Current through Register Vol. XLI, No. 24, June 14, 2024
Section 47-32-5 - Methodology, Quality Control and Record Keeping5.1. Methodology. 5.1.1. Sample collection, handling, and preservation techniques specified in 40 CFR §136.3 Table II, or other procedures approved by EPA or the Secretary are to be followed. 5.1.1.a. Samples requiring preservation will be preserved in accordance with 40 CFR §136.3 Table II for compliance with subsection 2.19.1 and the NPDES. All other samples will be preserved in accordance with applicable methods and regulations.5.1.1.b. Sample collection, handling and preservation techniques specified by the analytical methods will be followed for the parameters analyzed by those methods in the absence of guidance under paragraph 5.1.1.a.5.1.1.c. The chain of custody form must be completed at the time of sample collection and will state the sampling location, date and time of collection, collector's name, type(s) of preservation, number of containers per sample, type of sample (grab or composite) and any remarks.5.1.1.d. After the sample has been collected, the appropriate information as to identity of the sample is to be written on the label. The identity of the sample must be the same on the label and the chain of custody form. The label must remain affixed to the sample container and is not to be removed until the required analyses have been completed and the surplus sample has been discarded.5.1.1.e. The chain of custody must accompany the sample at all times. Custody of the sample must be documented on the chain of custody throughout the life of the sample (from collection to disposal of surplus sample after all required analyses have been completed). Any time the custody of the sample is transferred from one person to another, except analysts in the same laboratory, this transfer must be documented in the appropriate fields on the chain of custody form.5.1.1.f. Immediately upon delivery of the sample to the laboratory, the individual delivering the sample will complete the appropriate section(s) of the chain of custody form. A chain of custody form is not required where the sampler is also the analyst and in situations where the laboratory and the sample site(s) are within the property boundaries of the facility in which the laboratory is located.5.1.1.g. Prior to accepting custody of a sample, laboratory personnel must be reasonably assured that the sample has met the chemical and temperature preservation requirements. If the sample fails to meet these requirements, the sample chain of custody form is to be marked indicating the sample was improperly preserved. Analytical data resulting from improperly preserved samples must be accompanied by a statement indicating the condition of the sample upon receipt by the laboratory. Analytical data resulting from samples improperly preserved will not be accepted as being in compliance with this rule.5.1.1.h. When it is necessary to send samples by mail, bus, courier service, or private shipping, the chain of custody form is to be completed by the individual relinquishing custody of the sample for shipping and is to accompany the samples during shipping. Upon receipt of the samples in the laboratory, the provisions of paragraph 5.1.1.g are to be followed.5.1.2. Test procedures identified in 40 CFR §136.3, EPA publication SW-846 Test Methods for Evaluating Solid Waste, Physical/Chemical Methods or other methods approved by EPA or the Secretary will be utilized for the analysis of all samples required to be reported to the Department. 5.1.2.a. All procedures other than those set forth in subdivision 5.1.2 are considered alternate test procedures (ATP). Laboratories must make special application to the Department for the use of ATPs in accordance with 40 CFR §136.4.5.1.2.b. All laboratories which have previously been granted approval to use an ATP by the EPA will be allowed to continue using such method after submitting written proof of the approval to the Department.5.1.3. General Laboratory Practices.5.1.3.a. Chemistry -- Inorganic Nonmetals and Trace Metals. 5.1.3.a.A. Laboratories utilizing visual comparison devices must calibrate the standards incorporated into devices of this type at least once every four months. The laboratory will make and maintain records of the date and method of each calibration.5.1.3.a.B. Distilled and deionized water is to have a resistivity value [GREATER THAN EQUALS TO] 0.5 megohms-cm at 25 degrees Celsius.5.1.3.a.C. Analytical Reagent grade chemicals should be used for most analyses. Detailed information on reagent grades is set forth in the approved analytical methods and their recommendations must be followed for the reagent quality to be used for each test or analysis.5.1.3.a.D. Where applicable, method detection limits must be determined for all categories and parameters. The method found in 40 CFR Part 136, Appendix B must be used for this calculation.5.1.3.a.E. Field blanks must be prepared and analyzed for the test categories and parameters identified in subdivisions 3.2.1 and 3.2.2, at a minimum of two times per year, once during the cold wet season and once during the warm dry season.5.1.3.a.F. Field duplicates must be collected and analyzed for the test categories and parameters identified in subdivisions 3.2.1, 3.2.2, 3.2.10, and 3.2.11, at a minimum of two times per year, once during the cold wet season and once during the warm dry season.5.1.3.b. Microbiology. 5.1.3.b.A. All practices and procedures for the conduct of microbiological examinations must follow the guidance in methods approved in 40 CFR §136.3 Table IA.5.1.3.b.B. The temperature of incubators, water baths and heat blocks must be monitored in accordance with approved methods or as specified by regulation. 5.1.3.b.B.1. Each incubator, water bath or heat block must have a thermometer placed so as to give a representative temperature measurement for the device.5.1.3.b.B.2. Incubators, water baths and heat blocks must be clean and properly maintained in accordance with the manufacturer's instructions.5.1.3.b.C. Autoclaves must meet the specified temperature tolerances in the approved method. The use of a pressure cooker is not recommended.5.1.3.b.C.1. A continuous temperature recording device or a maximum temperature registering thermometer must be used to measure the temperature during each autoclave cycle.5.1.3.b.C.2. The laboratory must use a sterilization verification technique such as autoclave tape to indicate proper sterilization of equipment and contaminated materials.5.1.3.b.C.3. Autoclaves must be clean and properly maintained in accordance with the manufacturer's instructions.5.1.3.b.C.4. Autoclaves must be serviced annually by a qualified person. Servicing must include a pressure check and calibration of temperature devices.5.1.3.b.D. Hot air sterilization ovens must be of sufficient size to prevent crowding and constructed to give uniform sterilization.5.1.3.b.D.1. Hot air sterilization ovens must be clean and properly maintained according to the manufacturer's instructions.5.1.3.b.E. Appropriate optical counting equipment must be used in accordance with approved methods.5.1.3.b.F. Appropriate inoculating equipment must be used in accordance with approved methods.5.1.3.b.G. Appropriate membrane filters, pads and dishes must be used in accordance with approved methods.5.1.3.b.H. A sterility blank must be analyzed: 5.1.3.b.H.1. with each lot or batch of media, either purchased or prepared in the laboratory;5.1.3.b.H.2. with each lot of membrane filters, pads and dishes;5.1.3.b.H.3. with each lot or batch of sample containers, either purchased or prepared in the laboratory;5.1.3.b.H.4. with each lot or batch of rinse/dilution water, either purchased or prepared in the laboratory; and5.1.3.b.H.5. with each lot or batch of culture tubes, either purchased or prepared in the laboratory.5.1.3.b.I. Field blanks must be prepared and analyzed for the test categories and parameters identified in subdivision 3.2.6, at a minimum of two times per year, once during the cold wet season and once during the warm dry season.5.1.3.b.J. Field duplicates must be collected and analyzed for the test categories and parameters identified in subdivision 3.2.6, at a minimum of two times per year, once during the cold wet season and once during the warm dry season.5.1.3.b.K. All equipment and reagents must be sterilized prior to use. All contaminated equipment must be sterilized prior to reuse. All contaminated material must be rendered innocuous prior to disposal.5.1.3.c. Whole Effluent Toxicity Testing.5.1.3.c.A. Natural or artificial sources of water may be used, but natural sources are preferred.5.1.3.c.B. Natural sources are to be free of pollution, low in turbidity, high in dissolved oxygen, low in B.O.D., and the pH must be favorable to the maintenance of the organisms.5.1.3.c.C. Municipal water supplies are acceptable. Water from a municipal source must be passed through a filter to remove organic chemicals and chlorine before use, and be conditioned for the species under test.5.1.3.c.D. Test organisms are to be fed as outlined in the approved methods, subdivision 3.2.7.5.1.3.c.E. Treatment of diseased or parasitized organisms is to be in accordance with the procedures given in the approved methods, subdivision 3.2.7.5.1.3.c.F. Organisms treated for disease or parasites are not to be used in whole effluent toxicity tests for at least 10 days after treatment.5.1.3.d. Radiochemistry. 5.1.3.d.A. Analytical reagent grade (AR) chemicals will be used for all analyses, unless otherwise required for an individual analytical procedure.5.1.3.d.B. Radioactive standards and radioactive wastes are to be stored in an enclosed and properly labeled area, either within the laboratory or in a separate room or facility. All radioactive materials must be safely stored in suitable containers.5.1.3.d.C. Standards and samples are to be prepared in an area of the laboratory specifically designated for and exclusively used for the preparation of radioactive standards and samples. Adequate precautions must be taken in this area to ensure against radioactive contamination.5.1.3.e. Volatile Organic, Extractable, and Semi-volatile Organic Testing. Equipment must be capable of meeting the quality control requirements specified in subdivision 5.2.6.5.1.3.e.A. Trip blanks must be prepared, transported and analyzed for each batch of samples for analysis for Nonpotable Volatile Organic Chemicals, subdivision 3.2.3.5.1.3.e.B. A method blank must be analyzed with each batch of samples.5.1.3.e.C. A laboratory control sample must be analyzed with each batch of samples.5.1.3.e.D. A matrix spike and a matrix spike duplicate must be analyzed with each batch of samples. In situations where the laboratory does not receive sufficient sample volume or quantity to perform a matrix spike and a matrix spike duplicate, a laboratory control sample and a laboratory control sample duplicate must be analyzed.5.1.3.e.E. Surrogate spike compounds must be added to all samples and quality control standards prior to preparation/extraction and analysis where applicable. The recovery of surrogate compounds must be compared to acceptance limits established in the appropriate method. If acceptance limits are not provided in the method, the laboratory must use appropriate procedures to establish in-house acceptance limits.5.1.3.e.F. Any time criteria are not met with respect to blanks, laboratory control samples, matrix spikes, matrix spike duplicates, or surrogates, data must be reported with appropriate qualifiers describing the situation and explaining the effect on the results.5.2. Quality Control Programs -- Each laboratory will develop, and have on file available for inspection a written description of the current laboratory Quality Assurance Program Plan. This written description will outline the procedures the laboratory uses in meeting the quality control requirements set forth in this subsection. Managers, supervisors, and analysts should participate in developing the Quality Assurance Program Plan. Each participant within the laboratory is to have access to a copy of the quality control program Quality Assurance Program Plan and the detailed guidelines for implementation of the participant's responsibility. A record of analytical control tests and quality control checks on media, materials, and equipment will be prepared by the laboratory and retained for at least three years.5.2.1. A written description includes, but need not be limited to, the following for each category: 5.2.1.a. Procedures which the laboratory will use in meeting the quality control requirements of this rule pertaining to laboratory equipment and instrumentation, and the frequency with which these procedures will be performed.5.2.1.b. Each laboratory will develop and maintain a written standard operating procedure (SOP) manual, which sets forth, in detail, the methods the laboratory will use in chemical analyses or tests for all parameters for which the laboratory is seeking certification.5.2.1.c. Each laboratory must record and retain all raw data and calculations derived from analyses and quality control procedures in a manner that will provide easy verification of the data and calculations during on-site inspections.5.2.2. Laboratories conducting analyses for Inorganic Nonmetals and Trace Metals must perform the following internal quality control checks:5.2.2.a. Each analytical balance, with the exception of electronic balances without internal calibration controls, is to be checked and adjusted annually by a balance service technician. The accuracy of each analytical balance must be checked on each day of use using at least three Class-S weights covering the range expected to be encountered during routine analysis. The weights used, weight detected, dates on which checks were performed, analyst, record of balance level check and other pertinent information is to be recorded in a log book. The daily weighing check will be used as an indication of proper operation of electronic balances.5.2.2.b. The accuracy of the wavelength setting of spectrophotometers without built-in automatic system diagnostics is to be checked yearly by comparing the wavelength setting to the absorption maxima appropriate standards. Any observed variation of the wavelength setting from the expected value must be within the manufacturer's stated tolerance for the instrument. The check data must be recorded in a logbook.5.2.2.c. pH meters are to be calibrated prior to use with two pH buffer standards bracketing the value to be measured and the calibration recorded. Records of pH meter standardization must be maintained in a laboratory notebook that documents the date of standardization, calibration buffers used and the initials of the individual conducting the standardization. If the meter displays a slope or other indicator of performance, this information must also be recorded.5.2.2.c.A. Aliquots of standard buffers may not be used for longer than one day.5.2.2.d. The linearity of conductivity meters must be checked over the range of the instrument using at least five concentrations of standard solutions yearly. The cell constant, k, is to be determined from this data. The meter must be calibrated using at least one standard with each use. The results of these calibrations must be recorded in a log book.5.2.2.e. A daily record of the drying oven temperature must be maintained for each day on which the drying oven is in use. The oven thermometer must be kept in a sand bed or other inert material.5.2.2.e.A. The oven temperature must be recorded immediately prior to placing samples in the oven and then again immediately prior to removing samples at the end of the drying cycle.5.2.2.f. The temperature of each refrigerator and each incubator is to be either recorded continuously or recorded daily from in-place thermometers immersed in liquid and placed on one of the shelves being used. The refrigerator thermometer must be kept in a low vapor pressure liquid such as 50/50 water/Ethylene Glycol.5.2.2.g. The accuracy of all thermometers used to monitor temperatures will be verified by comparing the readings of such thermometers with the readings of a certified thermometer. Refer to paragraphs 4.2.7.c and 4.2.7.d.5.2.2.h. A calibration curve must consist of one calibration blank and 4 at least four standards to be prepared for each analysis requiring a calibration curve. This curve will be verified prior to each subsequent analysis by analyzing at least one calibration blank and one standard at or near the midpoint of the curve. These verifications are considered satisfactory if the result for the calibration blank is less than the method detection limit and the result for the midpoint standard is within 10 per cent of the expected value following vendor approved procedures for instrument calibration.5.2.2.i. Standard curves used in the analysis of parameters in the Trace Metals category will be prepared in accordance with approved methods.5.2.2.j. Where practicable, duplicate sample analyses are to be conducted for parameters in the Inorganic Nonmetals and Trace Metals categories to verify the precision of the method. Duplicate analyses will be performed at a frequency of 5 percent. Where less than 20 samples are analyzed at one time the analyst is to verify the precision once per analysis batch. Documentation will be made, in tabular form and on control charts, of precision testing. 5.2.2.j.A. In cases where sample results are normally below the method detection limit, precision must be determined by analysis of matrix spikes and matrix spike duplicates.5.2.2.k. Where practicable, spiked sample analyses will be conducted to verify the accuracy of the method at the same frequency as set forth in paragraph 5.2.2.j of this rule. Documentation will be made, in tabular form and on control charts, of accuracy testing.5.2.2.l. Where practicable, standard deviations are to be calculated and documented for all applicable measurements being conducted in the Inorganic Nonmetals and Trace Metals categories (spiked sample recoveries). Standard deviations must be documented in tabular form and on control charts.5.2.3. Microbiology. 5.2.3.a. A start and finish membrane filter (MF) sterile control test of rinse water, media and supplies will be conducted for each sample filtration series. If the control tests indicate contamination, then all data which has been generated through tests involving the use of the contaminated materials will be rejected and the laboratory must request immediate resampling of those samples associated with the observed contamination.5.2.3.b. When analyzing duplicate aliquots to assess precision, the same series of volumes/dilutions must be utilized for the sample and the duplicate.5.2.3.c. The method detection limit for bacteria by the membrane filter method is defined as 1 colony /100 ml, adjusted as necessary for filtered volumes other than 100 ml.5.2.3.d. The most probable number (MPN) test for bacteria must be carried through the "confirmed" stage for Fecal Coliform.5.2.4. Whole Effluent Toxicity Testing -- An acceptable degree of precision for definitive toxicity tests is the 95 percent confidence level or fiducial intervals within less than +-30 percent of the 48 hour or incipient LC50 value. 5.2.4.a. Five reference toxicant tests on each reference toxicant and species combination evaluated by the laboratory are to be performed to establish the validity of effluent toxicity data generated by bioassay laboratories.5.2.4.a.A. After completion of the requirements in paragraph 5.2.4.a, a reference toxicant test must be performed each month in which whole effluent toxicity testing is conducted using the same method and species as used for the whole effluent toxicity testing.5.2.4.b. Quality control and proficiency test samples are available from commercial sources.5.2.4.c. The reference toxicant test must be conducted within 7 days immediately preceding a whole effluent toxicity test or concurrently with the whole effluent toxicity test.5.2.4.d. A control chart, as described in approved methods, should be prepared for each reference toxicant/species combination, and successive LC-50's plotted and examined to determine if the results are within prescribed limits.5.2.4.e. If the LC-50 of a reference toxicant does not fall in the expected range for the test organisms, the sensitivity of the test system is suspect. In this case, the test procedure should be examined for defects, and a different batch of test organisms should be employed in repeating the reference toxicant and effluent toxicity test.5.2.5. Radiochemistry -- Permanent records must be maintained of preventive maintenance, periodic inspections, testing, and calibration for the proper operation of radiation instruments and analytical balances; validation of methods; evaluation of reagents and volumetric equipment; surveillance of results; and remedial actions taken in response to detected defects. Such records must be kept on file by the laboratory for a period of at least five years. 5.2.5.a. To verify internal laboratory precision, duplicate analyses equal to ten percent of sample analyses shall be performed. The differences between duplicate measurements shall be less than twice the standard deviation of the specific analysis as described in Environmental Radioactivity Laboratory Intercomparison Studies Program, EPA 600/4-77-001 and other guidance from EPA or the Secretary.5.2.5.b. One background and one calibration standard must be tested each day at a 5 percent level or fraction thereof.5.2.5.c. Work records of quantitative tests are to indicate final results together with all corresponding instrument readings and calculations. Where instrumentation produces tracings or printouts, such tracings or printouts may serve as the work record.5.2.6. Volatile Organic, Extractable and Semi-volatile Organic Testing. 5.2.6.a. The frequency and procedures for satisfying each of the requirements listed in paragraphs 5.2.6.b and 5.2.6.c are described in detail in EPA publication SW-846, 40 CFR Part 136, and/or in the US EPA Contract Laboratory Program Statement of Work for Organics Analysis.5.2.6.b. Minimum quality control operations necessary to satisfy the analytical requirements associated with the determination of semi-volatile and volatile organic compounds by gas chromatographic methods will include the following: 5.2.6.b.A. Evaluation of Appropriate Blank Materials.5.2.6.b.B. Surrogate Spike Response Monitoring.5.2.6.b.C. Matrix Spike and Duplicate Analyses or Matrix Spike Duplicate.5.2.6.b.D. Verification of Response and Calibration.5.2.6.b.E. Conformational Analysis.5.2.6.c. Minimum quality control operations to satisfy the analytical requirements associated with gas chromatographic/mass spectrometry determinations of semi-volatile and volatile compounds will be as follows:5.2.6.c.A. Documentation of GC/MS Mass Calibration and Tune Abundance Patterns.5.2.6.c.B. Documentation of GC/MS Response Factor Stability.5.2.6.c.C. Internal Standard Response and Retention Time Documentation.5.2.6.c.D. Surrogate Spike Recovery Monitoring5.2.6.c.E. Matrix Spike and Duplicate Analyses or Matrix Spike Duplicate.5.3. Records and Data Reporting. 5.3.1. Records of analyses, including but not limited to all raw data, calculations, quality control data, and laboratory reports, are to be kept by the laboratory for at least five years unless otherwise specified.5.3.2. The following information is to be retained by the laboratory as part of the records of analysis and the records of custody:5.3.2.a. The laboratory number or other form of identification of the sample;5.3.2.b. The chain of custody form as required under paragraph 5.1.1.c;5.3.2.c. The date and time when the laboratory received the sample, whether the sample was received preserved or unpreserved;5.3.2.d. The date and time of analysis of the sample;5.3.2.e. The person or persons who performed the analysis;5.3.2.f. The type of analysis performed and the analytical method or methods employed;5.3.2.g. The raw data generated by the analysis and results of the analysis; and5.3.2.h. The name and address of the laboratory to which the sample was forwarded, if the analysis was not performed at the laboratory which first received the sample.5.3.3. If the chain of custody information is reported on a chain of custody form, a copy of the form must be attached to the sample report form.5.3.4. The results of each analysis are to be calculated and entered on the sample report form which is to be forwarded to the person requesting the analysis of the sample. A careful check is to be made to assure that each result entered on the sample report form is the same as the result generated by the analysis and entered on the bench sheet or other raw data document.5.3.5. The original or true duplicate of the results of the test or analysis is to be sent promptly to the person who requested such tests or analysis, and must be signed by the laboratory manager or a designee whose designation has been documented in the laboratory Quality Assurance Manual or other instrument describing pertains within the laboratory.5.3.6. Whenever a laboratory subcontracts samples to another laboratory, the person ordering the examination is to receive the original laboratory report or a true duplicate of that report on the form generated by the subcontract laboratory that actually performed the test or analysis.5.3.7. If results are entered into a computer storage system, a printout of the data must be verified with the raw data.5.3.8. The final data report must contain the following:5.3.8.a. The name, address, and contact information of the laboratory performing the analyses;5.3.8.b. Sample identification number (unique identifier assigned by the laboratory);5.3.8.c. Sample description;5.3.8.d. Date sample was collected;5.3.8.e. Date sample was received at the laboratory;5.3.8.f. Date of each individual analysis;5.3.8.g. Method detection limit for each parameter;5.3.8.h. Identity of the test method(s);5.3.8.i. Deviations from the test method, if applicable;5.3.8.j. Disclosure of contract laboratory and original or true copy of the results from the contract laboratory; and5.3.8.k. Identity of the responsible agent.