Results of Proficiency Test Gasoline (ASTM specification) February 2017

Transcription

1 Results of Proficiency Test Gasoline (ASTM specification) February 2017 Organised by: Author: Correctors: Report: Spijkenisse, the Netherlands ing. C.M. Nijssen-Wester dr. R.G. Visser & ing. R.J. Starink iis17b01astm April 2017

2 Spijkenisse, April Empty page - page 2 of 67 Gasoline: iis17b01astm

3 Spijkenisse, April 2017 CONTENTS 1 INTRODUCTION SET UP ACCREDITATION PROTOCOL CONFIDENTIALITY STATEMENT SAMPLES STABILITY OF THE SAMPLES ANALYSES RESULTS STATISTICS GRAPHICS Z-SCORES EVALUATION EVALUATION PER TEST PERFORMANCE EVALUATION FOR THE GROUP OF LABORATORIES COMPARISON OF THE RESULTS OF FEBRUARY 2017 WITH PREVIOUS PTS Appendices: 1. Data, statistical results and graphic results z-scores distillation ASTM D Number of participants per country Abbreviations and literature Gasoline: iis17b01astm page 3 of 67

4 Spijkenisse, April INTRODUCTION Since 1995, the (iis) organizes a proficiency scheme for Gasoline. During the annual proficiency testing program 2016/2017, it was decided to continue the round robin for the analysis of Gasoline in accordance with the most recent version of the specification ASTM D4814. In this interlaboratory study, in total 122 laboratories in 64 different countries registered for participation. See appendix 3 for the number of participants per country. In this report, the results of the 2017 proficiency test are presented and discussed. This report is also electronically available through the iis website 2 SET UP The (iis) in Spijkenisse, the Netherlands, was the organizer of this proficiency test. Sample analyzes for fit-for-use and homogeneity testing were subcontracted to an ISO/IEC accredited laboratory. In this proficiency test, the participants received, depending on their registration, 1*1 litre bottle Gasoline euro 95 (labelled #17010) and/or 1*1 litre bottle (± 75% filled) Gasoline euro 95 (labelled #17011) for DVPE only, and/or 2*1 litre bottle Gasoline euro 95 (labelled #17012) for RON/MON only. To get maximum information from this study it was decided to spike the bulk material with approx. 4.2 mg Lead, 3.9 mg Manganese and 1.8 mg Phosphorus per liter. Participants were requested to report rounded and unrounded test results. The unrounded test results were preferably used for statistical evaluation. 2.1 ACCREDITATION The in Spijkenisse, the Netherlands, is accredited in agreement with ISO/IEC 17043:2010 (R007), since January 2000, by the Dutch Accreditation Council (Raad voor Accreditatie). This PT falls under the accredited scope. This ensures strict adherence to protocols for sample preparation and statistical evaluation and 100% confidentiality of participant s data. Feedback from the participants on the reported data is encouraged and customer s satisfaction is measured on regular basis by sending out questionnaires. 2.2 PROTOCOL The protocol followed in the organization of this proficiency test was the one as described for proficiency testing in the report iis Interlaboratory Studies: Protocol for the Organisation, Statistics and Evaluation of March 2017 (iis-protocol, version 3.4). This protocol is electronically available through the iis website from the FAQ page. 2.3 CONFIDENTIALITY STATEMENT All data presented in this report must be regarded as confidential and for use by the participating companies only. Disclosure of the information in this report is only allowed by means of the entire report. Use of the contents of this report for third parties is only allowed by written permission of the. Disclosure of the identity of one or more of the participating companies will be done only after receipt of a written agreement of the companies involved. page 4 of 67 Gasoline: iis17b01astm

5 Spijkenisse, April SAMPLES The necessary sample material, Gasoline Euro 95 was obtained from a local petrol station in the Netherlands. From this batch, approximately 325 litres of Gasoline was spiked with the elements Phosphorus (from tricresyl phosphate), Lead (from tetra-ethyl lead) and Manganese (from tricarbonyl(methylcyclopentadienyl)manganese). After mixing and homogenisation in a 500 liter mixing vessel, 140 amber glass bottles of 1 litre were filled and labelled #17010 for the main round and 140 amber glass bottles of 1 litre were filled and labelled #17012 for the determination of RON/MON. The homogeneity of the subsamples #17010 and #17012 were checked by determination of Density at 15 C in accordance with ASTM D4052 on 10 stratified randomly selected samples. Density at 15 C in kg/m 3 Sample #17010/ Sample #17010/ Sample #17010/ Sample #17010/ Sample #17010/ Sample #17010/ Sample #17010/ Sample #17010/ Sample #17010/ Sample #17010/ Table 1: homogeneity test results of subsamples #17010 and #17012 From the same gasoline batch, approximately 200 liters were used to fill 100 bottles of 1 litre with approx. 750 ml and labelled #17011 for DVPE only. The homogeneity of the subsamples #17011 was checked by determination of Dry Vapour Pressure Equivalent in accordance with ASTM D5191 on 8 stratified randomly selected samples. DVPE in psi Sample # Sample # Sample # Sample # Sample # Sample # Sample # Sample # Table 2: homogeneity test results of subsamples #17011 From the above test results (table 1 and 2), the repeatabilities were calculated and compared with 0.3 times the corresponding reproducibilities in agreement with the procedure of ISO 13528, Annex B2 in the next table: Gasoline: iis17b01astm page 5 of 67

6 Spijkenisse, April 2017 Density at 15 C in kg/m 3 DVPE in psi r (sample #17010 and #17012) r (sample #17011) reference test method D4052:16 ASTM D5191: x R (ref. test method) Table 3: repeatabilities of subsamples #17010 (and #17012) and #17011 The calculated repeatabilities of the results of the homogeneity tests for Density and DVPE were less than 0.3 times the reproducibilities of the reference test methods. Therefore, the homogeneities of subsamples #17010 (and #17012) and #17011 were assumed. To the participants, depending on their registration, 1*1 litre bottle of sample #17010 and/or 1*1 litre bottle (± 750 ml filled) of sample #17011 and/or 2*1 litre bottle of sample #17012 were sent on February 1, An SDS was added to the sample package. 2.5 STABILITY OF THE SAMPLES The stability of Gasoline, packed in the brown glass bottles, was checked. The material was found sufficiently stable for the period of the proficiency test. 2.6 ANALYZES The participants were requested to determine API Gravity, Aromatics by FIA, Benzene, Copper Strip Corrosion, Silver corrosion, Density at 15 C, Distillation (automated or manual), Doctor Test, Existent gum (washed), Lead, Manganese, Olefins by FIA, Oxidation Stability, Oxygenates (Ethanol, MTBE, Other Oxygenates), Oxygen content, Phosphorus and Sulphur on sample # On sample #17011, the participants were requested to determine Total Vapour Pressure and Dry Vapour Pressure (acc. ASTM D5191 and EPA). On sample #17012, the participants were requested to determine RON and/or MON. To get comparable test results, a detailed report form and a letter of instructions are prepared. On the report form, the reporting units are given as well as the reference test methods that will be used during the evaluation. The detailed report form and the letter of instructions are both made available on the data entry portal The letter of instructions can also be downloaded from the iis website 3 RESULTS During five weeks after sample dispatch, the test results of the individual laboratories were gathered via the data entry portal The reported test results are tabulated per determination in appendix 1 of this report. The laboratories are presented by their code numbers. Directly after the deadline, a reminder was sent to those laboratories that had not reported test results at that moment. page 6 of 67 Gasoline: iis17b01astm

7 Spijkenisse, April 2017 Shortly after the deadline, the available test results were screened for suspect data. A test result was called suspect in case the Huber Elimination Rule (a robust outlier test) found it to be an outlier. The laboratories that produced these suspect data were asked to check the raw data of reported test results (no reanalyzes). Additional or corrected test results are used for data analysis and original test results are placed under Remarks the test result tables in appendix 1. Test results that came in after the deadline were not taken into account in this screening for suspect data and thus these participants were not requested for checks. 3.1 STATISTICS Statistical calculations were performed as described in the report iis Interlaboratory Studies: Protocol for the Organisation, Statistics and Evaluation of March 2017 (iis-protocol, version 3.4). For the statistical evaluation the unrounded (when available) test results were used instead of the rounded test results. Test results reported as < or > were not used in the statistical evaluation. First, the normality of the distribution of the various data sets per determination was checked by means of the Lilliefors-test, a variant of the Kolmogorov-Smirnov test and by the calculation of skewness and kurtosis. Evaluation of the three normality indicators in combination with the visual evaluation of the graphic Kernel density plot, lead to judgement of the normality being either unknown, OK, suspect or not OK. After removal of outliers, this check was repeated. If a data set does not have a normal distribution, the (results of the) statistical evaluation should be used with due care. In accordance with ISO 5725 the original test results per determination were submitted subsequently to Dixon s, Grubbs and/or Rosner s outlier tests. Outliers are marked by D(0.01) for the Dixon s test, by G(0.01) or DG(0.01) for the Grubbs test and by R(0.01) for the Rosner s test. Stragglers are marked by D(0.05) for the Dixon s test, by G(0.05) or DG(0.05) for the Grubbs test and by R(0.05) for the Rosner s test. Both outliers and stragglers were not included in the calculations of averages and standard deviations. For each assigned value, the uncertainty was determined in accordance with ISO Subsequently the calculated uncertainty was evaluated against the respective requirement based on the target reproducibility in accordance with ISO When the uncertainty passed the evaluation, no remarks are made in the report. However, when the uncertainty failed the evaluation it is mentioned in the report and it will have consequences for the evaluation of the test results. Finally, the reproducibilities were calculated from the standard deviations by multiplying them with a factor of GRAPHICS In order to visualise the data against the reproducibilities from literature, Gauss plots were made, using the sorted data for one determination (see appendix 1). On the Y-axis the reported test results are plotted. The corresponding laboratory numbers are on the X-axis. The straight horizontal line presents the consensus value (a trimmed mean). The four striped lines, parallel to the consensus value line, are the +3s, +2s, -2s and -3s target reproducibility Gasoline: iis17b01astm page 7 of 67

8 Spijkenisse, April 2017 limits of the selected reference test method. Outliers and other data, which were excluded from the calculations, are represented as an x. Accepted data are represented as a triangle. Furthermore, Kernel Density Graphs were made. This is a method for producing a smooth density approximation to a set of data that avoids some problems associated with histograms. Also a normal Gauss curve was projected over the Kernel Density Graph for reference. 3.3 Z-SCORES To evaluate the performance of the participating laboratories the z-scores were calculated. As it was decided to evaluate the performance of the participants in this proficiency test (PT) against the literature requirements, e.g. ASTM reproducibilities, the z-scores were calculated using a target standard deviation. This results in an evaluation independent of the variation of this interlaboratory study. The target standard deviation was calculated from the literature reproducibility by division with 2.8. In case no literature reproducibility was available, other target values were used. In some cases, a reproducibility based on former iis proficiency tests could be used. When a laboratory did use a test method with a reproducibility that is significantly different from the reproducibility of the reference test method used in this report, it is strongly advised to recalculate the z-score, while using the reproducibility of the actual test method used, this in order to evaluate whether the reported test result is fit-for-use. The z-scores were calculated in accordance with: z (target) = (test result - average of PT) / target standard deviation The z (target) scores are listed in the test result tables in appendix 1. Absolute values for z<2 are very common and absolute values for z>3 are very rare. The usual interpretation of z-scores is as follows: z < 1 good 1 < z < 2 satisfactory 2 < z < 3 questionable 3 < z unsatisfactory 4 EVALUATION In this interlaboratory study, problems were encountered with the dispatch of the samples. Participants in Afghanistan, Brazil, India, Kazakhstan and Saudi Arabia received the samples late or not at all. For the main round (117 participants), 13 participants did not report test results. For the DVPE round (86 participants), 8 participants did not report test results. For the RON/MON round (56 participants), 8 participants did not report test results. Finally, in total 111 laboratories reported 1489 numerical test results. Observed were 39 outlying results, which is 2.6%. In proficiency studies, outlier percentages of 3% - 7.5% are quite normal. page 8 of 67 Gasoline: iis17b01astm

9 Spijkenisse, April EVALUATION PER TEST In this section, the reported test results are discussed per test. The methods, which were used by the various laboratories, are taken into account for explaining the observed differences where possible and applicable. These methods are also in the tables together with the reported test data. The abbreviations, used in these tables, are listed in appendix 4. Not all original data sets proved to have a normal Gaussian distribution. These are referred to as not OK or suspect. The statistical evaluation of these data sets should be used with due care, see also paragraph 3.1. API Gravity: This determination was not problematic. One statistical outlier was observed. The calculated reproducibility after rejection of the statistical outlier is in agreement with the requirements of ASTM D4052:16. Aromatics by FIA: This determination was problematic. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of ASTM D1319:15. Benzene: This determination was not problematic. One statistical outlier was observed. The calculated reproducibility after rejection of the statistical outlier is in agreement with the requirements of ASTM D3606:10e1. Copper Corrosion:No problems have been observed. All participants agreed on classification 1. Silver Corrosion: No problems have been observed. All participants, except two, agreed on classification 0. Density at 15 C: This determination was not problematic. Three statistical outliers were observed. However, the calculated reproducibility after rejection of the statistical outliers is in good agreement with the requirements of ASTM D4052:16. Distillation Doctor Test: The distillation was not problematic. In total eleven statistical outliers were observed. For the automated mode, the calculated reproducibilities, except for Initial Boiling Point, after rejection of the statistical outliers are in agreement with the requirements of ASTM D86:16a (automated mode). For the manual mode, the calculated reproducibilities, except for Initial and Final Boiling Point, are in agreement with the requirements of ASTM D86:16a (Manual mode). Almost all the laboratories agreed on the absence of Mercaptans and reported Negative. One laboratory reported sweet and one laboratory reported Positive. Gasoline: iis17b01astm page 9 of 67

10 Spijkenisse, April 2017 Existent Gum: Lead: Manganese: Olefins by FIA: This determination was not problematic. Three statistical outliers were observed. However, the calculated reproducibility after rejection of the statistical outliers is in agreement with the requirements of ASTM D381:12. The determination was problematic for a large number of laboratories. Thirteen participants did not detect any lead and reported a false negative test result. Three statistical outliers were observed. However, the calculated reproducibility after rejection of the suspect data is in full agreement with the requirements of ASTM D3237:12. The average recovery of Lead (theoretical increment of 4.15 mg Lead/L) may be good: approx. 100%. The determination was not problematic. No statistical outliers were observed, but three participants did not detect any manganese and reported a false negative test result. The calculated reproducibility after rejection of the suspect data is in agreement with the requirements of ASTM 3831:12. The average recovery of Manganese (theoretical increment of 3.91 mg Manganese/L) may be good: approx. 106% (the actual blank Manganese content is unknown). This determination was problematic. One statistical outlier was observed. The calculated reproducibility after rejection of the statistical outlier is not in agreement with the requirements of ASTM D1319:15. Oxidation stability: All laboratories agreed that the Oxidation Stability is >360 minutes. Ethanol: MTBE: This determination was not problematic. Three statistical outliers were observed. However, the calculated reproducibility after rejection of the statistical outliers is in agreement with the requirements of ASTM D4815:15b. This determination was problematic. Two statistical outliers were observed. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the requirements of ASTM D4815:15b. Other Oxygenates: No other oxygenates were found positive by the participating laboratories. Therefore, no significant conclusions were drawn. Oxygen content: This determination was not problematic. Two statistical outliers were observed. However, the calculated reproducibility after rejection of the statistical outliers is in full agreement with the requirements of ASTM D4815:15b and D5599:15. page 10 of 67 Gasoline: iis17b01astm

11 Spijkenisse, April 2017 Phosphorus: Sulphur: TVP: DVPE: RON: MON: This determination was very problematic. One statistical outlier was observed. However, the calculated reproducibility after rejection of the statistical outlier is not at all in agreement with the requirements of ASTM D3231:13. The average recovery of Phosphorus (theoretical increment of 1.78 mg Phosphorus/L) may be good: approx. 103% (the actual blank of Phosphorus content is unknown). The low number of reported test results may (partly) explain the observed large variation. This determination was not problematic. Three statistical outliers were observed. However, the calculated reproducibility after rejection of the statistical outliers is in full agreement with the requirements of ASTM D5453:12. This determination was not problematic. One statistical outlier was observed. The calculated reproducibility after rejection of the statistical outlier is in full agreement with the requirements of ASTM D5191:15. The conversions of the measured Total Vapour Pressure to the corresponding Dry Vapour Pressure Equivalent (DVPE) as described in ASTM D5191:15 and to the U.S. EPA guidelines (40 CFR Part 80, App. E, Method 3), show in total four statistical outliers. Both calculated reproducibilities after rejection of the statistical outliers are in agreement with the respective requirements of ASTM D5191:15 and EPA guidelines. No calculations errors were observed. This determination was problematic. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of ASTM D2699:15a. This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in full agreement with the requirements of ASTM D2700:16. Gasoline: iis17b01astm page 11 of 67

12 Spijkenisse, April PERFORMANCE EVALUATION FOR THE GROUP OF LABORATORIES A comparison has been made between the reproducibility as declared by the relevant standard and the reproducibility as found for the group of participating laboratories. The average results of sample #17010, #17011 and #17012, calculated reproducibilities and reproducibilities, derived from literature standards (in casu ASTM standards) are compared in the next table. Parameter Unit n mean 2.8 * sd R (lit) API Gravity Aromatics by FIA %V/V Benzene % V/V Copper Corrosion 3 hrs at 50 C n.a. n.a. Silver Corrosion 3 hrs at 50 C n.a. n.a. Density at 15 C kg/m Distillation Auto Manual - Initial Boiling Point C Temp. at 10% evaporated C Temp. at 50% evaporated C Temp. at 90% evaporated C Final Boiling Point C Doctor Test negative n.a. n.a. Existent Gum (washed) mg/100ml Lead as Pb mg/l Manganese as Mn mg/l Olefins by FIA %V/V Oxidation Stability min. 46 >360 n.a. n.a. -Ethanol %V/V MTBE %V/V Oxygen content %M/M Phosphorus as P mg/l Sulphur mg/kg Table 4: performance evaluation sample #17010 Parameter Unit n mean 2.8 * sd R (lit) TVP psi DVPE acc. to ASTM D5191 psi DVPE acc. EPA psi Table 5: performance evaluation sample #17011 Parameter Unit n mean 2.8 * sd R (lit) RON MON Table 6: performance evaluation sample #17012 Without further statistical calculations, it can be concluded that for many tests there is a (good) compliance of the group of participants with the relevant standards. The problematic tests have been discussed in paragraph 4.1. page 12 of 67 Gasoline: iis17b01astm

13 Spijkenisse, April COMPARISON OF THE PROFICIENCY TEST OF FEBRUARY 2017 WITH PREVIOUS PTS February 2017 March 2016 February 2015 February 2014 February 2013 Number of rep. p articipants Number of results reported Statistical outliers Percentage outliers 2.6% 1.7% 2.4% 3.8% 3.2% Table 7: comparison with previous proficiency tests In proficiency tests, outlier percentages of 3% - 7.5% are quite normal. The performance of the determinations of the proficiency tests was compared against the requirements of the respective standards. The conclusions are given in the following table: Parameter February 2017 March 2016 February 2015 February 2014 February 2013 API Gravity Aromatics by FIA Benzene Density at 15 C Distillation Automated Distillation Manual /- Existent Gum (washed) Lead as Pb +/- n.e. n.e. n.e. n.e. Manganese as Mn + n.e. n.e. n.e. n.e. Olefins by FIA Ethanol +/- + +/- + +/- MTBE Oxygen content +/- +/- +/- + +/- Phosphorus as P n.e. n.e. Sulphur +/- +/- +/- +/- +/- TVP +/ DVPE +/ /- RON /- + MON +/- - +/- +/- +/- Table 8: comparison determinations against the standard The performance of the determinations against the requirements of the respective standards is listed in the above table. ++: group performed much better than the standard + : group performed better than the standard +/-: group performance equals the standard - : group performed worse than the standard -- : group performed much worse than the standard n.e.: not evaluated Gasoline: iis17b01astm page 13 of 67

14 Spijkenisse, April 2017 APPENDIX 1 Determination of API Gravity on sample #17010; lab method value mark z(targ) remarks 52 D D D D D D D D D D D D D D R(0.01) D D D D D D D D D D D D D D D D D D D D D D D D D D D D D Calc D page 14 of 67 Gasoline: iis17b01astm

15 Spijkenisse, April D D D D D D D D D D D D D4052Conversion C 0.02 first reported: D D normality not OK n 59 outliers 1 mean (n) st.dev. (n) R(calc.) R(D4052:16) Kernel Density Gasoline: iis17b01astm page 15 of 67

16 Spijkenisse, April 2017 Determination of Aromatics by FIA on sample #17010; results in %V/V lab method value mark z(targ) remarks D D D D D D D D D D D D C 1.18 first reported: D D D D EN D D C 0.17 first reported: D D D D D D D D D D ISO D D page 16 of 67 Gasoline: iis17b01astm

17 Spijkenisse, April D D D D D D D D D D D D EN D D D D normality OK n 49 outliers 0 mean (n) st.dev. (n) R(calc.) 4.53 R(D1319:15) Kernel Density Gasoline: iis17b01astm page 17 of 67

18 Spijkenisse, April 2017 Determination of Benzene on sample #17010; results in %V/V lab method value mark z(targ) remarks D D D D D D D R(0.01) D D D D ISO EN D D D D D D D D D D D6277b D D D D ISO ISO page 18 of 67 Gasoline: iis17b01astm

19 Spijkenisse, April D D D D EN D D D D D D D EN EN EN EN ISO EN ISO ISO In house EN D normality suspect n 54 outliers 1 mean (n) st.dev. (n) R(calc.) R(D3606:10e1) Compare R(D5580:15) = Kernel Density Gasoline: iis17b01astm page 19 of 67

20 Spijkenisse, April 2017 Determination of Copper Corrosion 3hrs at 50 C on sample #17010; lab method value mark z(targ) remarks 52 D130 1a D130 1b D130 1A D130 1a D130 1a D130 1a D130 1a D130 1a D130 1A D130 1a D D130 1a D130 1a D130 1a D130 1a D130 1A D130 1A D130 1A D130 1a D130 1a D130 1 A D130 1A D130 1A D130 1a D130 1a D130 1A D130 1b D D130 1A ISO D130 1A D130 1A D130 1A D D130 1A D130 1A D130 1a D130 1a D130 1A D130 1a D130 1a D130 1a D130 1a D130 1a D130 1a D130 1a D130 1a D130 1A D130 1a D130 1a D130 1a D130 1a D130 1a D130 1a D130 1A D130 1A D130 1a D130 1A page 20 of 67 Gasoline: iis17b01astm

21 Spijkenisse, April D130 1a D130 1a D130 1a D130 1a ISO2160 1a D130 1A D130 1A D130 1A D130 1A D130 1A D130 1a D130 1A D130 1A ISO2160 1a D D130 1a D130 1a D130 1a D130 1a D130 1A D130 1a ISO D130 No ISO2160 1A D130 1A D130 1a D130 1a ISO2160 1a D130 1a n 87 mean (n) 1 Gasoline: iis17b01astm page 21 of 67

22 Spijkenisse, April 2017 Determination of Silver Corrosion 3hrs at 50 C on sample #17010; lab method value mark z(targ) remarks 52 D7671-A D7671-A D7671-A D7671-A D7671-A D7671-A D7671-A D7671-A D7671-A D7671-A D7671-A D7671-A D7667-A D7671-A D7671-A D7671-A D7671-A D7671-A D4814-A page 22 of 67 Gasoline: iis17b01astm

23 Spijkenisse, April D7671-A D7671-A D7671-A D7667-A D7671-A D7667-A n 25 mean (n) 0 Gasoline: iis17b01astm page 23 of 67

24 Spijkenisse, April 2017 Determination of Density at 15 C on sample #17010; results in kg/m 3 lab method value mark z(targ) remarks 52 D D D D D D D D D D D D D D D R(0.01) D D D C 0.04 first reported: D D D D D D D D D D D D D IP D D D ISO D D D D D D D D D D D D D D D D D D D D D D D D ISO IP D D page 24 of 67 Gasoline: iis17b01astm

25 Spijkenisse, April D D D D D C 0.01 reported: , probably a unit error? 1161 D D R(0.01) D D D D D D D D D D D D R(0.01) D D D ISO D ISO ISO ISO D ISO D ISO ISO ISO D D ISO D normality not OK n 98 outliers 3 mean (n) st.dev. (n) R(calc.) R(D4052:16) Kernel Density Gasoline: iis17b01astm page 25 of 67

26 Spijkenisse, April 2017 Determination of Distillation at 760 mm Hg ASTM D86 on sample #17010; results in C lab method IBP mark 10% eva mark 50% eva mark 90% eva mark FBP mark 52 D86-Automated D86-Automated R(0.05) D86-Automated D86-Automated D86-Automated D86-Automated C D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Manual R(0.01) D86-Manual D86-Manual R(0.05) R(0.05) D86-Manual D86-Manual R(0.05) D86-Manual D86-Manual D86-Manual D86-Automated D86-Automated D86-Automated D86-Automated 31.7 R(0.05) D86-Automated D86-Automated D86-Automated IP123-Automated D86-Manual D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated D86-Manual D86-Automated D86-Automated D86-Manual D86-Manual ISO3405-Automated D86-Automated D86-Automated page 26 of 67 Gasoline: iis17b01astm

27 Spijkenisse, April D86-Automated D86-Automated D86-Automated D86-Manual D86-Automated C 52.0 C R(0.05) D86-Automated D86-Manual D86-Automated D86-Manual R(0.01) D86-Automated D86-Automated D86-Automated D86-Manual R(0.05) D86-Automated D86-Automated D86-Automated D86-Automated D86-Automated R(0.05) D86-Automated D86-Manual ISO3405-Automated ISO3405-Automated D86-Automated D86-Automated ISO3405-Automated D86-Manual ISO3405-Automated ISO3405-Automated ISO3405-Automated D86-Automated D86-Automated ISO3405-Automated D86-Automated C R(0.05) normality OK OK OK OK OK n outliers mean (n) st.dev. (n) R(calc.) R(D86:16a Automated) R(D86:16a Manual) (4.27) (3.42) (3.39) (3.85) (3.10) Lab 140 first reported for temperature at 10% evaporated: 47.8 Lab 1186 first reported for IBP: 43 and for temperature at 10% evaporated: 57 Lab 6101 first reported for temperature at 10% evaporated: Gasoline: iis17b01astm page 27 of 67

28 Spijkenisse, April 2017 page 28 of 67 Gasoline: iis17b01astm Kernel Density Kernel Density Kernel Density Kernel Density Kernel Density IBP 10% evaporated 50% evaporated 90% evaporated FBP

29 Spijkenisse, April empty page - Gasoline: iis17b01astm page 29 of 67

30 Spijkenisse, April 2017 Determination of Doctor Test on sample #17010; lab method value mark z(targ) remarks 52 D4952 Neg D4952 Negative D4952 Negative D4952 Negative D4952 Negative D4952 negative D4952 Negative D4952 negative D4952 Negative D4952 Negative D4952 Negative D4952 Negative IP30 Negative IP30 NEGATIVE D4952 Negative D4952 Negative IP30 Negative D4952 Negative D4952 Negative IP30 Negative D4952 sweet D4952 Positive Possible false positive result? D4952 negative D4952 Negative D4952 Negative D4952 negative C D4952 negative D4952 negative D4952 Negative D4952 negative D4952 Negative D4952 Negative D4952 Negative D4952 Negative D4952 negative D4952 neg D4952 negative page 30 of 67 Gasoline: iis17b01astm