Pulsed Flame Photometric Detector Research Articles

A method to test the detectability of GC/PFPD for an extended concentration range with respect to reduced sulfur compounds

In this study, a possible means to extensively expand the quantifiable range of reduced sulfur compounds (RSC) in air has been investigated by a combined application of GC with pulsed flame photometric detector (PFPD) and a multifunction thermal desorber (TD) system. To comply with the purpose of this study, gaseous RSC standards containing the equimolar concentrations of H(2)S, CH(3)SH, DMS, DMDS, and CS(2 )were prepared at 11 concentration levels (i. e., 10 ppb-10 ppm (over 10(3 )range)). These standards were then used to derive three-point calibrations based on the modified injection through a TD (MITD). If the mean calibration slopes of each concentration level are normalized to that of CH(3)SH, the relative ordering is found as 0.65 (H(2)S): 1 (CH(3)SH): 1.34 (DMS): 2.24 (DMDS). The reproducibility of MITD method, when assessed in terms of relative standard error (RSE) for all calibration slopes, had the most stable pattern for DMDS (5.77%) and the least stable one for H(2)S (12.8%). The sensitivity of the MITD-based calibration generally improved with an increase in concentration levels of standard gas. Based on our study, the MITD technique is useful to extend quantification of GC/PFPD by allowing RSC detection over a 10(3) range.

Determination of Organotins in Aquatic Food by Gas Chromatography with Pulsed Flame Photometric Detection

A method based on gas chromatography (GC)-pulsed flame photometric detection (PFPD) was developed to determine the levels of organotins in aquatic food. After being purified by gel-permeation chromatography in ethyl actate-tetrahydrofuran, the organotin compounds were derivatized by pentylmagnesium bromide. The derivative products were injected into the GC system and detected by PFPD (sulfur mode). The method was validated by analysis of the certified reference material and spiked samples. Recoveries of organotins ranged from 84.1 to 116.6% with relative standard deviation between 1.3 and 16.0% when spiked at levels of 2, 10, and 40 microg/kg. The limits of detection varied from 0.1 to 1.2 microg/kg for shellfish and 0.1 to 0.5 microg/kg for fish. The proposed method was suitable for determining organotins in aquatic foods.

The fundamental properties of the direct injection method in the analysis of gaseous reduced sulfur by gas chromatography with a pulsed flame photometric detector

In this study, the fundamental aspects of gas chromatography with a pulsed flame photometric detector were investigated through the calibration of gaseous reduced sulfur compounds based on the direct injection method. Gaseous standards of five reduced sulfur compounds (hydrogen sulfide, methane thiol, dimethyl sulfide, carbon disulfide, and dimethyl disulfide) were calibrated as a function of injection volume and concentration level. The results were evaluated by means of two contrasting calibration approaches: fixed standard concentration method (variable volumetric injection of standard gases prepared at a given concentration) and fixed standard volume method (injection of multiple standards with varying concentrations at a given volume). The optimum detection limit values of reduced sulfur compounds, when estimated at 100 μL of injection volume, ranged from 2.37 pg (carbon disulfide) to 4.89 pg (dimethyl sulfide). Although these detection limit values improved gradually with decreasing injection volume, the minimum detectable concentration (e.g., in nmol mol −1 scale) remained constant due to a balance by the sample volume reduction. The linearity property of pulsed flame photometric detector also appeared to vary dynamically with changes in its sensitivity. According to this study, the performance of pulsed flame photometric detector, when tested by direct injection method, is highly reliable to precisely describe the behavior of reduced sulfur compounds above ∼20 nmol mol −1.

Comprehensive study of the parameters influencing the detection of organotin compounds by a pulsed flame photometric detector in sewage sludge

An investigation of the operating conditions of a pulsed flame photometric detection (PFPD) system for the determination of organotin compounds (OTCs) in sewage sludge is reported. During the analyses, some spectral interferences were observed. For their elimination detector parameters such as gate delay and gate width were investigated. In addition, the applicability of three different internal standards was evaluated. Under optimised analytical conditions (gate delay 3 ms, gate width 2 ms, tripropyltin as internal standard) limits of detection (LOD) were determined. The LOD for butyltins ranged between 8 and 16 ng Sn g −1, for phenyltins around 8 ng Sn g −1 and for octyltins between 5 and 10 ng Sn g −1. Since there is no certified reference material (CRM) available for sewage sludge, the accuracy of the analytical procedure was checked by the analysis of CRM PACS-2 (marine sediment) and a spiked sludge sample. Good agreement between determined and certified values was obtained. Sewage sludge from a local wastewater treatment plant was analysed and the results compared with data from the literature.

Evaluation of a combined fractionation and speciation approach for study of size-based distribution of organotin species on environmental colloids

Results relating to the first original application of an analytical approach combining asymmetric flow field-flow fractionation (As-Fl-FFF) with multi-detection and chemical speciation for determination of organotins in a landfill leachate sample are presented. The speciation analysis involved off-line head-space solid-phase microextraction (HS-SPME)-gas chromatography with pulsed-flame photometric detection (GC-PFPD) performed after three consecutive collections of five different fractions of interest from the As-Fl-FFF system and cross-flow part (assumed to be representative of the <10 kDa phase). After 0.45 microm filtration and without preconcentration before fractionation and speciation analysis, limits of detection (LOD) were 4-45 ng (Sn) L(-1) in the sample, with relative standard deviations (RSD) of 3-23%. The As-Fl-FFF fractionation of this sample enables characterization of two distinct populations-organic-rich and inorganic colloids with gyration radius up to 120 nm. Total Sn and mono and dibutyltins (MBT and DBT) appear to be distributed over the whole colloidal phase. Tributyl, monomethyl, monooctyl, and diphenyltins (TBT, MMT, MOcT, and DPhT) were also detected. Quantitative speciation analysis performed on the two colloidal populations and in the <10 kDa phase revealed concentrations from 130 +/- 10 (MMT) to 560 +/- 50 ng (Sn) L(-1) (DPhT).

Butyltin speciation in sediments from Todos os Santos Bay (Bahia, Brazil) by GC-PFPD

Butyltin compounds were investigated in surface sediments from 17 stations in Todos os Santos Bay. Analytical conditions for organotin determination in marine sediments were optimized for GC with pulsed flame photometric detection. Detection limits were: 5.4 µg kg-1 for TBT; 0.2 µg kg-1 for DBT; and 2.1 µg kg-1 for MBT, using a 610-nm filter. In general, TBT concentrations were low and in the range of <DL to 15.9 µg kg-1. Only in one of the investigated stations DBT and MBT were above detection limit despite the oxic to slightly anoxic conditions in the sediments. The presence of paint particles in the sediments and degradation in the water column during resuspension events followed by removal of the more soluble DBT and MBT may explain these observations.

Organotin speciation in French brandies and wines by solid-phase microextraction and gas chromatography—Pulsed flame photometric detection

An analytical method devoted to organotin compounds (OTC) determination in brandy and wine was developed. It is based on solid-phase microextraction (SPME) of ethylated organotins. The following operating factors were examined: SPME mode/nature of fibre coating, sample volume/dilution, and sampling time. The optimisation work led to dilute the sample in an aqueous buffer (1/11, v/v ratio) in order to satisfactorily decrease the matrix effects due to competitive sorption of non-OTC species onto/into fibre coating. The optimised operating conditions consist of polydimethylsiloxane (PDMS) coated fibre used in headspace mode for 30 min. In wines, the limits of detection (LOD) and quantification (LOQ) ranged from 1 to 40 and 3 to 80 ng(Sn) L −1 respectively, according to the species. The analytical validation was made by evaluating the accuracy of OTC determination in spiked samples with various concentrations over the whole calibration range, i.e. from LOQ to 1000 ng(Sn) L −1. Recovery was around 80–110% and precision (relative standard deviation, RSD) was between 12% and 25%. Despite the presence of two chromatographic peaks corresponding to sulphur compounds during brandy analysis, the selectivity of the method is adequate. The analysis confirmed the analytical performances and applicability of the method to wine and brandy samples. The obtained results emphasise the contamination of brandy and wine by organotins, the storage in plastic container seeming to be confirmed as the main OTC source.

Study on the contamination level and intake of organotins of Chinese dietary

To obtain the baseline data of organotins' pollution of Chinese meal in order to carry on primary danger analysis of the exposure. The samples of the third Chinese total diet study were determined by gas-chromatography pulsed flame photometric detector to estimate dietary intake of organotins. The dietary intake of organotins was estimated according to the contamination level of organotins and food consumption. Only several kinds of organotin were founded in several foods and no organotins was found in fruit, sugar and alcoholic beverages. Dimethyltin (DMT) were detected in some samples from Southern 1 area, the content ranged from 1.5 microg/kg to 4.1 microg/kg. Butyltin compounds existed in seafoods from Southern 1 area, the contents of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MTB) being 0.9 microg/kg, 1.1 microg/kg, 1.4 microg/kg respectively. The lower limit and upper limit of exposure to tributyltin were from 0.003 microg x kg(-1) x d(-1) to 0.006 microg x kg(-1) x d(-1) and from 0.004 microg x kg(-1) x d(-1) to 0.019 microg x kg(-1) x d(-1) respectively. Comparing to ADI of tributyltin (WHO), the Chinese dietary intake of tributyltin only accounted for 2.5% and that of butyltin only accounted for 3.5%. To identify the contamination source of organotins in Southern 1 area, the individual samples of aquatic food from individual province were analyzed, revealing that Fujian province and Shanghai City were the main contributors of organotins pollution in this area. The belt fish and yellow croaker were typical pollution samples. Higher levels of DMT were detected in seafood samples from Shanghai. The exposure level of Chinese dietary was relative low, however the sources of organotin pollution needs further investigation.

Field sampling method for quantifying volatile sulfur compounds from animal feeding operations

Volatile sulfur compounds (VSCs) are a major class of chemicals associated with odor from animal feeding operations (AFOs). Identifying and quantifying VSCs in air is challenging due to their volatility, reactivity, and low concentrations. In the present study, a canister-based method collected whole air in fused silica-lined (FSL) mini-canister (1.4 L) following passage through a calcium chloride drying tube. Sampled air from the canisters was removed (10–600 mL), dried, pre-concentrated, and cryofocused into a GC system with parallel detectors (mass spectrometer (MS) and pulsed flame photometric detector (PFPD)). The column effluent was split 20:1 between the MS and PFPD. The PFPD equimolar sulfur response enhanced quantitation and the location of sulfur peaks for mass spectral identity and quantitation. Limit of quantitation for the PFPD and MSD was set at the least sensitive VSC (hydrogen sulfide) and determined to be 177 and 28 pg S, respectively, or 0.300 and 0.048 μg m −3 air, respectively. Storage stability of hydrogen sulfide and methanethiol was problematic in warm humid air (25 °C, 96% relative humidity (RH)) without being dried first, however, stability in canisters dried was still only 65% after 24 h of storage. Storage stability of hydrogen sulfide sampled in the field at a swine facility was over 2 days. The greater stability of field samples compared to laboratory samples was due to the lower temperature and RH of field samples compared to laboratory generated samples. Hydrogen sulfide was the dominant odorous VSCs detected at all swine facilities with methanethiol and dimethyl sulfide detected notably above their odor threshold values. The main odorous VSC detected in aged poultry litter was dimethyl trisulfide. Other VSCs above odor threshold values for poultry facilities were methanethiol and dimethyl sulfide.

Dual low thermal mass gas chromatography–mass spectrometry for fast dual-column separation of pesticides in complex sample

A method is described for fast dual-column separation of pesticides by use of dual low thermal mass gas chromatography–mass spectrometry (dual LTM-GC–MS) with different temperature programming. The method can provide two total ion chromatograms with different separation on DB-5 and DB-17 in a single run, which allows improved identification capability, even with short analysis time (<17 min). Also simultaneous detection with MS and elemental selective detector, e.g. pulsed flame photometric detection (PFPD) was evaluated for fast dual-column separation of 82 pesticide mixtures including 27 phosphorus pesticides. Dual LTM-GC–MS/PFPD was applied to analysis of pesticides in a brewed green tea sample with dual stir bar sorptive extraction method (dual SBSE).

Comparison of Three Lychee Cultivar Odor Profiles Using Gas Chromatography−Olfactometry and Gas Chromatography−Sulfur Detection

Odor volatiles in three major lychee cultivars (Mauritius, Brewster, and Hak Ip) were examined using gas chromatography-olfactometry, gas chromatography-mass spectrometry, and gas chromatography-pulsed flame photometric detection. Fifty-nine odor-active compounds were observed including 11 peaks, which were associated with sulfur detector responses. Eight sulfur volatiles were identified as follows: hydrogen sulfide, dimethyl sulfide, diethyl disulfide, 2-acetyl-2-thiazoline, 2-methyl thiazole, 2,4-dithiopentane, dimethyl trisulfide, and methional. Mauritius contained 25% and Brewster contained 81% as much total sulfur volatiles as Hak Ip. Cultivars were evaluated using eight odor attributes: floral, honey, green/woody, tropical fruit, peach/apricot, citrus, cabbage, and garlic. Major odor differences in cabbage and garlic attributes correlated with cultivar sulfur volatile composition. The 24 odor volatiles common to all three cultivars were acetaldehyde, ethanol, ethyl-3-methylbutanoate, diethyl disulfide, 2-methyl thiazole, 1-octen-3-one, cis-rose oxide, hexanol, dimethyl trisulfide, alpha-thujone, methional, 2-ethyl hexanol, citronellal, (E)-2-nonenal, linalool, octanol, (E,Z)-2,6-nonadienal, menthol, 2-acetyl-2-thiazoline, (E,E)-2,4-nonadienal, beta-damascenone, 2-phenylethanol, beta-ionone, and 4-vinyl-guaiacol.

Determination of Organophosphorus Pesticides in Vegetables by GC with Pulsed Flame-Photometric Detection, and Confirmation by MS

The suitability of gas chromatography with pulsed flame-photometric detection (GC–PFPD) for determination of 24 organophosphorus (OP) pesticides in vegetables has been assessed. Pesticides were extracted with dichloromethane and analyzed without cleanup. The performance of the method was fit for purpose; recovery was between 73 and 110% and precision was better than 15%. Calculated lower limits of detection were typically <0.01 mg kg−1, much lower than the maximum residue levels stipulated by European legislation. Three pesticides were detected in vegetable samples. Their presence was confirmed by GC with tandem mass spectrometric detection (GC–MS–MS).

Effect of High-Pressure−Moderate-Temperature Processing on the Volatile Profile of Milk

The effects of high hydrostatic pressure on volatile generation in milk were investigated in this study. Raw milk samples were treated under different pressures (482, 586, and 620 MPa), temperatures (25 and 60 degrees C), and holding times (1, 3, and 5 min). Samples submitted to heat treatments alone (25, 60, and 80 degrees C for 1, 3, and 5 min) were used for comparison. Trace volatile sulfur compounds were analyzed using solid-phase microextraction (SPME) and gas chromatography (GC) with pulsed-flame photometric detection (PFPD), whereas the rest of the volatile compounds were analyzed using SPME-GC with flame ionization detection (FID). Multivariate analysis of variance (MANOVA) and principal component analysis (PCA) were used to study the effect of pressure, temperature, and time on volatile generation. Relative concentration increases of 27 selected volatile compounds were compared to an untreated sample. It was found that pressure, temperature, and time, as well as their interactions, all had significant effects (P < 0.001) on volatile generation in milk. Pressure and time effects were significant at 60 degrees C, whereas their effects were almost negligible at 25 degrees C. The PCA plot indicated that the volatile generation of pressure-heated samples at 60 degrees C was different from that of heated-alone samples. Heat treatment tended to promote the formation of methanethiol, hydrogen sulfide, methyl ketones, and aldehydes, whereas high-pressure treatment favored the formation of hydrogen sulfide and aldehydes.

Comparison of various detection limit estimates for volatile sulphur compounds by gas chromatography with pulsed flame photometric detection

This paper addresses the variations that presently exist regarding the definition, determination, and reporting of detection limits for volatile sulphur compounds by gas chromatography with pulsed flame photometric detection (GC-PFPD). Gas standards containing hydrogen sulphide (H 2S), carbonyl sulphide (COS), sulphur dioxide (SO 2), methyl mercaptan (CH 3SH), dimethyl sulphide (DMS), carbon disulphide (CS 2), and dimethyl disulphide (DMDS) in concentrations varying from 0.36 ppb (v/v) up to 1.5 ppm (v/v) in nitrogen were prepared with permeation tubes and introduced in the gas chromatograph using a 0.25-ml gas sampling loop. After measuring the PFPD response versus concentration, the method detection limit (MDL), the Hubaux–Vos detection limit ( x D), the absolute instrument sensitivity (AIS), and the sulphur detectivity ( D s) were determined for each sulphur compound. The results show that the MDL determined by the US Environmental Protection Agency procedure consistently underestimates the minimum concentrations of volatile sulphur compounds that can be practically distinguished from the background noise with the PFPD. The Hubaux–Vos detection limits and the AIS values are several times higher than the MDL, and provide more conservative estimates of the lowest concentrations that can be reliably detected. Sulphur detectivities are well correlated with AIS values but only poorly correlated with MDL values. The AIS is recommended as a reliable and cost-effective measure of detection limit for volatile sulphur compounds by GC-PFPD, since the AIS is easier and faster to determine than the MDL and the Hubaux–Vos detection limit. In addition, this study confirmed that the PFPD response is nearly quadratic with respect to concentration for all volatile sulphur compounds.

Determination of organotins in aquatic plants by headspace SPME followed by GC-PFPD determination

Optimal conditions of headspace solid-phase microextraction followed by gas chromatography coupled to pulsed flame photometric detection (SPME–GC–PFPD) have been investigated to validate the analysis of 11 organotin compounds in plant matrices including methyl-, butyl-, and phenyltin compounds. The extraction of organotin compounds from vegetal matrices has been carried out using optimized conditions of HCl-based extraction. The use of headspace SPME to preconcentrate the analytes allowed most of the detection limits to be obtained sub-0.5 ng(Sn) g−1. The precision evaluated using RSD with six replicates ranges between 5 and 10% (except for triphenyltin: 17%). The accuracy of the method was validated on spiked or polluted vegetal samples taken from Bizerte Lagoon (Tunisia) and by comparison with classical liquid–liquid extraction (LLE). These results highlight the suitability of the selected method for organotin control in complex environmental matrices such as aquatic plants.

Quantification of Trace Volatile Sulfur Compounds in Milk by Solid-Phase Microextraction and Gas Chromatography–Pulsed Flame Photometric Detection

Volatile sulfur compounds have been reported to be responsible for the sulfurous off-flavors generated during the thermal processing of milk; however, their analysis has been a challenge due to their high reactivity, high volatility, and low sensory threshold. In this study, reactive thiols were stabilized and the volatile sulfur compounds in milk were extracted by headspace solid-phase microextraction, and analyzed by gas chromatography and pulsed-flame photometric detection. Calibration curves for 7 sulfur-containing compounds were constructed in milk by the standard addition technique. Raw, pasteurized, and UHT milk samples with various fat contents were analyzed. Compared with raw and pasteurized samples, UHT milk contained substantially higher concentrations of hydrogen sulfide, methanethiol, carbon disulfide, dimethyl trisulfide, and di-methyl sulfoxide. The high odor activity values calculated for methanethiol and dimethyl trisulfide suggested that these 2 compounds, in addition to di-methyl sulfide reported in a previous study, could be the most important contributors to the sulfurous note in UHT milk.

The properties of calibration errors in the analysis of reduced sulfur compounds by the combination of a loop injection system and gas chromatography with pulsed flame photometric detection

In order to evaluate the extent of analytical biases involved in the GC calibration, we conducted a series of experiments to examine the calibration methods of trace gas components. For the purpose of this comparative study, gaseous standards of reduced sulfur compounds (RSC) including hydrogen sulfide (H 2S), methanethiol (CH 3SH), dimethyl sulfide (DMS), carbon disulfide (CS 2), and dimethyl disulfide (DMDS) were calibrated by the combination of a GC/PFPD technique and a loop-injection method. In the course of this study, two different types of calibration methods were tested and compared: incremental-injection of a given standard with the fixed standard concentration (FSC) versus injection of multiple standards (with different concentrations) at the fixed standard volume (FSV). In the case of the FSV calibration, a notable increase in the GC sensitivity is apparent with decreasing loop size (or injection volume). For instance, the calibration slope for RSC obtained using a 10 μl loop system was approximately three times higher than that for a 250 μl one. However, the results obtained by the FSC method exhibit much poorer sensitivity than its counterpart with slight differences in their sensitivities across different standard concentrations (due to such factors as the matrix effect from varying injection volumes). Thus, the overall results of this study confirm that the detailed characterization of the selected calibration method (e.g., the use of FSV approach relative to FSC) is of primary significance to perform an accurate quantification of trace gases.

Deep desulfurization of diesel oil and crude oils by a newly isolated Rhodococcus erythropolis strain.

The soil-isolated strain XP was identified as Rhodococcus erythropolis. R. erythropolis XP could efficiently desulfurize benzonaphthothiophene, a complicated model sulfur compound that exists in crude oil. The desulfurization product of benzonaphthothiophene was identified as alpha-hydroxy-beta-phenyl-naphthalene. Resting cells could desulfurize diesel oil (total organic sulfur, 259 ppm) after hydrodesulfurization. The sulfur content of diesel oil was reduced by 94.5% by using the resting cell biocatalyst for 24 h at 30 degrees C. Biodesulfurization of crude oils was also investigated. After 72 h of treatment at 30 degrees C, 62.3% of the total sulfur content in Fushun crude oil (initial total sulfur content, 3,210 ppm) and 47.2% of that in Sudanese crude oil (initial total sulfur, 1,237 ppm) were removed. Gas chromatography with pulsed-flame photometric detector analysis was used to evaluate the effect of R. erythropolis XP treatment on the sulfur content in Fushun crude oil, and it was shown that most organic sulfur compounds were eliminated after biodesulfurization.

Determination of organotin compounds by headspace solid-phase microextraction–gas chromatography–pulsed flame-photometric detection (HS-SPME–GC–PFPD)

A method based on Headspace solid-phase microextraction (HS-SPME, with a 100 mum PDMS-fiber) in combination with gas-chromatography and pulsed flame-photometric detection (GC-PFPD) has been investigated for simultaneous determination of eight organotin compounds. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), and the semi-volatile diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOcT), and dioctyltin (DOcT) were determined after derivatization with sodium tetraethylborate. The conditions used for the extraction and preconcentration step were optimised by experimental design methodology. Tripropyltin (TPrT) and diheptyltin (DHepT) were used as internal standards for quantification of volatile and semi-volatile organotin compounds, respectively. The analytical precision (RSD) for ten successive injections of a standard mixture containing all the organic tin compounds ranged between 2 and 11%. The limits of detection for all the organotin compounds were sub ng (Sn) L(-1) in water and close to ng (Sn) kg(-1) in sediments. The accuracy of the method was evaluated by analysis of two certified reference material (CRM) sediment samples. The HS-SPME-GC-PFPD was then applied to the analysis of three harbour sediment samples. The results showed that headspace SPME is an attractive tool for analysis of organotin compounds in solid environmental matrices.

Determination of Acephate in Human Urine

Acephate is a commonly used organophosphate insecticide applied on agricultural crops and in residential communities. Because very little acephate is metabolized prior to excretion, the parent pesticide compound can be measured in human urine. The residue method must be sensitive enough to determine human exposure and potential health risk for both agricultural workers and their families who may be exposed by pesticide drift or by inadvertent carry-home residues. A reliable and sensitive method was developed to measure acephate concentrations in human urine. Urine was diluted with water and acetone, adjusted to a neutral pH, and partitioned twice in acetone-methylene chloride (1 + 1, v/v), with NaCl added to aid separation. The solvent-reduced organic phase extracts were clarified by activated charcoal solid-phase extraction and then adjusted to a final volume with the addition of a D-xylose analyte protectant solution to reduce matrix enhancement effects. Acephate concentrations in urine were determined by gas chromatography using pulsed flame photometric detection. The method limit of detection was established at 2 microg/L, with a method limit of quantitation of 10 microg/L. The average recovery from urine fortified with 10-500 microg/L was 102 +/- 12% (n = 32).