Bio-refinery as the bio-inspired process to bulk chemicals

This paper describes several examples of knowledge-intensive technologies for the production of chemicals from biomass, which take advantage of the biomass structure in a more efficient way than the production of fuels or electricity alone. The depletion in fossil feedstocks, increasing oil prices, and the ecological problems associated with CO(2) emissions are forcing the development of alternative resources for energy, transport fuels, and chemicals, such as the replacement of fossil resources with CO(2) neutral biomass. Allied with this is the conversion of crude oil products utilizes primary products (ethylene, etc.) and their conversion into either materials or (functional) chemicals with the aid of co-reagents such as ammonia, by various process steps to introduce functionalities such as -NH(2) into the simple structures of the primary products. Conversely, many products found in biomass often contain functionalities. Therefore, it is attractive to exploit this in order to by-pass the use, and preparation of, co-reagents as well as to eliminate various process steps by utilizing suitable biomass-based precursors for the production of chemicals.     

Determination of chemical warfare agents and related compounds in environmental samples by solid-phase microextraction with gas chromatography

Solid phase microextraction (SPME) is an increasingly common method of sample isolation and enhancement. SPME is a convenient and simple sample preparation technique for chromatographic analysis and a useful alternative to liquid-liquid extraction and solid phase extraction. SPME is speed and simply method, which has been widely used in environmental analysis because it is a rather safe method when dealing with highly toxic chemicals. A combination of SPME and gas chromatography (GC) permits both the qualitative and quantitative analysis of toxic industrial compounds, pesticides and chemical warfare agents (CWAs), including their degradation products, in air, water and soil samples. This work presents a combination of SPME and GC methods with various types of detectors in the analysis of CWAs and their degradation products in air, water, soil and other matrices. The combination of SPME and GC methods allows for low detection limits depending on the analyte, matrix and detection system. Commercially available fibers have been mainly used to extract CWAs in headspace analysis. However, attempts have been made to introduce new fiber coatings that are characterized by higher selectivities towards different analytes of interest. Environmental decomposition of CWAs leads to the formation of more hydrophilic products. These compounds may be isolated from samples using SPME and analyzed using GC however, they must often be derivatized first to produce good chromatography. In these cases, one must ensure that the SPME method also meets the same needs. Otherwise, it is helpful to use derivatization methods. SPME may also be used with fieldportable mass spectrometry (MS) and GC-MS instruments for chemical defense applications, including field sampling and analysis. SPME fibers can be taken into contaminated areas to directly sample air, headspaces above solutions, soils and water.     

Solid-phase microextraction: a powerful sample preparation tool prior to mass spectrometric analysis

Sample preparation is an essential step in analysis, greatly influencing the reliability and accuracy of resulted the time and cost of analysis. Solid-Phase Microextraction (SPME) is a very simple and efficient, solventless sample preparation method, invented by Pawliszyn in 1989. SPME has been widely used in different fields of analytical chemistry since its first applications to environmental and food analysis and is ideally suited for coupling with mass spectrometry (MS). All steps of the conventional liquid-liquid extraction (LLE) such as extraction, concentration, (derivatization) and transfer to the chromatograph are integrated into one step and one device, considerably simplifying the sample preparation procedure. It uses a fused-silica fibre that is coated on the outside with an appropriate stationary phase. The analytes in the sample are directly extracted to the fibre coating. The SPME technique can be routinely used in combination with gas chromatography, high-performance liquid chromatography and capillary electrophoresis and places no restriction on MS. SPME reduces the time necessary for sample preparation, decreases purchase and disposal costs of solvents and can improve detection limits. The SPME technique is ideally suited for MS applications, combining a simple and efficient sample preparation with versatile and sensitive detection. This review summarizes analytical characteristics and variants of the SPME technique and its applications in combination with MS.     

Passive sampling of airborne furan indoors by solid-phase microextraction

Furan may be formed in food under heat treatment and is highly suspected to appear in indoor air. The possible exposure to indoor furan raises concerns because it has been found to cause carcinogenicity and cytotoxicity in animals. To determine airborne furan, solid-phase microextraction (SPME) technique was utilised as a diffusive sampler. The Carboxen/Polydimethylsiloxane (CAR/PDMS, 75 μm) fibre was used, and the SPME fibre assembly was inserted into a polytetrafluoroethene tubing. Furan of known concentrations was generated in Tedlar gas bags for the evaluation of SPME diffusive samplers. After sampling, the sampler was inserted into the injection port of a gas chromatograph coupled with a mass spectrometer (GC/MS) for thermal desorption and analysis. Validation of the SPME device with active sampling by charcoal tube was performed side by side as well. The charcoal tube was desorbed by acetone before analysis with GC/MS. The experimental sampling constant of the sampler was found equal to (9.93 ± 1.28) × 10^?3 (cm³ min^?1) at 25°C. Furthermore, side-by-side validations between SPME device and charcoal tube showed linear relationship with r = 0.9927. The designed passive sampling device for furan has the advantages of both passive sampling and SPME technique and looks suitable for assessing indoor air quality.     

Time-weighted average water sampling with a diffusion-based solid-phase microextraction device

A new diffusion-based solid-phase microextraction (SPME) time-weighted average (TWA) field water sampling device was developed and investigated by field trial. The sampler is constructed with copper tube and caps and a commercial SPME fiber assembly. The device possesses all advantages of SPME; it is solvent-free, reusable, combines sampling, isolation and enrichment into one step, and the fiber can be directly injected into a gas chromatograph for analysis with a commercial SPME fiber holder, without further treatment. Field trials in Laurel Creek (Waterloo, Ont., Canada) and Hamilton Harbour (Hamilton, Ont., Canada) illustrated that the device is durable, easy to deploy, and the mass uptake of the device is independent of the face velocity. The device provides good precision [relative standard deviations (RSDs) are less than 20%] and the data obtained with this device are quite comparable to those obtained with the spot sampling method, which demonstrates that the newly developed SPME water sampling device is suitable for long-term monitoring of organic pollutants in water.     

Optimization and performance evaluation of the analysis of glyphosate and AMPA in water by HPLC with fluorescence detection

Summary The object of this work was to optimize and validate an analytical method for the analysis of glyphosate and its main metabolite AMPA (aminomethylphosphonic acid) in natural and drinking water, for sanitary control. The method uses a derivatization step which transforms glyphosate and AMPA into fluorescent products by reaction with 9-fluorenylmethylchloroformate (FMOC-Cl). The kinetics and yield of this reaction were studied by use of different samples. The derivatization products were injected directly into the liquid chromatograph and separated on an amino-functionalized silica gel column. The performance of the method (detection limit, quantification limit, linearity, and relative standard deviation) was studied and the results obtained showed the method was suitable for routine analysis of glyphosate and AMPA. An interlaboratory test with five laboratories confirmed that good results were obtained by use of this method.     

Analysis of trace amount of bank dye and lachrymators from exploding bank devices by solid-phase microextraction and gas chromatography-mass spectrometry

Solid-phase microextraction (SPME) is a fast, solvent-free alternative to conventional sample preparation techniques. This technique involves exposing a fused silica fiber that has been coated with a stationary phase to an aqueous solution or its headspace to selectively extract compounds from their matrix. The fiber is then removed, and the analytes are thermally desorbed in the injector of a gas chromatograph. By sampling from the headspace above sample matrices, SPME can be used to extract target analytes from very complex matrices. In this study, SPME in the headspace is used in developing a method for the dye 1-methylaminoanthraquinone (MAAQ) and two lachrymators: orthochlorobenzalmalononitrile (CS) (tear gas) and 2-chloroacetophenone (CN) (tear gas). The focus is to develop a robust method to minimize sample preparation and to reduce matrix interferences encountered by other extraction techniques. In developing the method, several fibers are studied for their affinity for the compounds of interest. Although this method is developed for qualitative analysis, the extraction time and temperature profile are thoroughly investigated to provide the optimal conditions. The use of a salt solution is evaluated to increase the partitioning of MAAQ into the headspace. Using this method, qualitative extraction is achieved for the analysis of CN, CS, and MAAQ from its matrices. CN and CS are extracted in less than 5 min, though MAAQ needed more than 15 min to achieve a reasonable response. If more sensitivity is required, the use of a salt solution increases the response of MAAQ by 90-fold.     

Development of a method based on sorbent trapping followed by solid-phase microextraction for the determination of synthetic musks in indoor air

Synthetic musks are extensively used as fragrance components in a wide range of consumer and personal care products such as detergents, shampoos, perfumes and other cosmetic products. Amongst them, galaxolide and tonalide have become ubiquitous pollutants due to their continuous releasing into the environment. Because of their nature as artificial fragrances, inhalation should be considered as an important exposure pathway, especially in indoor environments. However, up to now very few studies have been carried out to determine these emergent pollutants indoors. In this work, a simple and highly sensitive methodology for the analysis of synthetic musk fragrances in indoor air samples is presented. The proposed methodology combines solid-phase extraction (SPE) and solid-phase microextraction (SPME), followed by gas chromatography-mass spectrometry (GC/MS). To the best of our knowledge, this is the first method based on SPME for the analysis of musks in air. By active sampling, musks present in air were adsorbed onto 25mg Tenax and then transferred to a SPME fiber in the headspace mode (HS). An experimental design strategy was used to optimize main factors potentially affecting the microextraction process such as fiber coating, temperature and the addition of a microvolume of organic solvent to the solid sorbent prior to SPME. Breakthrough of the SPE sorbent was studied from 1 to 10m(3) without significant losses. Recovery studies were performed at two concentration levels (2 and 20ngm(-3)), obtaining quantitative recoveries (>/=85%) by external calibration. A comprehensive study was performed in order to estimate the limits of detection taking into account the contamination risks and laboratory blanks. Values at the sub ngm(-3) level were achieved for all the target compounds sampling 5m(3) air. External calibration, not requiring the complete sampling process, demonstrated to be suitable for the quantification of all musk compounds. Finally, several indoor environments were analyzed using the proposed method.     

Applications of solid-phase microextraction in food analysis

Food analysis is important for the evaluation of the nutritional value and quality of fresh and processed products, and for monitoring food additives and other toxic contaminants. Sample preparation, such as extraction, concentration and isolation of analytes, greatly influences the reliable and accurate analysis of food. Solid-phase microextraction (SPME) is a new sample preparation technique using a fused-silica fiber that is coated on the outside with an appropriate stationary phase. Analyte in the sample is directly extracted to the fiber coating. The SPME technique can be used routinely in combination with gas chromatography (GC), GC–mass spectrometry (GC–MS), high-performance liquid chromatography (HPLC) or LC–MS. Furthermore, another SPME technique known as in-tube SPME has also been developed for combination with LC or LC–MS using an open tubular fused-silica capillary column as an SPME device instead of SPME fiber. These methods using SPME techniques save preparation time, solvent purchase and disposal costs, and can improve the detection limits. This review summarizes the SPME techniques for coupling with various analytical instruments and the applications of these techniques to food analysis.     

Quantitative prediction of biodegradability,metabolite distribution and toxicity of stable metabolites

An evaluation of the capability of organic chemicals to mineralize is an important factor to consider when assessing their fate in the environment. Microbial degradation can convert a toxic chemical into an innocuous one, and vice versa, or alter the toxicity of a chemical. Moreover, primary biodegradation can convert chemicals into stable products that can be difficult to mineralize. In this paper, we present some new results obtained on the basis of a recently developed probabilistic approach to modeling biodegradation based on microbial transformation pathways. The metabolic transformations and their hierarchy were calibrated by making use of the ready biodegradability data from the MITI-I test and expert knowledge for the most probable transformation pathways. A model was developed and integrated into an expert software system named CATABOL that is able to predict the probability of biodegradation of organic chemicals directly from their structure. CATABOL simulates the effects of microbial enzyme systems, generates the most plausible transformation pathways, and quantitatively predicts the persistence and toxicity of the biodegradation products. A subset of 300 organic chemicals were selected from Canada's Domestic Substances List and subjected to CATABOL to compare predicted properties of the parent chemicals with their respective first stable metabolite. The results show that most of the stable metabolites have a lower acute toxicity to fish and a lower bioaccumulation potential compared to the parent chemicals. In contrast, the metabolites appear to be generally more estrogenic than the parent chemicals.     

Solid phase microextraction associated with microwave assisted extraction of food products

Veltol® (2-methyl 3-hydroxy 4-pyrone) and Veltol-Plus® (2-ethyl 3-hydroxy 4-pyrone) are patented flavor ingredients in food products. Only Veltol® can occur naturally, but both Veltol® and Veltol-Plus® are often added to food products. In order to monitor the use of these compounds in food products, lower detection limits were needed. The Solid Phase Microextraction (SPME) technique for beverages and SPME coupled with Microwave Assisted Extraction (MAE) for solid food samples were studied. The influence of the pH, salt content, SPME adsorption time, GC inlet conditions, and the conditioning of the SPME fiber were investigated. Different food products were tested including coffee, beverages, chewing gums and potato chips. The coupled MAE and SPME shows good results for solid food samples. The reproducibility of the technique was less than 13%RSD and the detection limit was 10 ppb for Veltol® and 2 ppb for Veltol-Plus® using the SIM mode in GC/MS. The technique also shows good selectivity for the target compounds investigated in different food samples.     

Analysis of organic compounds in environmental samples by headspace solid phase microextraction

The analysis of samples contaminated by organic compounds is an important aspect of environmental monitoring. Because of the complex nature of these samples, isolating target organic compounds from their matrices is a major challenge. A new isolation technique, solid phase microextraction, or SPME, has recently been developed in our laboratory. This technique combines the extraction and concentration processes into one step; a fused silica fiber coated with a polymer is used to extract analytes and transfer them into a GC injector for thermal desorption and analysis. It is simple, rapid, inexpensive, completely solvent-free, and easily automated. To minimize matrix interferences in environmental samples, SPME can be used to extract analytes from the headspace above the sample. The combination of headspace sampling with SPME separates volatile and semi-volatile analytes from non-volatile compounds, thus greatly reducing the interferences from non-target compounds. This paper reports the use of headspace SPME to isolate volatile organic compounds from various matrices such as water, sand, clay, and sludge. By use of the technique, benzene, toluene, ethyl-benzene, and xylene isomers (commonly known as BTEX), and volatile chlorinated compounds can be efficiently isolated from various matrices with good precision and low limits of detection. This study has found that the sensitivity of the method can be greatly improved by the addition of salt to water samples, water to soil samples, or by heating. Headspace SPME can also be used to sample semi-volatile compounds, such as PAHs, from complex matrices.     

Quantitative prediction of biodegradability,metabolite distribution and toxicity of stable metabolites

An evaluation of the capability of organic chemicals to mineralize is an important factor to consider when assessing their fate in the environment. Microbial degradation can convert a toxic chemical into an innocuous one, and vice versa , or alter the toxicity of a chemical. Moreover, primary biodegradation can convert chemicals into stable products that can be difficult to mineralize. In this paper, we present some new results obtained on the basis of a recently developed probabilistic approach to modeling biodegradation based on microbial transformation pathways. The metabolic transformations and their hierarchy were calibrated by making use of the ready biodegradability data from the MITI-I test and expert knowledge for the most probable transformation pathways. A model was developed and integrated into an expert software system named CATABOL that is able to predict the probability of biodegradation of organic chemicals directly from their structure. CATABOL simulates the effects of microbial enzyme systems, generates the most plausible transformation pathways, and quantitatively predicts the persistence and toxicity of the biodegradation products. A subset of 300 organic chemicals were selected from Canada's Domestic Substances List and subjected to CATABOL to compare predicted properties of the parent chemicals with their respective first stable metabolite. The results show that most of the stable metabolites have a lower acute toxicity to fish and a lower bioaccumulation potential compared to the parent chemicals. In contrast, the metabolites appear to be generally more estrogenic than the parent chemicals.     

Degradation of an ether–alcohol (3-ethoxypropan-1-ol) by photo-Fenton-generated <Superscript>•</Superscript>OH radicals: products analysis and formation pathways; relevance to atmospheric water-phase chemistry

We have chosen 3-ethoxypropan-1-ol (EtOPrOH) as a typical short-carbon-chain ether–alcohol used as industrial solvent and have analyzed the degradation products resulting from its attack by ^•OH radicals generated by the photo-Fenton reaction. The laboratory conditions were representative of those found in tropospheric water droplets. Twelve products have been identified by use of GC–MS analysis, either directly or after extraction by SPME fibers, and by HPLC–UV analysis with a special column for carboxylic acids and after reaction of carbonyl groups with 2,4-dinitrophenylhydrazine. These products contain one to three carbon atoms (instead of five in EtOPrOH), among which one or two are oxidized. According to the reaction pathways proposed, seven products—including methanal—can result from attack by one ^•OH only, three products imply attack by a second ^•OH, as expected from their higher oxidation number, and it is suggested that reaction between two organic radicals is needed for formation of only two products. The relevance of this investigation to the fate of EtOPrOH and similar ether–alcohols in the troposphere is briefly discussed.     

A simple,inexpensive, rapid,sensitive and solventless technique for the analysis of accelerants in fire debris based on SPME

The current method of choice for the extraction of flammable or combustible liquid resides from fire debris samples is passive headspace concentration using activated charcoal strips (ACS) for adsorption of the liquid residues followed by elution with carbon disulfide or other suitable solvent. Presently, we report a new technique based on headspace solid-phase microextraction which has been successfully applied to the identification of a wide range of accelerants commonly seen in arson analysis. The SPME technique developed is simple, inexpensive, rapid, and eliminates the use of the highly flammable and toxic solvent carbon disulfide. Results using this SPME method have been directly compared to results obtained via the ACS technique for light, medium, and heavy petroleum distillates as well as gasoline. All of the accelerants studied were accurately identified by the SPME method with equal or greater sensitivity compared to the ACS method.     

Continuous Synthesis and Purification by Coupling a Multistep Flow Reaction with Centrifugal Partition Chromatography

Continuous‐flow multistep synthesis is combined with quasi‐continuous final‐product purification to produce pure products from crude reaction mixtures. In the nucleophilic aromatic substitution of 2,4‐difluoronitrobenzene with morpholine followed by a heterogeneous catalytic hydrogenation, the desired monosubstituted product can be continuously separated from the co‐ and by‐products in a purity of over 99 % by coupling a flow reactor sequence to a multiple dual‐mode (MDM) centrifugal partition chromatography (CPC) device. This purification technique has many advantages over HPLC, such as higher resolution and no need for column replacement or silica recycling, and it does not suffer from irreversible adsorption.     

Further research on the photo-SPME of triclosan

In this study the photoinduced degradation of triclosan has been investigated by photo-solid-phase microextraction (photo-SPME). In photo-SPME, photodegradation is carried out on the SPME fibre containing the target compound. Triclosan was extracted from aqueous solutions by use of polydimethylsiloxane SPME fibres and these were subsequently exposed to UV irradiation (power 8 W, wavelength 254 nm) for different times (from 2 to 60 min). The photodegradation kinetics of triclosan were investigated, the photoproducts generated were tentatively identified, and the photochemical behaviour of these products was studied by use of this on-fibre approach followed by gas chromatographic–mass spectrometric analysis. Eight photoproducts were tentatively identified, including chlorinated phenols, chlorohydroxydiphenyl ethers, 2,8-dichlorodibenzo-p-dioxin, and a possible dichlorodibenzodioxin isomer or dichlorohydroxydibenzofuran. The main photodegradation mechanisms were postulated and photodegradation pathways proposed. The effect of pH on triclosan degradation and on triclosan-to-dioxin conversion was also investigated. Triclosan degradation occurred, and generation of 2,8-dichlorodibenzo-p-dioxin was confirmed, throughout the pH range studied (from 3 to 9).      

Biocatalysis and Biomass Conversion in Alternative Reaction Media

In this Minireview, the state of the art in the use of ionic liquids (ILs) and deep eutectic solvents (DESs) as alternative reaction media for biocatalytic processes and biomass conversion is presented. Initial, proof‐of‐concept studies, more than a decade ago, involved first‐generation ILs based on dialkylimidazolium cations and non‐coordinating anions, such as tetrafluoroborate and hexafluorophosphate. More recently, emphasis has switched to more environmentally acceptable second‐generation ILs comprising cations, which are designed to be compatible with enzymes and, in many cases are derived from readily available, renewable resources, such as cholinium salts. Protic ionic liquids (PILs), prepared simply by mixing inexpensive amines and acids, are particularly attractive from both an environmental and economic viewpoint. DESs, prepared by mixing inexpensive salts with, preferably renewable, hydrogen‐bond donors such as glycerol and amino acids, have also proved suitable reaction media for biocatalytic conversions. A broad range of enzymes can be used in ILs, PILs and DESs, for example lipases in biodiesel production. These neoteric solvents are of particular interest, however, as reaction media for biocatalytic conversions of substrates that have limited solubility in common organic solvents, such as carbohydrates, nucleosides, steroids and polysaccharides. This has culminated in the recent focus of attention on their use as (co)solvents in the pretreatment and saccharification of lignocellulose as the initial steps in the conversion of second‐generation renewable biomass into biofuels and chemicals. They can similarly be used as reaction media in subsequent conversions of hexoses and pentoses into platform chemicals.     

自制固相微萃取装置对水中5种农药残留量的分析

合成了一种丙烯酸酯聚合物,并将其作为固相微萃取涂层,使用自制的SPME装置和气质联用仪对水样中5种农药残留量进行分析,该装置制作简单、价格低廉.对影响分析灵敏度的各种实验因素进行了优化,在优化条件下分析5种农药标准样品质量浓度在1～1000 μg/L内与色谱峰面积呈良好的线性关系(r=0.995～0.999),检出限为0.391～1.170 ng/L.将自制涂层与商品涂层(PA)进行了比较,自制涂层对5种农药具有优良的吸附特性,较低的检出限.     

Methods for the determination of phenolic brominated flame retardants, and by-products, formulation intermediates and decomposition products of brominated flame retardants in water

Brominated flame retardants (BFRs) are the chemicals of high importance within the REAch framework. In addition to polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA), other BFRs such as bromophenols, intermediates in FR formulation like bromoanilines, and their brominated and non-brominated by-products such as bromoanisoles, bromotoluenes, bromoalkanes and 1,5,9-cyclododecatriene, respectively should be monitored and controlled because of their toxicity and their very low odour and taste thresholds, below sub-nanogram-per liter levels. In the present study several analytical methods for the simultaneous determination, i.e., combining one single sample treatment and one analysis step, of these compounds in water have been developed, optimized and evaluated. The methods involve a (pre-concentration)-extraction technique, such as liquid-liquid (LLE), solid-phase (SPE), headspace (HS) extraction or solid-phase microextraction (SPME), followed by gas chromatography (GC)-mass spectrometry (MS) analysis with either electron capture negative ionization (ECNI) or electron impact (EI) as ionization techniques. ECNI is more sensitive than EI for analytes with more than one bromine atom. HS and SPME were previously optimized by means of a multifactorial experimental design. Extraction temperature and the liquid/headspace volume ratio were the most significant factors in HS extraction. In SPME, the variables studied were the nature of the fiber, the mode of extraction and the extraction temperature. Polydimethylsiloxane (PDMS) fibers appeared to be more suitable than carboxen-polydimethylsiloxane (CAR-PDMS) for the analysis of the target compounds with more than one bromine atom. The extraction of 2,4-dibromoaniline was only achieved in a direct immersion mode, in which the optimal extraction temperature was 60 degrees C. The methods LLE-GC-(ECNI)MS, LLE-GC-(EI)MS, SPE-GC-(ECNI)MS, SPE-GC-(EI)MS, HS-GC-(EI)MS and SPME-GC-(EI)MS were evaluated in terms of linearity, precision, detection limits and trueness. All methods, with the exception of HS-GC-(EI)MS, were linear in a range of at least two orders of magnitude, giving recoveries above 75% and detection limits at the low ng/L level for most of the target analytes. SPE-GC-(ECNI)MS is the most sensitive and reliable method for the determination of most of the bromine compounds, whereas SPE-GC-(EI)MS is the most suitable to quantify the three isomers of 1,5,9-cyclododecatriene. Both methods together with SPME-GC-(EI)MS (for qualitative confirmation) were applied to water samples from the Western Scheldt (The Netherlands), where 2,6-dibromophenol and 2,4,6-tribromoanisole could be detected at levels higher than their respective odour thresholds.