In-transit fumigation of shipping containers with ethyl formate + nitrogen on road and continued journey on sea.

Fumigation is required as an appropriate biosecurity measure to exterminate insect pests in shipping containers. The aim of this study was to determine if ethyl formate (EF) + nitrogen could be safely applied as an in-transit fumigant for containers transported on land and then by sea. In-transit fumigation trials were conducted in four 20 ft shipping containers during a four-day journey in December 2019 in Western Australia. Ethyl formate (90 g m-3) was released with nitrogen into the containers. Ethyl formate concentrations inside the containers and the surrounding environment on the barge were monitored at timed intervals throughout the overnight voyage. This study added new data on in-transit fumigation with ethyl formate + nitrogen via road and has successfully demonstrated safety of in-transit fumigation with ethyl formate + nitrogen via the marine sector. There was no detectable risk to the public, crew members on the barge or workers throughout the journey. In addition, all tested containers were ready to be opened and unloaded with 5-10 minutes aeration or without aeration upon arrival.

Commercial trials evaluating the novel use of ethyl formate for in-transit fumigation of shipping containers.

The use of shipping containers for cargo transportation has the potential to transport insect pests from infested to non-infested areas. Therefore, fumigation is required as an appropriate biosecurity measure to exterminate these pests. In-transit fumigation trials were conducted in two 20 ft shipping containers during a two-day journey in both September and December 2017. Ethyl formate (90 g m-3) was purged with nitrogen (EF + N2) into the containers. Ethyl formate concentration inside containers and the surrounding environment were monitored at timed intervals throughout the journey. Fumigation achieved sufficient concentration × time (Ct) products in the containers during the journey, which can exterminate all stages of most common insect pests. The Ct products in-transit were greater than those in a shipping container being fumigated in a stationary position at a dose rate of 90 g m-³ for 24 hours exposure. Levels of EF in the environment between 1-15 m downwind from the containers and driver's cabin were less than 0.5 ppm at each of the timed intervals, 200 times below 100 ppm of EF Threshold Limit Value (TLV). Our study indicates that in-transit EF + N2 technology has the potential to deliver cost savings in the fumigation process through reduction of the Labor cost, elimination of the time a container and cargo must remain stationary in a fumigation yard and a significant decrease in total supply chain time (between container packing and receival).

Physical, chemical and biological behaviour of fumigants on cottonseed.

Fumigation is required to protect cottonseed in storage and pre-shipment from insect pests and/or microorganisms. Fumigation of cottonseed with carbon disulphide (CS2), carbonyl sulphide (COS), ethanedinitrile (C2N2), ethyl formate (EF), methyl bromide (MB) and phosphine (PH3) showed that >85% of the fumigants disappeared within 5 h of exposure. COS maintained >20 mg L-1 for 24 h. After 1 day of aeration, 75%-85% of the absorbed COS and MB and 20%-40% of the absorbed CS2, EF and PH3 were released from treated cottonseed. The fumigant residues were reduced by 80% for COS, 50% for EF or MB and 25% for CS2 after 1 day of aeration. After 13 days of aeration, fumigant residues were reduced by 95% for MB, 65% for EF, 55% for CS2 and to natural levels in the COS residue. Carbon disulphide, COS, PH3, EF and C2N2 had no effect on the germination of cottonseed, but germination was reduced to 50% by MB. COS has potential as a fumigant for control of insect pests in cottonseed because it dissipates quickly and does not negatively impact germination. On the other hand, MB appears to strongly absorb and requires an extended period for residues to dissipate, and it negatively impacts germination.

Tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescent determination of ethyl formate.

Ethyl formate is extensively used as food flavor, fungicide, and larvicide. It naturally exists in coffee, fruits, honey, brandy, and rum as well as dust clouds in an interstellar space of the Milky Way galaxy. Herein, its electrochemiluminescence (ECL) property has been firstly investigated. It shows intense ECL in reaction with Ru(bpy)32+ as luminophore, and thus a rapid and sensitive detection method for ethyl formate is proposed. Effects of pH, working potential, scan rate, and concentration of Ru(bpy)32+ were studied. ECL spectrum analysis was used to reveal the reaction mechanism. At the optimized experimental conditions, a linear relationship between ECL intensities and concentrations of ethyl formate is observed from 3.0 µM to 1.0 mM (R2 = 0.997). The limit of detection for ethyl formate is 0.7 µM (S/N = 3). The relative standard deviation with 1.0 mM concentration of ethyl formate for nine analyses is 2.7%. A 101.20-102.10% recovery was obtained in a real samples analysis. Graphical Abstract ᅟ.

Ethyl Formate: A Potential Disinfestation Treatment for Eucalyptus Weevil (Gonipterus platensis) (Coleoptera: Curculionidae) in Apples.

Export of Pink Lady apples from Australia has been significantly affected by infestations of adult eucalyptus weevils (Gonipterus platensis Marelli). These weevils cling tenaciously to the pedicel of apple fruit when selecting overwintering sites. As a result, apples infested with live G. platensis adults lead to rejection for export. Since the Montreal Protocol restricted use of methyl bromide as postharvest treatment, it was necessary to consider alternative safer fumigants for disinfestation of eucalyptus weevil. Laboratory experiments were conducted using concentrations of 5, 10, 15, 20, 25, 30, 40, and 80 mg/liter of ethyl formate. Complete control (100% mortality) was achieved at 25-30 mg/liter of ethyl formate at 22-24°C for 24-h exposure without apples. However, with 90-95% of the volume full of apples, complete control was achieved at 40 mg/liter of ethyl formate at 22-24°C for 24-h exposure. No phytotoxicity was observed and after one day aeration, residue of ethyl formate declined to natural levels (0.05-0.2 mg/kg). Five ethyl formate field trials were conducted in cool storages (capacity from 250-900 tons) and 100% kill of eucalyptus weevils were achieved at 50-55 mg/liter at 7-10°C for 24 h. Ethyl formate has great potential for preshipment treatment of apples. Its use is considerably cheaper and safer than already existing fumigants like methyl bromide and phosphine.

Highly selective and sensitive determination of free and total amino acids in Apocynum venetum L. (Luobuma tea) by a developed HPLC-FLD method coupled with pre-column fluorescent labelling.

Amino acids (AA) are important chemical constituents of tea leaves remarkably influencing the quality of tea. In this study, free AA and total AA in Apocynum venetum L. (Luobuma tea) were estimated by HPLC equipped with fluorescent detector using 2-[2-(7H-dibenzo[a,g]carbazol-7-yl)-ethoxy] ethyl chloroformate (DBCEEC) as a fluorescent labelling reagent. Different parameters for derivatization and separation were optimized. AA were rapidly derivatized within 3 min at room temperature with DBCEEC. In conjunction with a gradient elution, a baseline resolution of 20 analytes was achieved on a reversed-phase Hypersil BDS C18 column. LC separation for the derivatized AA showed good reproducibility. Twenty AA were detected and showed significant linear responses with correlation coefficients (>0.9992). This developed method offered the low detection limit of 2.88-23.4 fmol.

Evaluation of microwave irradiation for analysis of carbonyl sulfide, carbon disulfide, cyanogen, ethyl formate, methyl bromide, sulfuryl fluoride, propylene oxide, and phosphine in hay.

Fumigant residues in hay were "extracted" by microwave irradiation. Hay, in gastight glass flasks, was placed in a domestic microwave oven, and fumigants were released into the headspace by microwave irradiation. Power settings for maximum release of fumigants were determined for carbonyl sulfide (COS), carbon disulfide (CS(2)), cyanogen (C(2)N(2)), ethyl formate (EF), methyl bromide (CH(3)Br), sulfuryl fluoride (SF), propylene oxide (PPO), and phosphine (PH(3)). Recoveries of fortified samples were >91% for COS, CS(2), CH(3)Br, SF, PPO, and PH(3) and >76% for C(2)N(2) and EF. Completeness of extraction was assessed from the amount of fumigant retained by the microwaved hay. This amount was determined from further microwave irradiation and was always small (<5% of the amount obtained from the initial procedure). Limits of quantification were <0.1 mg/kg for COS, CS(2), C(2)N(2), EF, and PH(3) and <0.5 mg/kg for CH(3)Br, SF, and PPO. These low limits were essentially due to the absence of interference from solvents and no necessity to inject large-volume gas samples. The microwave method is rapid and solvent-free. However, care is required in selecting the appropriate power setting. The safety implications of heating sealed flasks in microwave ovens should be noted.

Analysis of methanol and its derivatives in illegally produced alcoholic beverages.

INTRODUCTION: Illegal alcohol production remains as a common issue worldwide. Methanol poisoning mostly occurs because of the methanol used in production of counterfeit alcohol instead of ethyl alcohol due to its low price or by drinking the liquids containing methyl alcohol. Pectolytic enzymes results in an increase of methanol levels in many fermentation products such as ciders or wines. Methanol poisonings are infrequently encountered in forensic medicine practice. However, sporadic cases due to methanol intoxication as well as epidemic cases have been reported. In this study, we aimed to identify existence of methanol and its metabolites in illegally produced alcoholic beverages used in Antakya region. MATERIAL AND METHODS: Twelve legally produced alcohol samples and Fifty-six different illegally produced alcohol samples were collected from the markets and local producers. Existence of methanol, formic acid, methyl amine, methyl formate and trioxan were determined using GC-MS method in these samples. RESULTS: Fifty-six different illegal alcohol samples were analyzed in this study and methanol was detected in 39 (75%) of samples. Formic acid was detected in 3, formamide in 1, methyl amine in 6, methyl formate in 10 and trioxan in 2 samples. CONCLUSION: Overwhelming majority of illegal alcoholic beverages was detected to contain methanol. Interestingly this study also revealed the presence of trioxane, which has not previously reported among toxic agents in illegal alcohol samples.

Volatile compounds and sensory analysis of both harvests of double-cut Yakima peppermint (Mentha piperita L.).

North American peppermint oils are widely regarded as some of the most superior peppermint oils commercially available. Amongst them is Yakima double-cut peppermint oil (Mentha piperita L.). It has an aroma described as strong, refreshing, minty, slightly creamy, and very herbaceous with some of the most desirable flavor notes among peppermint oils. The peppermint is grown in the Yakima Valley of Washington State, USA. As one of the most northerly grown peppermints with longer days, it is unique as there are 2 harvests of the mint leaves in one season. For this study, samples of fresh and dried (hay) leaves were collected from both harvests; 1st cut, July and 2nd cut, September. Steam-distilled oils were produced from each harvest and analyzed by gas chromatography-mass spectrometry to give detailed profiles. The aroma and taste sensory attributes of each oil were evaluated. In addition, menthyl formate has previously been reported only once in the literature, but not as definitively as required by current flavor-regulatory bodies for use as a natural flavoring ingredient. It was conclusively reported in these peppermint oils.

Field evaluation of vaporised ethyl formate and carbon dioxide for fumigation of stored wheat.

BACKGROUND: Vapormate is a cylinderised non-flammable mixture of ethyl formate (16.7% by weight) and carbon dioxide (CO(2)) that has been developed as a rapid fumigant of stored grain. Four field trials were undertaken on wheat in 50 t farm silos to demonstrate the feasibility of dynamic application. To assess treatment efficacy, each trial tested mixed stages of Rhyzopertha dominica F. (>11,000), Tribolium castaneum (Herbst.) (>1500) and Sitophilus oryzae (L.) (>13,000) in mesh cages positioned through the centre of the grain bulk and on the grain surface. Ethyl formate and CO(2) concentrations were measured in the silo during fumigation and in ambient air outside the 6 m fumigation zone. Application rates of 420, 660 and 940 g m(-3) of ethyl formate/CO(2) formulation and exposure times of 24, 3 and 72 h, respectively, were examined using wheat of 10.4-11.7% moisture content and grain temperatures between 2 and 32 degrees C. RESULTS: All life stages of R. dominica and T. castaneum were fully controlled under all conditions tested, and mortality of all life stages of S. oryzae was greater than 98%. CONCLUSION: Dynamic application of vaporised ethyl formate and CO(2) to 50 t silos proved safe to operators and rapidly effective against stored-grain insects on cold to warm grain.

Identification of ethyl formate as a quality marker of the fermented off-note in coffee by a nontargeted chemometric approach.

The quality of coffee is influenced by many factors such as coffee variety, agricultural and postharvest conditions, roasting parameters, and brewing. The pleasure of drinking coffee may be affected by off-notes such as burnt, green, earthy, or fermented. Their presence is related to the variety, fermentation during postharvest processing, or over-roasting of the beans. Sensory expert panels trained for the evaluation of coffee are able to detect off-notes and select coffees by well-defined quality criteria. The application of instrumental approaches detecting quality markers related to the perceived off-notes is shown to be useful to assist sensory panels. This paper describes the discovery of a new marker compound related to the fermented off-note occasionally perceived in coffees. The application of untargeted chemometric methods on volatile compounds revealed correlations between individual compounds and the sensory attribute. The new marker compound was identified as ethyl formate, which can be measured in the headspace of roasted and ground coffee by various analytical techniques including online proton transfer reaction mass spectrometry.

Application of ethyl chloroformate derivatization for gas chromatography-mass spectrometry based metabonomic profiling.

A new combined gas chromatography and mass spectrometry (GC-MS) method has been developed suitable for the urine sample treatment in aqueous phase with ethyl chloroformate (ECF) derivatization agents. The method has been extensively optimized and validated over a broad range of different compounds and urine samples. Analysis of test metabolite derivatives, containing spiked standards, or rat urine exhibited acceptable linearity, satisfactory intra-batch precision (repeatability) and stability, relative standard deviations (R.S.D.) less than 10 and 15% within 48 h, respectively. The quantification limits were 150-300 pg on column for most metabolites. Recovery of several representative compounds, at different concentrations, ranged from 70 to 120%, with R.S.D. better than 10% for rat urine. We were able to generally eliminate potentially confounding variables such as medium complexity, different urea concentrations, and/or derivatization procedure variability. Metabonomic profiling of 1,2-dimethylhydrazine (DMH)-induced precancerous colon rat urine using GC-MS with ECF derivatization was performed to evaluate the proposed method. The analytical variation of the method was smaller than the biological variation in the rat urine samples, proving the suitability of the method to analyze differences in the metabonome of a living system with perturbed metabolic network. Thus, the proposed GC-MS analytical method is reliable to analyze a large variety of metabolites and can be used to investigate human pathology including disease onset, progression, and mortality.

The contribution of gas chromatography to the resynthesis of the post-Byzantine artist's technique.

Gas chromatographic analysis of ethyl chloroformate derivatives of samples taken from the paint layers of post-Byzantine panel paintings permitted the successful characterisation of the different binding media used in them. This paper describes an analytical study of various post-Byzantine binding media such as egg yolk and egg/oil emulsion, using gas chromatography. The characterisation of these icons' binding media is an important task, as it contributes to our understanding of and the reconstruction of the post-Byzantine artists' palette. It also enables us to investigate the validity of our assumptions about the influences of Venetian style on Greek icon painting techniques from the sixteenth to the early nineteenth century, which up to now have been based on information in artists' handbooks. The methodology involves two experimental steps: (1) hydrolysis of the proteins and triglycerides in the binding media to obtain free amino acids and fatty acids, and (2) the formation of ethyl chloroformate derivatives via derivatization with ethyl chloroformate (ECF). This methodology is of considerable interest, since it permits the identifcation of the nature of the proteinaceous binders used in these works through the simultaneous derivatization and determination of amino acids and fatty acids. Advantages of this methodology include the small quantity of sample required and the minimum preparation time involved. The proteinaceous media can be determined based on the ratios of seven stable amino acids, while the type of emulsions and drying oils used can be determined from the fatty acid ratio.

Interferometric observations for oxygen-containing organic molecules toward Orion-KL.

High spatial resolution observations (approximately 5") were made for the 3 mm transitions of methanol (CH3OH), methyl formate (HCOOCH3), and dimethyl ether [(CH3)2O] toward Orion-KL using the Nobeyama Millimeter Array. The 15(3)-14(4) A- CH3OH emission appears to be elongated along the line connecting IRc2 and "the southern condensation (SC)", which may suggest a relation between methanol and the outflow from IRc2. The HCOOCH3 (7(1,6)-6(1,5)) and (CH3)2O (15(2,13)-15(1,14)) emissions appear to be well concentrated toward SC with an angular size of approximately 6".5 (at the 2 sigma level). There also exists another oxygen-rich condensation to the west of IRc2 (angular size approximately 4".5) having column densities of HCOOCH3 and (CH3)2O comparable to those of SC. We derive the total column densities 6.8 x 10(16) cm-2, 1.4 x 10(16) cm-2 and 2.7 x 10(16) cm-2 for CH3OH, HCOOCH3, and (CH3)2O, respectively, at the core of SC.

Isolation and identification of free amino acids as crystalline N-t-butyloxycarbonyl, O-phenacyl derivatives.

A general and efficient method for the quantitative isolation of free amino acids from natural sources and their identification as crystalline N-t-butyloxycarbonyl amino acid phenacyl esters is described. The applicability of this method is illustrated in the isolation and characterization of major free amino acids from the Mediterranean fruit fly Ceratitis capitata.

Synthesis and acid ionization constants of cyclic cystine peptides H-Cys-(Gly)n-Cys-OH (n = 0-4).

Cyclic peptide disulfides of the general formula H-Cys-(Gly)n-Cys-OH (n = 0-4) were synthesized from the corresponding peptide derivatives [Boc-Cys(Trt)(Gly)-n-Cys(Trt)-OBut] by oxidation with iodine in methanol and by subsequent removal of the terminal groups with trifluoroacetic acid. Acid ionization constants of the obtained peptides were determined by potentiometric titration in aqueous KCl (0.1 mol/L) medium. All compounds have two dissociable hydrogens, corresponding to carboxyl (pK1 = 2.35-2.84) and to terminal amino group (pK2 = 5.61-6.93); pK1 values show first an upward and then a downward trend with the increase in ring size; the opposite is true for pK2 values. These trends could be tentatively attributed to the intramolecular salt bridge (-COO- ----NH+3-) formation.

[Bouquet qualification of wines by gas chromatography. 1. Experimental method for gas phase analysis]. / Uber die gaschromatographische Duftqualifizierung von Weinen 1. Mitt. Versuchsmethode zur Gasphasenanalyse

In the course of our investigations we tried to find a method for the bouquet qualification of wines by gas chromatography. For this purpose, instead of aroma research studies requiring complex equipment and laboursome precise laboratory work, we developed a method for head space analysis functioning with simple experimental instruments and being sufficiently fast for serial routine work. By the method developed, the head space of a great number of samples taken from 7 different wine-types have been successfully examined. Errors of measurement were checked by standard deviation analysis and the values obtained (3,23%) were found satisfactory. According to the above, our head space analysis may provide a satisfactory basis for elaborating a method for the instrumental bouquet qualification of wines.

Urinary methanol and formic acid as indicators of occupational exposure to methyl formate.

OBJECTIVE: To evaluate the validity of methanol (MeOH) and formic acid (FA) in urine as biological indicators of methyl formate (MF) exposure in experimental and field situations. METHODS: The subjects were 28 foundrymen and two groups of volunteers (20 control and 20 exposed). Exposure assessment of the workers was performed by personal air and biological monitoring. Methyl formate vapour collected on charcoal tube was analysed by gas chromatography. The concentration of MF in the exposure chamber (volunteer-study) was monitored by two independent methods [flame ionisation detection (FID) and Fourier transformation infra-red detection (FTIR)]. Urinary metabolites (MeOH and FA) were analysed separately by headspace gas chromatography. RESULTS: The volunteers exposed to 100 ppm MF vapour at rest for 8 h excreted 3.62 +/- 1.13 mg MeOH/l (mean +/- SD) at the end of the exposure. This was statistically different (P < 0.001) from pre-exposure MeOH excretion (2.15 +/- 0.80 mg/1), or from that of controls (1.69 +/- 0.48 mg/l). The urinary FA excretion was 32.2 +/- 11.3 mg/g creatinine after the exposure, which was statistically different (P < 0.001) from pre-exposure excretion (18.0 +/- 9.3 mg/g creatinine) or that of controls (13.8 +/- 7.9 mg/g creatinine). In foundrymen, the urinary FA excretion after the 8 h workshift exposure to a time weighted average (TWA) concentration of 2 to 156 ppm MF showed a dose-dependent increase best modelled by a polynomial function. The highest urinary FA concentration was 129 mg/g creatinine. The pre-shift urinary FA of the foundrymen (18.3 +/- 5.6 mg/g creatinine) did not differ from that of controls (13.8 +/- 7.9 mg/g creatinine). The urinary MeOH excretion of the foundrymen after the shift, varied from < 1 to 15.4 mg/l, while the correlation with the preceding MF exposure was poor. The foundrymen excreted more (P = 0.01) FA (2.12 +/- 3.56 mg/g creatinine) after the workshift than experimentally, once-exposed volunteers (0.32 +/- 0.11 mg/g creatinine) at a similar inhaled MF level of 1 ppm). CONCLUSIONS: In spite of its high background level in non-exposed subjects, urinary FA seems to be a useful biomarker of methyl formate exposure. The question remains as to what is the reason for the differences in chronic and acute exposure respectively.

Analysis of amino acids as formamidene butyl esters by electrospray ionization tandem mass spectrometry.

Amino acid formamidene butyl esters are optimally prepared by heating amino acids with dimethylformamide dimethylacetal (DMF-DMA) for 2 minutes at 65 degrees C and then with n-butanol/hydrogen chloride for 15 minutes at 65 degrees C. The formamidene butyl esters of simple alpha-amino acids and beta-amino acids afford between 1.1 and 20 times the signal intensity of the corresponding butyl esters during electrospray ionization tandem mass spectral analysis. Complex alpha-amino acids, such as ornithine, arginine and citrulline, and gamma-amino acids are better analyzed as butyl esters. Secondary alpha-amino acids, such as proline and sarcosine, give a mixture of two iminium salts with the DMF-DMA derivatization method. A derivative incorporating two molecules of the amino acid predominates at higher derivatization temperatures. Contrary to a previous report, N-formylamino acids were not detected. The presence of secondary amino acids in amino acid mixtures, derivatized as formamidene butyl esters, affords derivatives that incorporate two different amino acids. The new formamidene butylation method is unlikely to replace the butylation procedure used by neonatal blood spot screening programs for amino acid disorders, since a much poorer response was obtained with formamidene butyl esters of arginine and citrulline, important in the diagnosis of arginase deficiency and citrullinaemia.