Complex treatment of oily polluted waters by modified melamine foams: from colloidal emulsions to a free oil removal.

This study deals with the efficient, low-cost, and scalable treatment of oily polluted waters including colloidal emulsions, oil-in-water mixtures, and free oil removal using melamine foams (MFs) modified by ferric chloride (FeCl3). Modified foams have superhydrophobic character due to the coordination of Fe3+ with free electron pairs on nitrogen and oxygen atoms within the melamine structure. The water contact angles (WCA) were 146° ± 2°, 148° ± 4°, 153° ± 2°, and 150° ± 4° for foams modified by the solutions with concentrations of 0.001 M, 0.005 M, 0.01 M, and 0.02 M, respectively. This modification enables the efficient treatment of various oil/water systems, including oil/water colloidal emulsions (99 vol% of the droplets have dimensions below 500 nm), oil-in-water mixtures up to 40 weight % of the oil component, and "free" oil removal as it was demonstrated in this study for the first time. The emulsions containing 100 ppm diesel oil (DO) were separated with 91.4% efficiency, and the mixtures containing 20 and 40 weight % DO were separated with 99.9% efficiency. Modified foams also quickly remove free DO from the water surface, absorbing 95 g/g DO, whereas water sorption was negligible. The separation of colloidal oil in water emulsions represents the key finding of this study as it indicates the applicability of the treated MFs for the treatment of emulsified industrial wastewater. The demulsification mechanism is based on multiple diffusion processes running at different time scales, including diffusion of the emulsion into the foam and diffusion of oil droplets within the foam, combined with parallel adsorption of oil droplets onto the solid skeleton of the foam. A multiplied usage of these foams for all these niche operations was also proven. The application of our current study with previous studies on modified MFs and polyurethane for water oil separation utilization is summarized in Table S1 ESI.

Multifunctional Oil Absorption with Macroporous Polystyrene Fibers Incorporating Silver-Doped ZnO.

Hydrophobic microporous polystyrene (PS) fibers are fabricated by a solvent-induced phase-separation-assisted electrospinning method. Zinc oxide (ZnO) and silver-doped zinc oxide (Ag-ZnO) nanomaterials with variable morphologies are added to the PS fibers, to investigate the influence of multifunctional nanofiller addition on the porosity and consequent oil-adsorbing properties for different oil types. The doping of silver as well as the uniformity in particle distribution are confirmed by scanning electron microscopy and the energy-dispersive spectral analyses. The porosity of the fibers and their crystallinity effect depend on the hydrophobicity and surface properties of these microporous nanofilled fibers. Ag-ZnO, specifically in 2 wt %, enhanced the pore size and distribution in PS porous fibers, thereby enhancing the oil-adsorbing property and its hydrophobicity. In-depth analysis of the oil adsorption mechanism is done for the fibers, both qualitatively and quantitatively, to demonstrate its correlation with the structural integrity of the fibers. The PS/2Ag-ZnO composite also exhibits the highest antibacterial performance against Staphylococcus aureus, a general indication of antibiological fouling properties of these oil-separating films. The antifouling/antibacterial activity of the nanoparticles and high oil sorption capacity of the highly porous PS composites show great potential for use in water-treatment-related applications.

The Separation of Emulsified Water/Oil Mixtures through Adsorption on Plasma-Treated Polyethylene Powder.

This paper addresses the preparation and characterization of efficient adsorbents for tertiary treatment (oil content below 100 ppm) of oil/water emulsions. Powdered low-density polyethylene (LDPE) was modified by radio-frequency plasma discharge and then used as a medium for the treatment of emulsified diesel oil/water mixtures in the concentration range from 75 ppm to 200 ppm. Plasma treatment significantly increased the wettability of the LDPE powder, which resulted in enhanced sorption capability of the oil component from emulsions in comparison to untreated powder. Emulsions formed from distilled water and commercial diesel oil (DO) with concentrations below 200 ppm were used as a model of oily polluted water. The emulsions were prepared using ultrasonication without surfactant. The droplet size was directly proportional to sonication time and ranged from 135 nm to 185 nm. A sonication time of 20 min was found to be sufficient to prepare stable emulsions with an average droplet size of approximately 150 nm. The sorption tests were realized in a batch system. The effect of contact time and initial oil concentrations were studied under standard atmospheric conditions at a stirring speed of 340 rpm with an adsorbent particle size of 500 microns. The efficiency of the plasma-treated LDPE powder in oil removal was found to be dependent on the initial oil concentration. It decreased from 96.7% to 79.5% as the initial oil concentration increased from 75 ppm to 200 ppm. The amount of adsorbed oil increased with increasing contact time. The fastest adsorption was observed during the first 30 min of treatment. The adsorption kinetics for emulsified oils onto sorbent followed a pseudo-second-order kinetic model.

Protocol for Preparing Synthetic Solutions Mimicking Produced Water from Oil and Gas Operations.

Produced water (PW) is the water associated with hydrocarbons during the extraction of oil and gas (O&G) from either conventional or unconventional resources. Existing efforts to enhance PW management systems include the development of novel membrane materials for oil-water separation. In attempting to evaluate these emerging physical separation technologies, researchers develop various formulations of test solutions aiming to represent actual PW. However, there is no clear scientific guideline published in the literature about how such a recipe should be prepared. This article develops a protocol for preparing synthetic solutions representing the characteristics and behavior of actual PW and enabling the performance comparisons of different oil-water separation membranes at the bench scale level. In this study, two different brine recipes were prepared based on salts present in actual PW, crude oil was used as the hydrocarbon source, and a surfactant was added to disperse the oil into the aqueous phase. The recipe is accessible to the wider scientific community and was proven to be reproduceable, homogenous, stable, and comparable to actual PW field samples through analytical monitoring measurements and bench scale evaluations.

Vertically oriented nanoporous block copolymer membranes for oil/water separation and filtration.

The separation of oil from water and filtration of aqueous solutions and dispersions are critical issues in the processing of waste and contaminated water treatment. Membrane-based technology has been proven as an effective method for the separation of oil from water. In this research, novel vertical nanopores membrane, via oriented cylindrical block copolymer (BCP) films, suitable for oil/water filtration has been designed, fabricated and tested. We used a ∼100 nm thick model poly(styrene-block-methymethacrylate) (PS-b-PMMA) BCP as the active top nanofiltration layer, processed using a roll-to-roll (R2R) method of cold zone annealing (CZA) to obtain vertical orientation, followed by ultraviolet (UV) irradiation selective etch of PMMA cylinders to form vertically oriented nanopores as a novel feature compared to meandering nanopores in other reported BCP systems. The cylindrical nanochannels are hydrophilic, and have a uniform pore size (∼23 nm), a narrow pore size distribution and a high nanopore density (∼420 per sq. micron). The bottom supporting layer is a conventional microporous polyethersulfone (PES) membrane. The created asymmetric membrane is demonstrated to be effective for oil/water extraction with a modestly high throughput rate comparable to other RO/NF membranes. The molecular weight dependent filtration of a water soluble polymer, PEO, demonstrates the broader applications of such membranes.

White Graphene-Cobalt Oxide Hybrid Filler Reinforced Polystyrene Nanofibers for Selective Oil Absorption.

In this work, stable hydrophobic nanocomposites are made from electrospun fibers of polystyrene (PS) containing a hybrid filler combination of (i) hexagonal boron nitride (hBN) and (ii) cobalt oxide (Co3O4) nanomaterials. Good synergistic interaction is observed between the nanomaterials, since the growth of Co3O4 was carried out in presence of white graphene nanosheets. Filler synergy modifies the PS surfaces, by enhancing the filler-polymer interfacial interactions and provides good tensile strength. The hydrophobic films are gamma irradiated to improve crosslinking within the polymer nanocomposites. Since gamma irradiation enhances the surface roughness, its hydrophobicity/oleophilicity increases much and the final nanofibers show good oil-water separation efficiency. The nanofibers act as sponge clothing to skim the oil from a mixture of oil and water. Durability of the fibers in hot water and in presence of ultrasonic waves is also tested and good response is achieved. Contact angle studies are performed to investigate the surface properties and to check the influence of gamma irradiation on the surface wettability. The gamma-irradiated PS nanocomposite fiber shows a contact angle of 152° ± 2° compared to the 140° ± 1° of the neat PS fiber, evidencing the superhydrophobicity. Both the effects of crosslink density enhancement and hybrid filler distribution make the composite fibers stronger in oil absorption application even at higher operation temperatures. The fibers are reported to be robust and durable, in addition.

An empirical determination of the whole-life cost of FO-based open-loop wastewater reclamation technologies.

Over the past 5-10 years it has become apparent that the significant energy benefit provided by forward osmosis (FO) for desalination arises only when direct recovery of the permeate product from the solution used to transfer the water through the membrane (the draw solution) is obviated. These circumstances occur specifically when wastewater purification is combined with saline water desalination. It has been suggested that, for such an "open loop" system, the FO technology offers a lower-cost water reclamation option than the conventional process based on reverse osmosis (RO). An analysis is presented of the costs incurred by this combined treatment objective. Three process schemes are considered combining the FO or RO technologies with membrane bioreactors (MBRs): MBR-RO, MBR-FO-RO and osmotic MBR (OMBR)-RO. Calculation of the normalised net present value (NPV/permeate flow) proceeded through developing a series of empirical equations based on available individual capital and operating cost data. Cost curves (cost vs. flow capacity) were generated for each option using literature MBR and RO data, making appropriate assumptions regarding the design and operation of the novel FO and OMBR technologies. Calculations revealed the MBR-FO-RO and OMBR-RO schemes to respectively offer a ∼20% and ∼30% NPV benefit over the classical MBR-RO scheme at a permeate flow of 10,000 m3  d-1, provided the respective schemes are applied to high and low salinity wastewaters. Outcomes are highly sensitive to the FO or OMBR flux sustained: the relative NPV benefit (compared to the classical system) of the OMBR-RO scheme declined from 30% to ∼4% on halving the OMBR flux from a value of 6 L m-2. h-1.

Polymeric adsorbents for oil removal from water.

In this study, the application of four synthetic resins for the removal of emulsified oil from produced water was investigated. Key experimental parameters such as adsorbent dosage, contact time, initial oil concentration and pH were evaluated for Optipore L493, Amberlite IRA 958, Amberlite XAD 7 and Lewatit AF 5. Oil removal rates upwards of 98% were achieved using AF 5, XAD 7 and L493. IRA 958 recorded very modest removal rates of less than 25%. Isotherm data were further investigated and fitted using Langmuir, Freundlich, Toth, Flory Huggins and Dubinin-Radushkevich models. The results show that the adsorption onto XAD 7 and L 493 is a multilayer adsorption process over a heterogeneous surface that is best illustrated by the Freundlich and Toth models respectively. The Dubinin-Radushkevich best described the removal using AF 5 resin that assumes that the adsorption process occurs on a heterogenous surface with a gaussian energy distribution. Kinetic studies assessing the rate of removal for each resin were conducted. Experimental results were best fitted using pseudo second order kinetics. It is concluded that XAD 7 had the highest kinetics among all tested resins. Also, AF 5 exhibited the highest adsorption capacity. Overall, the study confirmed the applicability of the resins for the removal of oil from produced water.

Designing Carbon Nanotube-Based Oil Absorbing Membranes from Gamma Irradiated and Electrospun Polystyrene Nanocomposites.

Carbon-based materials are outstanding candidates for oil spill clean-ups due to their superhydrophobicity, high surface area, chemical inertness, low density, recyclability, and selectivity. The current work deals with the fabrication of membrane oil absorbents based on carbon nanotube (CNT) reinforced polystyrene (PS) nanocomposites by electrospinning technique. The spun membranes are also irradiated with the gamma radiation to induce enough crosslinks and thus good polymer-filler interactions. The structural, morphological, and surface properties in addition to the oil/water separation efficiency were investigated by varying the concentration of CNT and the dose of γ-irradiation. Fabricated nanofiber membranes show superior hydrophobicity and selective oil absorption at 0.5 wt.% of CNT concentration. The best mechanical properties are also obtained at this particular concentration and at 15 KGy optimum γ-irradiation dosage. The gamma irradiated PS/0.5 wt.% CNT membrane also exhibits good antibacterial effects against the bacteria, Escherichia coli, in the form of bacterial inhibition rings around the membranes. The present study thus shows the environmental applicability of the fabricated PS/CNT membranes in treating oil-contaminated water.

Application of Hollow Fiber Forward Osmosis Membranes for Produced and Process Water Volume Reduction: An Osmotic Concentration Process.

Produced and process water (PPW) from oil and gas operations, specifically in Qatar, are disposed of by deep well injection in onshore facilities. Disposing large volumes of PPW may affect deep well formation sustainability highlighting the need for effective PPW management. Forward osmosis (FO) was applied as an "osmotic concentration" process to reduce PPW injection volumes by 50% using brines and seawater as draw solutions (DS). The energy intensive step of restoring the salinity of the DS was eliminated; the diluted DS would be simply discharged to the ocean. Both hollow fiber and flat sheet FO membranes were tested and the former exhibited better flux and rejection; they are the focus of this study. Optimization experiments, conducted using Box-Behnken statistical design, confirmed that temperature and DS concentration had a substantial effect on performance. To validate the concept, a long-term experiment, under optimized conditions, was conducted with PPW as feed and brine from thermal desalination plant as DS which yielded an average flux of 24 L/m(2)h. The results confirmed that low-energy osmotic concentration FO has the potential for full-scale implementation to reduce PPW injection volumes. Pilot testing opportunities are being evaluated to demonstrate the effectiveness of this technology under field conditions.

Occurrence and removal of microbial indicators from municipal wastewaters by nine different MBR systems.

Nine different membrane bioreactor (MBR) systems with different process configurations (submerged and external), membrane geometries (hollow-fiber, flat-sheet, and tubular), membrane materials (polyethersulfone (PES), polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE)) and membrane nominal pore sizes (0.03-0.2 µm) were evaluated to assess the impact of influent microbial concentration, membrane pore size and membrane material and geometries on removal of microbial indicators by MBR technology. The log removal values (LRVs) for microbial indicators increased as the influent concentrations increased. Among the wide range of MBR systems evaluated, the total and fecal coliform bacteria and indigenous MS-2 coliphage were detected in 32, 9 and 15% of the samples, respectively; the 50th percentile LRVs were measured at 6.6, 5.9 and 4.5 logs, respectively. The nominal pore sizes of the membranes, membrane materials and geometries did not show a strong correlation with the LRVs.

Peak flux performance and microbial removal by selected membrane bioreactor systems.

A pilot study was conducted over a period of 18 months at the Point Loma Wastewater Treatment Plant (PLWWTP) in San Diego, CA to evaluate the operational and water quality performance of six selected membrane bioreactor (MBR) systems at average and peak flux operation. Each of these systems was operated at peak flux for 4 h a day for six consecutive days to assess peak flux performance. Virus seeding studies were also conducted during peak flux operation to assess the capability of these systems to reject MS-2 coliphage. When operating at steady state, these MBR systems achieved an effluent BOD concentration of <2 mg/L and a turbidity of <0.1 NTU. Peak flux for the MBR systems ranged from 56 to 76 L/m2/h (liters per square meter per hour) with peaking factors in the range of 1.5-3.2. When switching from average to peak flux operation, a reversible drop of 22-32% in temperature-corrected permeability was observed for all submerged MBR systems. The percent drop in permeability increased as MLSS concentration in the membrane tank increased from 11,100 mg/L to 15,300 mg/L and was observed to be highest for the system operating at highest MLSS concentration. Such trends were not observed with an external MBR system. Each MBR system was able to sustain a 4-h-a-day peak flow for six consecutive days with only moderate membrane fouling. The membrane fouling was quantified by measuring the drop in temperature-corrected permeability. This drop ranged from 13 to 33% over six days for different submerged MBR systems. The MBR systems achieved microbial removal in the range of 5.8-6.9 logs for total coliform bacteria, >5.5 to >6.0 logs for fecal coliform bacteria and 2.6 to >3.4 logs for indigenous MS-2 coliphages. When operating at peak flux, seeded MS-2 coliphage removal ranged from 1.0 to 4.4 logs, respectively. The higher log removal values (LRVs) for indigenous MS-2 coliphage among different MBR systems were probably the result of particle association of indigenous coliphage. Differences in membrane pore size (0.04-0.2 microm) amongst the MBR systems evaluated did not have a substantial impact on indigenous MS-2 coliphage removal, but seeded MS-2 coliphage removal varied among the different MBR systems.

Kinetics of nitrate and perchlorate reduction in ion-exchange brine using the membrane biofilm reactor (MBfR).

Several sources of bacterial inocula were tested for their ability to reduce nitrate and perchlorate in synthetic ion-exchange spent brine (30-45 g/L) using a hydrogen-based membrane biofilm reactor (MBfR). Nitrate and perchlorate removal fluxes reached as high as 5.4 g Nm(-2)d(-1) and 5.0 g ClO(4)m(-2)d(-1), respectively, and these values are similar to values obtained with freshwater MBfRs. Nitrate and perchlorate removal fluxes decreased with increasing salinity. The nitrate fluxes were roughly first order in H(2) pressure, but roughly zero-order with nitrate concentration. Perchlorate reduction rates were higher with lower nitrate loadings, compared to high nitrate loadings; this is a sign of competition for H(2). Nitrate and perchlorate reduction rates depended strongly on the inoculum. An inoculum that was well acclimated (years) to nitrate and perchlorate gave markedly faster removal kinetics than cultures that were acclimated for only a few months. These results underscore that the most successful MBfR bioreduction of nitrate and perchlorate in ion-exchange brine demands a well-acclimated inoculum and sufficient hydrogen availability.

Perchlorate and nitrate treatment by ion exchange integrated with biological brine treatment.

Groundwater contaminated with perchlorate and nitrate was treated in a pilot plant using a commercially available ion exchange (IX) resin. Regenerant brine concentrate from the IX process, containing high perchlorate and nitrate, was treated biologically and the treated brine was reused in IX resin regeneration. The nitrate concentration of the feed water determined the exhaustion lifetime (i.e., regeneration frequency) of the resin; and the regeneration condition was determined by the perchlorate elution profile from the exhausted resin. The biological brine treatment system, using a salt-tolerant perchlorate- and nitrate-reducing culture, was housed in a sequencing batch reactor (SBR). The biological process consistently reduced perchlorate and nitrate concentrations in the spent brine to below the treatment goals of 500 microg ClO4(-)/L and 0.5mg NO3(-)-N/L determined by equilibrium multicomponent IX modeling. During 20 cycles of regeneration, the system consistently treated the drinking water to below the MCL of nitrate (10 mgNO3(-)-N/L) and the California Department of Health Services (CDHS) notification level of perchlorate (i.e., 6 microg/L). A conceptual cost analysis of the IX process estimated that perchlorate and nitrate treatment using the IX process with biological brine treatment to be approximately 20% less expensive than using the conventional IX with brine disposal.

Effect of membrane configuration on bench-scale MF and UF fouling experiments.

Hollow fiber and flat sheet membranes were compared in side-by-side bench-scale experiments to evaluate whether the configuration has an impact on the rate of membrane fouling. Both microfiltration (MF) and ultrafiltration (UF) membranes were evaluated. In general, flat sheet membranes fouled more rapidly than hollow fiber membranes. Pretreatment such as coagulation generally affected both configurations similarly, but in some cases coagulation reduced fouling on hollow fiber membranes but increased fouling on flat sheet membranes. Prefiltration to remove foulants above 1microm in size had a consistent effect on both configurations. A bench-scale apparatus employing a single-fiber module that allows testing over multiple filter runs with integral backwashing capabilities was demonstrated to provide more detailed information about fouling, which can be applied to full-scale applications. When bench-scale tests are to be used to screen treatment options for full-scale applications, the use of a backwashable hollow fiber system is recommended.

Beneficial phosphate recovery from reverse osmosis (RO) concentrate of an integrated membrane system using polymeric ligand exchanger (PLE).

Phosphorus (P) discharge to surface water is a major environmental problem. Wastewater treatment is targeted towards removal of this nutrient to prevent degradation of surface water. Integrated membrane systems (IMS) are increasingly being considered for wastewater reclamation, and provide excellent removal of P compounds. However, reverse osmosis (RO), which forms an integral part of these IMSs, concentrates most dissolved substances including P-species such as phosphates in the RO waste stream. In this study, removal of phosphate from this stream using polymeric ligand exchange (PLE) resins was investigated. Further, the possibility of phosphate recovery through struvite (MgNH(4)PO(4).6H(2)O) precipitation was tested. Struvite has been promoted as a slow release fertilizer in recent years. This study demonstrates that PLEs can be successfully used to remove phosphate from RO-concentrate, and to recover more than 85% of the adsorbed phosphorus from the exhausted media and precipitated as a beneficial product (struvite). The approach, presented in this study, suggests advantages of providing economic benefit from a waste product (RO) while avoiding phosphorus discharge to the environment.

Performance investigation of membrane bioreactor systems during municipal wastewater reclamation.

Four commercially available membrane bioreactor (MBR) systems were operated at the pilot scale, to investigate performance during the reclamation of municipal wastewater. The MBR performance was evaluated under a variety of operating conditions, including two types of feed wastewater (raw and advanced primary effluent), hydraulic retention times (HRTs) ranging from 2 to 6 hours, and permeate fluxes between 20 and 41 lmh. Test results showed that MBR systems were capable of operating on advanced primary effluent, despite the possible presence of coagulant and/or polymer residual, with minimal membrane fouling. Membrane performance data generated during this study was also used to quantify the relationship between permeate flux and membrane fouling. Cleaning intervals at various flux conditions were estimated as follows: 69 days at 20 lmh, 58 days at 25 lmh, and 30 days for operation between 31 and 41 lmh. It was also demonstrated that the MBR process could be optimized to operate with minimal fouling under high hydraulic (flux = 37 lmh) and organic loading (HRT = 2 hours and food-to-microorganism ratio = 0.33 g COD/g VSS x d) conditions. Water quality monitoring conducted throughout the study showed that each MBR system consistently produced an oxidized (5-day biochemical oxygen demand < 2 mg/L) and nitrified (ammonia < 1 mg-N/L) effluent low in particulate matter (turbidity < 0.1 NTU), under all conditions tested.

Investigation of seawater reverse osmosis fouling and its relationship to pretreatment type.

Desalination of seawater using reverse osmosis (RO) technology is an important option available to water-scarce coastal regions. A major challenge to seawater reverse osmosis (SWRO) is membrane productivity decline due to fouling. Systematic studies in the area of SWRO fouling are lacking as compared to RO fouling by freshwater. The effect of the type of pretreatment employed ahead of the SWRO process has been recognized to be of critical importance in SWRO fouling. The objective of this study was to evaluate the effect of pretreatment on SWRO performance using bench scale experiments. The effect of different pretreatment strategies on SWRO flux decline was simulated using prefiltration of the SWRO feedwater using different filtration size ranges. The prefiltration size ranges used were selected to mimic the size fractions associated with different SWRO pretreatment processes. It was found that particulate matter greater than 1 microm (representing media filtration) caused most of the RO fouling. On the other hand, significant reduction in fouling was observed when membrane filtration was used (microfiltration represented by 0.1 microm prefiltration and ultrafiltration represented by 100 kDa prefiltration). There was no significant difference in flux decline between these two membrane filtration types. The lowest RO flux decline was observed when a tight ultrafiltration membrane (20 kDa) was used as prefiltration. The RO fouling observed was modeled using the gel layertheory, which could be used to satisfactorily describe fouling by different dissolved fractions of seawater. The observed SWRO fouling trends were confirmed using specially adapted attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy of the fouled membrane surface.

Effect of coagulation on the size of MF and UF membrane foulants.

Microfiltration (MF) and ultrafiltration (UF) have become common water treatment technologies for the removal of particles from natural waters. Many water utilities are now integrating MF/UF with other treatment processes to provide treatment for nonparticulate contaminants. Research is needed to understand the impact that other processes have on MF/UF performance. This study was conducted to investigate the interactions between water quality, coagulation, and membrane fouling. The study examined the fouling of MF/UF membranes by natural waters with and without coagulation by specific fractions of constituents in natural water, separated by size. This research found thatthe component of natural organic matter (NOM) smaller than 100 kDa contributes relatively little to fouling during filtration of either raw or coagulated water. The fraction between 1 microm and 100 kDa contributes a significant portion of the fouling. After coagulation pretreatment, fouling due to various size fractions in the feedwater can change.