Reactive membranes for groundwater remediation of chlorinated aliphatic hydrocarbons: competitive dechlorination and cost aspects.

A nanocomposite membrane incorporating reactive Pd-Fe nanoparticles (NPs) was developed to remediate chlorinated aliphatic hydrocarbons (CAHs) from groundwater. Other than recapturing the produced Fen+ for in-situ regeneration, the functionalized polyanions prevented NPs agglomeration and resulting in a spherical Fe0 core (55 nm, O/Fe = 0.05) and an oxidized shell (4 nm, O/Fe = 1.38). The reactive membranes degraded 92% of target CAHs with a residence time of 1.7 seconds. After long-term treatment and regeneration, reusability was confirmed through recovered reactivity, recurrence of Fe0 in X-ray photoelectron spectroscopy, and >96% remaining of Fe and Pd. The total cost (adjusted present value for 20 years) was estimated to be 13.9% lower than the granular activated carbon system, following an EPA work breakdown structure-based cost model. However, non-target CAHs from groundwater can compete for active sites, leading to decreased surface-area normalized dechlorination rate (ksa) by 28.2-79.9%. A hybrid nanofiltration (NF)/reactive membrane was proposed to selectively intercept larger competitors, leading to 54% increased dechlorination efficiency and 1.3 to 1.9-fold enlarged ksa. Overall, the practical viability of the developed reactive membranes was demonstrated by the stability, reusability, and cost advantages, while the optional NF strategy could alleviate competitive degradation towards complex water chemistry.

Ion and organic transport in Graphene oxide membranes: Model development to difficult water remediation applications.

The role of steric hindrance and charge interactions in governing ionic transport through reduced graphene oxide (rGO) and commercial (DOW-Filmtec NF270) membranes was elucidated by a comprehensive study of experimental and established mathematical analysis based on Nernst-Planck equation. A charge-dominated salt exclusion mechanism was observed for the rGO membranes, which exhibited retention from low (7%) to moderate (70%) extent depending on the nature of ions (5 mM). Swelling of GO (1.2 nm interlayer distance) in water beyond the hydrated diameter of ions was attributed as a primary cause for lowering steric hindrance effects. The influence of parameters affecting charge interactions, such as pH and ionic strength, on the extent of salt rejection was modelled. The potential impact of the membrane's charge density, GO loading and interlayer spacing on salt retention was quantified by performing sensitivity analyses. For a high TDS produced water sample, the rGO membranes partially retained divalent cations (Ca:13%) and exhibited high dissolved oil rejection. The membranes were found to be suitable for the treatment of high TDS water with the goal of selectively removing organic impurities, and thus minimizing the impact of osmotic pressure effect. Performance of the membranes was also investigated for retention of water remediation related organic anions, using perfluoro octanoic (PFOA) acid as a model compound. rGO membranes exhibited a charge-dominated exclusion mechanism for retention (90%) of PFOA (1 ppm).

Pd/Fe nanoparticle integrated PMAA-PVDF membranes for chloro-organic remediation from synthetic and site groundwater.

The poly(methacrylic acid) (PMAA) was synthesized in the pores of commercial microfiltration PVDF membranes to allow incorporation of catalytic palladium/iron (Pd/Fe) nanoparticles for groundwater remediation. Particles of 17.1 ± 4.9 nm size were observed throughout the pores of membranes using a focused ion beam. To understand the role of Pd fractions and particle compositions, 2-chlorobiphenyl was used as a model compound in solution phase studies. Results show H2 production (Fe0 corrosion in water) is a function of Pd coverage on the Fe. Insufficient H2 production caused by higher coverage (> 10.4% for 5.5 wt%) hindered dechlorination rate. With 0.5 wt% Pd, palladized-Fe reaction rate (surface area normalized reaction rate, ksa = 0.12 L/(m2-h) was considerably higher than isolated Pd and Fe particles. For groundwater, in a single pass of Pd/Fe-PMAA-PVDF membranes (0.5 wt% Pd), chlorinated organics, such as trichloroethylene (177 ppb) and carbon tetrachloride (35 ppb), were degraded to 16 and 0.3 ppb, respectively, at 2.2 seconds of residence time. The degradation rate (observed ksa) followed the order of carbon tetrachloride > trichloroethylene > tetrachloroethylene > chloroform. A 36 h continuous flow study with organic mixture and the regeneration process show the potential for on-site remediation.

Thermo-responsive adsorption-desorption of perfluoroorganics from water using PNIPAm hydrogels and pore functionalized membranes.

Perfluorochemicals (PFCs) are emerging contaminants in various water sources. Responsive polymers provide a new avenue for PFC adsorption/desorption from water. Poly-N-isopropylacrylamide's (PNIPAm's) temperature-responsive behavior and hydrophilic/hydrophobic transition is leveraged for reversible adsorption and desorption of PFCs. Adsorption of PFOA (perfluoro-octanoic acid) onto PNIPAm hydrogels yielded Freundlich distribution coefficients (Kd) of 0.073 L/g at 35 °C (above LCST) and 0.026 L/g at 22°C. Kinetic studies yielded second order rate constants (k2) of 0.012 g/mg/h for adsorption and 12.6 g/mg/h for desorption, with initial rates of 28 mg/g/h and 41 mg/g/h, respectively. Interaction parameters of PNIPAm's functional groups in its different conformational states, as well as the hydrophobic fluorinated carbon tails and hydrophilic head groups of PFOA are used to describe relative adsorption. Polyvinylidene difluoride (PVDF) provides a robust membrane structure for the commercial viability of polymeric adsorbents. Temperature swing adsorption of PFOA using PNIPAm functionalized PVDF membrane pores showed consistent adsorption and desorption capacity over 5 cycles. PFOA desorption percentage of 60% was obtained in pure water at temperatures below PNIPAm's lower critical solution temperature (LCST) while 13% desorption was obtained at temperatures above the LCST, thus showing the importance of the LCST on desorption performance.

Reductive Degradation of CCl4 by Sulfidized Fe and Pd-Fe Nanoparticles: Kinetics, Longevity, and Morphology Aspects.

In this study a systematic comparison in morphology, long-term degradation, regeneration and reuse were conducted between palladized and sulfidized nanoscale zero-valent iron (Pd-Fe and S-Fe). Pd-Fe and S-Fe were prepared, after the synthesis of precursor Fe0 nanoparticles (spherical, ~35 nm radius) for carbon tetrachloride (CTC) treatment. With HAADF-TEM-EDS characterization, dispersive Pd islets were found on the Fe core of Pd-Fe. However, the Fe core was covered by the FeSx shell of S-Fe (FeS/FeS2 = 0.47). With an excessive Pd dose (10 mol%), the Pd-Fe were dramatically deformed to dendritic structures which significantly decreased reactivity. For CTC degradation, Pd-Fe (0.3 atomic% Pd) increased the degradation rate by 20-fold (ksa= 0.580 Lm-2min-1) while S-Fe presented a greater life time. The major intermediate chloroform (CF) was further degraded and less than 5% CF was observed after 24 h using Pd-Fe or S-Fe while above 50% CF remained using Fe. During aging, the Fe core was converted to FeOOH and Fe3O4/γ-Fe2O3. The restoration of Fe0 was achieved using NaBH4, which regenerated Fe and Pd-Fe. However, the formed FeSx shell on S-Fe was disappeared. The results suggest that S-Fe extends longevity of Fe, but the loss of FeSx after aging makes S-Fe eventually perform like Fe in terms of CTC degradation.

Role of membrane pore polymerization conditions for pH responsive behavior, catalytic metal nanoparticle synthesis, and PCB degradation.

This article describes the effects of changing monomer and cross-linker concentrations on the mass gain, water permeability, Pd-Fe nanoparticle (NP) loading, and the rate of degradation of 3,3',4,4',5-pentachlorobiphenyl (PCB 126) of pore functionalized polyvinylidene fluoride (PVDF) membranes. In this study, monomer (acrylic acid (AA)) and cross-linker (N, N'- methylene-bis (acrylamide)) concentrations were varied from 10 to 20 wt% of polymer solution and 0.5-2 mol% of monomer concentration, respectively. Results showed that responsive behavior of membrane could be tuned in terms of water permeability over a range of 270-1 L m-2 h-1 bar-1, which is a function of water pH. The NP size on the membrane surface was found in the range of 16-23 nm. With increasing cross-linker density the percentage of smaller NPs (< 10 nm) increases due to smaller mesh size formation during in-situ polymerization of membrane. NP loading was found to vary from 0.21 to 0.94 mg per cm2 of membrane area depending on the variation of available carboxyl groups in membrane pore domain. The NPs functionalized membranes were then tested for use as a platform for the degradation of PCB 126. The observed batch reaction rate (Kobs) for PCB 126 degradation for per mg of catalyst loading was found 0.08-0.1 h-1. Degradation study in convective flow mode shows 98.6% PCB 126 is degraded at a residence time of 46.2 s. The corresponding surface area normalized reaction rate (K sa ) is found about two times higher than K sa of batch degradation; suggesting elimination of the effect of diffusion resistance for degradation of PCB 126 in convective flow mode operation. These Pd-Fe-PAA-PVDF membranes and nanoparticles are characterized by TGA, contact angle measurement, surface zeta potential, XRD, SEM, XPS, FIB, TEM and other techniques reveal the details about the membrane surface, pores and nanoparticles size, shape and size-distribution. Statistical analysis based on experimental results allows us to depict responsive behavior of functionalized membrane. In our best knowledge this paper first time reports detail study on responsive behavior of pore functionalized membrane in terms of permeability, NPs size, metal loading and its effect on PCB 126 degradation in a quantified approach.

Pore Functionalized PVDF Membranes with In-Situ Synthesized Metal Nanoparticles: Material Characterization, and Toxic Organic Degradation.

Functionalized PVDF membrane platforms were developed for environmentally benign in-situ nanostructured Fe/Pd synthesis and remediation of chlorinated organic compounds. To prevent leaching and aggregation, nanoparticle catalysts were integrated into membrane domains functionalized with poly (acrylic acid). Nanoparticles of 16-19 nm were observed inside the membrane pores by using focused ion beam (FIB). This technique prevents mechanical deformation of the membrane, compared to the normal SEM preparation methods, thus providing a clean, smooth surface for nanoparticles characterization. This allowed quantification of nanoparticle properties (size and distribution) versus depth underneath the membrane surface (0-20 µm). The results showed that nanoparticles were uniformly sized and evenly distributed inside the membrane pores. However, the size of nanoparticles inside the membrane pores was 13.9% smaller than those nanoparticles located on the membrane surface. Investigating nanoparticles inside membrane pores increases the accuracy of kinetic analysis and modeling aspects. Furthermore, the Fe/Pd immobilized membranes showed excellent performance in the degradation of chlorinated organics: Over 96% degradation of 3,3',4,4',5-pentachlorobiphenyl (PCB 126) was achieved in less than 15 s residence time in convective flow mode. The regeneration and reuse of this catalytic membrane system were also studied. Particles were examined in XRD upon formation, after deliberate oxidation, and after regeneration. The regenerated sample showed the same crystalline pattern as the original sample. Repeated degradation experiments demonstrated successful PCB 126 dechlorination with nanoparticles regenerated for four cycles with only a small loss in reactivity. It demonstrated that Fe/Pd immobilized membranes have the potential for large-scale remediation applications.

Peracetic acid as an alternative disinfection technology for wet weather flows.

Rain-induced wet weather flows (WWFs) consist of combined sewer overflows, sanitary sewer overflows, and stormwater, all of which introduce pathogens to surface waters when discharged. When people come into contact with the contaminated surface water, these pathogens can be transmitted resulting in severe health problems. As such, WWFs should be disinfected. Traditional disinfection technologies are typically cost-prohibitive, can yield toxic byproducts, and space for facilities is often limited, if available. More cost-effective alternative technologies, requiring less space and producing less harmful byproducts are currently being explored. Peracetic acid (PAA) was investigated as one such alternative and this research has confirmed the feasibility and applicability of using PAA as a disinfectant for WWFs. Peracetic acid doses ranging from 5 mg/L to 15 mg/L over contact times of 2 to 10 minutes were shown to be effective and directly applicable to WWF disinfection.

Dual-Functional Nanofiltration and Adsorptive Membranes for PFAS and Organics Separation from Water.

Challenges associated with water separation technologies for per- and polyfluoroalkyl substances (PFASs) require efficient and sustainable processes supported by a proper understanding of the separation mechanisms. The solute rejections by nanofiltration (NF) at pH values near the membrane isoelectric point were compared to the size- and mass-transfer-dependent modeled rejection rates of these compounds in an ionized state. We find that the low pK a value of perfluorooctanoic acid (PFOA) relates to enhanced solute exclusions by minimizing the presence and partitioning of the protonated organic compound into the membrane domain. The effects of Donnan exclusion are moderate, and co-ion transport also contributes to the PFAS rejection rates. An additional support barrier with thermo-responsive (quantified by water permeance variation) adsorption/desorption properties allows for enhanced separations of PFAS. This was possible by successfully synthesizing an NF layer on top of a poly-N-isopropylacrylamide (PNIPAm) pore-functionalized microfiltration support structure. The support layer adsorbs organics (178 mg PFOA adsorbed/m2 membrane at an equilibrium concentration of 70 mg/L), and the simultaneous exclusion from the NF layer allows separations of PFOA and the smaller sized heptafluorobutyric acid from solutions containing 70 µg/L of these compounds at a high water flux of 100 L/m2-h at 7 bar.

Community Forum Identifies Opportunities to Engage with Eastern Kentucky Community Leaders about Chronic Disease and Environmental Pollution.

The NIEHS-sponsored Appalachian Health & Well-Being Community Forum held in Eastern Kentucky brought various community members together to communicate and establish better coordination of efforts to improve health and address regional environmental issues. The two-hour forum discussion provided bi-directional feedback about the needs and interests of community members. Top concerns of community members included obesity and obesity-related diseases and environmental pollution. Healthful lifestyles were identified as part of the remedy to protect health from potential adverse health effects associated with environmental pollution. This study highlights opportunities to engage with Appalachian communities around topics related to health and environmental pollution.

Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems.

The primary objective of this research was to model and understand the chelate-modified Fenton reaction for the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. The addition of a nontoxic chelate (L), such as citrate or gluconic acid, allows for operation at near-neutral pH and controlled release of Fe(II)/Fe(III). For the standard Fenton reaction at low pH in two-phase systems, an optimum H(2)O(2):Fe(II) molar ratio was found to be between 1:1 and 2:1. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinated TCE in both the aqueous and organic phases at pH 6-7 using low H(2)O(2):Fe(II) molar ratios (4:1 to 8:1). Increasing the L:Fe ratio was found to decrease the rate of H(2)O(2) degradation in both Fe(II) and Fe(III) systems at near-neutral pH. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using literature-reported hydroxyl radical reaction kinetics and mass transfer relationships. Additional aspects of this work include the reusability of the Fe-citrate complex under repeated H(2)O(2) injections in real water systems as well as packed column studies for simulated groundwater injection.

Reduced graphene oxide-metal nanoparticle composite membranes for environmental separation and chloro-organic remediation.

This study explores the integration of separation performance of rGO membrane with heterogeneous oxidation reactions for remediation of organic contaminants from water. Herein, an approach was introduced based on layer-by-layer assembly for functionalizing rGO membranes with polyacrylic acid and then by in situ synthesis of Fe based reactive nanoparticles. TEM characterization of the cross-section lamella of the membranes showed a high density of nanoparticles (12% Fe) in the functionalized domain, signifying the importance of polyacrylic acid for in situ synthesis of nanoparticles. The membranes exhibited a pure water permeability of 1.9 LMH bar-1. The membranes had low to moderate salt retention, and more than 90% neutral red retention (organic probe molecule, size: 1.2 nm). The membranes also exhibited high retention of humic acids (80%), preventing these organics from entering the reactive domain, and thus potentially reducing the formation of undesired by-products. A persulfate mediated oxidative pathway was employed to demonstrate the reactive removal of organic contaminants. The membranes achieved >95% conversion by convectively passing 2 mM persulfate feed at a transmembrane pressure of 0.4 bar. Successful degradation of TCE (up to 61%) was achieved in a single pass by convective flowing of the feed solution through the membrane, generating up to 80% of the theoretical maximum chloride as one of the byproducts. Elevated temperatures significantly enhanced persulfate mediated TCE oxidation extent from 24% at 23 oC to 54% at 40 o C under batch operating conditions.

Functionalization of flat sheet and hollow fiber microfiltration membranes for water applications.

Functionalized membranes containing nanoparticles provide a novel platform for organic pollutant degradation reactions and for selective removal of contaminants without the drawback of potential nanoparticle loss to the environment. These eco-friendly and sustainable technology approaches allow various water treatment applications through enhanced water transport through the membrane pores. This paper presents "green" techniques to create nanocomposite materials based on sponge-like membranes for water remediation applications involving chlorinated organic compounds. First, hydrophobic hollow fiber microfiltration membranes (HF) of polyvinylidene fluoride were hydrophilized using a water-based green chemistry process with polyvinylpyrrolidone and persulfate. HF and flat sheet membrane pores were then functionalized with poly(acrylic acid) and synthesized Fe/Pd nanoparticles. Surface modifications were determined by contact angle, surface free energy and infrared spectroscopy. The synthesized nanoparticles were characterized by electronic microscopy, X-ray spectrometry and image analysis. Nanoparticle sizes of 193 and 301 nm were obtained for each of the membranes. Depending on the concentration of the dopant (Pd) in the membrane, catalytic activity (established by trichloroethylene (TCE) reduction), was enhanced up to tenfold compared to other reported results. Chloride produced in reduction was close to the stoichiometric 3/1 (Cl-/TCE), indicating complete absence of reaction intermediates.

Development of PVDF Membrane Nanocomposites via Various Functionalization Approaches for Environmental Applications.

Membranes are finding wide applications in various fields spanning biological, water, and energy areas. Synthesis of membranes to provide tunable flux, metal sorption, and catalysis has been done through pore functionalization of microfiltration (MF) type membranes with responsive behavior. This methodology provides an opportunity to improve synthetic membrane performance via polymer fabrication and surface modification. By optimizing the polymer coagulation conditions in phase inversion fabrication, spongy polyvinylidene fluoride (PVDF) membranes with high porosity and large internal pore volume were created in lab and full scale. This robust membrane shows a promising mechanical strength as well as high capacity for loading of adsorptive and catalytic materials. By applying surface modification techniques, synthetic membranes with different functionality (carboxyl, amine, and nanoparticle-based) were obtained. These functionalities provide an opportunity to fine-tune the membrane surface properties such as charge and reactivity. The incorporation of stimuli-responsive acrylic polymers (polyacrylic acid or sodium polyacrylate) in membrane pores also results in tunable pore size and ion-exchange capacity. This provides the added benefits of adjustable membrane permeability and metal capture efficiency. The equilibrium and dynamic binding capacity of these functionalized spongy membranes were studied via calcium ion-exchange. Iron/palladium catalytic nanoparticles were immobilized in the polymer matrix in order to perform the challenging degradation of the environmental pollutant trichloroethylene (TCE).

Polymerization and Functionalization of Membrane Pores for Water Related Applications.

Poly(vinylidene fluoride) (PVDF) was modified by chemical treatments in order to create active double bonds to obtain covalent grafting of poly(acrylic acid) (PAA) on membrane. The attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectrum confirms the formation of conjugated C=C double bonds with surface dehydrofluorination. The membrane morphology was studied by scanning electron microscopy (SEM). The surface composition was characterized by X-ray photoelectron spectroscopy (XPS). The thermal stability of the dehydrofluorinated membrane (Def-PVDF) and functionalized membranes were investigated by differential scanning calorimetry (DSC) analysis. The influence of covalently attached PAA on Def-PVDF membrane has been investigated to determine its effect on the transport of water and charged solute. Variations in the solution pH show an effect on both permeability and solute retention in a reversible fashion. Metal nanoparticles were also immobilized in the membrane for the degradation of toxic chlorinated organics from water. In addition, PVDF membranes with an asymmetric and sponge-like morphology were developed by immersion-precipitation phase-inversion methods in both lab-scale and large-scale. The new type of spongy PVDF membrane shows high surface area with higher yield of PAA functionalization. The ion-capacity with Ca2+ ions was also investigated.

Reactive Functionalized Membranes for Polychlorinated Biphenyl Degradation.

Membranes have been widely used in water remediation (e.g. desalination and heavy metal removal) because of the ability to control membrane pore size and surface charge. The incorporation of nanomaterials into the membranes provides added benefits through increased reactivity with different functionality. In this study, we report the dechlorination of 2-chlorobiphenyl in the aqueous phase by a reactive membrane system. Fe/Pd bimetallic nanoparticles (NPs) were synthesized (in-situ) within polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) membranes for degradation of polychlorinated biphenyls (PCBs). Biphenyl formed in the reduction was further oxidized into hydroxylated biphenyls and benzoic acid by an iron-catalyzed hydroxyl radical (OH•) reaction. The formation of magnetite on Fe surface was observed. This combined pathway (reductive/oxidative) could reduce the toxicity of PCBs effectively while eliminating the formation of chlorinated degradation byproducts. The successful manufacturing of full-scale functionalized membranes demonstrates the possibility of applying reactive membranes in practical water treatment.

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water.

The potential for using hydroxyl radical (OH•) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H2O2 addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80-100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H2O2 by NP surface generated OH• were investigated. Depending on the ratio of iron and H2O2, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.

Nutrition can modulate the toxicity of environmental pollutants: implications in risk assessment and human health.

BACKGROUND: The paradigm of human risk assessment includes many variables that must be viewed collectively in order to improve human health and prevent chronic disease. The pathology of chronic diseases is complex, however, and may be influenced by exposure to environmental pollutants, a sedentary lifestyle, and poor dietary habits. Much of the emerging evidence suggests that nutrition can modulate the toxicity of environmental pollutants, which may alter human risks associated with toxicant exposures. OBJECTIVES: In this commentary, we discuss the basis for recommending that nutrition be considered a critical variable in disease outcomes associated with exposure to environmental pollutants, thus establishing the importance of incorporating nutrition within the context of cumulative risk assessment. DISCUSSION: A convincing body of research indicates that nutrition is a modulator of vulnerability to environmental insults; thus, it is timely to consider nutrition as a vital component of human risk assessment. Nutrition may serve as either an agonist or an antagonist (e.g., high-fat foods or foods rich in antioxidants, respectively) of the health impacts associated with exposure to environmental pollutants. Dietary practices and food choices may help explain the large variability observed in human risk assessment. CONCLUSION: We recommend that nutrition and dietary practices be incorporated into future environmental research and the development of risk assessment paradigms. Healthful nutrition interventions might be a powerful approach to reduce disease risks associated with many environmental toxic insults and should be considered a variable within the context of cumulative risk assessment and, where appropriate, a potential tool for subsequent risk reduction.