Common document of CEN/TC 230 and DG ENV Activity CMA-3 Support to Standardisation

Transcription

1 Date CEN/TC 230 N 585 revised "Water analysis" Common document of CEN/TC 230 and DG ENV Activity CMA-3 Support to Standardisation Status box Version no.: 5.0 (final) Date: 16 th October 2007 Author(s): Peter Lepom (DE), Ulrich Borchers (Chair CEN/TC 230), Andreas Paetz (Secretary CEN/TC 230) With contributions/comments from: members of DG ENV CMA-3 working group (6 th Meeting in Berlin on 2 nd May 2007), members of CEN/TC 230 / WG1 working group (23 rd Meeting on 15 th June 2007 in Vienna, Austria), Circulation and received comments: 1 st version edited by Peter Lepom ( ) with comments by Joan Staeb (NL). 2 nd version with amendments and comments by Ulrich Borchers ( ), editorial comments by DIN (Schmidt), technical comments from AFNOR (Arnaud Gaudrier). 3 rd and 4 th version with amendments by Peter Lepom ( ). 5 th version especially with comments received by CMA enquiry in Oct. 07: Spain (Alejandra Puig), Italy (Mario Carere), Germany (Markus Lehmann). Status of agreement: 1) Agreed by CEN /TC 230 / WG1 members at Vienna meeting. 2) Agreed by CMA group by writing/commenting CEN_Methods_For_WFD_Monitoring_Final_ Doc page 1 / 13

2 LIST OF ISO AND EN STANDARDS RELEVANT TO WFD CHEMICAL MONITORING OF PPIORITY SUBSTANCES 1 Introduction Based on the outcome of the work carried out under the Chemical Monitoring Activity (6 th CMA meeting in Berlin on 2 nd May 2007) and the consultation with experts of CEN/TC230/ad hoc WG 1 the following list of standardised methods (see clause 5) for the analysis of priority substance in water will be considered for inclusion in Annex V of the WFD. The reason for the choice of a certain standard on the list will be given including information on limitations in applicability, uncertainties in assessing the performance of the method and open questions, which cannot be answered at the moment. To facilitate the reading the methods are categorised according to the quality of available information in 3 categories (see clause 2, 3 and 4) as follows: 2 Category A The lower limit of the application range of the standard method meets the performance criteria set in the draft proposal of a Commission Decision adopting technical specifications for chemical monitoring and quality of analytical results in accordance with Directive 2000/60/EC of the European Parliament and of the Council (LoQ 30 % of EQS) The result of the CMA survey on method performance criteria (LoQ, U) amongst national monitoring laboratories conducted in May/June 2007 verified the result of the assessment of the standard method. All or nearly all laboratories confirmed that they were able to meet both the above mentioned LoQ as well as the measurement uncertainty criterion (U 50%) when applying the corresponding standard method. Moreover, no problems in respect to the pre-treatment of samples containing substantial amounts of solid particulate matter were indicated. The results of a former survey on method performance conducted by CEN/TC 230 Water quality in 2004 and information from various member states do not imply specific problems with the analysis of the particular substance. 3 Category B The lower limit of the application range of the standard method does not meet the performance criteria set in the draft proposal of a Commission Decision adopting technical specifications for chemical monitoring and quality of analytical results in accordance with Directive 2000/60/EC of the European Parliament and of the Council (LoQ 30 % of EQS) However, the result of the CMA survey on method performance criteria (LoQ, U) amongst national monitoring laboratories conducted in May/June 2007 indicated that CEN_Methods_For_WFD_Monitoring_Final_ Doc page 2 / 13

3 a respectable number of laboratories confirmed that they were able to meet both the above mentioned LoQ as well as the measurement uncertainty criterion( U 50%) when applying the corresponding standard method. Moreover, no problems in respect to the pre-treatment of samples containing substantial amounts of solid particulate matter were reported. The results of a former survey on method performance conducted by CEN/TC 230 Water quality in 2004 and information from various member states do not imply specific problems with the analysis of the particular substance. 4 Category C The lower limit of the application range of the standard method does not meet the performance criteria set in the draft proposal of a Commission Decision adopting technical specifications for chemical monitoring and quality of analytical results in accordance with Directive 2000/60/EC of the European Parliament and of the Council (LoQ 30 % of EQS) The result of the CMA survey on method performance criteria (LoQ, U) amongst national monitoring laboratories conducted in May/June 2007 indicated that only wellequipped laboratories with highly qualified staff were able to meet both LoQ (LoQ 30 % of EQS) as well as the measurement uncertainty criterion (U 50%) when applying the corresponding standard method. Moreover, special care is necessary to minimize blanks. Analytical problems may arise with samples containing substantial amounts of solid particulate matter or other limitations occur. This gives rise to reservations in stating that the method is already fit for compliance checking under routine conditions. Please note the specific comments given for methods classified in category C. 5 List of standardised methods for the analysis of priority substance in water to be considered for an inclusion in Annex V of the WFD 5.1 ISO 6468:1996 (category A/C) ISO 6468:1996: Water quality -- Determination of certain organochlorine insecticides, polychlorinated biphenyls and chlorobenzenes -- Gas chromatographic method after liquid-liquid extraction ISO 6468 describes a method for determining certain organochlorine insecticides, polychlorinated biphenyls (PCBs) and chlorobenzenes (except the mono- and dichlorobenzenes) in drinking water, ground water, surface waters and waste waters. The method is applicable to samples containing up to 0.05 g/l of suspended solids. CEN_Methods_For_WFD_Monitoring_Final_ Doc page 3 / 13

4 (1) Alachlor 1 (17) Hexachlorobutadiene 1 (31) Trichlorobenzenes Under optimised conditions also applicable to the analysis of: (9b) DDT (16) Hexachlorobenzene (18) Hexachlorocyclohexane Although the method is applicable to a variety of organochlorine pesticides and PCBs, LoQs reported by national monitoring laboratories were too high to allow compliance checking for the cyclodiene pesticides Aldrin, Dieldrin, Endrin, and Isodrin as well as for Endosulfane and Pentachlorobenzene. According to the results of the CMA survey, a sufficiently low LoQ for compliance checking is difficult to achieve or even impossible for DDT, hexachlorocyclohexane and hexachlorobenzene. A new work item proposal entitled Water quality Determination of non-polar substances in water Gas chromatography with mass spectrometric detection (GC-MS) has been submitted to ISO/TC147, which would replace EN ISO 6468 in the future. It requires further clarification whether the draft method proposal will meet the requirements set in the draft proposal of a Commission Decision adopting technical specifications for chemical monitoring and quality of analytical results in accordance with Directive 2000/60/EC of the European Parliament and of the Council (LoQ 30 % of EQS). 5.2 ISO 10301:1997 (category A) ISO 10301:1997: Water quality - Determination of highly volatile halogenated hydrocarbons - Gas-chromatographic methods ISO specifies two methods for the determination of highly volatile halogenated hydrocarbons in drinking water, surface waters and ground water using either liquid/liquid extraction or a static headspace method both in combination with gas chromatography. Typical quantification limits are in the range 0.01 to 50 µg/l depending on the substance analysed for and the matrix. (6a) Tetrachloromethane 1 Alachlor and hexachlorobutadiene are not within the scope of the standard but national monitoring laboratories reported that EN6468 may be used for the determination of these compounds CEN_Methods_For_WFD_Monitoring_Final_ Doc page 4 / 13

5 (10) 1,2-Dichloroethane (12) Dichloromethane (17) Hexachlorobutadiene (29a) Tetrachloroethylene (29b) Trichloroethylene (32) Trichloromethane ISO 10695:2000 (category A) ISO 10695:2000: Water quality - Determination of selected organic nitrogen and phosphorus compounds - Gas chromatographic methods ISO specifies two methods for the determination of certain organics nitrogen and phosphorus compounds in waters by gas chromatography after liquid/liquid or liquid/solid extraction. The methods may be extended to include additional substances, provided the methods are validated for each individual case. The liquid/solids extraction method is applicable to samples of ground water, surface water and drinking water containing mass concentrations of organic nitrogen and phosphorus compounds of about 0.05 µg/l. (3) Atrazine (29) Simazine (33) Trifluralin 5.3 ISO 11369:1997 (category A) ISO 11369:1997: Water quality - Determination of selected plant treatment agents - Method using high performance liquid chromatography with UV detection after solidliquid extraction ISO describes a method for the determination of organic plant treatment agents in drinking and ground water using high performance liquid chromatography (HPLC) with UV detection after solid-liquid extraction. The method is applicable to the determination of selected plant treatment agents and some of their main degradation products (metabolites) in drinking water with a validated reporting limit of about 0.1 µg/l. (3) Atrazine CEN_Methods_For_WFD_Monitoring_Final_ Doc page 5 / 13

6 (13) Diuron (19) Isoproturon (29) Simazine ISO :1997 (category A) ISO :1997: Water quality - Determination of benzene and some derivatives - Part 1: Head-space gas chromatographic method ISO specifies a method for the determination of benzene, methylbenzene (toluene), dimethylbenzenes (xylenes) and ethylbenzene in homogeneous samples of water and waste water in concentrations above 2 µg/l by head-space gas chromatography. In samples that are organically polluted, the limit of quantification may, depending on the matrix of the sample, be higher. (4) Benzene 5.4 ISO 11885:2007 (category B) ISO 11885:2007: Water quality - Determination of selected elements by inductively coupled plasma optical emission spectrometry (ICP-OES) ISO 11885:2007 specifies a method for the determination of dissolved elements, elements bound to particles ("particulate") and total content of elements in different types of water (e.g. ground, surface, raw, potable and waste water) for the following elements: aluminum, antimony, arsenic, barium, beryllium, bismuth, boron, cadmium, calcium, chromium, cobalt, copper, gallium, indium, iron, lead, lithium, magnesium, manganese, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silver, sodium, strontium, sulfur, tin, titanium, tungsten, vanadium, zinc and zirconium. Taking into account the specific and additionally occurring interferences, these elements can also be determined in digests of water, sludges and sediments (for example, digests of water as specified in ISO or ISO ). The method is suitable for mass concentrations of particulate matter in waste water below 2 g/l. The scope of this method may be extended to other matrices or to higher amounts of particulate matter if it can be shown that additionally occurring interferences are considered and corrected for carefully. It is up to the user to demonstrate the fitness for purpose. (23) Nickel and its compounds CEN_Methods_For_WFD_Monitoring_Final_ Doc page 6 / 13

7 The method may be applied to the analysis of nickel if fully optimised. Determination of cadmium and lead may not be possible even though it is mentioned in the scope of the standard due to insufficient sensitivity of the method. 5.5 EN ISO 17852:2007 (category A) EN ISO 17852:2007: Water quality Determination of mercury Method using atomic fluorescence spectrometry EN ISO 17852:2007 specifies a method for the determination of mercury in drinking, surface, ground and rain water. The standard may be applied to industrial and municipal waste water after an additional digestion step under appropriate conditions. The potential linear dynamic range is approximately 1 ng/l to 100 µg/l. In practice, the working range is often from 10 ng/l to 10 µg/l. Samples containing mercury at concentrations higher than the working range can be analyzed following appropriate dilution of the sample. The method detection limit (x DL ) will be dependent on the selected operating conditions and calibration range. With high purity reagents a x DL of less than 1 ng/l is obtainable. (21) Mercury and its compounds 5.6 EN 12338:1998 (category A) EN 12338:1998: Water quality - Determination of mercury - Methods after enrichment by amalgamation This standard specifies a method for the determination of mercury in drinking, surface, ground and rain water. The standard may be applied to industrial and municipal waste water after an additional digestion step under appropriate conditions. The method provides two approaches for the determination of mercury using either tin (II) chloride or sodium tetrahydroborate as reducing agent. The enrichment step of this cold vapour method is using the amalgamation of mercury on a gold/platinum gauze. The working range of the method is between 0.01 μg/l and 1 μg/l. Samples containing mercury at concentrations higher than the working range can be analyzed following appropriate dilution of the sample. The total mercury content is determined after appropriate digestion of the samples (4 alternatives are described). CEN_Methods_For_WFD_Monitoring_Final_ Doc page 7 / 13

8 (21) Mercury and its compounds 5.7 EN 12673: 1998 (category A) EN 12673: 1998 Water quality - Gas chromatographic determination of some selected chlorophenols in water EN specifies a gas chromatographic method for the determination of 19 chlorophenols including trichlorophenols and pentachlorophenol (PCP) in drinking water, groundwater, rainwater, wastewater, sea water and surface water. The procedure comprises acetylation followed by a liquid/liquid extraction and determination by gas chromatography and electron capture detection or mass selective detection. It allows quantification of PCP concentrations of 0.1 µg/l. (27) Pentachlorophenol 5.8 EN 12918:1999 (category A) EN 12918:1999: Water quality - Determination of parathion, parathion-methyl and some other organophosphorus compounds in water by dichloromethane extraction and gas chromatographic analysis; German version EN 12918:1999 EN specifies extraction procedures and gas chromatographic (GC) methods for the determination of selected organophosphorus compounds including Chlorfenvinphos and Chlorpyrifos in drinking waters, surface waters and waste waters. The application range of the standard depends on the compound analysed for and the source of water. Typical reporting limit for drinking waters is 0.01 µg/l. (8) Chlorfenvinphos (9) Chlorpyrifos (9) (Chlorpyrifos-ethyl) 5.9 ISO 15680:2003 (category A) CEN_Methods_For_WFD_Monitoring_Final_ Doc page 8 / 13

9 ISO 15680:2003: Water quality - Gas-chromatographic determination of a number of monocyclic aromatic hydrocarbons, naphthalene and several chlorinated compounds using purge-and-trap and thermal desorption ISO specifies a general method for the determination of volatile organic compounds (VOCs) in water by purge-and-trap isolation and gas chromatography (GC). Annexes A, B and C provide examples of analytes that can be determined using ISO 15680:2003. They range from difluorodichloromethane (R-12) up to trichlorobenzene, including all non-polar organic compounds of intermediate volatility. Detection is preferably carried out by mass spectrometry in the electron impact mode (EI), but other detectors may be applied as well. The limit of detection largely depends on the detector in use and the operational parameters. Typically detection limits as low as 10 ng/l can be achieved. The working range typically is up to 100µg/l. The method is applicable to drinking water, ground water, surface water, seawater and to (diluted) waste water. (4) Benzene (6a) Tetrachloromethane (10) 1,2-Dichloroethane (11) Dichloromethane (17) Hexachlorobutadiene (22) Naphthalene (29a) Tetrachloroethylene (29b) Trichloroethylene (31) Trichlorobenzenes (32) Trichloromethane 5.10 ISO 15586:2003 (category B) ISO 15586:2003: Water quality - Determination of trace elements using atomic absorption spectrometry with graphite furnace ISO includes principles and procedures for the determination of trace levels of: Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, and Zn in surface water, ground water, drinking water, wastewater and sediments, using atomic absorption spectrometry with electrothermal atomization in a graphite furnace. The method is applicable to the determination of low concentrations of elements. The detection limit of the method for each element depends on the sample matrix as CEN_Methods_For_WFD_Monitoring_Final_ Doc page 9 / 13

10 well as of the instrument, the type of atomizer and the use of chemical modifiers. For water samples with a simple matrix (i.e. low concentration of dissolved solids and particles), the method detection limits will be close to instrument detection limits. The minimum acceptable detection limit values for a 20-microlitre sample volume are specified. (20) Lead and its compounds (23) Nickel and its compounds The method may routinely be applied to the analysis of lead and nickel. Determination of cadmium is not possible even though it is mentioned in the scope of the standard due to insufficient sensitivity of the method ISO :2003 (category B) ISO :2003: Water quality - Application of inductively coupled plasma mass spectrometry (ICP-MS) - Part 2: Determination of 62 elements ISO :2003 specifies a method for the determination of the elements aluminium, antimony, arsenic, barium, beryllium, bismuth, boron, cadmium, caesium, calcium, cerium, chromium, cobalt, copper, dysprosium, erbium, europium, gadolinium, gallium, germanium, gold, hafnium, holmium, indium, iridium, lanthanum, lead, lithium, lutetium, magnesium, manganese, molybdenum, neodymium, nickel, palladium, phosphorus, platinum, potassium, praseodymium, rubidium, rhenium, rhodium, ruthenium, samarium, scandium, selenium, silver, sodium, strontium, terbium, tellurium, thorium, thallium, thulium, tin, tungsten, uranium, vanadium, yttrium, ytterbium, zinc, and zirconium in water (for example drinking water, surface water, groundwater, wastewater and eluates). Taking into account the specific and additionally occurring interferences, these elements can also be determined in digests of water, sludges and sediments. The working range depends on the matrix and the interferences encountered. In drinking water and relatively unpolluted waters, the limit of application is between 0.1 µg/l and 1.0 µg/l for most elements. The detection limits of most elements are affected by blank contamination and depend predominantly on the laboratory air-handling facilities available. The lower limit of application is higher in cases where the determination is likely to suffer from interferences or in case of memory effects. CEN_Methods_For_WFD_Monitoring_Final_ Doc page 10 / 13

11 (6) Cadmium and its compounds (20) Lead and its compounds (23) Nickel and its compounds The method may routinely be applied to the analysis of lead and nickel. Determination of cadmium may be difficult in some cases due to the required low LoQ depending on the hardness class of the water to be analysed. Thorough implementation, validation and optimisation of the method is necessary for determination of cadmium to meet the required LoQ performance criterion ISO 17993:2002 (category A/C) ISO 17993:2002: Water quality - Determination of 15 polycyclic aromatic hydrocarbons (PAH) in water by HPLC with fluorescence detection after liquid-liquid extraction ISO 17993:2002 specifies a method using high performance liquid chromatography (HPLC) with fluorescence detection for the determination of 15 selected polycyclic aromatic hydrocarbons (PAH) [naphthalene, acenaphthene, phenanthrene, fluoranthene, benzo(a)anthracene, benzo(b)fluoranthene, benzo(a)pyrene, dibenzo(a,h)- anthracene, fluorene, anthracene, pyrene, chrysene, benzo(k)fluoranthene, indeno- (1,2,3-cd)pyrene, benzo(ghi)perylene] in drinking and ground water in mass concentrations greater than µg/l (for each single compound) and surface waters in mass concentrations above 0.01 µg/l. This method is, with some modification, also suitable for the analysis of waste water. This method may be applicable to other PAH, provided the method is validated for each case. (2) Anthracene (15) Fluoranthene (22) Naphthalene (28) Benzo(a)pyrene Under optimised conditions also applicable to the analysis of (28) Benzo(b)fluoranthene (28) Benzo(k)fluoranthene Although indeno(1,2,3-cd)pyrene (28) and benzo(ghi)perylene (28) are mentioned in the scope, compliance checking is not possible for these two compounds as the LoQ criterion cannot be met For benzo(k)fluoranthene and benzo(b)fluoranthene, a sufficiently low LoQ to allow compliance checking is difficult to achieve or even impossible. CEN_Methods_For_WFD_Monitoring_Final_ Doc page 11 / 13

12 The method has not been validated for water samples containing substantial amounts of suspended solids A new work item entitled Water quality - Determination of 16 polycyclic aromatic hydrocarbons (PAH) in water - Method using gas chromatography with mass spectrometric detection (GC-MS) has been launched at ISO/TC147, which has now reached the committee draft stage (ISO/CD 28540). It requires further clarification whether the draft method will meet the requirements set in the draft proposal of a Commission Decision adopting technical specifications for chemical monitoring and quality of analytical results in accordance with Directive 2000/60/EC of the European Parliament and of the Council (LoQ 30 % of EQS) ISO 18856:2004 (category C) ISO 18856:2004: Water quality - Determination of selected phthalates using gas chromatography/mass spectrometry ISO specifies a method for the determination of phthalates in water after solid phase extraction and gas chromatography/mass spectrometry. This method is applicable to the determination of phthalates in ground water, surface water, wastewater and drinking water in mass concentrations ranging from above 0.02 µg/l up to µg/l depending on the individual substance and the value of the blank. The applicability of this method to other phthalates is not excluded, but it is necessary to determine its applicability in each case. (12) Di(2-ethylhexyl)phthalate (DEHP) Although the method is applicable to the analysis of DEHP in surface water and allows for a sufficiently low LoQ for compliance checking in principle, many laboratories record serious blank problems and are hence, not able to meet the LoQ performance criterion (LoQ 30 % of EQS) 5.14 ISO :2005 (category C) ISO :2005: Water quality - Determination of selected alkylphenols - Part 1: Method for non-filtered samples using liquid-liquid extraction and gas chromatography with mass selective detection CEN_Methods_For_WFD_Monitoring_Final_ Doc page 12 / 13

13 ISO specifies a method for the determination of 4-nonylphenol (mixture of isomers) and 4-(1,1,3,3-tetramethylbutyl)phenol in non-filtered samples of drinking water, ground water and surface water. The method is applicable in a concentration range from 0,005 µg/l to 0.2 µg/l for 4-(1,1,3,3-tetramethylbutyl)phenol and from 0,02 µg/l to 0.2 µg/l for 4-nonylphenol (mixture of isomers). Depending on the matrix, the method is also applicable to waste water containing the analyzed compounds in the concentration range from 0.1 µg/l to 50 µg/l. Higher concentrations can be measured after appropriate dilution of the sample. (24) Nonylphenol ((4-(para)Nonylphenol)) (25) Octylphenol ((4-(1,1,3,3 -tetramethylbutyl)-phenol)) Although the method is applicable to the analysis of Nonylphenol and Octylphenol in principle, compliance checking for Octylphenol is only possible for inland surface water but not for other surface waters as the LoQ, reported by national monitoring laboratories, does not meet the LoQ performance criterion (LoQ 30 % of EQS). Additionally, many laboratories report serious blank problems with nonylphenol and thus, difficulties in performing compliance checking. In the meantime, ISO/TC147 is elaborating another standard for the analysis of alkylphenols in unfiltered water samples (ISO/CD Water quality - Determination of selected alkylphenols - Part 2: Determination of alkylphenols, alkylphenol ethoxylates and bisphenol A -Method for non-filtered samples using solid-phase extraction and gas chromatography with mass selective detection after derivation). It requires further clarification whether the draft method will meet the requirements set in the draft proposal of a Commission Decision adopting technical specifications for chemical monitoring and quality of analytical results in accordance with Directive 2000/60/EC of the European Parliament and of the Council (LoQ 30 % of EQS). 6 Annex A Annex A contains a summarised list of standardised methods for the analysis of priority substance in water (EXCEL sheet: CEN_TC230_ table of methods_ xls) with relevant information and the classification of methods according to the evaluation performed by the CMA-3 activity and experts of CEN/TC 230. Categories according to the definitions in clause 2, 3 and 4: Category A and B = boxes in green colour Category C = boxes in yellow colour Category D = boxes in red colour CEN_Methods_For_WFD_Monitoring_Final_ Doc page 13 / 13