Monitoring organic pollutants within the WFD: Why and How

Transcription

1 Monitoring organic pollutants within the WFD: Why and How T. P. Knepper Europa University of Applied Sciences Fresenius, Germany. Outline: Why do we need to monitor within the WFD? Strategy of monitoring Results of monitoring (WWTP-influent & -effluent; surface & ground water; soil) How to monitor Sampling campaigns Analysis Quality Assurance 1

2 Strategy of monitoring (WFD): Each compound -and also metabolite which could possibly appear has to be investigated..if an analytical method is available and the analysis not too costly Time shedule WFD: Dec. 2 Dec. 23 Dec. 24 Dec. 26 Dec. 29 Dec. 212 Dec. 215 In force National law implementation Characterisation and inventory Programs for monitoring are ready for application Program for measures and plans for management of river basin are finished Program for measure is implemented good condition (ecological + chemical); new plans for management of river basin 2

3 Priority Substances and Other Pollutants The Commission proposal (COM(26)397 final) setting environmental quality standards for surface waters of 41 dangerous chemical substances includes the 33 priority substances and 8 other pollutants. 1) Priority Substances 33 substances or group of substances are on the list of priority substances including selected existing chemicals, plant protection products, biocides, metals and other groups like Polyaromatic Hydrocarbons (PAH) that are mainly incineration by-products and Polybrominated Biphenylethers (PBDE) that are used as flame retardants.. Chemical status - 33 priority compounds Organic compounds (n = 16) (2) Anthracene (4) Benzene (5) Brominated diphenylethers (7) Chloroalkanes (C 1 -C 13 ) (1) 1,2-Dichloroethane (11) Dichloromethane (12) DEHP (15) Fluoranthene (17) Hexachlorobutadiene (22) Naphthalene (24) Nonylphenols (4-para-N) (25) Octylphenols (para-tert-o) (26) Pentachlorobenzene (28) PAK (Benzo-a-pyrene, Benzo-b-fluoranthene, Benzo-g,h,i-perylene, Benzo-k-fluoranthene, Indeno- 1,2,3-cd-pyrene) (31) Trichlorobenzenes (1,2,4-TB) (32) Trichlormethane Identified as priority dangerous compounds (n = 13) Metals (n = 4) (6) Cadmium (2) Lead (21) Mercury (23) Nickel Pesticides (n = 13) (1) Alachlor (3) Atrazine (8) Chlorfenvinphos (9) Chlorpyrifos (13) Diuron (14) Endosulfan (16) Hexachlorobenzene (18) HCH (Lindan) (19) Isoproturon (27) Pentachlorophenol (29) Simazine (3) TBT-cation (33) Trifluralin 3

4 European Water Framework Directive (WFD) Starting 27 the EU-member states have to conduct monitoring programs upon organic pollutants and others. Hesse, Germany carried out a prelimary monitoring to find appropriate sampling points. Pesticides: Monitoring of surface waters 24/25 (preliminary monitoring) 119 sampling locations 95 substances 6 measurements 24 or 25 therefrom 4 in April - June Increased mean values during 2 in October -November application time Presetting of WFD For I 12 samples/a For II, III and IV 4 samples/a 4

5 European Water Framework Directive (WFD) Regulation for Pesticides in surface waters I priority pesticides quality specifications by EU (in preparation) e.g. IPU, Diuron, Atrazine II river basin targeted pesticides quality specifications by Hesse/Working Group on water issues (LAWA) III further basin targeted pesticides so far no regulation IV river basin targeted pesticides quality standard suggestion by LAWA, e.g. Terbutryn Pesticide monitoring in 24/25 pesticide quality standard [µg/l] 9-perc. [µg/l] maximum value [µg/l] Isoproturon Mecoprop (MCPP) Dichlorprop (2,4-DP) n-chloridazon Bentazone MCPA Metazachlor Diuron Metobromuron Metamitron Ethofumesate Terbuthylazine Metolachlor Atrazine Terbutryn Epoxiconazole 2,4-D Propiconazole Metribuzin Fluoxypyr Tebuconazole Fenpropimorph Terbutylazine-desethyl Dichlobenil Haloxyfop.3 / 1. * / 1.8 * / 2.9 * < l.d..21 < l.d < l.d. < l.d..9.4 < l.d..7 < l.d..4.5 < l.d. < l.d. < l.d. < l.d approx. 7 samples 74 pesticides found, therefrom 25 with max. values l.d. = limit of detection annual average value / maximum value 5

6 sampling point pesticide detection limit [µg/l] quality standard [µg/l] mean [µg/l] maximum value [µg/l] Dichlorprop (2,4-DP) ,7 MCPA Bentazon Dimethoat n-chloridazon Metolachlor Gersprenz Terbuthylazine Diuron / Babenhs.-Harreshs. Isoproturon Terbutryn / Dicamba Ethofumesat Haloxyfop Iprodion Metamitron Metobromuron Metribuzin Tebuconazole Terbutylazine-desethyl Fanggraben Biebesheim Mecoprop (MCPP) Diuron Terbutryn / Exceedings of quality standards of pesticides at sampling locations 24/25: Pesticide with quality standard Pesticide without quality standard: compound No. of QSexceedings % positive results compound No. of sampling locations with mean >.1µg/L % positive results Terbutryn Metamitron Isoproturon Ethofumesate MCPA Bentazone Mecoprop (MCPP) Dichlorprop (2,4-DP) Diuron n-chloridazon Metolachlor 2,4-D Metazachlor Propiconazole Metobromuron Metribuzin Epoxiconazole Fluroxypyr Tebuconazole Fenpropimorph Haloxyfop Terbuthylazine 1 15 Atrazine 1 9 6

7 Pesticides 24/25 Emsbach average concentration Gersprenz Pesticides 24/25 Average concentration Ecotoxicological risk all Alle pesticides PSM only pesticides with Nur PSM quality mit QN standards Very low Low Increased High Very high Extremly high 7

8 preliminary monitoring WFD WFD Monitoring since 27 Number of sampling locations Number of measurements/ sampling location Number of sampling locations Number of measurements/ sampling location Basic physical parameter / Phosphorous 24 > >12 Pesticides Heavy metal, PAH, PCB, organotin compounds in suspended matter further 4 How do pesticides enter surface waters? 8

9 Sources of organic pollutants in municipal WWTP Industry Household Traffic Agriculture indirect discharge surface runoff yard runoff WWTP WWTP surface waters Pollutants: Entry into the watercycle household agriculture water works wastewater industry indirect discharge groundwater WWTP bankfiltration polluted rivers 9

10 Waste water treatment in agglomerations affected by sensitive areas and organic loads (data January 22) Member State Agglomeration concerned Complying treatment Level Non complying treatment level Load [p.e.] % % Belgium Denmark Germany Greece Spain France Ireland Italy Luxembourg P-Reduction 9% N-Reduction 74% Netherlands Austria Portugal Finland Sweden P-Reduction 79% N-Reduction 66% United Kingdom Total MS not applying Article Comparison of pesticide concentrations in waste and surface waters [µg/l] 1,6 1,4 1,2 1,,8 WW effluent, Hesse,, n=7, mean concentration,6,4,2,1, Metamitron Isoproturon MCPP 2,4-DP MCPA Bentazone Diuron n-chloridazon Ethofumesate DEET 2,4-D Fluoxypyr Terbuthylazine Tebuconazole Simazine Atrazine,9,8 [µg/l],7,6,5,4 Main, Germany, n=35, mean concentration,3,2,1, Isoproturon MCPP DEET Atrazinedesethyl Ref.: The Handbook of environmental chemistry, Volume 5 Series water pollution: The Rhine Atrazine Diuron 2,4-DP MCPA Bentazone Terbuthylazine 1

11 Balance of the stream Nidda to bordering WWTPs Compound Waste water treatment plant pestcide load in kg Nidda pesticide load in kg Share of load of pesticides from WWTP to total load in Nidda in % Atrazine 1,9 3,4 57 MCPP 5,2 7,7 67 2,4-DP 4,4 6,9 63 Isoproturon 8,5 14, 61 Diuron 6,6 1,4 64 Data gained 23/4/1994 to 24/5/1994 Numbers of waste water treatment plants Average pesticide entry from 16 Hessian waste water treatment plants (April/May 1999) <,2 <,4 <,8 <1,6 <3,2 <6,4 <13 <26 <52 Pesticide concentration without Diuron in µg/l 11

12 How to monitor? Sampling campaign! Monitoring Drinking water Surface water Waste water 12

13 P 3 -compounds in European wastewater effluents: concentration (µg/l) µg/l concentration (µg/l) BTri TTRI 1-1 µg/l DICLO1 OP BTSA NP IBU2 1 NP2EC Carbama SPC concentration (µg/l) EDTA NDSA17 NDSA16 OP2EC NP59EO NP1EO DICLO2 TCPP NDSA15 NDSA27 BAYACI NDSA13 IBU1 NDSA26 DEET TCEP OP1EC NP2EO.1-1 µg/l BT NSA2 DCBA NP1EC OHBT MTBT Sulfophenyl carboxylates concentration (µg/l) influent CAS MBR HOOC SPC SO 3 H /4 sample no. 3/5 13

14 Aerobic degradation of LAS by bacteria 3 Schleheck, D., Knepper, T.P., Fischer, K., Cook, A.M.; Appl. Environ. Microbiol., LAS WWTP-influent MBR-effluent WWTP-effluent log c [µg L -1 ] SRT 23 d SRT 26 d SRT 38 d SRT 322 d SRT 337 d SRT 347 d SRT 351 d SRT 363 d SRT 376 d SRT 386 d SRT 398 d SRT 411 d HRT 1 h HRT 7 h SPC WWTP-influent MBR-effluent WWTP-effluent c [µg L -1 ] SRT 23 d SRT 26 d SRT 38 d SRT 322 d SRT 337 d SRT 347 d SRT 351 d SRT 363 d SRT 376 d SRT 386 d SRT 398 d SRT 411 d HRT 1 h HRT 7 h 14

15 Nonylphenol-diethoxycarboxylate concentration (µg/l) influent H 19 C 9 CAS MBR sample no. O COOH NP2EC P 3 -compounds in European surface waters 1 concentration (µg/l) SPC EDTA > 1 µg/l.1-1 µg/l µg/l concentration (µg/l) BTRI BTSA BTSA NP3EO_L 17NDSA 16NDSA 15NDSA NP1EO TTRI 27NDSA 2NSA concentration (µg/l) NP2EO NP1EC 13NDSA BT 1NSA OHBT GALAXO 26NDSA TONALI MTBT MUSKKET NP NP2EC MUSKXYL 15

16 [µg/l] µg/l,1,9,8,7,6,5,4,3,2,1, Pesticides and metabolites in surface water Isoproturon MCPP DEET Atrazinedesethyl Atrazine Diuron (Main, Germany, ) 2,4-DP n=35, mean concentration MCPA Bentazone Terbuthylazine Ref.: The Handbook of environmental chemistry, Volume 5 Series water pollution: The Rhine [µg/l],2,18,16,14,12,1,8,6,4,2, MCPA Simazine 2,4-D Bentazone Atrazine 2,4,5-T 2,4-DP n= , mean concentration (Portugal, April May 2) MCPP Alachlor Metolachlor Linuron Dimethoate Ref.: S. Lacorte et al., J. Environ. Monit., 21, 3, How is the concentration in the water cycle correlated with the elimination during wastewater treatment?? 16

17 Balance of data gained for Hessian project* * to fulfill requirements of WFD Water samples of Emsbach stream compared with water samples of 4 Wastewater Treatment Plants (red dots) * Auswahl der kosteneffizientesten Maßnahmenkombinationen unter Berücksichtigung der Umweltziele und Ausnahmen nach Art. 4 WRRL anhand ausgewählter Wasserkörper im hessischen Teil des Bearbeitungsgebiets Mittelrhein Balance of entry of emerging contaminants into the aquatic environment via WWTP: 1 Load in g/2d Diclofenac Total for 2 month analysis (26): WWTP: 1.83 kg Stream: 1.77 kg (result different for degradable compounds) Stream date Total of 4 WWTP effluents 17

18 Ethofumesat 1, 8, Load in g/2d 6, 4, 2,, MCPA Date Kläranlagen gesamt Emsbach 25 Load in g/2d WWTP Effluent (Total of 4 WWTP effluents) Stream: Emsbach Date Kläranlagen gesamt Emsbach Isoproturon 5 4 Load in g/2d Stream Emsbach Emsbach Kläranlagen gesamt Total of 4 WWTP effluents Date 18

19 Can we estimate the concentration of P 3 in the water cycle?? What is the Water Cycle Spreading Index (WCSI)? Implemented by Reemtsma et. al.: WCSI = effluent concentration normalized removal in WWTP = c c in in c c out out Reemtsma, T., Weiss, S., Müller, J., Petrovic, M., Gonzalez, S., Barcelo, D., Ventura, F., Knepper, T.P.; Environ. Sci. Technol.,

20 WCSI: Concentration in the effluents of 3 WWTPs in a 1 month study period: log c [µg L -1 ] SPC WCSI: SPCs in contrast to other compounds: SPC 2

21 Where do persistent polar priority pesticides and metabolites remain in the environment? EDTA 2 15 WWTP-Influent MBR-Effluent WWTP-Effluent SRT 128 d SRT 164 d SRT 38 d [µg/l] 21

22 Values of EDTA in ground water wells EDTA in µg/l March '93 April '93 July '93 Aug. '93 Nov. '93 March '94 1 RRWB GWW1 GWW2 GWW3 GWW4 DW Sampling Points RRWB = River Rhine Water Basin; GWW1 = Groundwater Well (1 m); GWWW2 (8 m); GWW3 (145 m); GWW4 (16 m); DW = Drinking Water Occurrence of barbiturates in surface water Mulde at Pouch and Elbe: not detected!...but permanently in Dessau!!! 22

23 Occurrence of barbiturates in the river mulde conc. [µg/ 5 5,3 5,4 pentobarbital butalbital secobarbital phenobarbital 4, ,48 2 2,8 1,5 1,41 1,21, , ,1, ,12, , mix,3,29,39,28,3,19,4,22,51,27,98,88,3,86, Occurrence of barbiturates in irrigated ground water (Berlin) Groundwater, Berlin WW infiltration 4 y ago: Phenobarbital: up to 1.3 µg/l Others: between.5 and.8 µg/l 23

24 Selected pesticides and metabolites O Cl O Cl N N NH 2 H N N NH 2 Chloridazon Desphenyl - chloridazon H 3 C CH 3 H 3 C CH 3 HN N NH CH 3 HN N NH 2 H 2 N N NH CH 3 N N N N N N Cl atrazine desethyl-atrazine Cl Cl desisopropyl-atrazine Fate of atrazine degradation after spiking into bioreactor-influent influent (c ~25 µg L - 1 ): 1,4 MBR-influent MBR-effluent 1,2 1,,8 c/c,6,4,2 no biodegradation, Time [d] 24

25 Atrazine in surface water 5 25 In Germany 4 baned since 1991, 3 but still detectable Transport (kg) 2 Formation of 1 metabolites in soil IPU MCP 2,4 - DP Transport (kg) Atrazine Atrazine - desethyl Year ( ) Year ( ) Transport rates of atrazine, atrazine-desethyl in the Main river during the period of over the years 1989 to 2. - The problem: - atrazine application in the watershed was stopped in 2 (replaced by acetochlor) - groundwater of the Brévilles spring still exhibits contamination by atrazine and desethylatrazine with concentrations of.19 ±.7 µg/l and.59 ±.18 µg/l, respectively Do soil/rocks act as storage tank? 25

26 Sampling points (depth drilling): Bréville sampling points Results: Analyte (ng/g) -2cm P1 P11 P12 P13 4-6cm 6-75cm -2cm 2-4cm 4-6cm -2cm 2-4cm -2cm 2-4cm 4-6cm atrazine 2 n.d. n.d. 2 1 n.d <1 n.d. 2 <1 n.d. desethylatrazine n.d. n.d. n.d. <LOD <LOD n.d. n.d. n.d. <LOD n.d. n.d. n.d. n.d. n.d. desisopropylatrazine n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -2cm P15 2-4cm 4-6cm acetochlor 6 n.d. n.d <LOD <LOD <LOD <LOD Analyte (ng/g) -2cm 2-4cm -2cm 2-4cm 4-6cm -2cm 2-4cm 4-6cm 6-8cm -2cm 2-4cm atrazine 2 < n.d <1 n.d. n.d. n.d. 5 n.d. n.d. 2 <1 n.d. desethylatrazine n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. <1 n.d. n.d. n.d. n.d. n.d. desisopropylatrazine n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. acetochlor n.d. n.d. 3 n.d n.d. 4 n.d. n.d. n.d <LOD 4 n.d. n.d. Analyte (ng/g) -2cm P18 2-4cm 4-6cm P19 No atrazine nor metabolites could be detected in samples from below the root zone. 6-8cm -2cm 2-4cm -2cm P2 atrazine 3 n.d. n.d. n.d. 4 1 <1 <1 <1 <1 n.d. n.d n.d. desethylatrazine n.d. n.d. n.d. n.d. <1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. <1 n.d. n.d. n.d. n.d. desisopropylatrazine n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2-4cm -2cm 2-4cm P22 P24 P25 P26 P27 P28 4-6cm 4-6cm 6-8cm -2cm -2cm P23 2-4cm 2-4cm 4-6cm -2cm P29 2-4cm 4-6cm acetochlor n.d. n.d. n.d. n.d n.d. 2 n.d. n.d. n.d. 1 1 <LOD <LOD n.d. 26

27 How to monitor? Analysis & QA Analytical determination of micropollutants and their metabolites Complex matrices Low detection limits Selective/sensitive analytical methods Time and labour consuming procedures Extraction clean-up Filtration, solid phase extraction with various materials, derivatisation Separation High pressure liquid chromatograpy gas chromatography ion chromatography Identification of P 3 and their metabolites (after MBR treatment) and degradation products (after AOP treatment) via mass spectra and library searches (GC/MS) ESI very suitable for polar and ionic compounds Detection electrospray ionisation mass spectrometry (ESI-MS/MS) Electron impact quadrupole and ion trap MS/MS ESI-Q-TOF-MS.QQQQQQQ 27

28 SPE enrichment statistics for neutral analytes in wastewater, n=5 SPE enrichment statistics for acidic analytes in wastewater, n=5 28

29 Interlaboratory Experiments Interlaboratory Experiments 29

30 Conclusions The more pollutants are analysed the more can be detected main source for entry into the aquatic environment are WWTP. Monitoring campaigns need to be well thought of and organized metabolites need to be included Organic pollutants are present in surface waters all over Europe at comparable concentrations (for pesticides during application time) The WCSI may be used as an indicator for the potential of polar pollutants to be spread in the aquatic environment. Analytical methods need to be harmonized and thoroughly checked in the matrix analyzed. Acknowledgement EFF: Jutta Müller Manuela Peschka Marco Bernhard Jan Eubeler Heike Weil European Commission (Projects P-THREE; EMCO; Aquaterra; Innovamed Damia Barcelo, Mira Petrovic (CSIC) Christophe Mouvet (BRGM) Hessian Ministry for Environment Peter Seel 3