1、| | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | BRITISH STANDARD BS 8855-2:2000 ICS 13.080
2、.10 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW Soil analysis Part 2: Method for determination of coal tar-derived phenolic compoundsThis British Standard, having been prepared under the direction of the Health and Environment Sector Committee, was published under the auth
3、ority of the Standards Committee and comes into effect on 15 April 2000 BSI 04-2000 The following BSI references relate to the work on this standard: Committee reference EH/4/3 Draft for comment 99/561879 DC ISBN 0 580 33130 X BS 8855-2:2000 Amendments issued since publication Amd. No. Date Comments
4、 Committees responsible for this British Standard The preparation of this British Standard was entrusted by Technical Committee EH/4, Soil quality, to Subcommittee EH/4/3, Chemical methods, upon which the following bodies were represented: Association of Consulting Scientists B G Technology British
5、Ceramic Research Ltd. British Society of Soil Science Environment Agency Laboratory of the Government Chemist Ministry of Agriculture, Fisheries and Food Society of Chemical Industry Soil Survey and Land Research Centre Water Research Centre Water UKBS 8855-2:2000 BSI 04-2000 i Contents Page Committ
6、ees responsible Inside front cover Foreword ii 1 Scope 1 2 Normative references 1 3 Principle 1 4 Safety precautions 1 5 Reagents 1 6 Apparatus 1 7 Preparation of reagents and standards 2 8 Preparation of laboratory sample 2 9 Procedure 2 10 Calculations 3 Annex A (informative) Performance character
7、istics 4 Bibliography 5 Table 1 Analyte concentration ranges giving linear detector response 2 Table 2 Indicative retention times of phenolic compounds 3 Table A.1 Repeatability 4 Table A.2 Reproducibility 4ii BSI 04-2000 BS 8855-2:2000 Foreword This British Standard has been prepared by Subcommitte
8、e EH/4/3. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document
9、comprises a front cover, an inside front cover, pages i and ii, pages 1 to 5 and a back cover. The BSI copyright notice displayed in this document indicates when the document was last issued. BSI 04-2000 1 BS 8855-2:2000 1) For information on suitable equipment contact BSI Information Centre, Britis
10、h Standards House, 389 Chiswick High Road, London W4 4AL. 1 Scope This British Standard describes a method for determining the concentration of coal tar-derived phenols, namely catechol, resorcinol, phenol, cresols (ortho-, meta-, para-), xylenols (2,3; 2,4; 2,5; 2,6; 3,4 and 3,5); 2-isopropylphenol
11、, 1-naphthol and 2,3,5 trimethylphenol. It is applicable to all types of soil containing concentrations of phenols in the approximate range 0.02 mg/kg to 10 mg/kg soil. Some performance characteristics of the method are summarized in annex A. The method is not applicable to the determination of halo
12、genated phenols. The range can be extended by suitable dilution of the extracts as required. 2 Normative references The following normative documents contain provisions which, through reference in this text, constitute provisions of this part of this British Standard. For dated references, subsequen
13、t amendments to, or revisions of, any of these publications do not apply. For undated references, the latest edition of the publication referred to applies. BS 7755-3.1, Soil quality Part 3: Chemical methods Section 3.1: Determination of dry matter and water content on a mass basis by a gravimetric
14、method. BS 7755-3.5, Soil quality Part 3: Chemical methods Section 3.5: Pretreatment of samples for physico-chemical analyses. BS EN ISO 3696, Water for analytical laboratory use Specification and test methods. 3 Principle A sample of “as-received” soil is extracted with a 60:40 v/v methanol:water m
15、ixture. Reversed phase high-performance liquid chromatography (HPLC) with direct aqueous injection of the sample, and electrochemical detection, is used to determine the phenolic compound content. 4 Safety precautions Phenols are both toxic and corrosive and require handling with care. Methanol is t
16、oxic and sodium hydroxide is corrosive. Latex or nitrile gloves and eye protection should be worn at all times. Spills should immediately be wiped up with adsorbent tissue and placed in sealed containers used for the disposal of toxic chemicals. Samples should be treated as toxic and harmful. 5 Reag
17、ents 5.1 Citric acid, (HPLC grade for electrochemical detection). 5.2 Sodium acetate, (HPLC grade for electrochemical detection). 5.3 Sodium hydroxide, (HPLC grade for electrochemical detection). 5.4 Methanol, (HPLC grade for electrochemical detection). 5.5 De-ionized or distilled water, of at least
18、 Grade 1 as defined in BS EN ISO 3696. 5.6 Helium, (chromatography grade). 5.7 Phenol, (analytical grade). 5.8 o-, m-, p-cresols, (analytical grade). 5.9 3,4; 3,5; 2,5; 2,3; 2,4; 2,6 xylenols, (analytical grade). 5.10 2-iso-propylphenol, (analytical grade). 5.11 Catechol, (analytical grade). 5.12 Re
19、sorcinol, (analytical grade). 5.13 2,3,5-trimethylphenol, (analytical grade). 5.14 1-naphthol, (analytical grade). 6 Apparatus 6.1 An HPLC system 1) , capable of delivering an isocratic mobile phase at a rate of 1.0 ml/min, and fitted with an electrochemical detector (see 9.2 for set-up details). (M
20、ultiple pumping systems may be used if desired.) 6.2 A5m m octadecyl silica (ODS), 25 cm3 4.5 mm internal diameter column (or equivalent) 1) , fitted with a matching guard column. 6.3 An injection system 1) , either manual or automatic capable of injecting up to 100mlo f sample. 6.4 Glass syringe, f
21、or example 5 ml capacity is suitable. 6.5 Syringe filters, nylon, 0.45mm nominal pore size. 6.6 Glass fibre filters, 0.45mm nominal pore size. 6.7 Balance, capable of weighing to an accuracy of not less than 0.000 1 g.2 BSI 04-2000 BS 8855-2:2000 2) As phenols in soil biodegrade, it is common practi
22、ce for the sample containers to be filled on site to preserve the phenols. Laboratories pre-weigh bottles containing reagent and re-weigh on receipt in the laboratory. 7 Preparation of reagents and standards 7.1 Stock solutions 7.1.1 Solvent Prepare a 60:40 methanol:water mixture by adding 150 ml 1.
23、0 ml of methanol (5.4) to 100 ml 1.0 ml of distilled or de-ionized water (5.5). 7.1.2 Stock solutions of phenolic compounds Weigh accurately 80 mg of each of the phenolic compounds (5.7 to 5.14) and quantitatively transfer into the same, or separate 100 ml volumetric flasks, dissolving them in metha
24、nol:water (7.1.1), to give individual or mixed stock solutions. The concentration of each component is nominally 800 mg/l. Divide the stock solution(s) into 5 ml bottles with tight caps and store at2188C. 7.2 Standard solutions for calibration Prepare standard solutions for calibration from the stoc
25、k solutions prepared in accordance with 7.1.2. For the range 0.3 mg/l to 3.2 mg/l, dilute 0.1, 0.2, 0.3, 0.5, 0.7 and 1.0 ml ( 2 % of the respective volume) of the stock solution in 250 ml volumetric flasks with methanol:water (7.1.1) to provide calibration standards containing, respectively, 0.3, 0
26、.6, 0.9, 1.5, 2.1 and 3.2 mg/l ( 2 % of the respective mass) phenol. The linear range may be extended above 3.2 mg/l if required. Appropriate detector settings are shown in Table 1. For the range 16mg/l to 800mg/l prepare an intermediate working standard solution by diluting 2.5 ml 0.05 ml of the st
27、ock solution (7.1.2) to 100 ml in a volumetric flask with methanol:water (7.1.1). Further dilute, 0.2, 0.7, 1.0, 3.0, 5.0 and 10.0 ml ( 2 % of the respective volume) in 250 ml volumetric flasks with methanol:water (7.1.1) to provide calibration standards, containing respectively 16, 56, 80, 240, 400
28、 and 800mg/l ( 2 % of the respective mass) phenol. 7.3 Blank determinations Use de-ionized or distilled water (5.5) for blank determinations. 7.4 Preparation of the mobile phase Dissolve 12.2 g 0.1 g of citric acid (5.1), 4.4 g 0.1 g of sodium acetate (5.2) and 3.9 g 0.1 g of sodium hydroxide (5.3)
29、in 1 000 ml 5 ml of water (5.5) and mix the solution with methanol in the ratio 40:60. Filter through a 0.45mm glass-fibre filter (6.6) and de-gas with helium (5.6) for 30 min before use. Ensure that the mobile phase is at ambient temperature before use (the heats of mixing and dissolution will rais
30、e its temperature). 8 Preparation of laboratory sample If a bulk sample has been submitted to the laboratory, prepare a laboratory sample using an appropriate procedure, for example that given in BS 7755-3.5. Place 150 ml 5.0 ml of methanol:water (7.1.1) in a screw-topped glass bottle, weigh it and
31、record the mass in grams (M 1 ). Weigh out between 50 g and 100 g of the bulk sample and add it to the bottle. Reweigh the bottle and record the mass in grams (M 2 ). Calculate the mass of the laboratory sample (M s ) in grams from the following equation 2) : M s = M 2 2 M 1 Store the sample in the
32、dark at 48C and only remove it from this environment immediately prior to analysis. Before analysis, place the bottle onto a flask shaker for 30 min 5 min to extract the phenolic compounds from the sample. 9 Procedure 9.1 Sample for analysis Using a clean glass syringe (6.4) withdraw an amount of th
33、e methanol:water extract appropriate to the size of the autosampler vial, from the bottle containing the laboratory sample. Filter through a 0.45mm nylon syringe filter (6.5) into an auto-sample vial. Use polytetrafluoroethylene (PTFE)-faced septa as phenols adsorb onto silicone rubber causing low a
34、nalytical results. 9.2 Detector Set the potential on the electrochemical detector to +750 mV, that on the pre-treatment cell to +250 mV and that on the guard cell to +800 mV. Different detector amplifier ranges shall be used depending on the analyte concentration expected. Analyte concentration rang
35、es over which detector response is expected to be linear, expressed as a function of detector amplifier setting, are given in Table 1. Table 1 Analyte concentration ranges giving linear detector response Detector amplifier setting Limits of analyte concentration range mA Lower mg/l Upper mg/l 1 5 0.
36、2 2 10 0.4 5 20 2.0 10 40 4.0 20 80 8.0 50 200 20.0 BSI 04-2000 3 BS 8855-2:2000 The amplifier range appropriate to the expected analyte concentration shall be selected. 9.3 Chromatograph set-up Set the total flow rate to 1 ml/min. Use solutions of the individual phenols (e.g. 3.2 mg/l as prepared i
37、n 7.2) to determine the actual retention times of the analytes. Set the total flow rate to 1 ml/min. Adjust the chromatographic conditions to provide an optimal separation. Inject 100ml of calibration standards, blanks and samples using either an auto-sampler or manual injection system (6.3). Users
38、of manual injection systems shall ensure that identical volumes are injected. 10 Calculations Areas of the chromatographic peaks are used for quantification. Plot a calibration graph of concentration against peak area and convert sample peak areas into concentration by reading off the graph, or use
39、the appropriate regression line to convert peak areas into concentrations. Calculate the mass of phenolic compounds, P, in the soil sample, in milligrams per kilogram using the following equation: P = P 1 V M s where P 1 is the concentration of phenolic compounds in the methanol:water extract, in mi
40、lligrams per litre (mg/l); V is the volume of extract, in litres (l) (volume of methanol:water used in clause 8); M s is the mass of the laboratory soil sample, in kilograms (kg). If the dry matter content of the soil has also been determined according to BS 7755-3.1, then phenolic concentration may
41、 also be adjusted to a dry mass basis. Indicative retention times are given in Table 2. Table 2 Indicative retention times of phenolic compounds Compound Retention time min Ratio of retention time to that of phenol Resorcinol 3.7 0.63 Catechol 4.3 0.73 Phenol 6.0 1.0 m-cresol 9.0 1.5 p-cresol 9.0 1.
42、51 o-cresol 9.1 1.52 3,4 xylenol 13.4 2.24 2,6 xylenol 13.8 2.3 3,5 xylenol 14.2 2.38 2,3 xylenol 14.3 2.4 2,5 xylenol 14.9 2.49 2,4 xylenol 15.3 2.57 1-naphthol 19.5 3.27 2-isopropylphenol 24.3 4.07 2,3,5-trimethylphenol 24.6 4.12BS 8855-2:2000 4 BSI 04-2000 Annex A (informative) Performance charac
43、teristics Inter-laboratory trials were organized to test the method given in this British Standard. In these trials the concentrations of phenol, groups of phenolic compounds and the sum of the phenolic compounds determined was measured by a number of laboratories on a number of soils. The soils wer
44、e obtained from sites formerly used for the manufacture of gas from coal and therefore contained significant quantities of phenolic compounds. The repeatability (r) and the reproducibility (R) of the results of these analyses are given in Tables A.1 and A.2, respectively. These values have been calc
45、ulated based on the method in BS ISO 5725-2:1994. Table A.1 Repeatability Phenolic compound Number of replicates Mean concentration mg/kg Standard deviation (s r ) mg/kg Repeatability limit (r) mg/kg Phenol 11 1.2 0.06 0.17 Cresols 11 1.5 0.1 0.28 Xylenols 11 1.6 0.15 0.42 Total 11 5.5 0.55 1.5 NOTE
46、 Repeatability limit, r = 2.8s r . Table A.2 Reproducibility Phenolic compound Number of laboratories Mean concentration mg/kg Standard deviation (S R ) mg/kg Reproducibility limit (R) mg/kg Total 18 20.8 2.2 6.2 Total 20 298 48 135 Total 21 16.7 2.7 7.7 Total 27 6.5 1.8 5 Phenol 16 141 17 48 Phenol
47、 20 9 1.4 3.8 Cresols 14 7.3 0.6 1.6 Xylenols 16 3.2 0.5 1.4 NOTE 1 Reproducibility limit R = 2.8S R . NOTE 2 Total phenols in this table is related to the sum of the phenols analysed, and is not necessarily a measure of the total phenols in the sample. NOTE 3 Performance data are quoted for the sum
48、med cresols and xylenols, rather than the individual compounds, as this was the reporting requirement of BG Properties, who administered a proficiency testing scheme from which the information was obtained. BSI 04-2000 5 BS 8855-2:2000 Bibliography Standards publication BS ISO 5725-2:1994, Accuracy
49、(trueness and precision) of measurement methods and results Part 2: Basic methods for the determination of repeatability and reproducibility of a standard measurement method.BS 8855-2:2000 BSI 389 Chiswick High Road London W4 4AL | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | BSI British Standards Institution BSI is th
