolite added (2.5 g). A maximum sorption value of 72.0 mmol of arsenic per kg of SMZ (5400 mg/kg) was observed at 25 degrees C, and 42.1 mmol/kg (3150 mg/kg) at 15 degrees C. Total arsenic recoveries varied from 74 to 125%. Surfactant-modified zeolite removed up to 97% of dissolved organic carbon and decolorized the leachate solutions. Excluding the points for the highest arsenic to SMZ ratio, the sorption isotherms were well described by the linearized form of the Langmuir equation, with coefficients of determination greater than 0.90 at both temperatures. Sorption of arsenic by SMZ is attributed to anion exchange with counterions on the surfactant head groups, and/or partitioning of organic carbon-complexed arsenic into the surfactant bilayer.

Microbial reduction of hexavalent chromium under vadose zone conditions.

Hexavalent chromium [Cr(VI)] is a common contaminant associated with nuclear reactors and fuel processing. Improper disposal at facilities in and and semiarid regions has contaminated underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those in the vadose zone, and to evaluate the potential for enhancing biological Cr(VI) reduction through nutrient addition. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic C (molasses). Nutrient amendments resulted in up to 87% reduction of the initial 67 mg L(-1) Cr(VI) in an unsaturated batch experiment. Molasses and nitrate additions to 15 cm long unsaturated flow columns receiving 65 mg L(-1) Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-d experiment. All of the immobilized Cr was in the form of Cr(III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy, and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.

Electrokinetic ion transport through unsaturated soil: 2. Application to a heterogeneous field site.

Results of a field demonstration of electrokinetic transport of acetate through an unsaturated heterogeneous soil are compared to numerical modeling predictions. The numerical model was based on the groundwater flow and transport codes MODFLOW and MT3D modified to account for electrically induced ion transport. The 6-month field demonstration was conducted in an unsaturated layered soil profile where the soil moisture content ranged from 4% to 28% (m3 m(-3)). Specially designed ceramic-cased electrodes maintained a steady-state moisture content and electric potential field between the electrodes during the field demonstration. Acetate, a byproduct of acetic acid neutralization of the cathode electrolysis reaction, was transported from the cathode to the anode by electromigration. Field demonstration results indicated preferential transport of acetate through soil layers exhibiting higher moisture content/electrical conductivity. These field transport results agree with theoretical predictions that electromigration velocity is proportional to a power function of the effective moisture content. A numerical model using a homogeneous moisture content/electrical conductivity domain did not adequately predict the acetate field results. Numerical model predictions using a three-layer electrical conductivity/moisture content profile agreed qualitatively with the observed acetate distribution. These results suggest that field heterogeneities must be incorporated into electrokinetic models to predict ion transport at the field-scale.

Electrokinetic ion transport through unsaturated soil: 1. Theory, model development, and testing.

An electromigration transport model for non-reactive ion transport in unsaturated soil was developed and tested against laboratory experiments. This model assumed the electric potential field was constant with respect to time, an assumption valid for highly buffered soil, or when the electrode electrolysis reactions are neutralized. The model also assumed constant moisture contents and temperature with respect to time, and that electroosmotic and hydraulic transport of water through the soil was negligible. A functional relationship between ionic mobility and the electrolyte concentration was estimated using the chemical activity coefficient. Tortuosity was calculated from a mathematical relationship fitted to the electrical conductivity of the bulk pore water and soil moisture data. The functional relationship between ionic mobility, pore-water concentration, and tortuosity as a function of moisture content allowed the model to predict ion transport in heterogeneous unsaturated soils. The model was tested against laboratory measurements assessing anionic electromigration as a function of moisture content. In the test cell, a strip of soil was spiked with red dye No 40 and monitored for a 24-h period while a 10-mA current was maintained between the electrodes. Electromigration velocities predicted by the electromigration transport model were in agreement with laboratory experimental results. Both laboratory-measured and model-predicted dye migration results indicated a maximum transport velocity at moisture contents less than saturation due to competing effects between current density and tortuosity as moisture content decreases.

Anion exchange selectivity of surfactant modified clinoptilolite-rich tuff for environmental remediation.

Lately, the functionalization of industrial minerals with high technological properties, such as natural zeolites, is shaping as a promising approach in environmental sphere. In fact, under the specific conditions, the surface functionalization via adsorption of cationic surfactants reverses the surface charge of the mineral, enabling zeolites to simultaneously interact either with organic contaminants or inorganic anions. This aspect allows zeolites to be used in the remediation of contaminated fluids. The present research shed new light on some still not fully understood aspects concerning exchange kinetics such as anion-exchange mechanisms and selectivity of surface modified minerals. For this purpose the mineralogical characterization and the surface properties evaluation (X Ray Powder Diffraction, chemical analysis, thermal analysis, ECEC and AEC) of a clinoptilolite-rich tuff were performed, and the anion exchange isotherms of the sample, modified with hexadecyltrimethylammonium chloride or bromide (HDTMA-Cl/-Br), were determined. Ion-exchange equilibrium data of uni-uni valent reaction were obtained by solutions containing Br(-), Cl(-), NO3(-) or ClO4(-). Liquid phase was analysed via high performance liquid chromatography. Thermodynamic quantities (Ka and ΔG(0)) were determined and compared with the Hofmeister series. The value of the ECEC, calculated in batch conditions, was about 137 mmol/kg, in good agreement with that evaluated in dynamic conditions, while the AEC data were different for the SMNZ-Br and -Cl samples, amounting to 137 and 106 mmol/kg, respectively, thus indicating a different compactness of the bilayer formed in the two cases. Moreover, the anion isotherm results and the mathematical evaluation of the thermodynamic parameters, demonstrated the good affinity of SMNZ-Br towards chloride, nitrate and perchlorate, and of SMNZ-Cl for nitrate and perchlorate, also endorsing the possibility of using the same thermodynamic approach developed to describe cation exchange selectivity in zeolites. Finally, it was also verified that the zeolite modified with HDTMA-Cl is able to better exploit its anion exchange capacity compared to the same zeolite modified with HDTMA-Br.

Nonequilibrium sorption and transport of volatile petroleum hydrocarbons in surfactant-modified zeolite.

We characterized the nonequilibrium sorption and transport of benzene, toluene, ethylbenzene, and xylenes (BTEX) by surfactant-modified zeolite (SMZ) in batch and column tests. The SMZ was shown in previous studies to be an effective sorbent for removal of BTEX from oilfield wastewaters prior to disposal or reuse. A two-site, first-order chemical nonequilibrium model was used to determine sorption parameters from the batch results. Individual BTEX linear sorption coefficients, K(d), ranged from 7.5 to 37 L kg(-1) and were independent of BTEX concentration or competing solutes, suggesting that partitioning was the mechanism of sorption. The K(d) values were the same whether the zeolite was covered by a monolayer or bilayer of the surfactant hexadecyltrimethylammonium (HDTMA). Batch rate coefficients and the fraction of "instantaneous" sorption sites decreased with BTEX hydrophobicity and with total BTEX concentration. The fraction of "instantaneous" sites was 3-11 times greater for the monolayer as compared to the bilayer SMZ. These observations are consistent with a conceptual model in which BTEX are rapidly partitioned into hydrophobic monolayer surfaces and more slowly partitioned to hydrophilic bilayer surfaces. Results from the batch experiments were used to predict BTEX transport through columns of SMZ. Batch-derived rate and site-distribution parameters accurately described the transport dynamics, but the batch-derived K(d)s significantly underestimated BTEX retardation. Excess dissolved HDTMA in the batch experiments likely led to anomalously low K(d) values for those determinations.

Enhanced perchloroethylene reduction in column systems using surfactant-modified zeolite/zero-valent iron pellets.

Surfactant- (hexadecyltrimethylammonium, HDTMA) modified zeolite (SMZ)/zero-valent iron (ZVI) pellets having high hydraulic conductivity (9.7 cm s(-1)), high surface area (28.2 m2 g(-1)), and excellent mechanical strength were developed. Laboratory column experiments were conducted to evaluate the performance of the pellets for perchloroethylene (PCE) sorption/reduction under dynamic flow-through conditions. PCE reduction rates with the surfactant-modified pellets (SMZ/ZVI) were three times higher than the reduction rates with the unmodified pellets (zeolite/ZVI). We speculate that enhanced sorption of PCE directly onto iron surface by iron-bound HDTMA and/or an increased local PCE concentration in the vicinity of iron surface due to sorption of PCE by SMZ contributed to the enhanced PCE reduction by the SMZ/ZVI pellets. Trichloroethylene and cis-dichloroethylene production during PCE reduction increased with the surfactant-modified pellets, indicating that the surfactant modification may have favored hydrogenolysis over beta-elimination. PCE reduction rate constants increased as the travel velocity increased from 0.5 to 1.9 m d(-1), suggesting that the reduction of PCE in the column systems was mass transfer limited.