Quantification of Ethanedinitrile in Air Using a New and Accurate Gas Chromatography Method
Abstract
:1. Introduction
2. Materials and Methods
2.1. Preparation of Samples
2.2. Analytical Conditions and Equipment
2.3. Validation Guidelines
2.4. Linearity
2.5. Precision
2.6. Accuracy
2.7. Limit of Detection
2.8. Limit of Quantification
3. Results
3.1. Linearity
3.2. Precision
3.3. Accuracy
3.4. Limit of Detection and Limit of Quantification
3.4.1. LOD Calculation
3.4.2. LOQ Calculation
4. Discussion
5. Conclusion
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
- Barak, A.V.; Wang, Y.; Zhan, G.; Wu, Y.; Xu, L.; Huang, Q. Sulfuryl fluoride as a quarantine treatment for Anoplophora glabripennis (Coleoptera: Cerambycidae) in regulated wood packing material. J. Econ. Entomol. 2006, 99, 1628–1635. [Google Scholar] [CrossRef] [PubMed]
- Ren, Y.; Lee, B.; Padovan, B. Penetration of methyl bromide, sulfuryl fluoride, ethanedinitrile and phosphine into timber blocks and the sorption rate of the fumigants. J. Stored Prod. Res. 2011, 47, 63–68. [Google Scholar] [CrossRef] [Green Version]
- Sulbaek Andersen, M.P.; Blake, D.R.; Rowland, F.S.; Hurley, M.D.; Wallington, T.J. Atmospheric chemistry of sulfuryl fluoride: Reaction with OH radicals, Cl atoms and O3, atmospheric lifetime, IR spectrum, and global warming potential. Environ. Sci. Technol. 2009, 43, 1067–1070. [Google Scholar] [CrossRef]
- UNEP. Handbook for the Montreal Protocol on Substances that Deplete the Ozone Layer, 10th ed.; Secretariat of The Vienna Convention for the Protection of the Ozone Layer & The Montreal Protocol on Substances that Deplete the Ozone Layer: Nairobi, Kenya, 2016; Available online: http://www.efcc.eu/media/1079/2016-ods-montreal_protocol-handbook.pdf (accessed on 15 December 2018).
- Park, H.; Kim, H.; Kwon, J.-E.; Yoon, J.-Y.; Lee, J.-Y.; Chang, M.-I.; Rhee, G.-S. Development and validation of an analytical method for quantification of sulfuryl fluoride residues in agricultural products using gas chromatography with electron capture detection. Food Sci. Biotechnol. 2014, 23, 1799–1804. [Google Scholar] [CrossRef]
- BOC. BOC Field Trial Report—Ethanedinitrile Fumigant (EDN) Worker Exposure Field Trial, Timber Application under Tarp; BOC Australia: North Ryde, NSW, Australia, 2013. [Google Scholar]
- NZ-EPA. ERMA200981 Decision—Approval of Ethanedinitirle for Use in Containments; New Zealand Environmental Protection Authority: Wellington, New Zealand, 2011. Available online: https://www.epa.govt.nz/assets/FileAPI/hsno-ar/ERMA200981/ERMA200981-ERMA200981-Decision.pdf. (accessed on 15 December 2018).
- Caddick, L. Search for methyl bromide and phosphine alternatives. Outlooks Pest Manag. 2004, 15, 118–119. [Google Scholar] [CrossRef]
- Mattner, S.; Gounder, R.; Mann, R.; Porter, I.; Matthiessen, J.; Ren, Y.; Sarwar, M. Ethanedinitrile (C2N2)—A novel soil fumigant for strawberry production. Acta Hortic. 2004, 708. [Google Scholar] [CrossRef]
- Mattner, S.; Gregorio, R.; Ren, Y.; Hyland, T.; Gounder, R.; Sarwar, M.; Porter, I.J. Application techniques influence the efficacy of ethanedinitrile (C2N2) for soil disinfestation. In Proceedings of the Annual International Research Conference on Methyl Bromide Alternatives and Emission Reductions, San Diego, CA, USA, 3–6 November 2003; Available online: https://www.mbao.org/static/docs/confs/2003-sandiego/papers/127%20mattnerssummary%20-%20mattner%20poster.pdf (accessed on 15 December 2018).
- Jessup, A.J.; Golding, J.G. Qfly Proof of Concept for Ethane Dinitrile (EDN) Fumigation; Horticulture Australia Pty Ltd.: Sydney, Australia, 2012. [Google Scholar]
- Hall, M.; Najar-Rodriguez, A.; Pranamornkith, T.; Adlam, A.; Hall, A.; Brash, D. Influence of dose, bark cover and end-grain sealing on ethanedinitrile (C2N2) sorption by pine (Pinus radiata D. Don) logs. N. Z. Plant Prot. 2015, 68, 13–18. [Google Scholar]
- Lee, B.-H.; Yang, J.-O.; Beckett, S.; Ren, Y. Preliminary trials of ethanedinitrile (C2N2) fumigation of logs for eradication of Bursaphelenchus xylophilus and its vector insect Monochamus alternatus. Pest Manag. Sci. 2017. [Google Scholar] [CrossRef] [PubMed]
- Najar-Rodriguez, A.; Hall, M.; Adlam, A.; Hall, A.; Burgess, S.; Somerfield, K.; Page, B.B.C.; Brash, D.W. Developing new fumigation schedules for the phytosanitary treatment of New Zealand export logs: Comparative toxicity of two fumigants to the burnt pine longhorn beetle, Arhopalus ferus. N. Z. Plant Prot. 2015, 68, 19–25. [Google Scholar]
- Hall, M.; Najar-Rodriguez, A.; Adlam, A.; Hall, A.; Brash, D. Sorption and desorption characteristics of methyl bromide during and after fumigation of pine (Pinus radiata D. Don) logs. Pest Manag. Sci. 2017, 73, 874–879. [Google Scholar] [CrossRef] [PubMed]
- Minini, K.M.S.; Bueno, S.C.E.; da Silva, M.G.; Sthel, M.S.; Vargas, H.; Angster, J.; Miklós, A. Quantum cascade laser-based photoacoustic sulfuryl fluoride sensing. Appl. Phys. B 2017. [Google Scholar] [CrossRef]
- Hamel, J. A review of acute cyanide poisoning with a treatment update. Crit. Care Nurse 2011, 31, 72–82. [Google Scholar] [CrossRef] [PubMed]
- Conway, J.; Wilson, R., Jr.; Grosse, A. The temperature of the cyanogen-oxygen flame. J. Am. Chem. Soc. 1953, 75, 499–499. [Google Scholar] [CrossRef]
- Emery, R.; Ren, Y.; Newman, J.; Thalavasundaram, S. Evaluation of ethanedinitrile (EDN) as a methyl bromide alternative for eradication of European House Borer (EHB). In Proceedings of the 11th International Working Conference on Stored Product Protection, Chiang Mai, Thailand, 24–28 November 2014; Arthur, F.H., Kengkanpanich, R., Chayaprasert, W., Suthisut, D., Eds.; pp. 942–949. [Google Scholar]
- Park, C.G.; Son, J.-K.; Lee, B.-H.; Cho, J.H.; Ren, Y. Comparison of ethanedinitrile (C2N2) and metam sodium for control of Bursaphelenchus xylophilus (Nematoda: Aphelenchidae) and Monochamus alternatus (Coleoptera: Cerambycidae) in naturally infested logs at low temperatures. J. Econ. Entomol. 2014, 107, 2055–2060. [Google Scholar] [CrossRef] [PubMed]
- Pranamornkith, T.; Hall, M.; Adlam, A.; Somerfield, K.; Page, B.; Hall, A.; Brash, D.W. Effect of fumigant dose, timber moisture content, end-grain sealing, and chamber load factor on sorption by sawn timber fumigated with ethanedinitrile. N. Z. Plant Prot. 2014, 67, 66–74. [Google Scholar]
- Cho, D.; Moon, Y.; Choi, M.; Shin, C.; Lee, B.; Ren, Y. Efficacy of ethanedinitrile to wood relating pests: Japanese Termite and Yellow Minute Bark Beetles. In Proceedings of the Annual International Research Conference on Methyl Bromide Alternatives and Emissions Reductions, San Diego, MA, USA, 31 October–2 November 2011. [Google Scholar]
- Park, M.; Sung, B.; Hong, K.; Lee, B.; Ren, Y. The efficacy of ethanedinitrile to control wood related insect pests. In Proceedings of the Annual International Research Conference on Methyl Bromide Alternatives and Emissions Reductions, San Diego, MA, USA, 29 October–1 November 2007. [Google Scholar]
- Ren, Y.; Wang, Y.; Barak, A.V.; Wang, X.; Liu, Y.; Dowsett, H.A. Toxicity of ethanedinitrile to Anoplophora glabripennis (Coleoptera: Cerambycidae) larvae. J. Econ. Entomol. 2006, 99, 308–312. [Google Scholar] [CrossRef] [PubMed]
- Sarwar, M.; Mahon, D.; Ren, Y. Interaction of ethanedinitrile (C2N2) with contact materials used in grain storage. In Proceedings of the Proceedings of the Australian Postharvest Technical Conference, Canberra, Australia, 25–27 June 2003. [Google Scholar]
- O’Brien, I.G.; Desmarchelier, F.J.M.; Yonglin, R. Cyanogen Fumigants and Methods of Fumigation Using Cyanogen. U.S. Patents CA2192959A1, 14 December 1999. [Google Scholar]
- ICH. Validation of Analytical Procedures: Text and Methodology. 1995. Available online: https://www.ich.org/fileadmin/Public_Web_Site/ICH_Products/Guidelines/Quality/Q2_R1/Step4/Q2_R1__Guideline.pdf (accessed on 15 December 2018).
- EC. Technical Material and Preparations: Guidance for Generating and Reporting Methods of Analysis in Support of Pre- and Post-Registration Data Requirements for Annex II (Part A, Section 4) and Annex III (Part A, Section 5) of Directive 91/414. 1996. Available online: https://ec.europa.eu/food/sites/food/files/plant/docs/pesticides_ppp_app-proc_guide_phys-chem-ana_tech-mat-preps.pdf (accessed on 15 December 2018).
- APVMA. Guidelines for the Validation of Analytical Methods for Active Constituent, Agricultural and Veterinary Chemical Products. 2004. Available online: http://apvma.gov.au/sites/default/files/docs/guideline-69-analytical-methods.pdf (accessed on 15 December 2018).
- Kuhn, E.R. Water injections in GC—How wet can you get? LCGC Asia Pac. 2002, 5, 30–32. [Google Scholar]
Authors | Detection Method | Column | Concentration Range (ppm) a |
---|---|---|---|
Lee et al. [13] | GC–FID b | HP–5 | 0–20,000 |
Najar-Rodriguez et al. [14] | GC–FID | GS–Q | 0–25,000 |
Hall et al. [12] | GC–FID | GS–Q | 0–25,000 |
Emery et al. [19] | GC–FID | GS–Q | 0–20,000 |
Park et al. [20] | GC–FID | HP–5 | 0–75,000 |
Pranamornkith et al. [21] | GC–FID | GS–Q | 0–25,000 |
Ren et al. [2] | GC–NPD c | GS–Q | 0–25,000 |
Cho et al. [22] | GC–FID | DB–WAX | 0–40,000 |
Park et al. [23] | GC–FID | DB–WAX | 0–20,000 |
Ren et al. [24] | XK–3–TCD d | – | 0–10,000 |
Sarwar et al. [25] | GC–NPD e | J&W | 0–50,000 |
O’Brien et al. [26] | GC–NPD e | DB–WAX | 0–20,000 |
Variable | Parameter |
---|---|
Laboratory temperature | 25 ± 1 °C |
Column | Agilent J&W GS–Q |
Column dimensions | Length 30 m, internal diameter 0.53 mm, film thickness 0 mm |
Carrier gas | Helium |
Pressure | 27 psi |
Total flow | 239.79 mL/min |
Injection volume (sample loop volume) | 3 mL (250 µL) |
Split ratio | 5:1 @ 197.32 mL/min |
Temperature program | Isothermal 150 °C |
Detector temperature | 300 °C |
Inlet temperature | 150 °C |
H2 flow | 100 mL/min |
Air flow | 400 mL/min |
Makeup flow (nitrogen) | 0.5 mL/min |
Total runtime | 0.6 min |
APVMA a | ICH b |
---|---|
The LOD of an analytical method is the lowest amount of an analyte in a sample that can be detected, but not necessarily quantified as an exact value. | The DL of an individual analytical procedure is the lowest amount of analyte in a sample which can be detected but not necessarily quantified as an exact value. |
X = Average response SD = The standard deviation of the response | b = slope of the calibration curve SD = standard deviation of the response |
APVMA a | ICH b | EC c |
---|---|---|
The limit of quantification (LOQ) is the lowest amount of the analyte in the sample that can be quantitatively determined with defined precision under the stated experimental conditions. | The quantification limit (QL) of an individual analytical procedure is the lowest amount of analyte in a sample which can be quantitatively determined with suitable precision and accuracy. | Defined as the lowest concentration tested at which an acceptable mean recovery with an acceptable RSD is obtained. |
** Not given | ||
X = Average response SD = The standard deviation of the response | B = slope of the calibration curve SD = standard deviation of the response |
Peak Area | ||||||||
---|---|---|---|---|---|---|---|---|
Conc. (ppm) | Rep. 1 | Rep. 2 | Rep. 3 | Rep. 4 | Rep. 5 | Average | %SE a | %RSD b |
5000 | 2024 | 2010 | 2084 | 2154 | 2105 | 2075.19 | 1.146 | 2.56 |
10,000 | 3988 | 4038 | 3932 | 3966 | 3976 | 3979.95 | 0.389 | 0.87 |
15,000 | 5459 | 5308 | 5390 | 5361 | 5447 | 5392.94 | 0.463 | 1.03 |
20,000 | 7095 | 7291 | 7319 | 7368 | 7284 | 7271.45 | 0.573 | 1.28 |
25,000 | 9383 | 9133 | 9180 | 9391 | 9365 | 9290.39 | 0.533 | 1.19 |
40,000 | 14,527 | 14,719 | 14,735 | 15,034 | 14,723 | 14,747.40 | 0.493 | 1.10 |
Average | – | – | – | – | – | – | 0.607 | 1.36 |
Conc. (ppm) | Rep. 1 | Rep. 2 | Rep. 3 | Rep. 4 | Rep. 5 | Average | Conc. (ppm) a | Accuracy b |
---|---|---|---|---|---|---|---|---|
15,000 | 5459 | 5308 | 5390 | 5361 | 5447 | 5392.943 | 14,603.31 | 97.4 |
20,000 | 7095 | 7291 | 7319 | 7368 | 7284 | 7271.45 | 19,690.04 | 98.5 |
25,000 | 9383 | 9133 | 9180 | 9391 | 9365 | 9290.393 | 25,157.05 | 100.6 |
Average | – | – | – | – | – | – | – | 98.8 |
Rep. | Conc. (ppm) |
---|---|
1 | 0.636 |
2 | 0.565 |
3 | 0.693 |
4 | 0.566 |
5 | 0.597 |
6 | 0.542 |
7 | 0.620 |
8 | 0.659 |
9 | 0.653 |
10 | 0.583 |
Average | 0.611 |
SD a | 0.046 |
%RSD b | 7.543 |
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Brierley, S.E.; Adlam, A.R.; Hall, M.K.D. Quantification of Ethanedinitrile in Air Using a New and Accurate Gas Chromatography Method. Methods Protoc. 2019, 2, 1. https://doi.org/10.3390/mps2010001
Brierley SE, Adlam AR, Hall MKD. Quantification of Ethanedinitrile in Air Using a New and Accurate Gas Chromatography Method. Methods and Protocols. 2019; 2(1):1. https://doi.org/10.3390/mps2010001
Chicago/Turabian StyleBrierley, Sam E., Anthony R. Adlam, and Matthew K. D. Hall. 2019. "Quantification of Ethanedinitrile in Air Using a New and Accurate Gas Chromatography Method" Methods and Protocols 2, no. 1: 1. https://doi.org/10.3390/mps2010001