Proceedings of the International Cyanide Detection Testing Workshop

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Philippines 2000) obtained at a Live Food Fish Trade meeting held in Hong Kong in 2000 that only partially described the actual SOP used by IMA. No attempt was made by either Ms. Mak or Dr. Renneberg to contact IMA to obtain the correct SOP manual. The assertion by Mak et al (2005b) that “The refl ux distillation method together with an ISE was not sensitive enough for the determination of cyanide traces in postcyanide exposed fi sh” is incorrect (Rubec 2007). Since, this was associated with a discussion of the methods used by the IMA, the implication was that the IMA could not reliably measure cyanide concentrations below 0.26 mg/L. However, Mak (2003) did not use the same ISE equipment used by the IMA. She used a Pheonix ISE electrode (Cat No. CN01503); connected to a Jenway pH/ mV meter (model 3305); which has a range of detection on a linear semi-log plot of 0.26 to 260 ppm (mg/L). The IMA used a Thermo-Orion ISE electrode (#9406BN) that can reliably detect cyanide concentrations down to 0.03 mg/L on a linear semi-log plot (ASTM 1997). Likewise, the pH/ISE meter used by Mak (2003) differs from that used by the BFAR/IMA laboratories (Thermo-Orion Model 920A) (Manipula 1995, Manipula et al.2001c). The Thermo Orion ISE equipment (ISE electrodes and meter) is capable of detecting cyanide ion in solution with a straight-line calibration on a semi-log plot down to 0.02 mg/L (2 ppb) (Frant et al. 1972; Orion Research Inc. 1975, 1997; Sekerka and Lechner 1976). This was routinely done with daily calibrations conducted by the IMA laboratories using the Thermo Orion ISE equipment (Manipula et al. 2001c). This is similar to round-robin fi ndings by the ASTM (1987). 52 Mak et al. (2005b) reported that the lower range of detection for cyanide ion using a colorimetric method was 0.026 ppm. Hence, they claimed that the colorimetric method had a higher sensitivity than the ISE method (actually both have about the same lower limit of detection). They claimed that the cyanide refl ux distillation method together with the ISE was not sensitive enough for the determination of traces in post-cyanide exposed fi sh. A series of QA/QC experiments were conducted that are irrelevant considering that the wrong ISE equipment was utilized (Mak 2003). Mak et al. (2005b) mistakenly concluded: “The cyanide distillation method combined with the ISE described in the SOP manual and employed by the IMA laboratories requires considerable modifi cation and elaboration. A reliable and ultra sensitive system for cyanide detection in fi sh is urgently needed.” It should also be noted that the lower limit of detection for the biosensor method that Mak et al. (2005c) developed is 0.0286 ppm (mg/L), which is about the same as the Thermo Orion ISE method on a linear calibration (Sekerka and Lechner 1976). Hence, it is not more sensitive than the ISE method (ASTM 1997). The present authors, including Dr. Kobelski and Dr. Logue, believe that the ISE method associated with the SOP manual used by the IMA (Manipula 1995) and by the various agencies that also use the method (including APHA, ASTM, US-EPA and BFAR) is scientifi cally reliable, although this has not been demonstrated with fi sh tissue in controlled experiments. This is also the opinion of Dr. Ellen Gonter who helped develop the ISE method for ASTM, Dr. Martin Frant of Thermo Orion who developed the cyanide ISE electrode, and Dr. George Dixon, an expert concerning cyanide physiology in fi sh and Vice-Dean of Research at the University of Waterloo, Canada (all three provided letters
endorsing the IMA’s use of the ISE method after the fl awed MAC review). There was no need to develop a new method (MAC 2004, Mak 2003, Mak et al. 2005b), since the SOP using ISE presently being applied by BFAR (Manipula 1995, Manipula et al. 2001b, 2001c) is reliable and has international acceptance. Any new method would need to go through extensive evaluations and roundrobin comparisons before it could be accepted by the scientifi c community and by agencies regulating the marine aquarium trade. Dr. Kobelski near the end of the CDT Workshop suggested that round-robin comparisons needed to be conducted involving the ISE method and that comparisons needed to be made with an independent cyanide detection method. He suggested the use Gas Chromatography linked to Mass Spectrometric analyses (GC- MS), since this is the method used by the CDC (Kage et al.1996, Dumas et al. 2005, Murphy et al. 2006) and has recently been accepted by the US-EPA for the analysis of cyanide in drinking water. A GC-MS apparatus used in Texas to measure cyanide is depicted (Figure Figure 4. A gas chromatography-mass spectrometry (GC-MS) apparatus used to determine cyanide concentrations. Image provided by Dr. David Klein, Texas Department of State Health Services. 53 4). This would require that fi sh be dosed with cyanide and frozen samples be sent to two or three separate laboratories. He suggested that a statistically signifi cant number of samples should be analyzed by the ISE method. This could be time consuming and expensive, if done by laboratories in the U.S.A. According to Dr. Kobeski there are 46 laboratories in the CDC network, which are qualifi ed for trace analysis of cyanide in clinical samples. The Michigan Department of Community Health has been conducting fi sh exposure studies to detect cyanide using GC- MS. Preliminary results from the Michigan laboratory found a background level of cyanide in freshwater fi sh in the 0.01 mg/L (10 ppb) range. The Michigan laboratory has cross-validated the headspace GC-MS method with the distillation ISE method for the US-EPA using cyanide in solution. Dr. Logue suggested that there may be background levels of cyanide in MAF. It is possible that the cyanide concentrations detected in the fi sh tested by the BFAR/ IMA laboratories were background levels of cyanide rather than cyanide resulting from cyanide fi shing. Ms. Manipula (Chief Chemist for the BFAR/IMA laboratories) pointed out that the IMA had tested MAF caught with nets and found no detectable level of CN - (zero) present in the fi sh. Hence, she believes that the cyanide being detected resulted from cyanide fi shing. Some testing needs to be done to verify that MAF do not have background levels of cyanide, or that the background concentration is below the detectable limit (BDL) determined from the linear calibration for the ISE method. Dr. Kobelski agreed that the ISE method was probably reliable (Email: February 21, 2008). “I have repeatedly said that I believe that the ISE method is probably valid – my failure to
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Proceedings of the International Cy
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Proceedings of the Cyanide Detectio
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ACKNOWLEDGEMENTS The Proceedings of
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PREFACE The International Cyanide D
Page 11 and 12: EXECUTIVE SUMMARY The International
Page 13 and 14: ATCA) in homogenized fi sh tissue m
Page 15 and 16: Validation of the ISE method applie
Page 17 and 18: Importing countries should also req
Page 19 and 20: INTRODUCTION Cyanide fi shing is a
Page 21 and 22: through the implementation of a net
Page 23 and 24: Working Group 2 The Export Working
Page 25 and 26: o o o o Can the U.S. require verifi
Page 27 and 28: Polymeric membrane based ion select
Page 29 and 30: Goal 2: Provide recommendations on
Page 31 and 32: hands-on training that develops a d
Page 33 and 34: Goal 3: Identify research needs to
Page 35 and 36: Working Group 1 Participants Bob KO
Page 37 and 38: estimated at roughly 3 to 5 days. H
Page 39 and 40: Goal 2 : Identify steps, agreements
Page 41 and 42: 3) certifi cate, but tests positive
Page 43 and 44: Report from Working Group 3 The Par
Page 45 and 46: No. of Shipments 6,000 5,000 4,000
Page 47 and 48: Goal 3: Provide a recommendation wi
Page 49: Working Group 3 Participants Eric P
Page 53 and 54: Introduction Since the early 1960
Page 55 and 56: ainbow trout exposed to 40 mg SCN -
Page 57 and 58: Blennies, which were net-caught and
Page 59 and 60: electrical potential (similar to an
Page 61: in the Philippines under contract w
Page 65 and 66: The intended products from the rese
Page 67 and 68: WPCF 1992, 1998). Both of these stu
Page 69 and 70: ASTM (1997) Standard test methods f
Page 71 and 72: Kuegsen, M., Kloock, J.P., Knobbe,
Page 73 and 74: Philippines. In Proceedings from th
Page 75 and 76: 3) 4) 5) 6) the metabolism of cyani
Page 77 and 78: or new matrices. 5.2.3 Modifi catio
Page 79 and 80: Level Two: The method should be val
Page 81 and 82: of cyanide exposure and to identify
Page 83 and 84: Special considerations for the anal
Page 85 and 86: tissue samples indispensable. Altho
Page 87 and 88: y reduction and subsequent separati
Page 89 and 90: can also be used for analysis of cy
Page 91 and 92: thiocyanate in saliva and serum bas
Page 93 and 94: are many discrepancies in the liter
Page 95 and 96: Table 3. Analytical Methods to dete
Page 97 and 98: Poisoning, In Textbook of military
Page 99 and 100: (70) Odoul, M., Fouillet, B., Nouri
Page 101 and 102: V. (1975) Stable reagents for the c
Page 103 and 104: (159) Felscher, D. and Wulfmeyer, M
Page 105 and 106: Purpose of this Document The purpos
Page 107 and 108: day. One cyanide tablet (2 g) is mi
Page 109 and 110: 10-90% following exposure to cyanid
Page 111 and 112: existing cyanide detection methods
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- Plasma lactate — elevated plasm
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Method Advantages Disadvantages Hig
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Paper Method Matrix Detection Limit
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Table 4 lists experts identifi ed t
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X Jerry Thomas CDC Em Steve Borron
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References Barber, C. and Pratt, V.
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Rates of Recovery. Environmental Ma
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COUNTRY REPORTS
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The first three of these destructiv
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enforcement is minimal. There is an
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1. Management/guidance to the Minis
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in Vietnam now and requires more ef
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Figure 2: Administrative structure
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References Baquero, J. (1999) Marin
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Acronyms • CDT • Cyanide Detect
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Law/Ordinance/Decree /Decision 52/2
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of samples required for analysis. U
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Field test kit. BFAR recognizes the
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Political Will Having planted the s
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gravely by fi shing communities. Th
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ecome the partner and counterpart o
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Ion-Selective Electrodes for Cyanid
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References Alban, J., Manipula, B.E
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levels with mV readings recorded as
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Trends Determined by Cyanide Testin
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Implementing agencies: • Quaranti
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APPENDIX
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1:30 Overview of and Potential Cyan
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Kristine Johnson Director Kingfi sh
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Assessment of U.S. Role in Trade: U
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