Organic micropollutants in Rhine and Meuse a - Riwa

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Table 1 Detected pesticides and metabolites in the Rhine and the Meuse; peak heights relative to the internal standard (1 Jig/l atrazine = 7,300 units) (blank cell indicates not detected) Rhine monuron 375 oxadixyl 242 isoproturon 193 201 atrazine 69 201 731 428 382 dimethachlor 166 200 258 Meuse chloridazon 119 carbendazim 315 665 monuron 159 106 187 86 3,4- 250 442 140 102 187 267 dichlorophenylmethyl urea chlortoluron 11453 isoproturon 386 304 atrazine 138 304 1715 2438 1860 1125 1016 1351 diuron 365 420 2144 3744 856 1259 1435 1103 1693 dimethachlor 106 108 127 207 121 metobromuron 972 In Table 2, for atrazine, diuron and isoproturon, the peak heights are converted to concentrations and compared with the results of the specific determination methods used in the framework of the regular RIWA research (RIWA, 1998). In the HPLC/UV fingerprint of the Rhine, the indicated value for low diuron content was severely influenced by the presence of another peak. For this reason diuron was not included for the Rhine. With the exception of a single result, the table shows good to very good agreement between the methods, in particular where high contents are involved. III!!j Table 2 Concentrations ofisoproturon, atrazine and diuron as determined with the HPLC/UVfingerprint and as measured within the framework ofthe regular RIWA research (blank cell indicates not detected). \X+9i >/Wltt:W@@ Rhine isoproturon HPLC 0.1 * 0.1 * RIWA 0.05 0.05 atrazine HPLC om * 0.03* 0.10 0.06 0.05 RIWA 0.02 0.03 0.06 0.12 0.08 0.04 0.04 0.02 Meuse isoproturon HPLC 0.2* 0.2* RIWA 0.17 0.14 0.06 0.08 atrazine HPLC 0.02* 0.04* 0.23 0.33 0.25 0.15 0.14 0.18 RIWA 0.04 0.03 0.38 0.32 0.36 0.16 0.15 0.07 0.01 diuron HPLC 0.06 0.07 0.35 0.61 0.14 0.21 0.24 0.18 0.28 RIWA 0.06 0.12 0.44 0.74 0.21 0.21 0.22 0.21 0.17 * Accurate quantification not possible due to co-elution of atrazine and isoproturon peaks. RIIIN'A 17
In this study, a metabolite of diuron, 3,4-dichlorophenylmethyl urea, was studied for an extended period for the first time. Whenever diuron is present (in the Meuse), the metabolite is also present, albeit in much lower concentrations (see Figure 7). The metabolite reaches its highest concentration in June: approximately 0.08 !lg/l (diuron: approximately 0.6 !lg/l). Other metabolites of phenyl urea herbicides, for which a method has recently been developed (Reimers, 1998), were not encountered in relevant concentrations. 4000 3000 i_3A.OCPHMU.1 I ----,llJdluron ~ 2000 1000 Figure 7 Development ofthe peak heights ofdiuron and the metabolite 3,4 dichlorophenylmethyl urea in the Meuse 4.4 HPLCIUV fingerprint as an early warning system: chlortoluron The HPLC/UV fingerprint generates data on the overall water quality and on the presence of a broad range of individual (identified and unidentified) compounds. The method is thus highly suitable for use as an early warning system. Particularly since the fully automated method, which was applied in the laboratory in this study, can also be applied in an unmanned manner on location. This would only need a few adaptations of the instrument. This method also has the advantage that in the case of a positive signal (for example a peak that exceeds a threshold value set beforehand), the peak might be identified by mass spectrometry (LCIMS). Then it would be possible to reach a conclusion, on the basis of literature or an expert opinion, on the significance (for example the health implications) of the pollution. Chlortoluron incident A very good example of the possibilities offered by the HPLC/UV fingerprint as an early warning system is the sudden occurrence of chlortoluron in the Meuse in August 1997. An extremely high peak in the August sample from the Meuse led to a more detailed investigation. Comparison with the method for phenyl urea showed that the retention time and the UV absorption spectrum agreed perfectly with those of chlortoluron. Inquiries with a small number of water companies that treat Meuse water, and with RIZA in Lelystad, did not at first yield any agreement. Finally, the RIZA measuring station in Eijsden confirmed that at the time of sampling for the RIWA study there had been an increased concentration of chlortoluron in the Meuse, which had lasted only a few days. Because, by coincidence, the RIWA samples had 18 RIM.fA
Page 1 and 2: VERENIGING V A N RIVIERWATERBEDRIJV
Page 3 and 4: November 1999 Organic micropollutan
Page 5 and 6: APPENDIX? APPENDIX 8 APPENDIX 9 Ove
Page 7 and 8: 1 INTRODUCTION In the framework of
Page 9 and 10: 2 MEANING AND INTERPRETATION OF THE
Page 11 and 12: 1997). Not only can the peak patter
Page 13 and 14: 3.3 Processing of the data Peaks fr
Page 15 and 16: ------------------------ What is no
Page 17: 4.2 Individual compounds As stated
Page 21 and 22: Overlay at 215 nm 0,04 Meuse Octobe
Page 23 and 24: Table 3 Frequency ofoccurrence and
Page 25 and 26: 4.7.4 Notable monthly samples with
Page 27 and 28: Selection of unidentified substance
Page 29 and 30: metabolites) in the Rhine and the M
Page 31 and 32: APPENDIXl Sampling data Rhine (Lobi
Page 33 and 34: V-.l SanpleName: Rijn mrt' 97 S3IlI
Page 35 and 36: UJ ~ I SanpleNaIlIl: Haas maart' 97
Page 37 and 38: APPENDIX 5 Summed peak surface area
Page 39 and 40: 38 RllIN'A
Page 41 and 42: +:- Corrected IRhine 0 retention ti
Page 43 and 44: 42 RIMfA
Page 45 and 46: ..j::.. ..j::.. Corrected retention
Page 47 and 48: 46 RIMfA
Page 49 and 50: SPEC: Samp: Conun: Mode: Oper: Base
Page 51: Colophon Publisher Cover and printi

Organic micropollutants in Rhine and Meuse a - Riwa

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