2003 Bight03 Coastal Ecology Chemistry Results

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Identification_Information
Data_Quality_Information
Spatial_Data_Organization_Information
Spatial_Reference_Information
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Identification_Information:

Data_Quality_Information:

Attribute_Accuracy:

Attribute_Accuracy_Report: Coordinates accurate to within 100 ft

Logical_Consistency_Report:

The tables may be related by the StationID field or the SampleID field where applicable.

Completeness_Report:

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Methodology:

Methodology_Type: Lab

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Methodology_Keyword_Thesaurus: None
Methodology_Keyword: None

Methodology_Description:

QUALITY ASSURANCE OBJECTIVES A. Overview The primary goal of the QA/QC plan is to ensure that the data generated in the Bight'03 survey are comparable among particpants. Many different organizations will be participating in the collection and analysis of samples in Bight'03; encouraging and maintaining consistency in field and laboratory operations and ensuring data comparability will be critical to success of the project. Data comparability will be achieved through a combination of standardized methods (where appropriate) and performance based standards. Where standardized methods have been agreed upon for this project, QA/QC measures will be used to assure that methods are applied consistently. Where performance based standards are appropriate, QA/QC measurements will be used as a measure of performance. The appropriate QA/QC procedures for each of the Coastal Ecology monitoring program components (e.g., field operations, water quality, water, sediment and tissue chemical analyses, benthic analyses, demersal and pelagic fish analyses) have been established by the Bight'03 Steering Committee. B. General Approach To Quality Assurance The QA program for Bight'03 consists of two distinct but related activities: quality assurance and quality control. Quality assurance includes design, planning, and management activities conducted prior to implementation of the project to ensure that the appropriate kinds and quantities of data will be collected. The goals of quality assurance are to ensure that: 1) field collection, processing, and laboratory analytical techniques will be applied consistently and correctly; 2) the number of lost, damaged, and uncollected samples will be minimized; 3) the integrity of the data will be maintained and documented from sample collection to entry into the data record; 4) all data will be comparable; and 5) results can be reproduced. Quality control (QC) activities are implemented during the data collection phase of the project to evaluate the effectiveness of the QA activities. QC activities ensure that measurement error and bias are identified, quantified, and accounted for, or eliminated, if practical. QC activities include both internal and external checks. Typical internal QC checks include repeated measurements, internal test samples, use of independent methods to verify findings, and use of standard reference materials. Typical external QC checks include exchanging samples among laboratories for reprocessing to test comparability of results, independent performance audits, and periodic proficiency examinations. Many of the organizations participating in Bight'03 have well established monitoring programs. QA activities for Bight'03 have focused on developing a common field manual and documenting the comparability of laboratory methods. Training of field and laboratory personnel is focused on communicating goals and objectives of the survey, as well any modifications in methods or procedures that have been made to ensure data comparability. The porpose of this training is to verify that all participants will be able to implement the agreed upon procedures in a consistent manner with comparable proficiency. Quantitative measures of the overall effectiveness of training have been identified to translate QA activities such as communication and training into QC activities such as performance audits and proficiency examinations. These quantitative measures are known as measurement quality objectives (MQOs). C. Measurement Quality Objectives MQOs establish acceptable levels of uncertainty for each measurement process. MQOs typically address the major components of data quality: representativeness, completeness, precision, accuracy and comparability. Data comparability, or "the confidence with which one data set can be compared to another" (Stanley and Verner 1985), is a primary concern in this project because of the large number of particpants. Comparability of reporting units and calculations, data base management processes, and interpretative procedures must be ensured if the overall goals of the project are to be realized. Specific MQOs for precision and accuracy, the most readily quantifiable components of data quality, have been identified for Bight'03 to ensure that the data produced by the many field crews and laboratories involved in the project will be comparable. Accuracy is defined as the difference between the measured value of an indicator and its true or expected value, which represents an estimate of systematic error or net bias (Kirchner 1983, Hunt and Wilson 1986, Taylor 1987). Precision is the degree of mutual agreement among individual measurements and represents an estimate of random error (Kirchner 1983, Hunt and Wilson 1986, Taylor 1987). Together, accuracy and precision provide an estimate of the total error or uncertainty associated with a measured value. Requiring participating field crews and laboratories to achieve standard, quantitative MQOs for accuracy and precision will help to ensure that individual data sets are free of any crew and/or laboratory specific bias and that the degree of random error is consistent across data sets. Accuracy and precision goals for indicators to be measured during the Bight'03 are provided in Table 2 1. Accuracy and precision cannot be defined for all parameters because of the nature of the measurements. For example, accuracy measurements are not possible for toxicity testing, sample collection activities, and fish pathology measurements. Measurement of accuracy and precision in sediment toxicity testing would require the use of reference materials with a known level of toxicity that is stable during storage. Suitable reference materials for sediment toxicity are not available. TABLE 2-1. Measurement Quality Objectives for Bight'03 indicators and data. (NA - not applicable; SD - standard deviation). Indicators Accuracy Precision Completeness Sediment Properties sediment grain size NA 20% 90% total organic carbon 15% 20% 90% organic contaminants 30% 30% 90% inorganic contaminants 20% 30% 90% Benthic Infauna sample collection NA NA 90% sorting 5% NA 90% counting 10% NA 90% identification 10% NA 90% Sediment Toxicity amphipod survival NA 2 SD 90% Demersal fish and macroinvertebrates sample collection NA NA 90% counting NA 10% 90% identification 5% NA 90% length NA 10% 90% biomass NA 10% 90% gross pathology 5% NA 90% Contaminants in fish 30% 30% 90% __________________________________________________ _________________________ An MQO for completeness was also defined for Bight'03. Completeness is a measure of the proportion of the expected, valid data (i.e., data not associated with some criterion of potential unacceptability) that is actually collected during a measurement process. The MQO for completeness is 90% for each measurement process. The sampling design for the project is sufficiently redundant to absorb the loss of up to 10% of the samples without compromising the goals of the program, provided that the lost samples are not concentrated in a single subpopulation of interest. Redundancy was incorporated at this level because monitoring programs of this size typically lose as many as 10% of samples as a result of logistical difficulties or failure to achieve quality control criteria. D. Quality Assurance And Quality Control Activities Establishing MQOs is of little value if the proper quality assurance activities are not undertaken to ensure that such objectives will be met. Quality assurance in the Bight'03 will be achieved by: * Developing a common field manual, * Documenting the comparability of laboratory methods that are consistent with the MQOs, and * Implementing training workshops to ensure that participants are familiar with the methods and are able to achieve the MQOs. The effectiveness of quality assurance efforts will be measured by quality control activities that fall into two categories: * Routine QC checks coordinated by each laboratory or field crew's internal QA Officer, and * Performance audits conducted by the Bight'03 QA Officer or designee The goal of these activities is to quantify accuracy and precision, but, most importantly, they will be used to identify problems that need to be corrected as data sets are generated and assembled. A new Field Operations Manual (2003) has been prepared to standardize data collection efforts in the field. Each participating organization collecting samples in the field has identified a single point of contact for field operations (referred to as the Lead Scientist in the field operations manual). A single laboratory manual was not developed for the project since each of the participating laboratories have their own internal operating procedures. Comparability of laboratory efforts will be ensured through compliance with the requirements listed in this Quality Assurance Plan (QAP) which identifies performance based standards and the appropriate level of QA/QC. Procedures for benthic analyses appropriate to the Bight'03 Project are detailed in the Macrobenthic (Infaunal) Sample Analysis Laboratory Manual (2003) The manuals and the QA/QC requirements were prepared in coordination with the appropriate personnel from each of the participating organizations. Potential problem areas identified in the preparation and review of these manuals were resolved using a consensus based approach. Copies of these manuals have been distributed to all participants in the program. These manuals will form the basis for training workshops and provide a reference for field and laboratory personnel during sample collection and processing activities. A. Field Operations The Bight'03 survey will be conducted cooperatively by a number of organizations (including one or more contractors) which routinely monitor the marine environment according to their own protocol. It is important to the success of the Bight'03 study that comparable data are collected by each organization. Quality Assurance activities for field collection include: * The development of the field operations manual which details the procedures to be used in the Bight'03 survey, * A series of presurvey methods and taxonomy protocol intercalibration meetings/exercises to ensure that project participants understand the requirements outlined in the field manual, and * A presurvey audit of new participants, or participants who have experienced a significant turnover in personnel since Bight'98, to demonstrate understanding and capability. Quality Control measures for the field collection effort include: * Specific QC requirements outlined in the QAP, which will be the responsibility of the lead scientist of each vessel, and * Field audits of each vessel during the sampling period. Field operations manual Standard field procedures are documented in the Bight'03 Field Operations Manual (2003). The field manual includes detailed descriptions of collection procedures, criteria for acceptable samples, and conditions under which samples need to be recollected. The field operations manual will provide the basis for protocol calibration exercises and a reference for field personnel during sampling activities. The field manual provides an overview of field teams and activities and procedures related safety, protocol calibration, navigation requirements, sampling schedule and station types, procedures for benthic sampling, procedures for trawl sampling, procedures for packaging and shipping of samples, contingency plans, and procedures for managing information collected in the field. Lead Scientists and Boat Captains will be instructed on the field procedures to be followed during the survey and they, in turn, will instruct their field personnel on the proper procedures for the survey. The lead scientist of each organization is responsible for distributing the Bight'03 Field Operations Manual to all field personnel and ensuring that their staff understands and uses the protocols detailed in the manual.

Methodology_Type: Field 2

Methodology_Description:

Section2 Training and protocol calibration Proper training of field personnel is a critical aspect of quality assurance. Organizations participating in Bight'03 will provide personnel who have extensive field experience, but not necessarily with the standard methods selected for this project. Instruction for this project, therefore, will focus on ensuring consistency in data collection among all field personnel. Lead scientists and boat captains of all organizations participating in the survey will be required to attend a protocol calibration meeting, which will be conducted several weeks before the survey. The goals and objectives of the Bight'03 will be discussed at this meeting as well as the responsibilities of the chief scientist and boat captains during the Bight'03 survey. Each participating organization will be provided with a Workplan, Field Operations Manual and QA/QC Document for Bight'03 and will be instructed on field procedures to be used during the survey, including proper entry of data on field data forms. The meeting will emphasize decision-making procedures for determining whether a station should be abandoned and whether a sample is acceptable. Lines of communication within the project and QA/QC activities occurring on the boat during the survey will also be discussed. The Lead Scientist of each organization will train their field personnel, as needed, on the field operations to be conducted during the survey. It will be the responsibility of the Lead Scientist of each organization to review the Workplan and Field Operations Manual with their field crews and to ensure that they understand the field procedures and specific field QA/QC requirements that must be followed during the survey. It is also the Lead Scientist's responsibility to train their field crews, as needed, on operations to be performed. Personnel that cannot perform an operation as required by the project will not participate in that operation. Field audits Field sampling capability will be established by means of field audits conducted by the Field QA Auditor prior to sampling for the Bight'03 study. These pre-survey field audits will be conducted to assess equipment, vessels, and protocols used by participating organizations, and to instruct the crew as needed on the procedures described in the field operation manual and the QA/QC document. The priority for conducting field audits prior to the sampling period will begin with organizations that did not participate in the Bight'98 Survey or who have a significant number of staff members that did not participate in the Bight'98 Survey. If resources and time are still available after all of these organizations have been audited, the organizations that participated in the Bight'03 will be subject to a field audit to confirm the capabilities that existed and were documented for the Bight'03. A Field QA/QC Checklist, developed to provide comparability and consistency in this process, will be used to record the pre-cruise audit data. The Field QA Specialist will provide additional instruction when discrepancies are noted during the presurvey field QA audit. The Lead Scientist will also be notified of the audit results so that any problems can be corrected prior to sampling. Ongoing quality control during the sample period will be established through field audits. Each vessel will be visited at least once during the survey. In addition to the information contained on the QA/QC checklist. Each vessel will also be audited by a preassigned taxonomist, who will observe species identification in the field. This data will be recorded on a Taxonomy QA/QC data sheet. If there are errors in species identification, the taxonomist will inform the Lead Scientist of the cruise to take action to correct the problem. Field personnel will be instructed regarding the appropriate identifications. Navigation The ability to accurately locate sampling sites is critical to the success of the survey. At the very minimum, each vessel will be required to have the following instrumentation: A Differential Global Positioning System (DGPS); a radar; and a fathometer. A field computer for recording station and sampling information is recommended, but not required. The Boat Captains will be responsible for accurate occupation of the sampling sites and will assist as necessary in maintaining a record of all station occupation and sampling event information. The information required to be recorded for every station occupation and sampling event is described in the Bight'03 Field Operations Manual. The Cruise Leaders are required to assure that all field-collected data are complete and accurate and that station occupation and sampling event data are submitted in electronic form to the Information Management Officer on a weekly basis. These weekly submissions will be reviewed to track the overall sampling progress, identify strata that are at risk of being under-sampled due to unanticipated rates of station abandonment, and to verify that each field team is accurately and completely sampling each station. MEASUREMENTS OF FISH AND INVERTEBRATE ASSEMBLAGES AND FISH PATHOLOGY A. Overview This section presents Bight'03 QA/QC protocols and requirements for demersal fish and invertebrate assemblage analyses, from sample collection to final validation of the resultant data. Sample collection methods are documented in the Bight'03 Field Operations Manual (2003). The field crews will generate data on species identification, enumeration, biomass, length measurements (fish only), and gross external pathology. Field crews will conduct a standard 10-min trawl at selected stations (5-min in bays, harbors, and marinas). The Bight'03 Field Operations Manual contains a list of trawl stations and their locations. The contents of the net will be examined and fish and invertebrates will be identified to species, measured for length (fish only), counted, weighed, and examined for evidence of gross external pathologies. Organisms suspected of having pathologies will be fixed in 10% buffered formalin and shipped to SCCWRP. If appropriate, diseased specimens will be examined by a pathologist. B. Field Operations Trawling Field crews must adhere to prescribed sampling protocols because fish and invertebrate assemblage data (species identification, enumeration, biomass, and length) are significantly influenced by the collection methods. Factors influencing the catch are gear type, net deployment, trawl duration, and tow speed. All crews must have standard nets to ensure comparability of gear. The importance of maintaining the trawl duration and speed should be stressed during the presurvey protocol calibration meeting. During sampling, crews must record towing speed and trawl duration on the Trawl Cover Sheet. The Lead Scientist will be responsible for reviewing all trawl data sheets and the Boat Captain's log daily for investigating and correcting any discrepancies. The Field QA/QC Auditor will monitor adherence to collection

Methodology:

Methodology_Type: Lab 1
Methodology_Description:: Section 1 Laboratory Operations Several laboratories are participating in Bight'03. Quality assurance and quality control measures are necessary to ensure that the data generated by the participating laboratories are comparable. This section addresses only general laboratory operations. The sections on each indicator (i.e., chemistry, benthic analyses, and toxicity) present specific QA/QC requirements and procedures associated with the processing of specific samples. The quality assurance measures for Bight'03 include the following: o The development of MQO's for laboratory generated data, o The documentation of the participating laboratories general laboratory practices and internal QA/QC procedures o Mandatory participation in meetings to calibrate laboratory protocols and training to ensure that Bight'03 procedures and QA/QC requirements are understood. o Apresurvey demonstration of laboratory capability Quality control measures for laboratories participating in Bight'03 include the following: o An ongoing demonstration of laboratory capability o Development and implementation of QA/QC procedures for evaluating performance of laboratories relative to MQO's developed for the project MQOs for chemical analysis are provided in Chapter V of this document. MQOs for benthic analysis are provided in Chapter VI of this document. MQOs for toxicity are provided in Chapter VII of this document. Documentation of general laboratory practices All laboratories providing analytical support for chemical or biological analyses must have the appropriate facilities to store and prepare samples, and appropriate instrumentation and staff to provide data of the required quality within the time period dictated by the project. Laboratories are expected to conduct operations using good laboratory practices, including: o A program of scheduled maintenance of analytical balances, microscopes, laboratory equipment and instrumentation. o Routine checking of analytical balances using a set of standard reference weights (ASTM Class 3, NIST Class S 1, or equivalents). o Checking and recording the composition of fresh calibration standards against the previous lot. Acceptable comparisons are 2% of the previous value. o Recording all analytical data in bound logbooks in ink. o Daily monitoring and documenting the temperatures of cold storage areas and freezer units. o Verifying the efficiency of fume hoods. o Having a source of reagent water meeting American Society of Testing and Materials (ASTM) Type I specifications (ASTM 1984) available in sufficient quantity to support analytical operations. The conductivity of the reagent water should not exceed 1 S/cm at 25C. o Labeling all containers used in the laboratory with date prepared, contents, and initials of the individual who prepared the contents. o Dating and storing all chemicals safely upon receipt. Chemical are disposed of properly when the expiration date has expired. o Using a laboratory information management system to track the location and statsu of any sample received for analysis. Laboratories should be able to provide information documenting their ability to conduct the analyses with the required level of data quality. Such information might include results from interlaboratory comparison studies, control charts and summary data of internal QA/QC checks, and results from certified reference material analyses. Laboratories must also be able to provide analytical data and associated QA/QC information in a format and time frame specified by the Laboratory Coordinator or the Information Management Officer. In addition to the Bight'03 QAP, the following documents and information must be current, and they must be available to all laboratory personnel participating in the project: o Laboratory QA Plan: Clearly defined policies and protocols specific to a particular laboratory including personnel responsibilities, laboratory acceptance criteria for release of data, and procedures for determining the acceptability of results. o Laboratory Standard Operating Procedures (SOPs) Detailed instructions for performing routine laboratory procedures. In contrast to the Laboratory Methods Manual, SOPs offer step by step instructions describing exactly how the method is implemented in the laboratory, specific for the particular equipment or instruments on hand. o Instrument performance study information Information on instrument baseline noise, calibration standard response, analytical precision and bias data, detection limits, etc. This information usually is recorded in log books or laboratory notebooks. o Control charts Control charts must be developed and maintained throughout the project for all appropriate analyses and measurements (see section 4.2.5). Personnel in the laboratories should be well versed in good laboratory practices, including standard safety procedures. It is the responsibility of the laboratory manager and/or supervisor to ensure that safety training is mandatory for all laboratory personnel. The laboratory is responsible for maintaining a current safety manual in compliance with the Occupational Safety and Health Administration (OSHA), or equivalent state or local regulations. The safety manual should be readily available to laboratory personnel. Proper procedures for safe storage, handling and disposal of chemicals should be followed at all times; each chemical should be treated as a potential health hazard and good laboratory practices should be implemented accordingly. Protocol calibration and training Each participating laboratory has a representative to the Bight'03 Steering Committee. This individual serves as the point of contact for the QA Officer or his designee in identifying and resolving issues related to data quality. To ensure that the samples are analyzed in a consistent manner throughout the duration of the project, key laboratory personnel should participate in an orientation session conducted during an initial site visit or via communication with the QA Officer or his designee. The purpose of the orientation session is to familiarize key laboratory personnel with the QA program requirements and procedures. Complete and detailed procedures for processing and analysis of samples in the field are provided in the Bight'03 Field Operations Manual (2003). Procedures for benthic analyses are provided in the Infaunal Sample Analysis Laboratory Procedure (SCCWRP, 2003) which is attached as an appendix to this document. Procedures for chemistry, and toxicity analysis are referenced in the appropriate chapters. Demonstration and documentation of performance Laboratories are required to demonstrate acceptable performance before analysis of samples can proceed, as described for each indicator in subsequent sections. Initially, a QA assistance and performance audit will be performed by QA Officer or his designee to determine if each laboratory effort is in compliance with the procedures outlined in this document and to assist the laboratory where needed. Specific QA/QC procedures have been developed for Bight'03 to evaluate the quality of data being generated by the participating laboratories relative to the MQOs developed for this project. It is the responsibility of each participating laboratory to ensure that all the Bight'03 QA/QC procedures outlined in the subsequent chapters are followed. Quality control of laboratory operations will be evaluated on a continuous basis through the use of internal and external performance evaluations. Technical systems audits by the QA Officer or his designee may be conducted may be conducted at any time during the project. In addition, participating laboratories are required to participate in interlaboratory comparison studies detailed in the indicator section of this document (Chemistry, Benthic Analyses, Toxicity). ANALYSIS OF CHEMICAL CONTAMINANTS IN SEDIMENTS AND TISSUES Overview There are many aspects to assuring the quality of chemical measurements. This section presents Bight '03 QA/QC protocols and requirements covering a wide range of activities, from sample collection and laboratory analysis, to the final validation of the resultant data. Guidance for much of this section is based on USEPA SW846 and protocols developed for the EMAP-E Virginian Province, as well as those developed over many years by the National Oceanic and Atmospheric Administration's (NOAA) National Statsu and Trends (NS&T) Program. The protocols described herein are applicable to low parts-per-billion analyses of both marine sediment and fish samples unless, otherwise noted. The Bight '03 survey will measure a variety of organic and inorganic contaminants in marine sediment and whole fish samples (Table 5.1). In addition, the Bight '03 survey requires that the participating analytical laboratories demonstrate comparability continuously through strict adherence to common QA/QC procedures, routine analysis of Certified Reference Materials (CRMs), and regular participation in interlaboratory comparison exercises (round-robin analyses). The QA/QC program has adopted a "performance-based" approach to achieving quality assurance of low-level contaminants. Laboratories are not required to use the same analytical methods for each type of analysis. Instead, Teach laboratory is free to choose the best, or most feasible method available within the constraints of cost and equipment, and provided that the resulting data meets all of the specified QA/QC criteria for accuracy, precision and sensitivity.. Each laboratory must demonstrate its capability to meet the stated measurements quality objectives (MQOs) for each of the target analytes, in each respective matrix. Initially, each laboratory should establish a method detection limit (MDL) for each target analyte following the MDL protocol cited in 40 CFR Part 136. Laboratories must participate in any available on-going intercalibration exercises, and meet the performance criteria prior to analysis of the survey samples. The participating laboratories must review their laboratory performance on a continuous basis and make corrections if QA/QC criteria are not met. The comparability in performance among laboratories is continuously evaluated based on analysis of certified reference materials (CRMs), selected intercalibration samples, spiked samples, sample duplicates, and laboratory reagent blanks. Sample Collection, Preservation and HoldingTime Field personnel must strictly adhere to Bight '03 protocols to insure the collection of representative, uncontaminated sediment and fish tissue chemistry samples. These sample collection protocols are described in detail in the Field Operations Manual. Briefly, the key aspects of quality control associated with chemistry sample collection are as follows: o Field personnel must be thoroughly trained in the proper use of sample collection gear, and must be able to distinguish acceptable versus unacceptable sediment grab samples or fish trawls in accordance with pre-established criteria. o Field personnel must be thoroughly trained to recognize and avoid potential sources of sample contamination (e.g., engine exhaust, winch wires, deck surfaces, ice used for cooling). o Samplers and utensils that come in direct contact with the sample should be made of non-contaminating materials (e.g., glass, high-quality stainless steel and/or Teflon®) and should be thoroughly cleaned between sampling stations. o Sample containers should be of the recommended type (Table 5.2) and must be free of contaminants (i.e., carefully pre-cleaned) o Conditions for sample collection, preservation and holding times should be followed (Table 5.2).
Methodology_Type: Lab 2
Methodology_Description:: Section 2 Laboratory Operations Overview The Bight '03 survey will involve the distribution of sediment and tissue chemistry samples among several different laboratories. Each participating laboratory will analyze samples using existing methodology and report results only for the constituents listed in Table 5.1. The QA/QC requirements presented in the following sections are intended to provide a common foundation for the protocols used by each laboratory. The resultant QA/QC data will facilitate assessment of the comparability of results among the different laboratories and for the different analytical procedures. It should be noted that the QA/QC requirements specified in this plan represent the minimum requirements for any given analytical method. Additional method-specific requirements should always be followed, as long as the minimum requirements presented in this document have been met. The performance-based Bight '03 QA program for analytical chemistry laboratories is based on an initial demonstration of laboratory capability (e.g., performance evaluation) and an ongoing demonstration of capability. Control limit criteria and recommended frequency of analysis for each QA/QC element or sample type required in the Bight '03Bight '03 program are summarized in Tables 5.3-5.6. The following sections discuss general aspects of the QA/QC elements. Prior to the analysis of samples, each laboratory should calculate nominal MDLs for each analyte; establish an initial calibration curve for all analytes; and demonstrate acceptable performance on a known or blind accuracy-based material. Following a successful first phase, the laboratory must demonstrate its continued capabilities by participating in an on-going series of interlaboratory comparison exercises; repeated analysis of certified reference materials (CRMs); laboratory control standards; and analysis of laboratory method blanks and spiked samples. These steps are detailed in the following sections. The results for the various QA/QC samples should be reviewed by laboratory personnel immediately following the analysis of each sample batch. The results should then be used to determine when control limit criteria have not been met and corrective actions must be taken before any further sample analyses. To accomplish the objectives of the Bight '03 study, three criteria must be met for any analytical methods used: * Sufficient sensitivity must be obtained to achieve the required data reporting objectives for any target analytes (Table 5.7). The confidence of these reporting requirements is estimated by assessing the analytical variation resulting from repeated analyses of spiked samples close to these levels (sensitivity criteria). * Performance of any laboratory must be consistent with that of the other laboratories. Laboratories analyzing the Bight '03 samples must participate in the on-going intercalibration exercises. The acceptable performance for any given laboratory is that the concentrations of any measurable constituents must be within three standard deviations of the average measured concentrations reported by all of the laboratories that analyzed for that constituent (precision criteria). Alternatively, the results must be within specified limits agreed upon by the intercalibration groups. * Analyses of certified reference materials must yield values within the specified range of the certified values (Tables 5.3-5.6). However, due to the inherent variability in analyses near the method detection limit, control limit criteria for relative accuracy will only apply to analytes having certified values that are >10 times the MDL established by the laboratory (accuracy criteria). The on-going intercalibration exercises are used to provide an initial check on the performance of the participating laboratories against these criteria. Any laboratory that fails to meet these criteria should repeat analyses of the intercalibration samples before commencing analyses of actual Bight '03 survey samples. Continuous performance evaluation against these criteria can be achieved by analyses of sample duplicates, spiked blanks, matrix spikes, reporting level spikes, laboratory control standards, and certified reference materials. The data quality requirements for the Bight '03 study are summarized in Tables 5.3-5.6. Discussion of each component is detailed below. Initial calibration Equipment should be calibrated prior to the analysis of each sample batch, after each major equipment disruption, and whenever on-going continuing calibration checks do not meet recommended control limit criteria (Tables 5.3-5.6). Organics. Calibration range must be established for each constituent from a minimum of five analytical standards of increasing concentration. The calibration range should be well characterized and must be established prior to the analysis of samples. Only data that results from quantification within the demonstrated working calibration range may be reported by a laboratory without annotation (i.e., quantification based on extrapolation outside the calibration range is not acceptable). Samples with measured concentrations above the calibration range should be diluted as appropriate, and reanalyzed. For results below the lowest calibration point or reporting limit (RL), samples may be further concentrated, or the results must be "flagged" (annotated) as <RL. The latter is acceptable only if: (1) sample extraction/concentration steps were sufficient to meet the target analyte RL goals of the study, or (2) matrix problems have required sample dilution. Trace metals. ICP/AES and ICP/MS instruments are calibrated with a calibration blank and a minimum of one calibration standard. The atomic absorption spectrometers including flame atomic absorption (FAA), graphite furnace (GFAA), hydride generation, and cold vapor are calibrated using a minimum of 1 blank and three calibration standards. The linear coefficient of the calibration curve must be at least 0.995 to be acceptable. Initial documentation of method detection limits In the Bight '03 program, the MDL will be used to demonstrate the capability of a laboratory to reach the sensitivity required to measure a specific constituent and demonstrate acceptable precision. The MDL represents a quantitative estimate of low-level response detected at the maximum sensitivity of a method. The Code of Federal Regulations (40 CFR Part 136) gives the following rigorous definition: "The MDL is the minimum concentration of a substance that can be measured and reported with 99% confidence that the analyte concentration is greater than zero and is determined from analysis of a sample in a given matrix containing the analyte." The calculated MDL is a function of method precision at low analyte concentrations. Laboratories must submit documented MDLs for each analytical method (summarized in a spreadsheet) to the Chairperson of the Chemistry Technical Committee prior to analysis of field samples. The MDLs should be determined in both fish tissue and sediment, using "clean" sample matrices in ordre to minimize the interference by other compounds in a sample on the estimation of detection limits for the target analytes. Each laboratory is to follow the procedure specified in 40 CFR Part 136 (Federal Register, Oct. 28, 1984) to calculate nominal MDLs for each target analyte and each analytical method employed. Briefly, at least seven replicates of each representative matrix should be spiked at a concentration between one and five times the estimated detection limit (except for certain trace metals; see below for details), or at RL as a default. The amount of sample (i.e., mass of sediment or tissue) used in calculating the MDL should match, as closely as possible, the amount of sample typically used. The mean and standard deviation of the replicates are used to compute the MDL by multiplying the standard deviation by the Student t value for the 99% confidence interval (for n=7, t=3.143). Trace metals. The MDLs for aluminum, antimony, arsenic, barium, beryllium, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, and zinc could be determined on a certified reference material or be calculated from a spiked clean matrix. Reporting levels In the Bight '03 program, RLs are used to report concentrations of target analytes (Table 5.7). The Bight '03 Chemistry Committee, has defined RLs as the lowest concentration of any specific calibration range. The RL is therefore the lowest quantitative value that can be justified and reported in terms of calibration reliability. Values below the RL, but above the nominal MDL are reported when detected, but must be flagged or annotated using the footnote supplied for data reporting. Laboratories must demonstrate their capability to achieve the required RLs by matching the lowest level of calibration standards to the reporting level and meeting the control limit criteria for the initial calibration. Table 5.7 shows the Bight '03 Reporting Levels. Trace Metals. The maximum acceptable MDLs are set at one-fifth of the effects range low (ERL) NOAA sediment quality guideline, for those analytes for which an ERL has been developed. For the purpose of this study, reporting levels (RLs) are used interchangeably with maximum acceptable MDLs. In the case of analytes for which no ERL has been established, the RL will be set by the individual laboratories at the lowest reasonable level with consideration of the analyte, the matrix, and the analytical methods used. The RL for the whole fish samples will be set at three standard deviations above the calculated MDL for each respective analyte, with the understanding that this value will vary somewhat among laboratories. The reason for this are two-fold: 1) there are no fish concentration guidelines for metals similar to those established for sediments, and thus there is no basis for the establishment of an a priori target RL; and 2) the data from the fish metals analyses will be used primarily in the mass balance assessment component of the Bight '03 survey, and thus there is an impetus to push RLs as low as reasonably possible to account for as much of the mass of each trace element as possible within the fish "compartment" of the Southern California Bight. Although there are some guidelines established for fish and shellfish to protect humans and animals from risks due to consumption, these concentrations are in the parts-per-million range, and thus at least an ordre of magnitude above current analytical detection limits. Trace Organics. The RLs for the polynuclear aromatic hydrocarbons (PAHs), chlorinated pesticides, and polychlorinated biphenyls (PCBs) in sediments are set based on the combination of the ERL values and historical data. Fish tissue RLs for the chlorinated hydrocarbon analytes are based on tissue residue guidelines for protection of wildlife, as recommended by Environment Canada. Performance criteria at the RL The initial performance demonstration of precision near the RL can be derived from the MDL determination or separate analysis. The standard deviation of at least seven replicates of clean matrix spiked at or near the RL should be < 0.35 times the RL. In ordre for test performance to be estimated for ongoing organics analyses, each sample batch should include at least one spike at or near the RL (see section 5.3.10).
Methodology_Type: Lab 3
Methodology_Description:: Section 3 Calibration verification An initial calibration verification standard is analyzed at the beginning of each analysis following the calibration procedure to check the accuracy of the calibration. For all three analytical techniques, one initial calibration verification standard is made from a source different from the source that is used for the calibration standards. The initial calibration verification standard is near the mid-range of the calibration and must be within ±10% of the true value when analyzed. ICP/AES and ICP/MS also require a second initial calibration check standard of a substantially different concentration than the first initial calibration check standard; the second initial calibration check standard must also be within ±10% of the true value when analyzed. For continuing trace metal measurements, the continuing calibration verification (CCV) verifies that the instrument stays in calibration throughout the analysis. The CCV is prepared in the same acid matrix as the calibration standard. It is analyzed after every ten samples and at the end of the run. The CCV can come from any source that is near the mid-range of the calibration and must be within the ranges specified in Table 5.3. For trace organics measurements using full scan GC/MS, instrument tuning needs to be performed by analyzing 50 ng of decafluorotriphenylphosphine (DFTPP) prior to use of the instrument. The fragmentation profiles from this analysis have to be within the EPA-recommended criteria (see USEPA SW-846). The initial instrument calibration performed to establish calibration ranges for specific analytes is checked through the analysis of calibration verification standards (i.e., calibration standard solutions) prior to analysis of each batch of samples. Calibration verification standard solutions used for the calibration checks should contain all the analytes of interest at concentrations at or near the mid-level of a multi-point calibration range. If the control limit for analysis of the calibration verification standard is not met (Tables 5.3-5.6), the analyst(s) should identify and eliminate the source(s) causing the failure and perform another calibration verification. If problem persists, preventive maintenance or corrective actions must be performed. A calibration verification standard is injected. The results should be assessed using the calibration verification criteria (Tables 5.3-5.6). If the calibration verification criteria are not met, a new initial calibration must be performed. No sample analysis should begin until a satisfactory calibration verification is achieved. Calibration blanks (trace metals) Laboratories need to analyze calibration blanks (pure matrix used to prepare calibration standard solutions) prior to analysis of samples to ensure that the instrument is free of contamination. Concentrations of all target analytes obtained from analysis of the calibration blanks should be below MDLs. Method blanks Method blanks (also called procedural blanks) are used to assess laboratory contamination during all stages of sample preparation and analysis. For both organic and inorganic analyses, one laboratory reagent blank should be run in every sample batch. The method blank should be processed through the entire analytical procedure in a manner identical to the samples. Control limits for blanks (Tables 5.3-5.6) are based on the laboratory's maximum acceptable method detection limits (trace metals) or reporting levels (trace organics and TOC) as documented prior to the analysis of samples. For trace metals, the level of any analyte in the method blank must be below MDL or less than 5% of the level of the analyte in the samples. A reagent blank concentration equal to or greater than three times the MDL for one or more of the analytes of interest requires definitive corrective action to identify and eliminate the source(s) of contamination before proceeding with sample analysis. For trace organics, if the method blank contains any analyte with a measured concentration greater than RL, all samples for that batch should be re-analyzed if the analyte is detected in samples. Concentrations lower than RL should be reported, but not used to correct concentrations in the field samples. Sample duplicates Analysis of sample duplicates is used to assess the precision of an analytical method in quantifying target analytes and not required for all methods. The relative percent difference (RPD) between the sample and sample duplicate results is calculated as follows: RPD = (C1 - C2) _ x 100 (C1 + C2)/2 Where: C1 = the larger of the duplicate results for a given analyte, and C2 = the smaller of the duplicate results for a given analyte. The data from this process are typically used to establish a statistical range with which the precision of subsequent analyses can be assessed. Matrix spikes and matrix spike duplicates A laboratory spiked sample matrix (commonly called a matrix spike or MS) and a laboratory spiked sample matrix duplicate (commonly called a matrix spike duplicate or MSD) will be used both to evaluate the effect of the sample matrix on the recovery of the compound(s) of interest and to provide an estimate of analytical precision. A minimum of one MS should be analyzed for 10% of samples. The matrix spike solution should contain all the analytes of interest. The final spiked concentration of each analyte in the sample should be between 10 and 100 times the MDL for that analyte, as previously calculated by the laboratory. If the unspiked sample contains more than this amount, the sample should be spiked with one to five times the preexisting concentration in the sample. Recovery data for the fortified compounds ultimately are intended to provide a basis for determining the prevalence of matrix effects in the samples analyzed during the project. However, these data may not reflect the true magnitude of matrix interference with the analyses since recently spiked analytes often do not permeate the sample matrix to the same extent as in field contaminated sediments. This is particularly true for measurements of trace organics in complex matrices. Therefore, it is recommended that recovery data from analyses of MS and MSD samples be used only as an evaluation tool for methods measuring trace organics. For trace metals, the spike control limits are presented in Table 5.3. for all elements other than iron and aluminum due to their high concentrations. If the percent recovery for any analyte in the MS or MSD is lower than the control limits, the raw data quantitation reports should be reviewed. If the reason for a low percent recovery value is not discovered, the instrument response may be checked using a calibration standard. Low matrix spike recoveries may be a result of matrix interference and further instrument response checks may not be warranted, especially if the low recovery occurs in both the MS and MSD, and the other QC samples in the batch indicate that the analysis was "in control". An explanation for low percent recovery values for MS/MSD results should be given in the cover letter accompanying the data package. Corrective actions taken and verification of acceptable instrument response must be included. Analysis of the MS/MSD also is useful for assessing laboratory precision. The RPD between the MS and MSD results should be within the control limits (Tables 5.3-5.6 and 5.9) for at least one result per batch. If results for any analytes do not meet the control limit criteria, calculations and instruments should be checked. A repeat analysis may be required to confirm the results. Reporting level spikes (organics) Since a large number of samples are expected to contain organic analytes with concentrations near RLs, it is important to estimate the confidence of the measurements near these levels. For each batch of samples analyzed, a relatively clean matrix (clean sand or Orange Roughy) is spiked with a standard solution containing all analytes of interest at levels approximately 20% above RLs. This sample is processed and analyzed along with other field samples. Recovery data from all participating laboratories will be gathered and analyzed to yield a confidence range for each method measuring low-level target analytes. Certified reference materials Certified reference materials (CRMs) generally are the most useful QC samples for assessing the accuracy of a given analysis (i.e., closeness of a measurement to the "true" value). CRMs can be used to assess accuracy because they have "certified" concentrations of the analytes of interest, as determined through replicate analyses by a reputable certifying organization using two independent measurement techniques for verification. In addition, the certifying organization may provide "non-certified" or "informational" values for other analytes of interest. Such values are determined using a single measurement technique, which may introduce unrecognized bias. Therefore, non-certified values must be used with caution in evaluating the performance of a laboratory using a method which differs from the one used by the certifying organization. A list of reference materials used for the Bight '03 study is presented in Table 5.8. As an alternative, a laboratory control material (LCM) may be used in addition to, or as a replacement for a CRM. A LCM is similar to a CRM in that it is a homogeneous matrix that closely matches the samples being analyzed. For the Bight '03 study, two sediment materials from the Palos Verdes Shelf were used as LCMs in addition to CRMs. Although concentrations of the analytes of interest in these materials are not certified, they can be used to assess the precision (i.e., consistency) of a single laboratory, as well as to determine the degree of comparability among different laboratories. In practice, LCMs may be preferred for routine (i.e., day to day) analysis because CRMs are relatively expensive. Moreover, as-collected (i.e., wet) LCMs from the study area are more representative of the types of samples that will be delivered to the laboratories during the actual study. However, CRMs still must be analyzed at regular intervals (e.g., monthly or quarterly) to provide a check on accuracy. Routine analysis of CRMs and LCMs is a vital aspect of the "performance-based" Bight '03 QA philosophy. At least one CRM or LCM must be analyzed along with each batch of samples (Tables 5.3-5.6 and 5.9). For CRMs, both the certified and non-certified concentrations of the target analytes should be known to the analyst(s) and should be used to provide an immediate check on performance before proceeding with a subsequent sample batch. Performance criteria for both precision and accuracy have been established for analysis of CRMs or LCMs (Tables 5.3-5.6 and 5.9). If the laboratory fails to meet either the precision or accuracy control limit criteria for a given analysis of the CRM or LCM, the data for the entire batch of samples is suspect. Calculations and instruments should be checked; the CRM or LCM may have to be reanalyzed (i.e., re-injected) to confirm the results. If the values are still outside the control limits in the repeat analysis, the laboratory is required to find and eliminate the source(s) of the problem and repeat the analysis of that batch of samples until control limits are met, before continuing with further sample processing. The results of the CRM or LCM analysis should never be used by the laboratory to "correct" the data for a given sample batch. Surrogate standards Recovery surrogates are compounds chosen to simulate the analytes of interest in organic analyses. The recovery surrogate represents a reference analyte against which the signal from the analytes of interest is compared directly for the purpose of quantification. Recovery surrogates must be added to each sample, including QA/QC samples, prior to extraction. The reported concentration of each analyte should NOT be adjusted to correct for the recovery of the surrogate standards. The surrogate recovery data therefore should be carefully monitored; each laboratory must report the percent recovery of the surrogate(s) along with the target analyte data for each sample. If possible, isotopically labeled analogs of the analytes should be used as recovery surrogates for GC/MS analyses. Control limit criteria for surrogate recoveries are provided in Tables 5.4 -5.5. Each laboratory should set its own control limit criteria based on the experience and best professional judgment of the analyst(s). It is the responsibility of the analyst(s) to demonstrate that the analytical process is always "in control" (i.e., highly variable surrogate recoveries are not acceptable for repeat analyses of the same certified reference material and for the matrix spike/matrix spike duplicate). Internal standards (organics) Internal standards are added to each sample extract just prior to instrumental analysis to enable optimal quantification, particularly of complex extracts subject to matrix effects or retention time shifts relative to the analysis of standards. Internal standards are essential if the actual recovery of the surrogates added prior to extraction is to be calculated. The internal standards also can be used to detect and correct for problems in the instrument. The elements or compounds used as internal standards must be different from those already used as recovery surrogates. The analyst(s) should monitor internal standard retention times and recoveries to determine if instrument maintenance or repair, or changes in analytical procedures, are indicated. Corrective action should be initiated based on the experience of the analyst(s) and not solely because warning or control limits are exceeded. Instrument problems that may have affected the data or resulted in the reanalysis of the sample should be documented properly in logbooks and internal data reports and used by the laboratory personnel to take appropriate corrective action. Whole fish sample processing Whole fish samples will be processed as in the Bight'98 survey, by homogenization in a blender with an equal mass of ultra-pure water (~18 megaohom and organic free). In the Bight'03 survey, fish samples will be analyzed for trace metal constituents as well as for orgaincs, and thus every effort should be made to avoid both contamination by both organic and inorganic species. Therefore samples must be processed in a glass blender cup, prefereably fitted with titanium or tantalum blades. If titanium or tantalum blades cannot be obtained, then stainless steel blades may be used, acknowledging that this may introduce trace amounts of chromium and nickel contamination. The metals data from samples processed using stainless steel blades must be flagged with the appropriate caveats. Data evaluation procedures It is the responsibility of the Project Manager or his designee to acknowledge initial receipt of the data package(s), verify that the four data evaluation steps (see below) are completed. The analytical laboratory must be notified of any additional information or corrective actions deemed necessary after the data evaluation. Following satisfactory resolution of all "corrective action" issues, the final action is to notify the laboratory in writing that the submitted results have been officially accepted as complete. It may be necessary or desirable for a team of individuals (e.g., the QA Coordinator, Lab Coordinator and/or staff analytical chemists) to assist the Project Manager in technical evaluation of the submitted data packages. While the Project Manager has ultimate responsibility for maintaining official contact with the analytical laboratory and verifying that the data evaluation process is completed, it is the responsibility of the QA Coordinator to closely monitor and formally document each step in the process as it is completed. This documentation should be in the form of a data evaluation tracking form or checklist that is filled in as each step is completed. This checklist should be supplemented with detailed memos to the project file outlining any concerns with data omissions, analysis problems, or descriptions of questionable data identified by the laboratory. Evaluation of the data package should begin as soon as possible following its receipt, since delays increase the chance that information may be misplaced or forgotten. In addition, if holding times have been exceeded, options for reanalysis may be limited. The following steps are to be followed and documented in evaluating Bight '03 chemistry data: * Checking data completeness (verification) * Assessing data quality (validation) * Assigning data qualifier codes * Taking final actions Checking data completeness The first part of data evaluation is to verify that all required information has been provided in the data package. For the Bight'03 survey, this should include the following steps: * Project personnel should verify that the package contains the narrative explanations signed by the laboratory manager, hard copies of all results (including QA/QC results), and accompanying computer diskettes. * The electronic data file(s) should be parsed and entered into the Bight '03 chemistry database to verify that the correct format has been supplied. * Once the data have been entered into the appropriate Bight'03 database, automated checks should be performed to verify that results have been reported for all expected samples and all analytes. The Project Manager should contact the laboratory and request any missing information as soon as possible after receipt of the data package. If information was omitted because required analyses were not completed, the laboratory should provide and implement a plan to correct the deficiency. This plan may include submittal of a revised data package and possible reanalysis of samples.
Methodology_Type: Lab 4
Methodology_Description:: Section 4 Assessing data quality Data validation, or the process of assessing data quality, can begin after Bight'03 personnel have determined that the data package is complete. Normally, the first major part of validation involves checking 100% of the data for any possible errors resulting from transcription of tabulated results, misidentification or miscalculations. However, Bight'03 laboratories are expected to submit data that has been tabulated and checked thoroughly for accuracy; the raw data reports needed to perform these checks (e.g., chromatograms, original quantitation reports) are not submitted as part of the data package. The laboratory is required to maintain this raw data in an orderly manner and to have these records available for review by Bight'03 personnel upon request. The first step validation checks performed by Bight'03 personnel will be limited to the following: 1) A check to verify that all reporting units and numbers of significant figures are correct; 2) A check to verify that all of the laboratory's calculated percent recovery values (for calibration check samples, Laboratory Control Materials, and matrix spikes) and relative percent difference values (for duplicates) are correct; 3) A check to verify that the reported concentrations for each analyte fall within "environmentally realistic" ranges, determined from previous studies and expert judgment. In addition, past studies indicate that the different compounds in each classs of chemicals being measured on Bight'03 (e.g., PAHs, PCBs, DDTs and other chlorinated pesticides) typically occur in the environment in more or less fixed ratios to one another. For example, the DDT breakdown products p,p DDD and p,p DDE typically occur at higher concentrations than p,p DDT in marine sediments in off Southern California. If anomalous departures from expected relative concentrations are found, it may indicate a problem in the measurement or data reduction, which in turn warrants further investigation. The second major aspect of data validation is to compare the QA/QC data against established criteria for acceptable performance (specified earlier in this plan). This will involve the following steps: 1) Results for QA/QC samples should be tabulated, summarized and evaluated. A set of summary tables should be prepared from the database showing the percent recovery values and relative percent difference values (where applicable) for the CRMs, LCMs and matrix spike/matrix spike duplicate samples. The tables should indicate the percent recovery values for each individual batch of samples, as well as the average, standard deviation, coefficient of variation, and range for all batches combined. 2) Similar summary tables should be prepared for the laboratory reagent blank QA/QC samples. 3) The summary results, particularly those for the CRMs and/or LCMs should be evaluated by comparing them against the QA/QC warning and control limit criteria for accuracy, precision, and blank contamination specified in Table 5.3. 4) Method detection limits reported by the laboratory for each analyte should be tabulated. There are several possible courses of action to be taken if the reported data are deficient (i.e., warning and/or control limits exceeded) during the assessment of data quality. The laboratory's cover letter (narrative explanation) should be consulted to determine if the problems were satisfactorily addressed. If only warning limits were exceeded, then it is appropriate for the laboratory to report the results. Violation of control limits, however, will result in one of the following courses of action. Either all associated results will be qualified in the database as estimated values (explained in the following section), or the data will be rejected and deleted from the database because the analysis was judged to be out of control (based on the professional judgment of the reviewer). Assigning data qualifier codes Data qualifier codes are notations used by laboratories and data reviewers to briefly describe, or qualify, data and the systems producing data. Bight '03 data reviewers will assign data qualifier codes in situations where there are violations of control limit criteria. The most typical situation is when a laboratory fails to meet the accuracy control limit criteria for a particular analyte in a CRM or matrix spike sample. In these situations, the QA reviewer should verify that the laboratory did meet the control limit criteria for precision. If the lack of accuracy is found to be consistent (i.e., control limit criteria for precision were met), then it is likely that the laboratory experienced a true bias for that particular analyte. In these situations, all reported values for that particular analyte will be qualified with a code that has the following meaning: "The reported concentration is considered an estimate because control limits for this analyte were exceeded in one or more quality control samples." Because some degree of expert judgment and subjectivity typically is necessary to evaluate chemistry QA/QC results and assign data qualifier codes, data validation will be conducted only by qualified personnel. It is the philosophy of the Bight '03 that data which are qualified as estimates because of minor violation of a control limit in a QA/QC sample are still usable for most assessment and reporting purposes. However, it is important to note that all QA/QC data will be readily available in the database along with the results data, so that interested data users can make their own estimation of data quality. Taking final action Upon completion of the above steps, a report summarizing the QA review of the data package should be prepared, samples should be properly stored or disposed of, and laboratory data and accompanying explanatory narratives should be archived both in a storage file and in the database. Technical interpretation of the data begins after the QA review has been completed. Reports documenting the results of the QA review of a data package should summarize all conclusions concerning data acceptability and should note significant quality assurance problems that were found. These reports are useful in providing data users with a written record on data concerns and a documented rationale for why certain data were accepted as estimates or were rejected. The following items should be addressed in the QA report: 1) Summary of overall data quality, including a dscription of data that were qualified. 2) Brief dscriptions of analytical methods and the method(s) used to determine detection limits. 3) Dscription of data reporting, including any corrections made for transcription or other reporting errors, and dscription of data completeness relative to objectives stated in the QA Project Plan. 4) Dscriptions of initial and ongoing calibration results, blank contamination, and precision and bias relative to QA plan objectives (including tabulated summary results for CRMs, LCMs and matrix spike/matrix spike duplicates). The chemistry QA results will be presented in the appropriate Bight '03 technical reports,and will also become a permanent part of the database documentation (i.e., meta data). The QA/QC data collected by the Bight '03 will be used not only to assess the accuracy and precision of individual laboratory measurements, but ultimately to assess the comparability of data generated by multiple laboratories. Summary Of QA/QC Requirements For Analysis Of Chemical Contaminants In Sediments And Whole Fish The Bight '03 QA/QC requirements for chemical analysis are performance-based. Key quality assurance (QA) measures include: * MQOs for accuracy, precision and completeness (Table 2.1) * Specifications for sample collection and holding times (Table 5.2) * Control limit criteria and recommended frequency of analyses for each QA/QC sample type required in Bight '03 (Table 5.3-5.7) * Target reporting levels for each analyte (Table 5.7). * Pre-survey demonstration and documentation of performance by all participating laboratories that they can meet the detection level and precision objectives for each of the target analytes. * Requirement of participation in pre-survey interlaboratory calibration exercise to assess comparability of results with other participating laboratories. * Requirement of pre-survey analysis of certified reference materials to assess the Bight '03 accuracy criteria. The required quality control (QC) measure for the Bight '03 chemical analyses is: * Evaluation of the results from QA/QC samples by each laboratory after completion of each analytical sample batch.
Methodology_Type: Lab 5
Methodology_Description:: Section 5 Table 5.2 Summary of chemistry sample collection and holding time conditions for the Bight '03 Container Container Preservation Maximum Parameter Type Size (mL) Requirements Holding Time Sediment grain size plastic or glass 125 cold (4ºC) 6 months (80% full) Sediment total organic carbon glass 2500 frozen (-20ºC) 6 months (80% full) Sediment trace metals glass or plastic 250 frozen (-20ºC) 6 months (80% full) Sediment trace organics glass 250 frozen (-20ºC) 1 year (80% full) Fish trace organics aluminum foil wrapped whole fish frozen (-20ºC) 1 year in plastic bags Fish Trace Metals Plastic bags whole fish frozen (-20ºC) 1 year Fish Puree (organics) glass 250 frozen (-20ºC) 1 year (80% full) Fish Puree (trace metals) glass/plastic 250 frozen (-20ºC) 1 year (80% full) Table 5.3 Summary of the data quality requirements for the Bight '03 trace metal measurements MEASUREMENT FREQUENCY CONTROL LIMIT Method Blank 1/batch <MDL or <5% of the measured concentration in samples Certified Reference Materials 1/batch See Table 5.8 ERA Soil #540 RTC CRM016-050 ICP-AES Calibration Initial setup Minimum 1 blank and one calibration standard Interference check 1/run ±20% true value Initial calibration verification (ICV) 2 points/batch ±10% true value Continuing calibration verification 10% ±10% true value (CCV) Matrix spike 10% At least one matrix spike per batch must be within 30% true value. Should all spiked sample recoveries be outside 30% of true value, add a post-digestion spike to the unspiked sample and analyze. If all spike recoveries are outside 30% of true value, note matrix caused poor spike recovery. If all spike recoveries are within 30% of true value, repeat digestion. Spike duplicate results must have an RPD < 20% if MSD is analyzed. Spiked blank 1/batch ±25% true value Duplicate sample or matrix spike sample 10% Statistical process control analyses (within 3?) ICP-MS Tuning solution 4 at start of run RPD < 5% Calibration Initial setup Minimum 1 blank and three calibration standards Initial calibration verification (ICV) 2 points/batch ±10% true value Continuing calibration verification 10% ±10% true value (CCV) Calibraiton Blank 10% <MDL. If > MDL, run two more times, the average must be <MDL. If average > MDL, reanalyze. Matrix spike 10% At least one matrix spike per batch must be within 30% true value; ? 30% RPD for over 10 times MDL. If ? 30% RPD and Table 5.3 Summary of the data quality requirements for the Bight '03 trace metal measurements (Cont.) post-digestion spike recovery is > 25% note matrix problem. If > 20% RPD and post-digesiton spike recovery is ? 25% repeat digestion and analysis Spiked blank 1/batch ±25% true value Duplicate sample or matrix spike sample 10% Within ±30% RPD Intensity standard During run Intensity between 30 and 120% of the internal standard Atomic Absorption (AA, GFAA, Hydride Generation, Cold Vapor) Calibration Initial setup Minimum 1 blank and three calibration standards; linear coefficient ? 0.995 Initial calibration verification (ICV) 1/batch ±10% true value Continuing calibration verification 10% ±20% true value (CCV) Calibraiton Blank 10% <MDL. If > MDL, run two more times, the average must be <MDL. If average > MDL, reanalyze. Matrix spike 10% At least one matrix spike per batch must be within 30% true value. If all matrix spike analyses are ? 20%, interference test must be conducted Spiked blank 1/batch 15% true value Duplicate sample or matrix spike sample 10% Within ±30% RPD Interference check As required (a) Dilution test: Select typical sample with concentration 25 times the MDL. Dilute sample 5 times. The concentration of the undiluted sample and 5 times the concentration od thediluted sample must be within 10%. If > 10% or all samples are below 10 times the MDL, then proceed to (b). (b) Post-digestion spike: Spike sample to bring concentration to 2 to 5 times the original concentration or 20 times the MDL. The recovery must be within 15%. If not, perform the standard addition procedure described in USEPA SW846 Table 5.4 Summary of the data quality requirements for measurements of polycyclic aromatic hydrocarbons and linear alkylbenzenesa MEASUREMENT FREQUENCY CONTROL LIMIT Initial calibration Relative standard deviation (RSD) < 25% for all analytes Calibration verification 1 set/batch Calibration verification should be performed at the beginning and end of each batch. Relative percent difference (RPD) compared to intial calibration should be less than 20% for 80% of the analytes Method Blank 1/batch Below reporting levels for all analytes Matrix spikes/MS duplicates 1/batch For evaluaiton onlu as part of the on-going QA/QC efforts Reporting level spikes 1/batch For evaluaiton onlu as part of the on-going QA/QC efforts Certified reference material 1/batch Within ± 40% of specified value for 80% of the analytesb Surrogate spikes 1/sample Laboratories develop their own control limits Internal standards (Optional) 1/sample Laboratories develop their own aThere should be 20 samples or less in each extraction batch and a reasonable number of samples in one instrument batch. bCertified values were obtained by a different analytical procedure from what the participating laboratories are employing; therefore, direct comparison is impossible. The performance criteria agreed by the group is AVERAGE ± 3 standard deviations. Table 5.5 Summary of the data quality requirements for measurements of chlorinated hydrocarbonsa MEASUREMENT FREQUENCY CONTROL LIMIT Initial calibration Relative standard deviation (RSD) within ±15% for 80% of the analytes Calibration verification 1 set/batch Calibration verification should be performed at the beginning and end of each batch. Relative percent difference (RPD) compared to intial calibration should be less than 25% for 80% of the analytes Method Blank 1/batch Below reporting levels for all analytes Sample duplicates 1/batch RPD < 30% Reporting level spikes 1/batch For evaluation only as part of the on-going QA/QC efforts (performed on clean sediment or tissue) Certified reference material 1/batch Within ±40% of the true value for 80% of the analytes Surrogate spikes 1/sample Laboratories develop their own control limits Internal standards (Optional) 1/sample Laboratories develop their own Table 5.6 Summary of the data quality requirements for measurements of total organic carbona MEASUREMENT FREQUENCY CONTROL LIMIT Initial calibration RSD < 20% Calibration verification 1/batch RPD compared to inital calibraiton should be less than 20% Calibration blank 1/batch Below MDLs Method blank 1/batch Below reporting levels for all analytes Sample duplicates 1/batch RPD < 30% Certified reference material 1/batch Within ±20% of certified value aThere should be 20 samples or less in each extraction batch and a reasonable number of samples in one instrument batch. Table 5.7 Reporting objectives used for the Southern California Bight Pilot Project. Sediment Fish Sediment Fish (ng/g dry) (ng/g wet) (ng/g dry) (ng/g wet) Aluminum a NA PCB Congenersb 7.5 20c Antimony 10,000 NA 4,4'-DDT 1 10 Arsenic 1,600 NA 2,4'-DDT 1 10 Barium a NA 4,4'-DDD 1 10 Beryllium 200 NA 2,4'-DDD 1 10 Cadmium 200 NA 4,4'-DDE 1 10 Chromium 16,000 NA 2,4'-DDE 1 10 Copper 7,000 NA ?-Chlordane 1 10 Iron a NA ?-Chlordane 1 10 Lead 9,300 NA Total organic carbon a NA Mercury 30 NA Lipid NA a Nickel 4,200 NA Sediment grain size a NA Selenium 1,000 NA Silver 200 NA Zinc 30,000 NA Acenaphthene 50 NA Acenaphthylene 50 NA Anthracene 50 NA Benzo[a]anthracene 50 NA Benzo[a]pyrene 50 NA Benzo[b]fluoranthene 50 NA Benzo[e]pyrene 50 NA Benzo[g,h,i]perylene 100 NA Benzo[k]fluoranthene 50 NA Biphenyl 50 NA Chrysene 50 NA Dibenz[a,h]anthracene 100 NA Fluoranthene 50 NA Fluorene 50 NA Indeno(1,2,3-c,d)pyrene 100 NA Naphthalene 50 NA Perylene 50 NA Phenanthrene 50 NA Pyrene 50 NA 2,6-Dimethylnaphthalene 50 NA 1-Methylnapthalene 50 NA 1-Methylphenanthrene 50 NA 2-Methylnapthalene 50 NA 1,6,7-Trimethylnaphthalene 50 NA aReport value. bCongeners 18, 28, 37, 44, 49, 52, 66, 70, 74, 77, 81, 87, 99, 101, 105, 110, 114, 118, 119, 123, 126, 128, 138, 149, 151, 153, 156, 157, 158, 167, 168, 169, 170, 177, 180, 183, 187, 189, 194, 201, 206. cGC/MS method has a reporting level of 40 ng/g of fish homogenate (1:1 fish:water) and samples containing undetectable PCBs will be re-analyzed with a reporting level of 20 ng/g of fish homogenate. Table 5.8 Certified reference materials recommended by the Bight '03 Chemistry Technical Committee. Calibration solution SRM 1491 Aromatic hydrocarbons in hexane/toluene SRM 1492 Chlorinated pesticides in hexane SRM 1493 Polychlorinated biphenyl congeners in 2,2,4-trimethylpentane Environmental matrix (Organics) CRM 1944 (NIST) PAHs and chlorinated hydrocarbons in marine sediment LCMs (Field Sediments) PAHs and Chlorinated hydrocarbons in two marine sedimetns for the Palos Verdes shelf, PV7C and MRS032803; used for pre-survey laboratory intercalibration only; accepatance ranges are determined by the Bight'03 chemistry committee. CARP-2 (NRC Canada) Chlorinated hydrocarbons in whole fish Environmental matrix (Trace Metals) CRM-016-050 (RTC) Metals in stream sediment 540 (ERA) Priority Pollutant Soil Certified Standard DORM-2 Metals in Fish Muscle Tissue Environmental matrix (total organic carbon) PACS-1 (NRC Canada) TOC in marine sediment

Process_Step:

Process_Description: All data was processed through QA procedures
Process_Date: 20041004

Spatial_Data_Organization_Information:

Spatial_Reference_Information:

Horizontal_Coordinate_System_Definition:

Geodetic_Model:

Horizontal_Datum_Name: North American Datum of 1983
Ellipsoid_Name: Geodedic Reference System 80
Semi-major_Axis: 6378137
Denominator_of_Flattening_Ratio:: 298.257 4.2.2.1 Depth Datum Name:

Entity_and_Attribute_Information:

Detailed_Description:

Entity_Type:

Entity_Type_Label: tblChemistryResults
Entity_Type_Definition: TABLE
Entity_Type_Definition_Source: Bight03 Information Management Plan

Attribute:

Attribute_Label: AnalysisMethod

Attribute_Definition: From luList24_AnalysisMethodCodes

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition: Analysis Method Codes
Enumerated_Domain_Value_Definition_Source: Bight03 Information Management Plan

Attribute:

Attribute_Label: AlpKem RFA 300 Series Nutrient Analyzer

Attribute_Definition: AlpKem RFA 300 Series Nutrient Analyzer

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: CHN

Attribute_Definition: EA1108 CHN Elemental Analyzer

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: CVAA

Attribute_Definition: Cold Vapor Atomic Absorption Analysis

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: EPA 160.2

Attribute_Definition: Total Suspended Solids analysis method

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: EPA200.7

Attribute_Definition: From Standard Methods

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: FIMS

Attribute_Definition: Flow Injection Mercury System

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: FLUORO

Attribute_Definition:

Fliorometric analysis method for chlorophyll a and phaeopigment

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: GCMS

Attribute_Definition: GS/MS

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: GFAA

Attribute_Definition: Graphite Furnace Atomic Absorption Analysis

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: ICPAES

Attribute_Definition:

Inductively Coupled Plasma Atomic Emmision Spectrometer

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: ICPMS

Attribute_Definition: Inductively Coupled Plasma Mass Spectrometer

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: IONGCMS

Attribute_Definition: Ion Trap GC/MS

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: SW6010

Attribute_Definition: From Standard Methods

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: SW7060

Attribute_Definition: From Standard Methods

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: SW7740

Attribute_Definition: From Standard Methods

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: SW8081

Attribute_Definition: From Standard Methods

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: SW80818082

Attribute_Definition: From Standard Methods

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: SW8270

Attribute_Definition: From Standard Methods

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: HORIBA-LASER

Attribute_Definition: HORIBA-LASER

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute:

Attribute_Label: Beckman Coulter LS230 - laser grain size

Attribute_Definition: Beckman Coulter LS230 - laser grain size

Attribute_Definition_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Enumerated_Domain:

Enumerated_Domain_Value: AnalysisMethod
Enumerated_Domain_Value_Definition:: a luList24_AnalysisMethodCodes
Enumerated_Domain_Value_Definition_Source:: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values:

Codeset_Domain:

Codeset_Name: tblChemistryResults
Codeset_Source: Bight03 Information Management Plan

Attribute_Domain_Values: