Realising the sample type limitations of the online enrichment approach

Anthony Gravell

Matrix Effects (1)

Definition: It is the difference in the response of an analyte in a sample as compared to a standard solution

Matrix effects like signal enhancement or suppression can severely compromise quantitative analysis of environmental samples with LCESIMS Matrix effects are attributed to organic and/or inorganic components that co-elute with an analyte Can be highly variable between samples and difficult to predict Matrix effects are strongly dependent upon the chromatographic retention time

Matrix Effects (2)

The mechanism by which compounds interfere with each other during the ESI process is still not clear Unfortunately, a QQQ operating in the MRM mode is just as susceptible as a single quad

Standard addition of each analyte into each sample may be used to compensate

Cannot avoid the loss of sensitivity that is accompanied by signal suppression and the variability in method sensitivity that may occur between samples of a series

APCI is less matrix sensitive than ESI

APCI cannot serve all the highly polar and ionic analytes that are well amenable to ESI

Matrix Effects (3)

Matrix effects may be compensated by using internal standards More than one internal standard may be needed Matrix effects can be reduced by decreasing the flow that is delivered to the ESI interface Reducing the flow into the ESI interface reduces the amount of organic material that requires ionization at a given period of time. Droplet size decreases with decreasing flow and droplet surface area increases substantially Less competition between target analytes and sample matrix components during desolvation and ionization in ESI Increase the efficiency of nebulisation/evaporation by increasing nebuliser flow to maximum

Experimental set up for determining ion suppression with LC-MS-MS

Liquid Chromatograph

Mixing tee

Mass Spectrometer

Syringe pump

Extracted Ion Chromatograms Ion Suppression

Target analyte

Chromatogram clearly showing the ion suppression region at the same retention time as the target analyte

Recoveries of Acid Herbicides from Various Aqueous Matrices

Matrix DI water

Spike Level (ug/L) 0.1 %RSD % Recovery %RSD % Recovery

Clopyralid

Picloram

Phenoxyacetic acid

2,3,6 - TBA

Dicamba

Phenoxypropionic acid

Benazolin

Fluroxypyr

4 CPA

5.8 105.7 8.9 72.1

6.4 106.8 3.3 61.4

9.6 104.4 8.5 67.2

12.7 96.0 21.2 86.2

24.4 100.5 9.2 70.5

6.8 97.2 7.4 75.6

10.7 106.8 11.1 61.3

6.2 92.4 7.1 66.9

8.7 100.6 6.3 76.5

0.1 River water

Treated sewage effluent

0.1

%RSD % Recovery

9.8 63.8

8.9 69.5

10.5 64.2

20.3 68.5

6.0 72.8

14.8 58.3

6.2 62.1

11.0 77.0

Saline

0.1

%RSD % Recovery

20.3 100.1

11.2 94.1

22.5 123.0

28.3 90.5

11.7 95.3

10.8 84.5

17.9 83.7

14.2 77.8

14.2 101.7

Matrix DI water

Spike Level (ug/L) 0.1 %RSD % Recovery %RSD % Recovery

Phenoxybutyric acid

Bentazon

Bromoxynil

2,4-D

MCPA

Ioxynil

Dichlorprop

2,4,5-T

Mecoprop

2,4-DB

MCPB

Fenoprop

10.0 96.3 9.9 77.5

5.8 90.4 3.2 89.1

15.0 102.8 7.6 85.9

6.4 91.1 7.2 97.3

8.4 86.8 6.7 93.6

7.1 92.8 5.1 89.0

7.3 91.2 5.8 89.0

7.2 93.6 3.8 86.1

8.3 87.1 4.5 90.5

11.3 86.4 6.7 86.2

9.5 96.4 8.6 87.7

9.0 91.4 5.8 89.9

0.1 River water

Treated sewage effluent

0.1

%RSD % Recovery

7.4 83.2

4.6 90.5

10.4 91.2

11.3 83.9

3.7 81.7

6.6 87.1

4.3 93.0

7.8 87.7

8.6 78.6

12.2 91.6

11.5 85.9

8.4 87.6

Saline

0.1

%RSD % Recovery

13.0 72.7

11.2 92.2

16.2 123.9

21.3 28.8 10.4 106.6 108.4 119.6

18.3 109.4

12.3 106.3

26.6 105.2

18.2 78.2

12.4 82.9

14.7 109.7