Nick D.M.Z. Wilton, Ph.D.

A green chemistry solution is presented for the remediation of heavy hydrocarbon impacted soils. The two-phase recovery system relies on a plant-based biopolymer, which releases hydrocarbons from soil, and polystyrene foam beads, which recover them from solids and water. The efficiency of the process was demonstrated by comparisons with control experiments, where water, biopolymer, or beads alone yielded total petroleum hydrocarbon (TPH) reductions of 25%, 52%, and 58%, respectively, compared… Show more

A green chemistry solution is presented for the remediation of heavy hydrocarbon impacted soils. The two-phase recovery system relies on a plant-based biopolymer, which releases hydrocarbons from soil, and polystyrene foam beads, which recover them from solids and water. The efficiency of the process was demonstrated by comparisons with control experiments, where water, biopolymer, or beads alone yielded total petroleum hydrocarbon (TPH) reductions of 25%, 52%, and 58%, respectively, compared to 94% when 1.25 mL of 1% biopolymer and 15 mg beads per gram of soil were agitated for 30 min. Reductions in TPH content were substantial regardless of soil fraction, with removals of 97%, 91%, and 75% from sand, silt, and clay size fractions, respectively. Additionally, treatment efficiency was independent of carbon number, C13 to C43, as demonstrated by reductions in both diesel fuel (C13-C28) and residual-range organics (C25-C43) of ∼90%. Compared to other published polymer- and surfactant-based treatment methods, this system requires less mobilizing agent, sorbent, and mixing time. The remediation process is both efficient and sustainable because the biopolymer is re-useable and sourced from renewable crops and polystyrene beads are obtained from recycled materials. Show less

Alkylated polycyclic aromatic hydrocarbon (PAH) and polycyclic aromatic sulfur heterocycle (PASH) standardized methods often rely on gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM). The objective of this study is to develop a method that produces accurate data while minimizing sample preparation and achieving low levels of detection. Most standardized methods are based on acquiring a given homologue's molecular ion (1-ion). Some methods include a… Show more

Alkylated polycyclic aromatic hydrocarbon (PAH) and polycyclic aromatic sulfur heterocycle (PASH) standardized methods often rely on gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM). The objective of this study is to develop a method that produces accurate data while minimizing sample preparation and achieving low levels of detection. Most standardized methods are based on acquiring a given homologue's molecular ion (1-ion). Some methods include a second, confirming ion (2-ion) in the hopes of excluding non-target ion signals from the total homologue peak area. Although all methods use homologue-specific retention windows, these windows differ greatly among the methods. In this paper we evaluate, for the first time, errors in quantitation caused by using different windows as well as common ion effects when target and/or matrix compounds coelute. Two NIST-certified Standard Reference Materials (SRMs), crude oil SRM 1582 and marine sediment SRM 1941b, were analyzed by five standardized methods and by the new method we developed, which relies on spectral deconvolution of three to five ions per PAH/PASH and as many fragmentation patterns as needed to correctly identify the C1 to C4 homologues (MFPPH). All of the standardized methods overestimated the concentrations of the majority of alkylated homologues whereas MFPPH obtained values much closer to NIST-certified concentrations. Rather than straight-line integration of all peaks in the retention window or recognizing peak patterns, the MFPPH data analysis software integrates only those peaks that meet the compound identity criteria. Show less

A sustainable, green chemistry process is proposed for the cleanup of coal tar impacted sediment in two hours or less. A mixture of proteins and polypeptides, extracted from corn gluten meal and hemp, when mixed with sediment and polystyrene foam pellets (PFP), serves to mobilize tar, which sorbs onto PFP. Since the sorbent floats, coal tar is easily extracted from the agitation vessel. An empirically-derived 4-dimensional surface response model accurately predicts removal rates of the tar and… Show more

A sustainable, green chemistry process is proposed for the cleanup of coal tar impacted sediment in two hours or less. A mixture of proteins and polypeptides, extracted from corn gluten meal and hemp, when mixed with sediment and polystyrene foam pellets (PFP), serves to mobilize tar, which sorbs onto PFP. Since the sorbent floats, coal tar is easily extracted from the agitation vessel. An empirically-derived 4-dimensional surface response model accurately predicts removal rates of the tar and operational costs of the system under various experimental conditions. At optimum relative to cost, 81% of the two to six ring polycyclic aromatic hydrocarbons (PAH) and 73% of the total tar mass are removed despite the high sediment organic carbon content (16.4%) and silty fines (~ 85%). Multiple PFP extractions (n=2) of the same sediment/biosurfactant mixture yielded 94% extraction of PAH. Scanning electron microscope images illustrate free-phase tar (globule) sorption onto the foam. A field pilot was conducted in which 25 kg of sediment was processed. Results were in excellent agreement with both lab (10 g) experiments and model predictions. The process is considered sustainable and green because the active ingredients are derived from renewable crop materials, recycled polystyrene is used, and the biosurfactant is recyclable which reduces water demand and treatment costs, with the recovered tar used as fuel and sediment as beneficial reuse material.
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A new gas chromatography/mass spectrometry (GC/MS) method is proffered for the analysis of polycyclic aromatic hydrocarbons (PAH) and their alkylated homologs in complex samples. Recent work elucidated the fragmentation pathways of alkylated PAH, concluding that multiple fragmentation patterns per homolog (MFPPH) are needed to correctly identify all isomers. Programming the MS in selected ion monitoring (SIM) mode to detect homolog-specific MFPPH ions delivers the selectivity and sensitivity… Show more

A new gas chromatography/mass spectrometry (GC/MS) method is proffered for the analysis of polycyclic aromatic hydrocarbons (PAH) and their alkylated homologs in complex samples. Recent work elucidated the fragmentation pathways of alkylated PAH, concluding that multiple fragmentation patterns per homolog (MFPPH) are needed to correctly identify all isomers. Programming the MS in selected ion monitoring (SIM) mode to detect homolog-specific MFPPH ions delivers the selectivity and sensitivity that the conventional SIM and/or full scan mass spectrometry methods fail to provide. New spectral deconvolution software eliminates the practice of assigning alkylated homolog peaks via pattern recognition within laboratory-defined retention windows. Findings show that differences in concentration by SIM/molecular ion detection of C1-C4 PAH, now the standard, yield concentration differences compared to SIM/MFPPH of thousands of percent for some homologs. The SIM/MFPPH methodology is also amenable to the analysis of polycyclic aromatic sulfur heterocycles (PASH) and their alkylated homologs, since many PASH have the same m/z ions as those of PAH and, thus, are false positives in SIM/1-ion PAH detection methods. Show less

The accurate measurement of polycyclic aromatic hydrocarbons (PAH), polycyclic aromatic
sulfur heterocycles (PASH), and their alkylated homologues is essential at all levels of risk
assessment and remedial decision-making. In the field of environmental forensics, diagnostic
ratios of these compounds are used to delineate fossil fuel-based sources from one another
and to assess the degree of weathering occurring on-site. Fresh and weathered coal tar and
crude oil samples from… Show more

The accurate measurement of polycyclic aromatic hydrocarbons (PAH), polycyclic aromatic
sulfur heterocycles (PASH), and their alkylated homologues is essential at all levels of risk
assessment and remedial decision-making. In the field of environmental forensics, diagnostic
ratios of these compounds are used to delineate fossil fuel-based sources from one another
and to assess the degree of weathering occurring on-site. Fresh and weathered coal tar and
crude oil samples from different locations were analysed by gas chromatography/mass
spectrometry. The same files were analysed by selected ion extraction of one-ion and two-
ion signals from full-scan data and compared to a new data analysis method using spectral
information from homologous isomers. Findings showed that using too few ions produced
false positives and concentrations much higher than those found using the homologous
isomer spectral method, which adversely affected the corresponding diagnostic ratios used
by forensic scientists. Show less

Polycyclic aromatic sulfur heterocycles (PASH) are sulfur analogues of polycyclic aromatic hydrocarbons (PAH). Alkylated PAH attract much attention as carcinogens, mutagens, and as diagnostics for environmental forensics. PASH, in contrast, are mostly ignored in the same studies due to the conspicuous absence of gas chromatography/mass spectrometry (GC/MS) retention times and fragmentation patterns. To obtain these data, eight coal tar and crude oils were analyzed by automated sequential GC-GC.… Show more

Polycyclic aromatic sulfur heterocycles (PASH) are sulfur analogues of polycyclic aromatic hydrocarbons (PAH). Alkylated PAH attract much attention as carcinogens, mutagens, and as diagnostics for environmental forensics. PASH, in contrast, are mostly ignored in the same studies due to the conspicuous absence of gas chromatography/mass spectrometry (GC/MS) retention times and fragmentation patterns. To obtain these data, eight coal tar and crude oils were analyzed by automated sequential GC-GC. Sample components separated based on their interactions with two different stationary phases. Newly developed algorithms deconvolved combinatorially selected ions to identify and quantify PASH in these samples. Simultaneous detection by MS and pulsed flame photometric detectors (PFPD) provided additional selectivity to differentiate PASH from PAH when coelution occurred. A comprehensive library of spectra and retention indices is reported for the C(1)-C(4) two-, three-, and four-ring PASH. Results demonstrate the importance of using multiple fragmentation patterns per homologue (MFPPH) compared to selected ion monitoring (SIM) or extraction (SIE) to identify isomers. Since SIM/SIE analyses dramatically overestimate homologue concentrations, MFPPH should be used to correctly quantify PASH for bioavailability, weathering, and liability studies. Show less