United States Environmental Protection Agency I Environmental Monitoring and Support Laboratory Cincinnati OH 45268 Research and Development Project EPA-600/S4-84-aiA4iMiaJ 98. Summary EPA Mekhod Study 14 Method 604-Phenols Jack R. Hall, J. Ri chard Florance, Dennis L Strother, and Marlene N. Wass An interlaboratory study in which 20 laboratories participated was conducted to provide precision and accuracy statements for tie proposed EPA Method 604-Phenols for measuring concentrations of the Category 8 chemicals phenol, 2,4-dimethylphenol, 2-chlorophenol, i-chloro-3-methyl- phenol, 2,4-dichlbrophenol, 2,4,6- trichlorophenol, pentachlorophenol, 2- nitrophenol, 4-nitrophenol, 4,6-dinitro- 2-methylphenol, anjd 2,4-dinitrophenol in municipal and industrial aqueous discharges. The method provides for the determi- nation of the phenols by gas chroma- tography (GC) witjh flame ionization detection (FID) or derivatization and detection by electron capture (EC). The study design was based on Youden's plan for collaborative tests of analytical methods.I Three Youden pair samples of the tests compounds were spiked into six types of test waters and then analyzed. The] test waters were distilled water, nondechlorinated tap water, a surface iwater, and three different industrial wastewater effluents. A limited study was also conducted by applying the method for the analysis of the phenolics in dechlorinated tap water. The resulting data were statisti- cally analyzed usijng the computer program "Interlaboratory Method Vali- dation Study" (IMVS). Using the mean recovery for each of the subject com- pounds analyzed by the GC-FID proce- dure, the method recoveries were in the range of 40 to 89^6. Overall precision was in the range of 20 to 45% and single-analyst precision was in the range of 15 to 37%. Using the mean recovery for each of the subject com- pounds, when analyzed by the GC-EC procedure, the method recoveries were in the range of 32 to 76%. Overall precision was in the range of 38 to 64% and single-analyst precision was in the range of 29 to 48%. In general mean recoveries, overall standard deviations, (S) and the single-analyst standard deviations, (SR), were directly propor- tional to the true concentration levels. With the exception of the FID analysis of 2,4-dinitrophenol in three of the wastewaters, there were no discernible differences due to water types among mean recoveries, overall precisions, and single-analyst precisions. This Project Summary was developed by EPA's Environmental Monitoring and Support Laboratory, Cincinnati, OH, to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction EPA first promulgated guidelines establishing test procedures for the analysis of pollutants in 1973, following the passage of the Federal Water Pollution ' Control Act in 1972 by Congress. Pursu- ant to the amendment and publication of these guidelines, EPA entered into a Settlement Agreement—the Consent Decree—which required the study and, if necessary, regulation of 65 "priority" pollutants and classes of pollutants of known or suspected toxicity to the biota. Subsequently, Congress passed the Clean Water Act of 1977, mandating the control of toxic pollutants discharged into ambient waters by industry. In order to facilitate the implementation of the Clean Water Act, EPA selected for initial study 129 specific toxic pollutants, ------- 113 organic and 16J inorganic. The organic pollgtanjs werp divided into 12 categories "Based on their chemical structure. Analytical methods were developed by EPA for these 12 categories through in-house and contracted research and may eventually be required for the monitoring of the 113 toxic pollutants in industrial wastewater effluents, as specified by the Clean Water Act of 1977. This report describes the interlaboratory study of Method 604-Phenols which is proposed for the Category 8 chemicals: phenol, 2,4-dimethylphenol, 2-chIoro- phenol, 4-chloro-3-methylphenol, 2,4- dichlorophenol, 2,4,6-trichlorophenol, pentachlorophenol, 2-nitrophenol, 4- nitrophenol, 4,6-dinitro-2-methylphenol, and 2,4-dinitrophenol. The primary objective of the study was to characterize the behavior of Method 604-Phenols in terms of accuracy, overall precision, single-analyst precision, and effect of water type on accuracy and precision. The study was conducted with the cooperation of 20 participating laboratories under auspices of the Environmental Monitoring and Support Laboratory (EMSL)-Cincinnati. The data were collected from the 20 laboratories according to Youden's colla- borative testing design. Formal statistical techniques compatible with the Youden design were used to identify outliers, estimate the method's accuracy and pre- cision, and test for the effect of water type. The formal statistical analyses were carried out using the Interlaboratory Method Validation Study (IMVS) computer program. The information obtained from the statistical analyses was summarized and reduced to a descriptive form for the purpose of interpretation and presentation. Method 604-Phenols was developed by IT Enviroscience under a contract with the Physical and Chemical Methods Branch, EMSL-Cincinnati. Briefly, the method requires extraction with methylene chloride and concentration of the extract followed by the determination of the phenols using GC-FID. The concentrated extract may be more specifically analyzed for phenols by derivatization with penta- fluorobenzyl bromide, extract cleanup on activated silica gel, and final measure- ment by GC-EC. Procedure The interlaboratory study design was based on Youden's plan for collaborative evaluation of precision and accuracy for analytical methods. According to Youden's design, samples are analyzed in pairs. A Youden pair consists of two samples at similar, but distinctly different concentra- tions. The analyst is requested to do only a single analysis for each sample and report only one value as in routine use of the method. Select/on of Laboratories Of the 20 participating laboratories, 19 were selected as the result of competitive bidding after evaluating their technical capabilities and experience in trace organic analyses of wastewater. The twentieth laboratory was a volunteer from within the EPA. Preparation of Ampuls All starting materials were reagent grade quality or better. Distilled-in-glass 2-propanol was the solvent. Separate stock solutions for each of the eleven phenols were prepared by dissolving a precisely weighed amount of the compound into Class A volumetric glassware containing the above mentioned solvent. Appropriate volumes of the stock solutions were mixed and diluted to volume in 2000-mL volumetric flasks. The flasks were refrigerated overnight at 4°C. The follow- ing day, approximately 3 mL of the refrigerated solution was transferred into 5-mL glass ampuls using an all-glass or Teflon® delivery system. After the ampuls were cooled in a freezer at-30°C for three hours, they were sealed by a professional glass blower using the pull-and-twist technique. True Value and Stability of Concentrates An important segment of this study was to verify the true values and stability of the phenols in the 2-propanol concen- trates before they were used in the study. To achieve this verification, three repli- cate ampuls were randomly selected from each concentrate level batch and analyzed by triplicate injection into a gas chromatrograph equipped with a record- ing integrator. To check stability these analyses were carried out at 0,45, and 90 days after the ampuls were sealed and before the study was started. All concen- trate values determined experimentally were within instrumental error of the calculated true values. Preliminary Study Previous EPA method studies have shown that more realistic results can be obtained if all participants fully understand the analytical and sample handling procedures before undertaking the full study. To familiarize the analyst with the analytical method and handling proce- dures, each of the 20 laboratories was sent a low-level Youden pair of sample concentrates (different from those to be used in the actual study) for spiking distilled water. The analysts were also sent instructions, a copy of the method, and data report sheets. The results of these analyses were collected, statistically analyzed, and discussed with the laboratories' repre- sentatives in a one-day conference meeting at EMSL-Cincinnati. The meeting also allowed discussion of analytical problems and clarification of any method- ology procedures. Actual Interlaboratory Study A summary of the test design using Youden's nonreplicate technique based on pairs with slightly dissimilar analyte concentrations is given below: • Twenty laboratories were sent three Youden pairs in sealed glass ampuls containing various levels of the eleven phenols in 2-propanol. • When an analyst was ready to start the analyses, the ampuls were opened and aliquots were diluted to volume in the appropriate water types according to instructions. • Each sample (ampul) was analyzed only once. • The six water types were analyzed with and without spiking, and the added level of constituent was deter- mined by difference and reported as /ug/L in each water sample. • The three levels of phenols used in the study were within the working range of the method and represented the range of levels one would normally expect to encounter in application of the method to actual samples. Description and Distribution of Samples The individual laboratories provided their own samples of laboratory-distilled water, tap water, and a local surface water. The source for each surface water is listed in the final report. The wastewater effluent samples re- presentative of the industries of concern were collected by the prime contractor as grab samples in 55-gallon stainless steel drums which had been precleaned with acetone, methylene chloride, and dis- tilled water. The unfiltered wastewater samples were mixed and transferred into one-quart bottles using an all-Teflon sys- tem and stored in a refrigerator at 4°C un- til shipment to the laboratories. Each la- boratory was sent 36 ampul concentrates (six sets of three Youden pairs), seven ------- one-quart bottles each of the three indus- trial effluent types, instructions, and data report sheets. The wastewater samples were packed in ice in coolers and sent by air freight to minimize sample change and assure comparability of the waste- waters from laboratory to laboratory. Analysis and Reporting A water spiking technique involving a water-miscible solvent concentrate was used in this study. Each analyst was instructed to add separate 2.0-mL aliquots of each concentrate to the bottle containing approximately 1 L of water or wastewater. .The spiked sample was stirred for 15 minutes and then handled as a routine sample in the method. The results of the method's measurement for each constituent (in micrograms per liter of water) were then corrected by subtrac- ting any blank sample reading and reported on data sheets by ampul and water type. The method utilized by the participating laboratories. Method 604- Phenols, was used with no reported deviations. The data were reviewed for complete- ness and abnormal results. The data were then entered into the computer for statistical treatment. Any laboratory reporting unusually high or low data was requested to review its data for errors in calculations but was not told how its re- ported data varied from the true values. Treatment of Data The objective of this interlaboratory study was to obtain information aboutthe accuracy and precision associated with measurements generated by Method 604- Phenols. This objective was met through the use of statistical analysis techniques designed to extract and summarize the relevant information about accuracy and precision from the data reported by the participating laboratories. The statistical techniques were similar to the techniques recommended in the ASTM Standard Practice D2777-77. The algorithms required to perform the statistical analyses-were integrated into a system of computer programs referred to as IMVS {Interlaboratory Method Valida- tion Study). The analyses performed by IMVS included several tests for the rejection of outliers (laboratories and individual data points), summary statistics by concentration level for mean recovery (accuracy), overall and single-analyst standard deviation (precision), deter- mination of the linear relationship between mean recovery and concentra- tion level, determination of the linear relationship between the precision statistics and mean recovery, and a test for the effect of water type on accuracy and precision. Results and Discussion The IMVS computer program was designed to output the raw data in tabular form and to compile summary statistics including: number of data points, true value, mean recovery, accuracy as percent relative e-ror, overall standard deviation, overall percent relative standard deviation, single-a lalyst standard devia- tion, and single analyst percent relative standard deviation The statistical analy- ses performed by the IMVS program included the deter nination of the linear relationship between both the overall (S) and single-analyst i SR) precision statistics and mean recovery along with accuracy statements based on the determination of the linear relationship between mean recovery (X) and concentration level. The results of theregre apparent linear rel laboratory ranking ision analyses indicate ationships for each of the above cases. For all data for tie eleven compounds, analyzed by the FID procedure, 20% of the data were reject 3d as determined by and individual outlier tests. The data rejection was found to be non-uniform among laboratories. More than 60% of the rejected data were generated by six of the 20 participating laboratories. Of the 20 participating laboratories, one had 87% of its total raw data rejected. For compounds analyz 23% of the data v all data for the nine 3d by the EC procedure, 'ere rejected as deter- mined by laboratory ranking and individual outlier tests. The data rejection was found to be non-uniform among laboratories. More than 55% ofl the rejected data was generated by six of the 20 participating laboratories. Of |the 20 participating laboratories, two had more than 63% of their total raw data rejected. Regression equations for single-analyst precision, overall precision, and accuracy are presented in Tables 1 and 2. Mean recoveries of the eleven subject compounds when analyzed by the FID procedure were in the range of 40 to 89%. Overall precision was in the range of 20 to 45%, and single-analyst precision was in the range o recoveries of the n when analyzed by in the range of 15 to 37%. Mean ne subject compounds the EC procedure were 32 to 76%. Overall precision was in t ie range of 38 to 64%, and single-analys precision was in the range of 29 to 48'k>. With the except on of the FID analysis of 2,4-dinitrophenol, no significant difference in method performance was attributable to the water type from which the analyses were performed. A positive bias was established for the FID analyses of 2,4-dinitrophenol in surface waters and two of the industrial effluents. Examination of the chrornatograms revealed a reduction in peak resolution between 4,6-dinitro-2-methylphenol and 2,4-dinitrophenol when analyzing these three water types as compared to the peak resolution between these two compounds in distilled water. Conclusions and Recommendations Based on the results of the interlabora- tory method study, EPA Method 604- Phenols is a viable analytical method for measuring trace concentrations of the eleven Category 8 chemicals used in this study. As a result of the collaborative study conducted and the IMVS data analysis, the following conclusions and recommendations can be made concern- ing Method 604-Phenols. • The accuracy of the method, when using either the FID or EC procedures, could be expressed as a linear function of the true concentration. In the majority of equations the slope represents the percent recovery attributable to the method. • The precision of the method using either the FID or EC procedures could be expressed as a linear function of the mean recovery. In the majority of equations the slope represents the relative standard deviation attribu- table to the method, both as single- analyst and overall standard devia- tions. • The average mean recovery for each compound by either FID or EC at six concentrations in seven water types compared well with data generated on distilled water and industrial effluents during develop- ment of this method. • Direct comparison of the FID and EC procedures for the analysis of the nine common Category 8 chemicals (the two dinitrophenols are deter- mined by GC-FID only) indicates that the FID technique yielded fewer outliers, lower overall and single- analyst standard deviations, and higher mean recoveries. • Based on the IMVS test for the effect of water type on precision and accuracy, there was no statistical significance between distilled water and the other water types for any of the associated parameters except for ------- Table 1. Regression Equations for Accuracy and Precision for Compounds 1 - Water Type Applicable Cone, flange Distilled Water Single-Analyst Precision Overall Precision Accuracy Tap Water • Non DC Single-Analyst Precision Overall Precision Accuracy Surface Water Single-Analyst Precision Overall Precision Accuracy Waste Water 1 Single-Analyst Precision Overall Precision Accuracy Waste Water 2 Single-Analyst Precision Overall Precision Accuracy Waste Water 3 Single-Analyst Precision Overall Precision Accuracy Tap Water - DC Single-Analyst Precision Overall Precision Accuracy Phenol (18.40 - 252.00) SR = 0.20X - 0.88 S = 0.17X + 0.77 X =0.430+0.11 SR = 0.27X + 0.55 S = 0.61 X- 0.55 X =0.280 + 0.77 SR = 0. 19X - 0. 18 S = 0.22X - 0.04 X =0.420-0.13 SR = 0.27X + 0. 15 S =0.36X-0.11 X = 0.460 + 0.06 SR = 0.25X - 1.00 S = 0.27X + 0.69 X =0.420+1.75 SR = 0.17X + 0.24 S = 0.27X + 0.31 X = 0.400 + 0.30 SR = 0.24X - 0.53 S = 0.38X - 0.92 X = 0.440 - 1.50 2.4-Dimethylphenol (13.00 - 151.00) SR =O.36X - 1.38 S =0.28X + 0.30 X =0.630 - 1.82 SR = 0.66X - 0.44 S =0.75X + 0.14 X =0.350 - 1.68 SR = 0.24X - 0. 18 S = 0.31 X + 0.49 X =0.54C - 1.40 SR = 0.24X + 1. 18 S = 0.39X+1.43 X =0.510 - 1.87 SR = 0.21 X + 0.52 S =0.47X-0.53 X =0.420-0.58 SR = 0.57X - 1.16 S =0.63X-0.65 X =0.470-0.98 SR = 0.35X - 0.38 S =0.33X + 0.28 X =0.630-3.37 4 2-Chlorophenol (12.20 - 185.00) SR = 0.1 8X + 0,20 S = 0.21 X + 0.75 X = 0.830 - 0.84 SR=0.42X - 1.03 S = 0.47X + 0.01 X = 1.080 - 2.91 SR = 0.21 X - 0.20 S =0.28X-0.71 X = 0.830 - 0. 19 SR = 0.20X + 1.21 S = 0.20X + 2.89 X =0.820 + 0.91 SR = 0.21 X + 0.06 S = 0.25X + 0.97 X =0.720 + 0.81 SR = 0. 15X + 3.05 S = 0.21 X + 2.82 X =0.720+1.97 SR = 0.1 9X + 0.17 S = 0.25X - 0.04 X =0.720 - 1.09 4-Chloro-3-Methylphenol (30.00 - 450.00) SR = 0.11 X- 0.21 S = 0.1 6X+ 1.41 X = 0.870 - 1.97 SR = 0.32X + 1.36 S = 0.48X + 1.23 X =0.510 + 0.12 SR = 0. 16X + 1. 18 S =0.24X + 2.47 X = 0.82C - 1.03 SR =0.32X + 2.28 S = 0.40X - 0.02 X = 0.820 - 2.07 SR = 0.34X - 2.67 S = 0.32X + 1.80 X =0.810 - 1.74 SR = 0.17X + 1.12 S = 0.30X + 0.96 X =0.780-3.60 SR =0. 14X + 0.68 S =0. 16X + 1.68 X =0.810-4.50 Table 7. /Continued) Regression Equations for Accuracy and Precision for Compounds 5 - 8 Water Type Applicable Cone, flange Distilled Water Single-Analyst Precision Overall Precision Accuracy Tap Water - Non DC Single-Analyst Precision Overall Precision Accuracy Surface Water Single-Analyst Precision Overall Precision Accuracy Waste Water J Single-Analyst Precision Overall Precision Accuracy Waste Water 2 Single-Analyst Precision Overall Precision Accuracy 2.4-Dichlorophenol (14.80 - 214.00) SR=0.17X -0.02 S = 0.18X + 0.62 X =0.810 + 0.48 SR=0.24X - 1.56 S = 0.23X - 0.84 X =0.760+0.10 SR=0.17X -0.62 S =0.28X-0.75 X =0.810 + 0.23 SR = 0.31 X - 0.33 S = 0.31 X + 0.72 X =0.770+1.24 SR = 0.27X - 0.34 S = 0.26X + 1. 18 X =0.730 + 0.04 2,4,6- Trichlorophenol (20.40 - 236.00) SR = 0.10X + 0.53 S =0. 13X + 2.40 X = 0.860 - 0.40 SR=O.22X -0.13 S = 0.24X + 0.91 X = 0.920 + 0.81 SR = 0.17X -0.47 S = 0.24X + 0.80 X = 0.850 + 0.25 SR = 0.29X - 0.63 S = 0.26X + 3.94 X = 0.830 + 3.68 SR = 0.01 X + 12.82 S =0.35X + 4.18 X =0.760+10.29 Pentachlorophenol (16.20 - 226.00) SR = 0.22X - 0.58 S = 0.23X + 0.57 X =0.830 + 2.07 SR = 0.27X - 1.26 S =0.28X+1.04 X = 0.820 + 0.97 SR = 0. 16X + 2.80 S = 0.29X +1.01 X =0.770 + 3.99 SR = 0.27X + 21 .40 S =0.32X + 23.90 X =0.750 + 33.92 SR = 0.32X - 1.93 S =0.37X - 1.88 X =0.720 + 6.27 2-Nitrophenol (25.00 - 374.00) SR = 0. 15X + 0.44 S =0.14X + 3.84 X =0.810-0.76 SR = 0. 18X - 1.79 S = 0.21 X - 0.64 X =0.790+1.05 SR =0. 19X - 1.66 S = 0.23X - 0.94 X = 0.830 + 0.92 SR = 0.22X - 1.17 S =0.21X + 0.05 X = 0.800 + 0. 13 SR = 0.21X - 0.13 S =0. 19X + 4.88 X =0.770 + 2.90 ------- Table 1 . (Continued) Regression Equations for Accuracy and Precisi Water Type 2,4-Dichlorophenol 2,4,6 -Trh Waste Water 3 Single-Analyst Precision Overall Precision Accuracy Tap Water - DC Single-Analyst Precision Overall Precision Accuracy SR=0.26X - 1.36 SR = O. S = 0.25X + 0.70 S =0. X =0.730+1.99 X =0. SR = 0.24X - 1 .66 SR=0. S =O.22X - 1.39 S =0. X =0.770 + 0.08 X =0. Table 1. (Continued) Regression Equations for Accuracy and Precis Water Type Applicable Cone. Range Distilled Water Single-Analyst Precision Overall Precision Accuracy Tap Water - Non DC Single-Analyst Precision Overall Precision Accuracy Surface Water Single-Analyst Precision Overall Precision Accuracy Waste Water 1 Single-Analyst Precision Overall Precision Accuracy Waste Water 2 Single-Analyst Precision Overall Precision Accuracy Waste Water 3 Single-Analyst Precision Overall Precision Accuracy Tap Water - DC Single-Analyst Precision Overall Precision Accuracy 4-Nitrophenol (28.20 - 320.00) SR = 0.17X + 2.43 S =0.19X + 4.79 X =0.460 + 0.18 SR = 0.25X + 0.91 S = 0.31 X + 0.36 X =0.400 + 3.27 SR = 0.24X + 5.07 S = 0.32X + 3.43 X =0.400 + 4.61 SR = 0.34X - 1.44 S = 0.34X + 3.04 X =0.410 + 2.96 SR = 0.24X - 0. 15 S =0.39X + 0.53 X =0.350 + 2.78 SR = 0.26X -0.22 S =0.30X + 3.41 X = 0.390 + 3.07 SR = 0.22X + 3.95 S = 0.22X + 5.87 X =0.400+4.62 X = Mean Recovery C = True Value for the.Concentration on for Compounds 5-8 hloropheriol Pentachlorophenol 15X-0.56 SR = 0.25X + 2.99 20X + 1.04 S = 0.38X + 1. 13 320 + 0.94 X =0. 790 + 1.99 1 1X + 6.30 SR = 0.21 X - 1.14 15X + 5.01 S =0. 18X + 3. 71 55C + 2.14 X = 0.830 + 2.06 on for Compounds 9-11 4,6-Dinitro-2-Methylphenol (29.80 - 338.00) SR = 0.15X + 1.31 S =0.20X + 5.53 X =0.840 - 1.27 SR = 0.30X - 4.87 S =0.25X-0.44 X =0.840-0.24 SR = 0. 16X - 0. 16 S = 0.27X - 0.91 X = 0.840 + 1. 13 SR = O.26X - 2.89 S = 0.29X + 5.90 X = 0.900 - 0.90 SR = 0.32X - 5. 18 S = 0.37X - 3.86 X = 0.880 + 3.36 SR = 0.1 7X + 2.43 S = 0.30X + O.80 X =0.880 + 0.30 SR = 0.30X - 4.59 S = 0.31 X + O.08 X =0.84C- 1.79 2-Nitrophenol SR = 0.1 8X- 0.04 S = 0.21 X + 2.53 X =0.770+1.78 SR = 0. 15X + 1. 19 S =0.22X+1.92 X =0.770 - 1.44 2,4-Dinitrophenol (27.00 - 320.00) SR=0.27X - 1.15 S =0.29X + 4.51 X =0.800-1.58 SR = 0.38X - 5.88 S =0.35X + 0.45 X =0.850+3.01 SR = 0.24X + 2.52 S =0.35X+1.85 X =0.870 + 6.11 SR = 0.34X + 0.29 S =0.40X-0.42 X =0.940+1.62 SR = 0.32X - 2.09 S =0.34X + 4.61 X =0.990 + 5.37 SR = 0.1 6X+ 14.23 S =0.24X+ 12.93 X =0.840+12.36 SR=O.22X + 6.13 S = 0.66X-3.92 X = 0.970 - 3.59 Water Type Applicable Cone. Range Distilled Water Single-Analyst Precision Overall Precision Accuracy Tap Water - Non DC Single-Analyst Precision Overall Precision Accuracy Phenol f 18.40 - 252.00) SR = 0.21X + 0.99 S =0.41X+1.40 X = 0.36C - 0.05 SR = 0.54X + 0.02 S =0.72X-0.01 X = 0.31 C- 0.73 2, 4-Dimefhylphenol (13.00 - 1^51.00) . S/? = 0.3fX+ 1.03 S = 0.67X-0.24 X =0.670 - 1.15 SR = 0.77X - 0.26 S =O.79X-0.40 X =0.250+1.11 2-Chlorophenol (12.20 - 185.00) SR = 0.41 X - 0.59 S = 0.52X - 0.09 X = 0.550 + 0. 18 SR = 0.65X - 3.44 S =0.53X + 0.71 X = 0.80C - 2.08 4-Chloro-3-Methylpheno (30.00 - 450.00) SR = 0.31X+ 1.06 S -0.53X^1.18 X =0.720' -3.97 SR = 0.36X + 0. 19 S = 0.65X - 0. 16 X =0.470-3.69 ------- Table 2. (Continued) Regression Equations for Accuracy and Precision for Compounds 1 - 4 Water Type Surface Water Single-Analyst Precision Overall Precision Accuracy Waste Water 1 Single-Analyst Precision Overall Precision Accuracy Waste Water 2 Single-Analyst Precision Overall Precision Accuracy Waste Water 3 Single-Analyst Precision Overall Precision Accuracy Tap Water - DC Single-Analyst Precision Overall Precision Accuracy Phenol Sft = 0.33X - 1. 13 S = 0.29X + 3.95 X = 0.33C + 1.98 SR = 0.54X - 1.70 S = 0.48X + 2.05 X = 0.30C + 0.40 SR = 0.37X + 0.16 S = 0.39X + 3.71 X = 0.36C + 2.94 SR = 0.29X+ 1.67 S = 0.55X + 1.05 X = 0.32C + 0.57 SR = 0.33X - 0.92 S =0.58X-0.43 X =0.28C + 0.93 Table 2. (Continued) Regression Equations for Accuracy Water Type Applicable Cone. Range Distilled Water Single-Analyst Precision Overall Precision Accuracy Tap Water - Non DC Single-Analyst Precision Overall Precision Accuracy Surface Water Single-Analyst Precision Overall Precision Accuracy Waste Water 1 Single-Analyst Precision Overall Precision Accuracy Waste Water 2 Single-Analyst Precision Overall Precision Accuracy Waste Water 3 Single-Analyst Precision Overall Precision Accuracy Tap Water - DC Single-Analyst Precision Overall Precision Accuracy 2,4-Dichlorophenol (14.80 - 214.00) SR = 0.17X + 2.16 S = 0.37X+J.53 X =0.730-2.21 SR = 0.44X - 1.96 S =0.52X-0.33 X =0.770-3.74 SR = 0.35X + 1.51 S = 0.46X + 1.39 X = 0.71 C- 0.65 SR = 0.40X + 0.06 S = 0.43X+,0,78 X =0.710-0.20 SR=0.38X+ 1.69 S = 0.45X + 1. 15 X =0.710 + 0.60 SR = 0.33X + 0.83 S =0.43X+1.08 X =0.700-1.05 SR = 0.37 X - 0.63 S = 0.61 X- 2.82 X =0.980-4.76 2, 4-Dimethylphenol SR = 0.26X + 2.75 S =0.42X + 2.60 X = 0.490 - 0.26 SR = 0.55X - 1.08 S =0.50X + 0.60 X =0.410-0.16 SR = 0.70X - 0.96 S =0.77X + 0.01 X = 0.520 + 0.50 SR = 0.32X + 1.55 S =0.60X+1.63 X = 0.390 + 4.52 SR =0.45X - 1.39 S =0.70X - 1.67 X = 0.590 - 0.50 and Precision for Compounds 5 2, 4, 6- Trichlorophenol (20.4O - 236.00) SR = 0.32X - 0.51 S = 0.34X + 2.80 X = 0.800 - 4. 16 SR = 0.42X - 3.77 S =0.44X - 1.11 X = 0.83C - 3.27 SR = 0.26X + 5.54 S = 0.38X + 3.63 X =0.630 + 2.41 SR = 0.33X + 0.21 S =0.44X+1.70 X =0.780-0.33 SR = 0.56X - 2.68 S = 0.41 X + 2.03 X =0.710-0.41 SR = 0.24X + 1.52 S = 0.32X + 2.24 X =0.660 + 2.28 SR = 0.33X - 2.02 S =0.39X-2.70 X = 0.820 - 1.61 2-Chlorophenol SR =0.35X + 0.98 S =0.45X+1.57 X = 0.570 + 0.44 SR = 0.42X + 0.95 S = 0.47X + 2.20 X = 0.540 + 0.29 SR = 0.45X + 1.11 S =0.49X + 2.35 X =0.730-0.19 SR = 0.60X - 2.32 S = 0.68X - 1.58 X =0.710 + 0.35 SR = 0.26X - 0.81 S = 0.56X - 0.23 X = 0.500 + 0.40 -8 Pentachlorophenol (16.20 - 226.OO) SR = 0.33X - 0.92 S = 0.45X - 0. 15 X =0.740-2.34 SR = 0.35X + 1.06 S = 0.42X + 0.64 X =0.700 - 1.57 SR = 0.35X + 0.41 S = 0.51 X + 0.03 X =0.630-2.46 SR = 0.53X - 4.49 S =0.55X + 23.33 X =0.730 + 36.34 SR = 0.38X + 0.22 S = 0.38X + 0.32 X =0.660 + 0.48 SR = 0.34X + 0.04 S = 0.55X - 0.03 X = 0.580 + 1.27 SR = 0.1 4X + 0.02 S =0. 15X + 0.36 X =0.890 + 0.78 4-Chloro-3-Methylphenol SR = 0.22X + 6.26 S =0.47X + 2.W X = 0.630 + 0.58 SR = 0.52X - 3.59 S = 0.52X + 3.57 X =0.550 + 0.32 SR = 0.31 X + 0.09 S = 0.36X + 8.03 X = 0.590 + 3.19 SR = 0.40X + 2.00 S =0.54X + 2.35 X =0.460 + 3.21 SR = 0.32X - 3.35 S = 0.58X - 3.28 X = 0.540 - 5.39 2-Nitrophenol (25.00 - 374.00) SR=0.26X + 1.66 S = O.39X + 2.97 X =0.600-2.64 SR = 0.30X - 0.74 S = 0.45X + 0.29 X =0.580 - 1.53 SR = 0.32X + 1 .86 S = 0.45X + 2.43 X = 0.550 + 2.40 SR=0.35X -0.82 S =0.46X + 0.25 X = 0.580 + 1.06 SR = 0.37X- 1.65 S =0.42X + 2.17 X = 0.610 - 0.20 SR = 0.42X - 0.21 S = 0.51 X - 0.38 X = 0.58C - 0.98 SR=0.11X + 2.36 S =0.46X-1.40 X =0.600-1.61 ------- Table 2. (Continued) Regression Equations for Accuracy and Precis, Water Type 4-Nitrophenol on for Compound 9 Applicable Cone. Range Distilled Water Single-Analyst Precision Overall Precision Accuracy Tap Water — Non DC Single-Analyst Precision Overall Precision Accuracy Surface Water Single-Analyst Precision Overall Precision Accuracy Waste Water 1 Single-Analyst Precision Overall Precision Accuracy Waste Water 2 Single-Analyst Precision Overall Precision Accuracy Waste Water 3 Single-Analyst Precision Overall Precision Accuracy Tap Water - DC Single-Analyst Precision Overall Precision Accuracy (28.20 - 320.00! SR = 0.37X + 0.29 S = 0.48X+1.21 X = 0.43C - 2.55 SR = O.39X -O.J6 S = 0.4JX + 1.03 X =0.35C-2.64 SR = 0.28X + 3.04 S = 0.43X + 0.08 X = 0.32C + 0.75 SR = 0.32X + 1.71 S = O.39X + 2.35 X = 0.34C + 7.34 SR = 0.20X + 2.97 S = 0.28X + 1.95 X = 0.40C + 0.45 SR = 0.50X - 1.94 S = 0.64X-0.73 X =0.360-0.37 SR = 0.1 IX+ 2.66 S = 0.41 X - O.2O X = O.33C - 0.09 X = Mean Recovery C = True Value for the Concentration the three cases described for 2,4- dinitrophenol. Results from the limited study comparing the method performance on both nondechlorinated and de- chlorinated tap water prove the need to dechlorinate samples for phenols analysis as soon as possible after sample collection. Some of the problems encountered in applying the method during this study included: several laboratories had a problem with the separation of 4,6-dinitro-2-methylphenol and 2,4- dinitrophenol when using the SP- 1240DA column during use of the FID procedure. For each method of detection at least one laboratory had a problem in distinguishing between peaks in the standard mixture. One laboratory had trouble in concentra- ting the extract using the Kuderna- Danish apparatus. Some of the laboratories had to use peak height measurements for quantitation be- cause occasional interference peaks in wastewater created faulty integra- tion when usin 3 recording integrators. In future interlaboratory studies, very detailed instruction should be given to the participating laboratories to ensure labeling of each chromato- gram. In this study it was very difficult to interpret much of the raw chromatogranhic data because of inadequate labeling. Other points to be emphasized in future studies are that (a) blanks and spiked samples must be analyzed at the same sensitivity and (b) calculations and record keeping should be uniform or consistent to aid in data interpreta- tion. r U.S. GOVERNMENT PRINTING OFFICE: 1984 - 759-102/10610 ------- Jack R. Hall, J. Richard Florence, Dennis L Strother, and Marlene N. Wass are with IT Enviroscience, Knoxville, TN 37923. Edward L. Berg and Robert L. Graves are the EPA Project Officers (see below). The complete report, entitled "EPA Method Study 14, Method 604—Phenols," (Order No, PB 84-196 211; Cost: $22.00, subject to change! will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officers can be contacted at: Environmental Monitoring and Support Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G-35 Official Business Penalty for Private Use S300 EMSL0158933 JOHN WINTER EMSL-CIN BRCH CINCINNATI OH 45368 ------- |