Dioxins analysis in fly ash samples by using GC/MS/MS

Introduction

Method

The measurement was performed using GC triple quadrupole mass spectrometer JMS-TQ4000GC UltraQuad™ TQ. The measurement condition is shown in Table 1, and the selected reaction monitoring (SRM) transitions are shown in Table 2. The Japanese industrial standards (JIS) dioxin/furan calibration solution in nonane(Cambridge Isotope Laboratories, Inc.) was used as the standard sample. The concentration range is shown in Table 3.

Table 1 Measurement condition

Table 2 SRM transition

Table 3 Standard sample for calibration curve

Result

Peak detection status of CS1

The SRM chromatogram peaks created by averaging the SRM data for the CS1 quantitation ion and reference ion are shown in Figure 2. For the average SRM chromatogram peak, all isomers, including 2378-T4CDD, which is considered to be the most toxic isomer, were observed with good peak shape.

Figure 2 Average SRM chromatogram peaks of CS1

RSD of Av-RRF from CS1-5

The relative standard deviation (RSD) of the average relative response factor (Av-RRF) using the measurement data of CS1-5 (CS1: 5 times, CS2-5: 3 times each repeat measurement data, 17 points in total) is shown in Table 4. The JIS for GC/HRMS requires that a total of 15 or more data points over the entire concentration range be used to construct a calibration curve, and further specifies that the RSD of the Av-RRF should be less than 10%. The RSD obtained in this measurement ranged from 3.8 to 8.7%, and it was confirmed that all isomers met the reference value (10%) of the JIS for GC/HRMS.

Table 4 RSD of average RRF

IDL

The instrument detection limit (IDL) is shown in Table 5. The JIS for GC/HRMS specifies that the IDL is calculated by tripling the standard deviation of the quantification value obtained from five replicate measurements of the lowest concentration. The IDLs obtained in this measurement ranged from 0.033 to 0.148 pg, and it was confirmed that all isomers met the reference values of the JIS for GC/HRMS.

Table 5 IDL by CS1

Dioxins detection status in fly ash samples

The average SRM chromatogram peaks detected by the JMS-TQ4000GC and the average selected ion monitoring (SIM) chromatogram peaks detected by the JMS-800D are shown in Figure 3. The obtained peak pattern of 4-10 chlorinated isomers of JMS-TQ4000GC was almost the same as the peak pattern of JMS-800D. Next, the quantitative values obtained by JMS-TQ4000GC and JMS-800D are shown in Table 6, and the comparison results are shown in Figure 4. The correlation coefficient R2 was 0.999, confirming that the quantitative values obtained by JMS-TQ4000GC are equivalent to those of JMS-800D.

PCDDs

PCDFs

Figure 3 Comparison  average SIM chromatogram peaks by JMS-800D with average SRM chromatogram peaks by JMS-TQ4000GC

Conclusion

In this application note, the dioxins analysis using the GC/MS/MS “JMS-TQ4000GC” was investigated. As a result, all isomers are detected even in CS1, which is the lowest concentration standard sample. The RSD of Av-RRF in CS1-5, and the IDL in CS1 also met the reference value of the JIS for GC/HRMS. In addition, the quantitative values of dioxins in the fly ash samples were almost equivalent to those of the JMS-800D. These results confirm that the JMS-TQ4000GC is effective in the analysis of dioxins.

References

[1] JIS K0311(2020)
[2] JIS K0312(2020)
[3] COMMISSION REGULATION (EU) 2017/644 of 5 April 2017
[4] GB 5009, 205-2024

Solutions by field

Environment

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JMS-TQ4000GC UltraQuadTM TQ