1.0 INTRODUCTION 2.0 TERMS AND DEFINITIONS 3.0 QUALITY ASSURANCE OBJECTIVES 4.

0 SAMPLE CONTAINERS AND GLASSWARE PREPARATION 5.0 SAMPLE CUSTODY, PREPARATION, AND PRESERVATION 6.0 CALIBRATION AND ANALYTICAL PROCEDURES 6.1 Balance and Pipette Calibration 6.2 Calibration Standard Preparation 6.3 Calibration and Run Procedures for FIA, IC, AAS, and Carbon Analyzer 6.4 Calibration and Run Procedures for pH, ANC, and Specific Conductance 6.5 Method Detection Limit 7.0 INTERNAL QUALITY CONTROL CHECKS 7.1 Second Source Check Standard (SSCS) 7.2 Quality Control Check Samples (QCCS) 7.3 QCCS for pH, Conductivity, ANC, and TS 7.4 Laboratory Duplicates 7.5 Analytical Duplicate 7.6 Field Duplicate 7.7 Miscellaneous Laboratory Quality Control Procedures 8.0 CALCULATION OF DATA QUALITY INDICATORS 9.0 DATA REDUCTION, VALIDATION, AND REPORTING 10.0 PERFORMANCE AND SYSTEM AUDITS 11.0 REFERENCES 12.0 Annexes A. Methods and Detection Limits for lab scope of Analyses B. Quality Assurance Objectives for an Analytical Laboratory C. Sample Processing and Tracking Information D. Annual Sample Processing Schedule E. Annual Master Tracking Sheet F. Sample Tracking Sheet G. Examples of Holding Times H. Standard Preparation Log Sheet I. Example of a Run Log for an Analytical Instrument J. DATA PACKAGE COVER SHEET K. List of Standard Operating Procedures for the Analytical Laboratory 5 1.0 INTRODUCTION 2.0 TERMS AND DEFINITIONS 3.0 QUALITY ASSURANCE OBJECTIVES 4.0 SAMPLE CONTAINERS AND GLASSWARE PREPARATION 5.0 SAMPLE CUSTODY, PREPARATION, AND PRESERVATION 6.0 CALIBRATION AND ANALYTICAL PROCEDURES 6.1 Balance and Pipette Calibration 6.2 Calibration Standard Preparation 6.3 Calibration and Run Procedures for FIA, IC, AAS, and Carbon Analyzer 6.4 Calibration and Run Procedures for pH, ANC, and Specific Conductance 6.5 Method Detection Limit 7.0 INTERNAL QUALITY CONTROL CHECKS 7.1 Second Source Check Standard (SSCS) 7.2 Quality Control Check Samples (QCCS) 7.3 QCCS for pH, Conductivity, ANC, and TS 7.4 Laboratory Duplicates 7.5 Analytical Duplicate 7.6 Field Duplicate 7.7 Miscellaneous Laboratory Quality Control Procedures 8.0 CALCULATION OF DATA QUALITY INDICATORS 9.0 DATA REDUCTION, VALIDATION, AND REPORTING 10.0 PERFORMANCE AND SYSTEM AUDITS
2.1 Petroleum 2.1.1 Definitions 2.1.2 Composition 2.2 Crude Oil Evaluation 2.2.1 Type of Crude Oil According to: - American bureau of mines method - UOP (375/86) method 2.3 Petroleum Assay 2.3.1 Carbon Residue, Asphaltene Content

2.3.2 Density (Specific Gravity) 2.3.3 Distillation 2.3.4 Light Hydrocarbons 2.3.5 Metallic Constituents 2.3.6 Salt Content 2.3.7 Sulfur Content 2.3.8 Viscosity and Pour Point 2.3.9 Water and Sediment 2.3.10 Wax Content 2.3.11 Other Tests

Overview: Quality Control, Quality Assurance and Methods

I) Quality Assurance

A) Water Quality (effective 941025)

Deionized water with a specific conductance at or below 1.0 microsemens per centimeter is used for all analytical work. The 10-18 megohm/cm deionized water is produced by a Barnstead Type D4700 Nanopure Analytical Deionization System with an organic free cartridge. This system is attached to a Siemens Water Technology/US Filter Corporation Water System with an Activated Carbon Unit # 2937, a 10'' Ametek filtering system, and #2936 mixed bed Deionizers.

Previous Method (system disconnected July 1994): Deionized water with a specific conductance at or below 2.0 microsemens per centimeter is used for all analytical

work. The deionized water is produced by a Continental Water System Activated Carbon Unit #2937, 10'' Ametek filtering system and #2936 mixed bed Deionizers with a Millipore Model 8500 Ultrafiltration System.

B) Electrical Power Quality Clean, conditioned power is delivered to the instrumentation with uninterrupted power supplies.

C) Chemical Quality If available, chemicals are analytical reagent grade conforming to specifications of the Committee of Analytical Reagents of the American Chemical Society. D) Cleaning of Labware (effective 950215) 1) Labware to be reused is rinsed well with deionized water before soaking. 2) New and reused labware that comes in contact with the samples and standards is soaked for at least 24 hours in deionized water. All other labware is soaked at least overnight in a covered container containing a 10% Concentrated Hydrochloric Acid solution. NOTE: Goggles or safety glasses, acid gloves, and lab coats are worn at all times when working with 10% Concentrated Hydrochloric Acid. NOTE: Chloride, pH, ANC, and Specific Conductivity results may be affected by labware soaked in 10% Concentrated Hydrochloric Acid. Previous Method: Labware is soaked overnight in a covered container containing a 10% Hydrochloric Acid solution. 3) Rinse labware copiously five times with deionized water. 4) Dry glassware overnight. 5) Seal labware and store in cabinet space to minimize unnecessary exposure. 6) Rinse labware three times with deionized water immediately before use. Rinse labware that is to contain sample with a small amount of the sample whenever possible. E) Gloves Powder-free vinyl gloves are worn whenever handling samples or standards to avoid unnecessary contamination. F) Sample Handling (effective 950215)

1) Samples for major anions, cations, silica, conductivity, non-purgable organic carbon, total nitrogen and total phosphorus are collected in new, washed Nalgene High Density Polyethylene bottles. 2) A portion of the sample is filtered within one week of receipt of sample. A 47 mm 1.0-um binder free, glass fiber filter is used for non-low ionic concentration water samples. Glass fiber filter is rinsed with 300 mL of deionized water and then 25 mL of sample before filtrate collection. A 47-mm Nuclepore 1.0-um membrane is used to filter snow samples and water samples with low ionic concentrations. Nuclepore membrane is rinsed with at least 50 mL of deionized water and then 25 mL of sample before filtrate collection. Between samples, filters are rinsed with at least 100 mL of deionized water and 25 mL of next sample. 3) A 100 mL aliquot of filtered sample is refrigerated at 2-8oC in an HDPE bottle for the analysis of NH4+, Mn, Ca2+, Mg2+, Na+, K+, Cl-, NO2-, NO3-, SO42-, PO43-, and Silica. 4) A 25 mL aliquot of filtered sample is stored frozen at or below 0oC in an HDPE bottle for Total Dissolved Nitrogen and Total Dissolved Phosphorus. 5) A 12 mL aliquot of filtered sample is stored frozen at or below 0oC in an HDPE bottle for Non-Purgable Organic Carbon, 6) A 25 mL aliquot of unfiltered sample is stored frozen at or below 0oC in an HDPE bottle for Total Nitrogen and Total Phosphorus. 7) PH, Conductivity, and ANC are analyzed on unfiltered sample within one week of receipt of sample. 8) NH4+ is run immediately upon receipt of sample. If this is not possible, an aliquot of the sample is frozen until analysis. G) Calibration Protocol 1) Calibration standard dilutions are discarded after one week. Calibration standard dilutions for NH4+ are used within two days. 2) Calibration standard dilutions are prepared that bracket the sample concentration range. Dilute any sample that has a nonlinear concentration range. 3) Calibration standard controls are distributed at 5% frequency throughout analytical runs as a check against calibration drift. Calibration is repeated if variation is greater than 10% of actual standard value. H) Blank A deionized water sample is analyzed with each run.

II) Quality Control A) Analytical Bias A synthetic charge balance control (CBC) consisting of six ions is prepared with CaCl2, MgSO4, and NaNO3. Unfiltered CBC's are included with each analytical run. Values are calculated from calibration standards of different origin than those used for CBC's. The pH, ANC, and Conductivity of the CBC's are determined as well. Any persistent deviation in ion balance (sum of positive charge minus sum of negative charge/ sum of positive charge plus sum of negative charge) over the study period would suggest a bias. A value of zero implies no bias for the chemical methods that were employed. B) Accuracy 1) Recovery of Synthetic Standards Accuracy is assessed in each run by recovery of known addition of synthetic standards to deionized water. Mean percent recovery (R) is calculated as the ratio of measured value versus expected value. Synthetic standards are analyzed at the beginning of each run and after every 20 samples. 2) Interlaboratory Comparisons Sample duplicates are submitted and analyzed in parallel with NADP/NTN Central Analytical Laboratory in an ongoing interlaboratory comparison study effort. Results are compared with other laboratories when parallel samples are available. C) Precision 1) Within Run Precision Spiked samples are analyzed in duplicate with every 20 samples. Precision is measured by the standard deviation of means percent recovery (RSD). 2) Run to Run Precision Run to run precision is assessed by including in each run a control of deionized water spiked with a known addition of synthetic standards. Precision is measured by the standard deviation of means percent recovery (RSD). 3) Field Precision Field replicates are collected to assess field precision. Precision is measured by the standard deviation of means percent recovery (RSD). D) Detection Limits Method detection limits are determined in accord with the Scientific Apparatus Makers Association (SAMA) definition for detection limit: that concentration which yields an absorbance equal to the standard deviation of seven measurements of a solution whose concentration is detectable above, but close to, the blank absorbance.

E) Filtration Effectiveness To assess effectiveness of filtration followed by storage at 2-8oC as a means of preservation of chemical species, known additions of NH4+, Ca2+, Mg2+, Na+, K+, Cl-, NO3-, SO42-, and Silica are made to subportions of selected samples and laboratory deionized water blanks. Initial concentrations, pH, and conductivity for spiked and unspiked sample/blank set are analytically determined within one week. Final concentrations are analytically determined after 3 months storage at 2-8oC. F) Ion Desorption from and Adsorption to Labware To assess the effect of ion desorption from and adsorption to labware during storage, sample bottles are filled with deionized water and stored for one month. A subsample from each bottle is included in standard analysis suite to determine levels of desorption. A known concentration of synthetic standard is added to remaining sample in each bottle and sample is stored again for one month. Spiked samples are included in standard analysis suite to determine levels of adsorption. III) Analytical Methodology A) pH The pH measurements, corrected to 25oC, are measured using an Accumet AR10 Laboratory pH Meter, an Accumet pH Electrode and an automatic temperature compensator. The electrode is calibrated with pH 4.00 and pH 7.00 or pH 7.00 and pH 10.00 NBS traceable reference buffer solutions, whichever buffer solutions bracket the samples. Prior to measurement; electrode, thermistor, and sample beaker are rinsed three times with deionized water. Sample beaker and electrode are then prerinsed with a small amount of sample. Sample is briefly swirled and meter reading is allowed to stabilize 5 minutes before being recorded. NOTE: Samples with pH's above 7.00 may be standardized with 4.0 and 7.0 pH buffer solutions if the accuracy of the results are verified by repeating a few of the samples with a 7.0 and 10.0 pH buffer calibration. Repeats should be within 0.10 pH units. B) Conductivity Conductivity is measured using a Mettler Toledo SevenEasy Conductivity Meter with a Mettler Toledo InLab 720 2-plate conductivity sensor with automatic temperature compensation, calibrated against 84.0 uS/cm KCl solution according to manufacturer's instructions. Prior to measurement, cell and sample beaker are rinsed three times with deionized water. Cell and sample beaker are then pre-rinsed with a small amount of sample. Sample is briefly swirled and result is recorded after the meter reading is stabilized.

C) ANC (effective with 1992 samples) Acid Neutralization Capacity is measured using a manual pH titration using a 2.0-mL Buret micrometer. The pH measurements, corrected to 25oC, are measured using an

Accumet AR10 Laboratory pH Meter, an Accumet pH Electrode for low ionic strength titrations and an automatic temperature compensator. The electrode is calibrated with pH 4.00 and pH 7.00 NBS traceable reference buffer solutions. Prior to measurement; electrode, thermistor, and sample beaker are rinsed three times with deionized water. Sample beaker is pre-rinsed with a small amount of sample. Sample is titrated to pH 3.5 endpoint with 0.1 N HCl. Prior to each pH measurement, sample is stirred and allowed sufficient equilibration. Ten pH values between pH 4.5 and 3.5 and their corresponding titrant volumes added are recorded. ANC is calculated using an equivalence point determined by linear regression on a Gran's Plot. Perform the acidity procedure if initial sample pH is less than 4.5. Previous Method: The original sample pH is measured. The sample is then titrated to just below pH 4.5 with 0.1 N HCl. The original pH and the pH's just above and below pH 4.5 are recorded. 4.5 pH titrant volume=(4.5-bph)/ (aph-bph) X (atv-btv) + btv, and pH 4.5 alkanity HCO3=[(4.5 pH titrant volume X 0.1 X 1000000)/sample volume]/ 0.01639 X 1.219 where pH above 4.5=aph, pH below 4.5=bphi, pH above 4.5 titrant volume=atv, and pH below 4.5 titrant volume=btv

D) Lachat QuikChem 8000 Flow Injection Analyzer (effective 040301) Orthophosphate, total phosphorus and total dissolved phosphorus are analyzed using a Lachat QuickChem 8000 System Flow Injection Analyzer (FIA), employing spectrophotometric detection. Samples for total and total dissolved phosphorus are digested and oxidized prior to analysis with the orthophosphate method. Previous Method (Lachat QuikChem 4000 Flow Injection Analyzer effective 950313): Ammonium, nitrate+nitrite, orthophosphate, and silica are analyzed using a Lachat QuickChem 4000 System Flow Injection Analyzer (FIA), employing spectrophotometric detection. Samples for total and total dissolved nitrogen are digested and oxidized prior to analysis with the nitrate+nitrite method. Samples for total and total dissolved phosphorus are digested and oxidized prior to analysis with the orthophosphate method. Previous Method (Lachat QuikChem System IV Analysis): Ammonium, nitrate+nitrite, orthophosphate, and silica are analyzed using a Lachat QuickChem System IV Analyzer (FIA), employing spectrophotometric detection. Samples for total and total disso lved nitrogen are digested and oxidized prior to analysis with the nitrate+nitrite method. Samples for total and total dissolved phosphorus are digested and oxidized prior to analysis with the orthophosphate method. E) OI Analytical Flow Solution IV Analyzer (effective 040301) Ammonium, nitrite, nitrate+nitrite, total nitrogen, total dissolved nitrogen and silica are analyzed using an OI Analytical Flow Solution IV Analyzer, employing spectrophotometric detection. Samples for total and total dissolved nitrogen are digested and oxidized prior to analysis with the nitrate+nitrite method.

Previous Method (Lachat QuikChem 4000 Flow Injection Analyzer effective 950313): Ammonium, nitrate+nitrite, orthophosphate, and silica are analyzed using a Lachat QuickChem 4000 System Flow Injection Analyzer (FIA), employing spectrophotometric detection. Samples for total and total dissolved nitrogen are digested and oxidized prior to analysis with the nitrate+nitrite method. Samples for total and total dissolved phosphorus are digested and oxidized prior to analysis with the orthophosphate method. F) Metrohm 761 Compact Ion Chromatography Analyzer (effective 030121) The inorganic anions chloride, nitrate, and sulfate are analyzed by ion chromatography (IC) using a Metrohm 761 Compact Ion Chromatography Analyzer with a Metrosep A Supp 5 anion column. Chemical ion suppression and conductivity detection are employed. Previous Method (Dionex DX500 and 2010i System Ion Chromatography Analysis): The inorganic anions acetate, formate, chloride, nitrate, and sulfate are analyzed by ion chromatography (IC) using a Dionex D X500 System. The inorganic anions chloride, nitrate, and sulfate are analyzed by ion chromatography (IC) using a Dionex 2010i System. Chemical ion suppression and conductivity detection are employed. G) Perkin Elmer AAnalyst 100 Atomic Absorption Spectrometer (effective 990810) The inorganic cations calcium, magnesium, sodium, potassium and manganese are analyzed by atomic absorption using a Perkin Elmer AAnalyst 100 Atomic Absorption Spectrometer. 0.5% lanthanum solution is added to each standard and sample to prevent chemical and ionization interference. Previous Method (Perkin Elmer Model 2280 Atomic Absorption Spectrometer): The inorganic cations calcium, magnesium, sodium and potassium are analyzed by atomic absorption using a Perkin Elmer Model 2280 Atomic Absorption Spectrometer. 0.5% lanthanum solution is added to each calcium and magnesium standard and sample to prevent chemical and ionization interference.