Sulfur Chemiluminescence Detector Research Articles

Comparison of Techniques for the Quantitation of Reductive Aroma Compounds in White Wine: Links to Sensory Analysis and Cu Fractions.

Multiple analytical methodologies allow quantitation of H2S and methanethiol (MeSH) in wine, but confirmation that the determined concentrations are related to perceived off-aromas, or "reductive" faults, is yet to be provided. Fifty white wines underwent sensory evaluation and measurement of free and salt-treated H2S and MeSH concentrations by gas chromatography with sulfur chemiluminescence detection and/or gas detection tubes. The determined concentrations were compared across techniques and different analysis laboratories. Sulfhydryl off-odors in the wines were best described by boiled and rotten egg and natural gas/sewerage/durian aroma attributes. The wines with the highest ratings for both aromas had high concentrations of free H2S, free MeSH, and/or salt-treated MeSH but were unrelated to salt-treated H2S. The free sulfhydryl concentrations and their associated aromas appeared to be suppressed by specific Cu fractions in the wines. This study provides evidence of the relevant measures of reductive aroma compounds and their relation to off-odors and Cu fractions.

Analysis and characterization of sulfane sulfur

In the late 1970s, sulfane sulfur was defined as sulfur atoms covalently bound only to sulfur atoms. However, this definition was not generally accepted, as it was slightly vague and difficult to comprehend. Thus, in the early 1990s, it was defined as “bound sulfur,” which easily converts to hydrogen sulfide upon reduction with a thiol-reducing agent.H2S-related bound sulfur species include persulfides (R–SSH), polysulfides (H2Sn, n ≥ 2 or R–S(S)nS–R, n ≥ 1), and protein-bound elemental sulfur (S0). Many of the biological effects currently associated with H2S may be attributed to persulfides and polysulfides. In the 20th century, quantitative determination of “sulfane sulfur” was conventionally performed using a reaction called cyanolysis. Several methods have been developed over the past 30 years. Current methods used for the detection of H2S and polysulfides include colorimetric assays for methylene blue formation, sulfide ion-selective or polarographic electrodes, gas chromatography with flame photometric or sulfur chemiluminescence detection, high-performance liquid chromatography analysis with fluorescent derivatization of sulfides, liquid chromatography with tandem mass spectrometry, the biotin switch technique, and the use of sulfide or polysulfide-sensitive fluorescent probes. In this review, we discuss the methods reported to date for measuring sulfane sulfur and the results obtained using these methods.

Characterization of balsam sulfide via pyrolysis-gas chromatography-mass spectrometry/sulfur chemiluminescence detection and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

Balsam sulfide, produced by the reaction of turpentine/rosin and sulfur, has been used as one of the raw materials of liquid gold to decorate ceramics and tableware with thin gold film for more than 100years. The characterization of balsam sulfide is still insufficient because of its compositional complexity. In this study, balsam sulfide was characterized using pyrolysis-gas chromatography (Py-GC)-mass spectrometry (MS) and Py-GC with sulfur chemiluminescence detection (SCD) as well as matrix-assisted laser desorption/ionization time-of-flight MS (MALDI-TOFMS). Py-GC-MS/SCD analyses of balsam sulfide and its model samples revealed that the low molecular weight reaction products were mainly composed of compounds of one α-pinene unit reacted with 1-3 sulfur atoms. In the analysis of the high molecular weight components by MALDI-TOFMS, the products of two or three α-pinene units crosslinked by sulfur atoms were observed. It was found that dehydrogenation reaction proceeded gradually with the increase in the reaction time.

Unraveling the complexity of pyrolysates from residual fuels by Py-GCxGC-FID/SCD/TOF-MS with an innovative data processing method

Residual fuels, often called ’bottom-of-the-barrel’ are expected to play an important role in the transition towards a purely renewable energy market. Processes are required to upgrade such fuels and convert them into energy more cleanly and sustainably. To this goal, researchers aim to improve the understanding of their structure and reactivity. Given their complex nature and different chemical compositions, comprehensive two-dimensional gas chromatography (GCxGC) is well suited to provide a detailed characterization of the volatiles released during the pyrolysis of the residual fuels. This study reports a detailed characterization of pyrolysates released during the pyrolysis of two oil samples analyzed using a Py-GCxGC-FID/SCD/TOF-MS. The mass spectra generated with the electron impact ionization TOF-MS detection were used for species identification. An algorithm was developed and described here for the screening and post-processing of the detected peaks. Following algorithm post-processing, the species identification confirms that this workflow is suitable for unraveling the complex nature of the complex mixture released during the pyrolysis of the oil samples. The algorithm results were verified using information from a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD), and the extraction of fragmentation patterns based on the literature. The chemical structure of pyrolysis products is described and classified into 26 molecular classes. The methodology presented in this work can be extended to other complex mixtures, such as bio-oils, plastics, and biomasses.

Molecular characterization of non-polar sulfur compounds in the full boiling range crude oil fractions

Organic sulfur compounds (OSCs) are usually the most abundant heteroatomic compounds in crude oils and have very complex molecular composition. Thousands of sulfur-containing compounds have been identified from various petroleum fractions by different techniques. However, complete characterization of sulfur compounds in specific crude oils is rarely reported. In this study, molecular characterization of sulfur compounds in a whole crude oil was carried out with gas chromatographic and mass spectrometric techniques. The crude oil was separated into naphtha (<180 °C), middle distillate (180–350 °C), and the residual (>350 °C) by distillation. The naphtha was directly analyzed by gas chromatography coupled with a sulfur chemiluminescence detector. A methylation/demethylation method was carried out to separate aromatic sulfur compounds (ASCs) and sulfidic sulfur compounds (SSCs) from the middle distillate and the residue. The separated ASCs and SSCs were characterized by GC and mass spectrometry, as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). A global distribution of OSCs in the crude oil was obtained by the combination of the analysis results. The type and content of OSCs are significantly different among the distillation fractions. Hydrogen sulfide and mercaptans, accounting for 0.1 % and 1.2 % of the total sulfur content, respectively, mainly distribute in naphtha. SSCs, which are rich in thiadiamondoids, account for 15.5 % of the total sulfur content. ASCs are the most abundant identified species and account for 35.8 % of total sulfur content. Other OSCs such as complex polyheteroatomic compounds occupied 41.0 % of the total sulfur content.

Analysis of sulfur compounds for crude oil fingerprinting using gas chromatography with sulfur chemiluminescence detector

Oil spills are a severe problem worldwide due to the resulting damage to marine and coastal ecosystems and to local economies. Identification of the source of spilled oils can be challenging, especially if the oils have undergone severe weathering. Due to their high durability, biomarker compounds (e.g. hopanes, steranes) are widely used for oil fingerprinting. Some sulfur-containing heterocyclic compounds e.g. alkylated dibenzothiophenes are also considered to be highly resistant. In this study, the use of Gas Chromatography with Sulfur Chemiluminescence Detection was investigated as a means of oil fingerprinting using the distribution the sulfur compounds in five different fresh and weathered crude oils. Chemometric analysis was also performed. The results indicate that the sulfur compounds distribution is unique for each crude oil. The distributions of the heavy sulfur compounds (i.e., C2DBTs and C3DBTs) are unchanged after weathering. Therefore, the GC-SCD technique can be considered to support the oil spill identification.

Accurate quantification of ultra-trace sulfur compounds in hydrogen by integrating fill-less trap pre-concentration with gas chromatograph and sulfur chemiluminescence detector

Accurate quantification of ultra-trace impurities in hydrogen, e.g., <0.004 μmol·mol−1 for total sulfur compounds as specified in ISO 14687-2019, is of paramount importance to ensure the quality of hydrogen for fuel cell vehicles. Here, we developed a novel fill-less trap pre-concentration inlet system integrated with GC-SCD for measuring ultra-trace sulfides in hydrogen. This analytical system can achieve an optimum method detection limit range of 0.002–0.004 nmol mol−1 (ppb(v)) for sulfides by trapping 400 mL hydrogen sample. The modified fill-less trap inlet system can avoid the deviation of desorption efficiency from adsorbents and shows a wide linearity range of up to 150 ppb(v) in 400 mL that is one order of magnitude higher than existing packing pre-concentration. Response sensitivity biases from the calibration pattern of constant volumes exhibit better sensitivity with deviation of up to ∼10% smaller than constant concentrations at 0.1–10.0 ppb(v). The stability of sulfides in hydrogen at 0.1–4.0 ppb(v) stored in Silonite™ canisters are firstly investigated. Poor stability is observed for H2S and EtSH of which each about 30% loss after 3 days storage, indicating that the hydrogen sample stored in Silonite™ containers should be analyzed within 4 days. Therefore, the developed analytical system with appropriate calibration pattern is well suitable for the accurate quantification of trace sulfides in hydrogen sampling from refueling station and production processing.

Suppression of reductive characters in white wine by Cu fractions: Efficiency and duration of protection during bottle aging

Cu in wine can suppress sulfidic-odours, but the active forms and duration of protection are uncertain. Additions of 0, 0.3 or 0.6 mg/L Cu(II) were made to Chardonnay and Pinot Grigio at bottling. Throughout a 12- or 14-month storage period, Cu fractions were determined by colorimetry, and sulfhydryl compounds by gas chromatography with sulfur chemiluminescence detection. After Cu(II) addition, the dominant Cu fractions were associated with Cu(II)-organic acids (fraction I) and Cu(I)-thiol complexes (fraction II), and over 8-months their concentrations gradually fell below 0.015 mg/L. During this time, a fraction of Cu, predominantly attributed to sulfide-bound Cu, increased in concentration. Suppression of free hydrogen sulfide was assured when the combined Cu fractions I and II concentrations were above 0.015 mg/L, while free methanethiol suppression required Cu fraction I concentration above 0.035 mg/L. Decay rates for Cu fractions demonstrated that the duration that Cu can actively suppress sulfidic odours is wine-dependent.

Identification of volatile sulfur odorants emitted from ageing wastewater biosolids

Volatile sulfur compounds (VSCs) are important sources of unpleasant odours in biosolid emissions. However, the study of VSCs may be limited by complications in their gas phase measurements due to reactivity, transformations and varying reported odour detection thresholds. A range of methods were used to quantitatively analyse VSCs in wastewater biosolid emissions. VSCs were identified in aged biosolid emissions by gas chromatography (GC) with a sulfur chemiluminescence detector (SCD) and mass spectrometry coupled with olfactory detection port (MS/O). In total, 10 VSC's were identified with two volatile organic sulfur compounds (VOSCs), allyl methyl sulfide and methyl propyl sulfide being reported for the first time in biosolid emissions. The emission patterns of different VSCs varied as the biosolids aged. Initially, the median concentrations of H2S, dimethyl sulfide (DMS), dimethyl trisulfide (DMTS), methanethiol (MeSH) and ethanethiol (EtSH) were orders of magnitude greater than their reported odour detection threshold, suggesting they would contribute to the odorous impact of the biosolids. The maximum H2S value was equal to 59.9 × 103 μg/m3 and was at least one magnitude higher compared to VOSCs, such as dimethyl disulfide (DMDS) (3.8×103 μg/m3), DMS (4.53 × 103 μg/m3), EtSH (2.83 × 103 μg/m3) and MeSH (3.25 × 103 μg/m3). Among the identified VSCs, H2S was the prominent odorant in terms of the magnitude and the frequency of detection, both initially as well as throughout storage. However, DMTS should be considered as a high priority or key odorant due to its odour activity value (OAV) and frequency of detection (sensorially detected in more than 75% of samples, with an OAVs higher than 1).

Detailed characterization of sulfur compounds in fast pyrolysis bio-oils using GC × GC-SCD and GC–MS

Only trace amounts of sulfur (tens to thousands of ppm) are present in bio-oils produced from fast pyrolysis of lignocellulosic biomass. However, even such small amounts of sulfur-containing compounds can act as catalytic poisons during bio-oil upgrading. To improve the knowledge of sulfur speciation in bio-oils for process design and development, e.g. by hydrotreatment, comprehensive two-dimensional gas chromatography (GC ×GC) coupled with selective sulfur chemiluminescence detector (SCD) and headspace gas chromatography coupled to a quadrupole mass spectrometry (GC–MS) were combined. This allowed to quantify sulfur-containing compounds present in crude bio-oils produced from different types of biomass (beech wood, miscanthus, and straw) and straw bio-oil after hydrotreatment. Hydrogen sulfide, methanethiol, dimethyl disulfide, and several thiophenes were identified and quantified as the most abundant sulfur compounds. The detailed analysis of the hydrotreated bio-oil prepared at 360 °C and 8 MPa showed that most GC-detectable sulfur was related to hydrogen sulfide not sufficiently removed in the product separator. Used analytical methods brought an unprecedented level of details about bio-oil sulfur speciation and acquired data can help to drive further R&D in bio-oil upgrading.

Identification of volatile sulfur-containing compounds and the precursor of dimethyl sulfide in cold-pressed rapeseed oil by GC–SCD and UPLC–MS/MS

Volatile sulfur-containing compounds (VSCs) provide an important contribution to foods due to their special odors. In this study, VSCs in 21 cold-pressed rapeseed oils (CROs) from 9 regions in China were extracted and separated by headspace solid-phase microextraction combined with gas chromatography coupled with sulfur chemiluminescence detection. 19 VSCs were identified by authentic standards, and the total concentration of VSCs in all CROs ranged from 49.0 to 18129 μg/kg. Dimethyl sulfide (DMS), with its high odor activity value (7–14574), was the most significant aroma contributor to the CROs. Furthermore, S-methylmethionine (SMM) in rapeseed was first affirmed by ultra-performance liquid chromatography–tandem mass spectrometry and isotope quantitation. The positive correlation coefficient between DMS and SMM was 0.793 (p < 0.05), which confirmed SMM as a crucial precursor of DMS in CROs. This study provided a theoretical basis for selecting rapeseed materials by the distribution of essential VSCs and the source of DMS.

Detailed Group-Type Characterization of Plastic-Waste Pyrolysis Oils: By Comprehensive Two-Dimensional Gas Chromatography Including Linear, Branched, and Di-Olefins

Plastic-waste pyrolysis oils contain large amounts of linear, branched, and di-olefinic compounds. This makes it not obvious to determine the detailed group-type composition in particular to the presence of substantial amounts of N-, S-, and O-containing heteroatomic compounds. The thorough evaluation of different column combinations for two-dimensional gas chromatography (GC × GC), i.e., non-polar × polar and polar × non-polar, revealed that the second combination had the best performance, as indicated by the bi-dimensional resolution of the selected key compounds. By coupling the GC × GC to multiple detectors, such as the flame ionization detector (FID), a sulfur chemiluminescence detector (SCD), a nitrogen chemiluminescence detector (NCD), and a mass spectrometer (MS), the identification and quantification were possible of hydrocarbon, oxygen-, sulfur-, and nitrogen-containing compounds in both naphtha (C5–C11) and diesel fractions (C7–C23) originating from plastic-waste pyrolysis oils. Group-type quantification showed that large amounts of α-olefins (36.39 wt%, 35.08 wt%), iso-olefins (8.77 wt%, 9.06 wt%), and diolefins (4.21 wt%, 4.20 wt%) were present. Furthermore, oxygen-containing compounds (alcohols, ketones, and ethers) could be distinguished from abundant hydrocarbon matrix, by employing Stabilwax as the first column and Rxi-5ms as the second column. Ppm levels of sulfides, thiophenes, and pyridines could also be quantified by the use of selective SCD and NCD detectors.

Effects of iron catalyst and atmosphere on sulfur transformation during pressurized low-temperature pyrolysis of Baishihu coal

A vitrinite-rich low rank coal, Baishihu (BSH) coal with moderate sulfur content was treated by dehydration and crushing. The treated samples were pyrolyzed in an alloy tubular reactor under 2 MPa. Influence of iron catalyst and atmosphere on sulfur transformation during pressurized low-temperature coal pyrolysis was investigated. Molecular composition of sulfur compounds in tar was characterized by gas chromatography with sulfur chemiluminescence detector (GC-SCD) combined with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Sulfur K-edge XANES was used to study sulfur molecular structure after pyrolysis. Sulfur compounds in BSH coal are predominantly S1 class species in branch chain of the coal. Elemental sulfur in catalyst enters the tar and forms mercaptan or thioether compounds during pyrolysis. Iron catalyst promotes activation of hydrogen atoms in coal and contributes to hydrogenation saturation and cracking of aromatic sulfide in tar. The catalyst preferentially captures H2S to increase content of pyrite in char and inhibits formation of sulfate. Under H2 atmosphere, significant decrease of thiophene compounds is observed with catalyst coupled with decrease of sulfoxide compounds.

Methanethiol, dimethyl sulfide and acetone over biologically productive waters in the southwest Pacific Ocean

Abstract. Atmospheric methanethiol (MeSHa), dimethyl sulfide (DMSa) and acetone (acetonea) were measured over biologically productive frontal waters in the remote southwest Pacific Ocean in summertime 2012 during the Surface Ocean Aerosol Production (SOAP) voyage. MeSHa mixing ratios varied from below the detection limit (&lt; 10 ppt) up to 65 ppt and were 3 %–36 % of parallel DMSa mixing ratios. MeSHa and DMSa were correlated over the voyage (R2=0.3, slope = 0.07) with a stronger correlation over a coccolithophore-dominated phytoplankton bloom (R2=0.5, slope 0.13). The diurnal cycle for MeSHa shows similar behaviour to DMSa with mixing ratios varying by a factor of ∼ 2 according to time of day with the minimum levels of both MeSHa and DMSa occurring at around 16:00 LT (local time, all times in this paper are in local time). A positive flux of MeSH out of the ocean was calculated for three different nights and ranged from 3.5 to 5.8 µmol m−2 d−1, corresponding to 14 %–24 % of the DMS flux (MeSH ∕ (MeSH + DMS)). Spearman rank correlations with ocean biogeochemical parameters showed a moderate-to-strong positive, highly significant relationship between both MeSHa and DMSa with seawater DMS (DMSsw) and a moderate correlation with total dimethylsulfoniopropionate (total DMSP). A positive correlation of acetonea with water temperature and negative correlation with nutrient concentrations are consistent with reports of acetone production in warmer subtropical waters. Positive correlations of acetonea with cryptophyte and eukaryotic phytoplankton numbers, and high-molecular-weight sugars and chromophoric dissolved organic matter (CDOM), suggest an organic source. This work points to a significant ocean source of MeSH, highlighting the need for further studies into the distribution and fate of MeSH, and it suggests links between atmospheric acetone levels and biogeochemistry over the mid-latitude ocean. In addition, an intercalibration of DMSa at ambient levels using three independently calibrated instruments showed ∼ 15 %–25 % higher mixing ratios from an atmospheric pressure ionisation chemical ionisation mass spectrometer (mesoCIMS) compared to a gas chromatograph with a sulfur chemiluminescence detector (GC-SCD) and proton transfer reaction mass spectrometer (PTR-MS). Some differences were attributed to the DMSa gradient above the sea surface and differing approaches of integrated versus discrete measurements. Remaining discrepancies were likely due to different calibration scales, suggesting that further investigation of the stability and/or absolute calibration of DMS standards used at sea is warranted.

Determination of Molecular and “Truly” Free Sulfur Dioxide in Wine: A Comparison of Headspace and Conventional Methods

Conventional methods such as Ripper titration and aeration-oxidation (A-O) are widely used for the analysis of sulfur dioxide (SO2) in wine. However, the free SO2 reported by these procedures is overestimated due to dissociation of weakly bound SO2 forms during the analysis, particularly from anthocyanin-bisulfite complexes. “Truly” free SO2 in wine can be determined from the headspace SO2 concentration of an equilibrated wine sample. A headspace SO2 method based on gas detection tubes (HS-GDT) was recently described but is not readily automated. While solid phase microextraction (SPME) yielded poor precision in our experiments, our new method, based on static headspace gas chromatography and sulfur chemiluminescence detection (HS-GC-SCD), is readily automated and achieves high precision (

Trapping and preconcentration of volatile organic sulfur compounds in water samples by portable and battery-powered trapping device prior to gas chromatography-sulfur chemiluminescence determination

A simple, portable and battery-powered trapping device (iTrap) consisting of a purification tube, a trapping unit and a miniature air pump was developed for the pre-concentration of volatile organic sulfur compounds (VOSCs). The tested VOSCs, including methanthiol (MT), ethanethiol (ET), dimethyl sulfide (DMS), diethyl sulfide (DES) and dimethyl disulfide (DMDS), were firstly purged from water samples and then in situ pre-concentrated with the iTrap prior to their analysis by thermal desorption gas chromatography coupling with a sulfur chemiluminescence detector (TD-GC-SCD). Twenty-six adsorbents were studied to find the most suitable adsorbent for the efficient pre-concentration of VOSCs. Under optimal conditions, limits of detection of 6, 8, 6, 2 and 3 ng L−1 were obtained for MT, ET, DMS, DES and DMDS, respectively. The precisions were better than 5.3% (relative standard deviations, RSDs). The iTrap was successfully applied for the analysis of VOSCs in Certified Reference Materials, several surface water, underground water and wastewater samples collected from Pengzhou city, Sichuan, China. Moreover, the VOSCs trapped in the iTrap were much more stable than those directly stored in water samples and the recoveries for all samples could be maintained at acceptable levels (>73%), even their preservation time as long as 8 h.

Online Measurement of Sub-ppmv Total Sulfur in Biogas by Chemiluminescence

In order to safely use biogas in applications which are highly sulfur-sensitive, such as fuel cells or catalytic methanation processes, methods for accurate online measurement of total sulfur at sub-ppmv concentrations must be developed and validated. A method based on a sulfur chemiluminescence detector (SCD) is presented here for this purpose. Biogas-specific variations in gas composition were investigated for their effect on the technique. While the technique was neither affected by the use of different sulfur compounds nor by the existence of aromatic compounds (terpenes) in the biogas, it was found to be sensitive to the variable CH4 content in the bulk gas as well as to variable gas humidity levels. These effects were reduced or eliminated by optimizing the combustion parameters in the SCD for the variable CH4 effect and by using sulfur–inert materials to pretreat the biogas for removal of moisture. The effect of siloxanes on SCD measurements was discussed. After optimization of the operational parameters, a detection limit of 0.02 ppmv (20 ppbv) was achieved with no sample preconcentration in a gas matrix containing 60 v % CH4 and 40 v % CO2. Finally, the method was validated by demonstrating it in field operation on a slipstream of biogas produced from an industrial anaerobic digester processing biowaste.

Characterization of key aroma-active sulfur-containing compounds in Chinese Laobaigan Baijiu by gas chromatography-olfactometry and comprehensive two-dimensional gas chromatography coupled with sulfur chemiluminescence detection

Volatile sulfur-containing compounds (VSCs) often exist at extremely low concentrations, making them difficult to be determined. The VSCs in Laobaigan (LBG) Baijiu were analyzed by headspace solid-phase microextraction (HS–SPME) coupled with GC × GC–SCD, by which 12 VSCs were identified. Among the 65 odor-active compounds that were determined by GC–O with the aid of aroma extract dilution analysis (AEDA), benzenemethanethiol and 2-methyl-3-furanthiol were found to possess the highest FD values of 6561. The limits of detection (LODs) of the identified VSCs determined by GC × GC–SCD were found to be extremely low at 0.05–1.53 ng/L, with their analytical recoveries from 85% to 116%. The VSCs in the LBG samples were determined in a range of concentrations from 0.77 ± 0.02 µg/L to 60.04 ± 2.32 µg/L. Benzenemethanethiol, dimethyl trisulfide, 2-methyl-3-furanthiol and 2-furfurylthiol exhibited odor activity values (OAVs) > 100 and significantly contributed to the overall aroma of LBG Baijiu.

Compositional Analysis of Heteroatom Compounds in Huadian Shale Oil Using Various Analytical Techniques

Various analytical techniques were used to study the molecular composition and structure of heteroatom compounds in Huadian (HD) shale oil. On the basis of the results obtained from gas chromatography–nitrogen chemiluminescence detection and gas chromatography–sulfur chemiluminescence detection, the composition of nitrogen- and sulfur-containing compounds was estimated. Molecular composition and structural information of heteroatom compounds were characterized on the basis of their type (double-bond equivalence (DBE)), class (number of oxygen, nitrogen, and sulfur heteroatoms), and carbon number distribution using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). In the positive-ion ESI FT-ICR MS mode, a total of 14 different basic species were detected for basic nitrogen compounds. N1 class compounds dominated followed by N1O1 and N2 class compounds. The DBE value of N1OX compounds having high relative abundance values increased with the increase in the ...

Selective determination of semi-volatile thiophene compounds in water by molecularly imprinted polymer thin films with direct headspace gas chromatography sulfur chemiluminescence detection.

Water-compatible molecularly imprinted polymer (MIP) thin films are coupled with headspace gas chromatography sulfur chemiluminescence detection (HS-GC-SCD) to create a new approach for the determination of trace concentrations of thiophene compounds in water samples. Thiophene compounds are persistent, typically petrogenic, organic pollutants of concern due to their potential for biomagnification and bioaccumulation, mutagenicity, and carcinogenicity in terrestrial and aquatic fauna. Identification and quantitation in water, particularly following oil spills, is a priority. Following adsorption of the thiophenes to the MIPs, the MIP-bound analytes are analyzed directly by HS-GC-SCD, with minimal sample manipulation and virtually no organic solvent. Calibration curves of spiked seawater were linear from 5 μg L-1 to 100 μg L-1 and limits of detection (LOD) were in the range of 0.24-0.82 μg L-1. Low matrix effects were observed in the analysis of thiophene compounds in seawater making the method suitable for use in fresh and saline waters without modification. Acceptable reproducibility was obtained for analysis of thiophene compounds from spiked seawater samples at RSDs ≤7.0% (n = 3).