Lutz Alder

Reduction of Matrix Effects in Liquid Chromatography–Electrospray Ionization–Mass Spectrometry by Dilution of the Sample Extracts: How Much Dilution is Needed?

In this study, the relationship between matrix concentration and suppression of electrospray ionization (matrix effects) was investigated. Ion suppression of pesticides present in QuEChERS extracts was used as an example. Residue-free extracts of four different commodities, avocado, black tea, orange, and rocket (arugula), were fortified with 39 pesticides each. For many of the resulting 156 pesticide/matrix combinations, considerable matrix effects were observed if the coextracted matrix of 8 mg of equivalent sample (in the case of tea: 1.6 mg) was injected with the undiluted extracts. The reduction of these matrix effects was measured at 10 levels of dilution up to 1000-fold. The results obtained indicate a linear correlation between matrix effects and the logarithm of matrix concentration (or dilution factor) until the zero-effect level of further dilution was reached. Using the logarithmic equations, it could be shown that a dilution of extracts by a factor of 25-40 reduces ion suppression to less than 20% if the initial suppression is ≤80%. For stronger matrix effects or complete elimination of suppression, higher dilution factors were needed. The observed correlation was independent from the two instrument platforms used, but the degree of matrix effects differed slightly between the two mass spectrometers in this study.

Compensation of Matrix Effects by Postcolumn Infusion of a Monitor Substance in Multiresidue Analysis with LC−MS/MS

This study systematically compares matrix effects in liquid chromatography (LC) coupled by electrospray ionization (ESI) in the positive mode with tandem mass spectrometry (MS/MS) for 129 pesticides in 20 plant matrixes. In total, 2388 analyte/matrix combinations were evaluated. Permanent postcolumn infusion (PCI) of analyte standards was used to quantify matrix effects over the whole chromatographic run time. This allowed the analyte signal suppression or enhancement, by different coeluting matrix components, to be assessed throughout the duration of an entire chromatographic run, i.e., independent of a specific retention time. Matrix effects occurring at a certain retention time in one matrix were surprisingly similar for different analytes with diverse physicochemical properties. On the basis of this finding, a new approach for matrix effect compensation in multiresidue analysis was developed in which one single monitor substance is permanently added postcolumn. Signal intensities of all analytes obtained by LC-MS/MS analysis of sample extracts are then corrected for the matrix effect recorded by the monitor substance. With the use of this approach, strong matrix effects could be reduced and apparent recoveries increased from 45% to 85% on average. With dependence on the particular sample matrix, between 69% and 100% of the analytes showed recoveries between 60% and 140% after correction. Thus this approach may significantly reduce the number of cases in which standard addition is required to confirm violations of maximum residue levels.

Preparation and structure of high-chlorinated bornane derivatives for the quantification of toxaphene residues in environmental samples

SummaryThe HRGC-determination of Taxophene® residues in the presence of other chlorinated hydrocarbons with similar retention times is often difficult. This problem can satisfactorily be overcome by using purely isolated high-chlorinated bornane derivatives (7–17) as standard. The method is highly selective for measuring toxaphene in complex environmental matrices, such as fish, and can also be used for evaluating the changes in the relative distribution that may have resulted from bioaccumulation and environmental transformation.

A multimethod for the determination of 150 pesticide metabolites in surface water and groundwater using direct injection liquid chromatography-mass spectrometry.

Based on the information available on 293 pesticides (herbicides, insecticides, fungicides, biocides, growth regulators) 210 pesticide metabolites were selected for inclusion into a multimethod for the analysis of ground and surface water. With the final method 150 pesticide metabolites can be analysed from groundwater and surface water by direct injection-liquid chromatography-electrospray ionization-tandem mass spectrometry with multiple-reaction monitoring. For most of these metabolites this is the first method published. For all metabolites linear calibration in drinking water was possible, with a lower limit of calibration of 0.1 μg/L achieved for 142 analytes and of 0.01 μg/L for 113 of the analytes. Matrix effects in ground and surface water compared to those in the drinking water were moderate (±20%) for 87% of the analytes. For critical sample/analyte combinations standard addition has to be used for correct quantification. This method allows for an extensive study of the occurrence of previously unknown or undetectable pesticide metabolites in groundwaters and surface waters.

Emerging pesticide metabolites in groundwater and surface water as determined by the application of a multimethod for 150 pesticide metabolites.

A recently developed multimethod for the determination of 150 pesticide metabolites was exemplarily applied to 58 samples of groundwater and surface water. 37 of these metabolites were detected in at least two samples with a concentration ≥0.025 μg/L. The detected metabolites were ranked according to their concentration and frequency of detection. Findings are clearly dominated by metabolites of chloroacetanilide herbicides, but metabolites of sulfonylurea and thiocarbamate herbicides and other herbicides (dichlobenil) together with metabolites of some fungicides (tolylfluanid, chlorothalonil, trifloxystrobin) were also prominent. A number of 17 of the ranked metabolites are denoted as emerging metabolites because no reports on their previous detection in groundwater or surface water were found. Most of them, however, were correctly predicted to occur in the summary reports of the European pesticide approval process. Median total concentrations of the analysed pesticide metabolites summed up to 0.62 μg/L in groundwater and 0.33 μg/L in surface waters. While the concentration of the individual metabolites is usually low (<0.1 μg/L) the diversity of metabolites found in one sample can be large; between two and six metabolites were detected most frequently (maximum of 12 metabolites). Runoff from urban surfaces was investigated in this study and also here previously undetected pesticide (biocide) metabolites were detected. The emerging pesticide metabolites detected in environmental water samples in this study require more extended monitoring.

The influence of electrospray ion source design on matrix effects

This study investigates to which extent the design of electrospray ion sources influences the susceptibility to matrix effects (MEs) in liquid chromatography-tandem mass spectrometry (LC-MS/MS). For this purpose, MEs were measured under comparable conditions (identical sample extracts, identical LC column, same chromatographic method and always positive ion mode) on four LC-MS/MS instrument platforms. The instruments were combined with five electrospray ion sources, viz. Turbo Ion Spray, Turbo V(TM) Source, Standard ESI, Jet Stream ESI and Standard Z-Spray Source. The comparison of MEs could be made at all retention times because the method of permanent postcolumn infusion was applied. The MEs ascertained for 45 pesticides showed for each electrospray ion source the same pattern, i.e. the same number of characteristic signal suppressions at equivalent retention times in the chromatogram. The Turbo Ion Spray (off-axis geometry), Turbo V(TM) Source (orthogonal geometry) and the Standard Z-Spray Source (double orthogonal geometry) did not differ much in their susceptibility to MEs. The Jet Stream ESI (orthogonal geometry) reaches a higher sensitivity by an additional heated sheath gas, but suffers at the same time from significantly stronger signal suppressions than the comparable Standard ESI (orthogonal geometry) without sheath gas. No relation between source geometry and extent of signal suppression was found in this study.

Levels of toxaphene indicator compounds in fish

Abstract Three toxaphene indicator compounds were determined in more than 100 samples of fish. The investigated fish included nearly all important fish species consumed in Germany. Highest residue concentrations were found in marine fish with high or moderate fat content, e.g. halibut, herring, redfish and mackerel. In fresh water species and marine fish with low fat content less contamination was found. A significant relationship between the fishing ground and the toxaphene residue could not established. Contamination levels of most species were related to the age (length) of the fish. The daily intake of total toxaphene in Germany was estimated at 2.8–5.6 ng/kg body weight.

Collaborative study on toxaphene indicator compounds (chlorobornanes) in fish oil

A validation study of a method for the analysis of four toxaphene indicator compounds in a fatty matrix was carried out. The method of analysis consisted of cleanup by gel permeation and absorption chromatography followed by GC-ECD determination. In total, five materials with indicator compound concentrations in the range from 6 to 60 μg/kg and a blank material were analysed. The mean recovery was found to be between 77 and 100%. For three compounds, the analytical results have shown a relative standard deviation of reproducibility of 21 ± 4 %. A higher variation was found for the fourth compound (mean 29 %). The method is recommended for routine analysis in food inspection in Germany.

Targeted Pesticide Residue Analysis Using Triple Quad LC-MS/MS

The determination of pesticide residues by HPLC-MS/MS requires decisions on a multitude of analytical parameters. This includes the selection of eluents, columns and ion sources, but also the optimization of the tandem mass spectrometer for the selected target analytes. Another aspect is the use of the restricted acquisition time between two chromatographic data points. An appropriate selection of all these parameters as well as the measures to avoid interference by cross talks and wrong quantitative results by matrix effects is discussed in this chapter.

Variation of toxaphene indicator compounds in fish from single fishing grounds : Conclusions for sampling

The levels of three toxaphene indicator compounds were determined in individual lots of herring, redfish, Greenland halibut and farmed salmon. Concentration levels of the three marine fish species were characterised by a right-skewed frequency distribution whereas residue concentrations in farmed salmon were normally distributed. The toxaphene concentrations in the edible part of redfish, herring and Greenland halibut were found to be positively correlated to the sizes and thus to age. As results show, for representative sampling of a landed catch, not more than 10 individual fishes from typical size classes of a lot are necessary for a pooled sample.