Lee D. Wilson

Chemical fingerprinting of naphthenic acids and oil sands process waters—A review of analytical methods for environmental samples

This article provides a review of the routine methods currently utilized for total naphthenic acid analyses. There is a growing need to develop chemical methods that can selectively distinguish compounds found within industrially derived oil sands process affected waters (OSPW) from those derived from the natural weathering of oil sands deposits. Attention is thus given to the characterization of other OSPW components such as oil sands polar organic compounds, PAHs, and heavy metals along with characterization of chemical additives such as polyacrylamide polymers and trace levels of boron species. Environmental samples discussed cover the following matrices: OSPW containments, on-lease interceptor well systems, on- and off-lease groundwater, and river and lake surface waters. There are diverse ranges of methods available for analyses of total naphthenic acids. However, there is a need for inter-laboratory studies to compare their accuracy and precision for routine analyses. Recent advances in high- and medium-resolution mass spectrometry, concomitant with comprehensive mass spectrometry techniques following multi-dimensional chromatography or ion-mobility separations, have allowed for the speciation of monocarboxylic naphthenic acids along with a wide range of other species including humics. The distributions of oil sands polar organic compounds, particularly the sulphur containing species (i.e., OxS and OxS2) may allow for distinguishing sources of OSPW. The ratios of oxygen- (i.e., Ox) and nitrogen-containing species (i.e., NOx, and N2Ox) are useful for differentiating organic components derived from OSPW from natural components found within receiving waters. Synchronous fluorescence spectroscopy also provides a powerful screening technique capable of quickly detecting the presence of aromatic organic acids contained within oil sands naphthenic acid mixtures. Synchronous fluorescence spectroscopy provides diagnostic profiles for OSPW and potentially impacted groundwater that can be compared against reference groundwater and surface water samples. Novel applications of X-ray absorption near edge spectroscopy (XANES) are emerging for speciation of sulphur-containing species (both organic and inorganic components) as well as industrially derived boron-containing species. There is strong potential for an environmental forensics application of XANES for chemical fingerprinting of weathered sulphur-containing species and industrial additives in OSPW.

Chitosan-glutaraldehyde copolymers and their sorption properties.

This study reports the preparation of chitosan-glutaraldehyde (Chi-Glu) copolymers at modified reaction conditions such as the temperature prior to gelation, pH, and reagent ratios. The chitosan copolymers were characterized using infrared spectroscopy (FT-IR), CHN elemental analysis, and thermal gravimetric analysis (TGA). Evidence of self-polymerized glutaraldehyde was supported by CHN and TGA results. The sorption properties of Chi-Glu copolymers were evaluated in aqueous solutions containing p-nitrophenol at variable pH (4.6, 6.6, and 9.0). The sorption properties of the copolymers correlated with the level of the accessibility of the sorption sites in accordance with the relative cross-linker content. The relative sorption capacity of the Chi-Glu copolymers increases as the level of cross-linking increases. Chitosan displays the lowest sorptive uptake while an optimal sorption capacity was concluded at the 4:1 glutaraldehyde:chitosan monomer mole ratio, in close agreement with the three reactive sites (i.e. OH/NH) per glucosamine monomer. The PNP dye probe was determined to bind to chitosan through an electrostatic interaction due to the increased sorption capacity of the phenolate anion, as evidenced by the change in pH from 4.6 to 9.0.

Screening of oil sands naphthenic acids by UV-Vis absorption and fluorescence emission spectrophotometry

Oil sands extracted naphthenic acids fractions are known to contain impurities with various levels of unsaturation and aromaticity. These constituents contain functional groups that absorb ultraviolet-visible wavelength (UV-Vis) radiation and give intense florescence emission in contrast to the fully saturated alicyclic naphthenic acids. UV-Vis absorption and fluorescence emission spectrophotometry are presented here as inexpensive and quick screening methods that the detection of chromophoric surrogate compounds that serve as an internal standard for the indirect analysis of oil sands naphthenic acids. The method detection limit for the screening techniques was approximately 1 mg/L with an observed linear range of 1–100 mg/L. The precision of measurements was generally within 10% r.s.d. There was generally good agreement (within 20% r.s.d) for isotherm parameters from non-linear fitting of Langmuir, BET and Freundlich models for sorption of Athabasca oil sands naphthenic acid mixtures to activated carbon samples determined by UV-Vis absorption, fluorescence emission spectroscopy, and conventional direct injection electrospray ionization mass spectrometry.

Investigation of the sorption properties of β-cyclodextrin-based polyurethanes with phenolic dyes and naphthenates.

The sorption of p-nitrophenol (PNP), phenolphthalein (phth) and naphthenates (NAs) with β-cyclodextrin (β-CD) based polyurethane sorbents from aqueous solutions are reported. The copolymer sorbents were synthesized at various β-CD/diisocyanate monomer mole ratios (e.g., 1:1, 1:2, and 1:3) with diisocyanates of variable molecular size and hydrogen deficiency. The copolymer sorbents were characterized in the solid state using (13)C CP-MAS NMR spectroscopy, IR spectroscopy and elemental (C,H,N) analysis. The equilibrium sorption properties of the copolymer sorbents in aqueous solution were characterized using isotherm models at pH 4.6 and 9.0 for PNP, pH 9.0 for naphthenates and pH 10.5 for phth. UV-Vis spectroscopy was used to monitor the unbound fraction of the phenolic dyes in the aqueous phase, whereas, electrospray ionization mass spectrometry was used to monitor the unbound fraction of naphthenates. The sorption results of the copolymer sorbents were compared with a commercially available carbonaceous standard; granular activated carbon (GAC). The sorption properties and capacities of the copolymer sorbents (Q(m)) were estimated using the Sips isotherm. The sorption capacity for GAC was 2.15 mmol PNP/g, 0.0698 mmol phth/g, and 142 mg NAs/g, respectively, whereas the polymeric materials ranged from 0.471 to 1.60 mmol/g (PNP), 0.114 to 0.937 mmol/g (phth), and 0 to 75.5 mg/g (naphthenates), respectively, for the experimental conditions investigated. The observed differences in the sorption properties were attributed to the accessible surface areas and pore structure characteristics of the copolymer sorbents. The binding constant, K(eq), for copolymer materials for each sorbate is of similar magnitude to the binding affinity observed for native β-CD. PNP showed significant binding onto the copolymer framework containing diisocyanate domains, whereas, negligible sorption to the sites was observed for phth and naphthenates. The β-CD inclusion sites in the copolymer framework are concluded to be the main sorption site for phth and naphthenates through the formation of well-defined inclusion complexes.

Adsorption study of an organo-arsenical with chitosan-based sorbents

In this study, chitosan-based copolymers were prepared at various weight ratios of chitosan (C) to glutaraldehyde (G): 1:1 (CG11), 2:1 (CG21), and 3:1 (CG31). The sorption properties of these copolymers were investigated with roxarsone in simulated aquatic conditions at pH 7 in phosphate buffer, similar to that found in poultry litter leachate. The relative sorption capacity (Q(m); mmol/g) of the sorbents are listed in parentheses in descending order: CG11 (1.80)>CG31 (0.945)>CG21 (0.802)>chitosan (0.416). The sorptive properties of the copolymers are comparable to granular activated carbon (GAC), a standard carbonaceous sorbent material, where Q(m)=2.36 mmol/g. The adsorption properties of phenolic adsorbates such as o-nitrophenol, p-nitrophenol, and roxarsone with the CG copolymers and GAC were investigated at various pH and compared with phosphate and carbonate buffer systems.

Preparation and sorption studies of glutaraldehyde cross-linked chitosan copolymers.

Chitosan-glutaraldehyde copolymer sorbents were synthesized by reacting variable weight ratios (low, medium, and high) of glutaraldehyde with fixed amounts of chitosan. Two commercially available chitosan polymers with low (L) and high (H) relative molecular weights were investigated. The chitosan-glutaraldehyde (Chi-Glu) copolymer sorbents are denoted as CPL-X or CPH-X where X denotes the incremental level (X=-1, -2, -3) of glutaraldehyde. The copolymers were characterized using FT-IR spectroscopy and TGA. The solid-solution sorption isotherms in alkaline aqueous solution for the copolymers were characterized using absorbance and emission based spectroscopic methods for p-nitrophenol (PNP) and the arsenate oxoanion HAsO4(2-) species, respectively. The Sips isotherm model was utilized to obtain sorption parameters at pH 8.5 and 295K (i.e. sorbent surface area, sorption capacity and removal efficiency) for each copolymer sorbent. The sorbent surface areas for the low molecular weight chitosan copolymers are listed in parentheses (m(2)g(-1)), as follows: CPL-1 (124), CPL-2 (46.7) and CPL-3 (31.6). The high molecular weight chitosan copolymers are as follows: CPH-1 (79.8), CPH-2 (64.7) and CPH-3 (96.3). The removal efficiencies depend on the pH, temperature, and the relative amounts of sorbate and sorbent. The sorbent removal efficiencies for p-nitrophenol ranged between 7.1% and 49%, and the values for H2AsO4(2-) ranged between 31% to 93% for the low and high molecular weight copolymers.

Adsorption properties of cross-linked cellulose-epichlorohydrin polymers in aqueous solution

Cellulose was cross-linked with epichlorohydrin (EP) at variable levels (CLE-0.5, CLE-2 and CLE-4), where CLE-i denotes the cellulose to EP mole ratios. The cross-linked products were characterized by TGA and FT-IR spectroscopy, pH at the point of zero charge (pHpzc), water swelling, and dye-adsorption methods employing two types of dyes [phenolphthalein (phth) and p-nitrophenol (PNP)]. The characterization methods provide evidence of cross-linking of cellulose in accordance with variations in surface area, PZC, available surface hydroxyl groups, and thermal stability when compared against pristine cellulose. The pHpzc of the sorbent materials was ∼ 6.5 indicating a negative surface charge occurs above pHpzc. The cross-linked polymers possess greater swelling properties relative to pristine cellulose. Detailed adsorption studies were carried out at pH 9 for cellulose and CLE-i with five types single component carboxylate anions [2-hexyldecanoic acid (S1), trans-4-pentylcyclohexanecarboxylic acid (S2), 2-dicyclohexylacetic acid (S3), adamantane carboxylic acid (S4), and cyclohexane carboxylic acid (S5)] at 295 K. The uptake properties of PNP with cellulose and CLE-i were also compared at pH 5 and 9, respectively. CLE-2 had the highest uptake of PNP (Qm=1.22 × 10(-1)mmol/g, pH 9) and S1 (Qm=4.27 mg/g) while cellulose and CLE-4 had the strongest binding affinity (1.43 L/mmol and 5.90 × 10(-2)L/mg), respectively. Uptake of PNP by CLE-0.5 at pH 5 (Q m=5.30 × 10(-2)mmol/g) was higher than uptake at pH 9 (Qm=3.11 × 10(-2)mmol/g). Sorption of CLE-4 with S1, S2 and S3 showed that relative uptake of the surrogates had the following order: S3>S2>S1, where S2 had the strongest binding affinity to CLE-i. CLE-2 had the highest sorption capacity towards Si in an equimolar mixture with evidence of molecular selective uptake. At pH 9, low uptake was mainly related to electrostatic repulsion between the negatively charged sorbent surface and the carboxylate head groups of Si.

Magnetite/Polymer Brush Nanocomposites with Switchable Uptake Behavior Toward Methylene Blue

The grafting from approach was used to prepare pH-responsive polyacid brushes using poly(itaconic acid) (PIA) and poly(acrylic acid) (PAA) at the amine functional groups of chitosan. Hybrid materials consisting of polymer brushes and magnetite nanoparticles (MNPs) were also prepared. The products were structurally characterized and displayed reversible pH-responsive behavior and controlled adsorption/desorption of methylene blue (MB). Switchable binding of MB involves cooperative effects due to conformational changes of brushes and swelling phenomena in solution which arise from response to changes in pH. Above the pKa, magnetic nanocomposites (MNCs) are deprotonated and display enhanced electrostatic interactions with high MB removal efficiency (>99%). Below the pKa, MNCs undergo self-assembly and release the cationic dye. The switchable binding of MB and the structure of the polymer brush between collapsed and extended forms relate to changes in osmotic pressure due to reversible ionization of acid groups at variable pH. Reversible adsorption-desorption with variable binding affinity and regeneration ability was demonstrated after five cycles.

Porous Copolymer Resins: Tuning Pore Structure and Surface Area with Non Reactive Porogens

In this review, the preparation of porous copolymer resin (PCR) materials via suspension polymerization with variable properties are described by tuning the polymerization reaction, using solvents which act as porogens, to yield microporous, mesoporous, and macroporous materials. The porogenic properties of solvents are related to traditional solubility parameters which yield significant changes in the surface area, porosity, pore volume, and morphology of the polymeric materials. The mutual solubility characteristics of the solvents, monomer units, and the polymeric resins contribute to the formation of porous materials with tunable pore structures and surface areas. The importance of the initiator solubility, surface effects, the temporal variation of solvent composition during polymerization, and temperature effects contribute to the variable physicochemical properties of the PCR materials. An improved understanding of the factors governing the mechanism of formation for PCR materials will contribute to the development and design of versatile materials with tunable properties for a wide range of technical applications.

Polysaccharide-based materials and their adsorption properties in aqueous solution.

Polysaccharides (PS) of cellulose, soluble, corn- and maize-derived starches with variable amylose/amylopectin content were cross-linked with epichlorohydrin (EPI) to form polymeric adsorbents. The properties of the cross-linked PS-EPI materials were prepared by varying the synthesis conditions (nature of polysaccharide, temperature, and reagent ratios) to afford network polymer materials with tunable properties. The optimized polymers were obtained at a reaction temperature (50-54 °C) according their yield were characterized using spectroscopic (IR and NMR) methods, and thermal gravimetric analysis (TGA). The textural and adsorptive properties of the polymers were evaluated using nitrogen gas and dye-based methods using p-nitrophenol. Solvent uptake, nitrogen adsorption, and aqueous dye sorption show that the amylose and amylopectin content in the PS-EPI copolymers display a complex relationship with their physicochemical properties. Polymers with greater cross-linking did not show incremental changes in water or dye uptake. Structural variation of the polysaccharide (i.e. branching, molecular weight, and relative amylopectin/amylose content) contributed to the sorption properties by modifying their textural properties and surface chemistry.