March 2003 Environmental Technology Verification Report General Oceanics, Inc. Ocean Seven 316 Multi-Parameter Water Quality Probe/Sonde Prepared by Battelle Battelle . . . Putting Technology To Work In cooperation with the National Oceanic and Atmospheric Administration %I0 Under a cooperative agreement with £EPA U.S. Environmental Protection Agency etV etV eiV ------- March 2003 Environmental Technology Verification Report ETV Advanced Monitoring Systems Center General Oceanics, Inc. Ocean Seven 316 Multi-Parameter Water Quality Probe/Sonde by Jeffrey Myers Amy Dindal Zachary Willenberg Karen Riggs Battelle Columbus, Ohio 43201 and Paul Pennington Michael Fulton Geoffrey Scott NOAA CCEHBR ------- Notice The U.S. Environmental Protection Agency (EPA), through its Office of Research and Development, has financially supported and collaborated in the extramural program described here. This document has been peer reviewed by the Agency and recommended for public release. Mention of trade names or commercial products does not constitute endorsement or recommendation by the EPA for use. The National Oceanic and Atmospheric Administration (NOAA) does not approve, recommend, or endorse any proprietary product or material mentioned in this publication. No reference shall be made to NOAA in any advertising or sales promotion which would indicate or imply that NOAA approves, recommends, or endorses any proprietary product or proprietary material mentioned herein. 11 ------- Foreword The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the nation's air, water, and land resources. Under a mandate of national environmental laws, the Agency strives to formulate and implement actions leading to a compatible balance between human activities and the ability of natural systems to support and nurture life. To meet this mandate, the EPA's Office of Research and Development provides data and science support that can be used to solve environmental problems and to build the scientific knowledge base needed to manage our ecological resources wisely, to understand how pollutants affect our health, and to prevent or reduce environmental risks. The Environmental Technology Verification (ETV) Program has been established by the EPA to verify the performance characteristics of innovative environmental technology across all media and to report this objective information to permitters, buyers, and users of the technology, thus substantially accelerating the entrance of new environmental technologies into the marketplace. Verification organizations oversee and report verification activities based on testing and quality assurance protocols developed with input from major stakeholders and customer groups associated with the technology area. ETV consists of seven environmental technology centers. Information about each of these centers can be found on the Internet at http://www.epa.gov/etv/. Effective verifications of monitoring technologies are needed to assess environmental quality and to supply cost and performance data to select the most appropriate technology for that assessment. In 1997, through a competitive cooperative agreement, Battelle was awarded EPA funding and support to plan, coordinate, and conduct such verification tests for "Advanced Monitoring Systems for Air, Water, and Soil" and report the results to the community at large. Information concerning this specific environmental technology area can be found on the Internet at http://www.epa.gov/etv/centers/centerl .html. 111 ------- Acknowledgments The authors wish to acknowledge the support of all those who helped plan and conduct the verification test, analyze the data, and prepare this report. We would like to thank the National Oceanic and Atmospheric Administration's (NOAA's) National Ocean Service, National Centers for Coastal Ocean Science staff at the Center for Coastal Environmental Health and Biomolecular Research. In particular, we recognize Paul Pennington and Jennifer Tobias for their outstanding efforts. In addition, NOAA's Coastal Service Center is acknowledged for providing access to dock facilities on the Cooper River for the saltwater testing portion of this study. We also acknowledge the assistance of the ETV Advanced Monitoring Systems Center stakeholders Vito Minei, Christine Kolbe, and John Carlton. iv ------- Contents Page Notice ii Foreword iii Acknowledgments iv List of Abbreviations viii 1 Background 1 2 Technology Description 2 3 Test Design and Procedures 4 3.1 Introduction 4 3.2 Test Site Characteristics 4 3.3 Test Design 5 3.3.1 Saltwater Testing 7 3.3.2 Freshwater Testing 9 3.3.3 Mesocosm Testing 11 3.4 Materials and Equipment 12 4 Quality Assurance/Quality Control 13 4.1 Instrument Calibration 13 4.2 Field Quality Control 13 4.3 Sample Custody 13 4.4 Audits 14 4.4.1 Performance Evaluation Audit 14 4.4.2 Technical Systems Audit 15 4.4.3 Audit of Data Quality 15 4.5 QA/QC Reporting 15 4.6 Data Review 15 5 Statistical Methods 17 5.1 Pre-and Post-Calibration Results 17 5.2 Relative Bias 17 5.3 Precision 18 5.4 Linearity 18 5.5 Inter-Unit Reproducibility 18 v ------- 6 Test Results 19 6.1 Pre-and Post-Calibration Results 25 6.2 Relative Bias 28 6.3 Precision 31 6.4 Linearity 32 6.5 Inter-Unit Reproducibility 32 6.6 Other Factors 34 6.6.1 Ease of Use 34 6.6.2 Costs 34 6.6.3 Data Completeness 34 7 Performance Summary 43 8 References 45 Appendix A Reference Sample and Probe Readings A-l Figures Figure 2-1. General Oceanics, Inc., Ocean Seven 316 Water Probe 2 Figure 3-1. Saltwater Site 5 Figure 3-2. Freshwater Site 6 Figure 3-3. Mesocosm Tanks 6 Figure 3-4. Saltwater Deployment 9 Figure 6-la. Dissolved Oxygen Data Collected from GO 204 and GO 205 During the Verification Test 20 Figure 6-lb. Conductivity Data Collected from GO 204 and GO 205 During the Verification Test 21 Figure 6-lc. Temperature Data Collected from GO 204 and GO 205 During the Verification Test 22 Figure 6-Id. pH Data Collected from GO 204 and GO 205 During the Verification Test 23 Figure 6-le. Turbidity Data Collected from GO 204 and GO 205 During the Verification Test 24 Figure 6-2. Percent Accuracy of GO 204 and GO 205 During Calibration Checks 28 vi ------- Figure 6-3a. Relative Bias Data for Temperature 29 Figure 6-3b. Relative Bias Data for Conductivity 29 Figure 6-3c. Relative Bias Data for Dissolved Oxygen 30 Figure 6-3d. Relative Bias Data for pH 30 Figure 6-3e. Relative Bias Data for Turbidity 31 Figure 6-4a. Inter-Unit Reproducibility Data for Temperature During Saltwater Tests 35 Figure 6-4b. Inter-Unit Reproducibility Data for Temperature During Freshwater Tests 35 Figure 6-4c. Inter-Unit Reproducibility Data for Temperature During Mesocosm Tests 36 Figure 6-5a. Inter-Unit Reproducibility Data for Conductivity During Saltwater Tests 36 Figure 6-5b. Inter-Unit Reproducibility Data for Conductivity During Freshwater Tests .... 37 Figure 6-5c. Inter-Unit Reproducibility Data for Conductivity During Mesocosm Tests .... 37 Figure 6-6a. Inter-Unit Reproducibility Data for Dissolved Oxygen During Saltwater Tests 38 Figure 6-6b. Inter-Unit Reproducibility Data for Dissolved Oxygen During Freshwater Tests 38 Figure 6-6c. Inter-Unit Reproducibility Data for Dissolved Oxygen During Mesocosm Tests 39 Figure 6-7a. Inter-Unit Reproducibility Data for pH During Saltwater Tests 39 Figure 6-7b. Inter-Unit Reproducibility Data for pH During Freshwater Tests 40 Figure 6-7c. Inter-Unit Reproducibility Data for pH During Mesocosm Tests 40 Figure 6-8a. Inter-Unit Reproducibility Data for Turbidity During Saltwater Tests 41 Figure 6-8b. Inter-Unit Reproducibility Data for Turbidity During Freshwater Tests 41 Figure 6-8c. Inter-Unit Reproducibility Data for Turbidity During Mesocosm Tests 42 vii ------- Tables Table 3-1. Water Characteristics at the Test Sites 5 Table 3-2. Schedule for the Ocean Seven 316 Verification Test 7 Table 3-3. Schedule for Saltwater Sample Collection 8 Table 3-4. Schedule for Freshwater Sample Collection 10 Table 3-5. Schedule for Mesocosm Sample Collection 11 Table 3-6. Maximum Sample Holding Times 12 Table 4-1. Replicate Analysis Results 14 Table 4-2. Summary of Performance Evaluation Audits 14 Table 4-3. Summary of Data Recording Process 16 Table 6-1 a. Results from the Pre- and Post-Calibration Tests for GO 204 and GO 205 in Saltwater 26 Table 6-lb. Results from the Pre- and Post-Calibration Tests for GO 204 and GO 205 in Freshwater 27 Table 6-1 c. Results from the Pre- and Post-Calibration Tests for GO 204 and GO 205 in Mesocosm 27 Table 6-2. Average Relative Bias Results for GO 204 and GO 205 31 Table 6-3. Percent Relative Standard Deviation for GO 204 and GO 205 During Periods of Stable Operation 32 Table 6-4. Results of Linearity Analysis for GO 204 and GO 205 33 Table 6-5. Average Difference in GO 204 and GO 205 Readings for Each Parameter at Each Deployment Location 34 viii ------- List of Abbreviations AMS Advanced Monitoring Systems CCEHBR Center for Coastal Environmental Health and Biomolecular Research cm centimeter DAS data acquisition system DO dissolved oxygen EPA U.S. Environmental Protection Agency ETV Environmental Technology Verification L liter mg milligram mm millimeter ms millisecond mS millisiemen NIST National Institute of Standards and Technology NOAA National Oceanic and Atmospheric Administration NTU nephelometric turbidity unit PE performance evaluation QA quality assurance QA/QC quality assurance/quality control QMP Quality Management Plan RSD relative standard deviation s second TSA technical systems audit IX ------- Chapter 1 Background The U.S. Environmental Protection Agency (EPA) has created the Environmental Technology Verification (ETV) Program to facilitate the deployment of innovative environmental tech- nologies through performance verification and dissemination of information. The goal of the ETV Program is to further environmental protection by substantially accelerating the acceptance and use of improved and cost-effective technologies. ETV seeks to achieve this goal by provid- ing high-quality, peer-reviewed data on technology performance to those involved in the design, distribution, financing, permitting, purchase, and use of environmental technologies. ETV works in partnership with recognized testing organizations; with stakeholder groups consisting of buyers, vendor organizations, and permitters; and with the full participation of individual technology developers. The program evaluates the performance of innovative tech- nologies by developing test plans that are responsive to the needs of stakeholders, conducting field or laboratory tests (as appropriate), collecting and analyzing data, and preparing peer- reviewed reports. All evaluations are conducted in accordance with rigorous quality assurance (QA) protocols to ensure that data of known and adequate quality are generated and that the results are defensible. The EPA's National Exposure Research Laboratory and its verification organization partner, Battelle, operate the Advanced Monitoring Systems (AMS) Center under ETV. The AMS Center recently evaluated the performance of the General Oceanics, Inc., Ocean Seven 316 water probe. 1 ------- Chapter 2 Technology Description The objective of the ETV AMS Center is to verify the performance characteristics of environmental monitoring technologies for air, water, and soil. This verification report provides results for the verification testing of the Ocean Seven 316 water probe by General Oceanics, Inc. Following is a description of the Ocean Seven 316, based on information provided by the vendor. The information provided below was not verified in this test. The 16-bit, multi-parameter Ocean Seven 316 is available with two diameters: 100 millimeter (mm) and 75 mm. The measurement sensors have time constants of 50 milliseconds (ms) for physical parameters and 3 seconds (s) for chemical parameters. A high-precision resistor acts as a reference for the accuracy of the sensor electronic amplifiers. This resistor has a thermal drift of 1 part per million/°C and is temperature-compensated. The Ocean Seven 316 is microprocessor-controlled and can measure, store, and transmit sensor data. For real-time data acquisition, the Ocean Seven 316 operates unattended, and data are uploaded at the end of the measuring cycle. An automatic power management procedure switches the Ocean Seven 316 off between the data acquisitions. The internal battery package consists of 10 batteries that allow the Ocean Seven 316 to operate continuously for about 20 hours. The Ocean Seven 316 can be equipped with an external battery package that greatly extends operation time. The Ocean Seven 316 stores up to 32,000 data sets. Figure 2-1. General Oceanics, Inc., Ocean Seven 316 Water Probe 2 ------- The Ocean Seven 316 is equipped with sensors to measure pressure, temperature, conductivity, salinity, oxygen, pH, and oxidation-reduction potential. Salinity is automatically calculated from conductivity, temperature, and pressure values. The sensor specifications for the parameters tested are as follows: Parameter Dissolved Oxygen (DO) Conductivity Temperature PH (a)In air (b)At 1 m/sec flow rate Range 0 to 50 milligrams/ liter (mg/L) 0 to 500% sat. 0 to 64 millisiemen/ centimeter (mS/cm) -3 to +50°C Oto 14 Accuracy 0.1 mg/L 1% sat. 0.003 mS/cm 0.003°C 0.01 Resolution 0.01 mg/L 0.1% sat. 0.001 mS/cm 0.0005°C 0.001 Time Constant 3 s(a) 3 s 50 ms® 50 ms 3 s 3 ------- Chapter 3 Test Design and Procedures 3.1 Introduction This verification test was conducted according to procedures specified in the Test/QA Plan for Long-Term Deployment of Multi-Parameter Water Quality Probes Sondes01 The purpose of the verification test was to evaluate the performance of the Ocean Seven 316 under realistic operating conditions. The Ocean Seven 316s were evaluated by comparing pre- and post- calibration results and their measurements with standard reference measurements and handheld calibrated probes. Two Ocean Seven 316s were deployed in saltwater, freshwater, and laboratory environments near Charleston, South Carolina, during a 2 '/2-month verification test. Water quality parameters were measured by both the Ocean Seven 316s and by reference measurements consisting of both field portable instrumentation and water analyses of collected samples. During each phase, performance was assessed in terms of pre- and post-calibration results, relative bias, precision, linearity, and inter-unit reproducibility for each Ocean Seven 316. The Ocean Seven 316s were verified in terms of its performance on the following parameters: ¦ DO ¦ Conductivity ¦ Temperature ¦ pH ¦ Turbidity. 3.2 Test Site Characteristics The three test sites used for this verification were selected in an attempt to expose the Ocean Seven 316 to the widest possible range of conditions while conducting an efficient test. The three sites included one saltwater, one freshwater, and one controlled location. Approximate ranges for the target parameters at each of the test sites as determined by reference measurements are given in Table 3-1. 4 ------- Table 3-1. Water Characteristics at the Test Sites Saltwater F reshwater Mesocosm Parameter Low High Low High Low High DO 3 mg/L 7.3 mg/L 1.2 mg/L 13.4 mg/L 3.7 mg/L 7.3 mg/L Conductivity 20 mS/cm 40 mS/cm 0.2 mS/cm 0.45 mS/cm 0.5 mS/cm 38 mS/cm Temperature 28°C 32°C 20°C 35°C 24°C 31°C pH 7 8 6 9 7.3 8.5 Turbiditv 3 NTU 11 NTU 0.1 NTU 20 NTU 0.1 NTU 130 NTU 3.3 Test Design The verification test was designed to assess the performance of multi-parameter water probes and was closely coordinated with the National Oceanic and Atmospheric Administration (NOAA) through the CCEHBR. The test was conducted in three phases at a saltwater site in the Cooper River; a freshwater site at Lake Edmunds, approximately one mile from the Center for Coastal Environmental Health and Biomolecular Research (CCEHBR), and a controlled site at the CCEHBR mesocosm facility in Charleston, South Carolina. The first phase of the test was conducted at the saltwater site and lasted 31 days. The CCEHBR campus has access to the Charleston Harbor Estuary, which is a predominantly tidal body of water that receives some riverine input; its salinities range from 20 to 35 parts per thousand. Figure 3-1 shows the saltwater site at the Cooper River. The second phase of the test was conducted at the freshwater site and lasted 24 days. The freshwater site was at a five-acre pond, named Lake Edmunds, approximately one mile from the CCEHBR facility. Figure 3-2 shows the freshwater site. The third phase was conducted over seven days at the CCEHBR's mesocosm facility. This facility contains modular mesocosms that can be classified as "tidal" or "estuarine." Figure 3-3 shows one of the modular mesocosms. At each test site, two Ocean Seven 316s were deployed as close to each other as possible to assess inter-unit reproducibility. Figure 3-1. Saltwater Site The schedule for the various testing activities is given in Table 3-2. The saltwater tests began in a small tidal creek tributary of the Charleston Harbor near the CCEHBR facilities. Testing at this location lasted approximately two weeks, but had to be discontinued due to a structural failure of the pier. A new site at NOAA Pier Romeo on the Cooper River was selected to complete the testing. This site is approximately 10 miles from the CCEHBR facility and is operated by NOAA's Coastal Services Center. 5 ------- am#* Figure 3-2. Freshwater Site Figure 3-3. Mesocosm Tanks 6 ------- Table 3-2. Schedule for the Ocean Seven 316 Verification Test Activity Date Vendor setup Begin saltwater test at CCEHBR small tidal creek End saltwater test at CCEHBR small tidal creek due to structural failure Setup at Cooper River (Pier Romeo) Begin saltwater test End saltwater test Set up freshwater test at Lake Edmunds Begin freshwater test End freshwater test Vendor setup for mesocosm test at CCEHBR Begin mesocosm test End mesocosm test Vendor removal of equipment June 10 June 17 July 9 July 11 July 15 August 14 August 19 August 21 September 13 September 16 September 19 September 25 September 30 3.3.1 Saltwater Testing Saltwater testing was conducted at two locations. The planned location was in the Charleston River near the NOAA CCEHBR facility. However, due to structural problems at that site, the probes were redeployed in the Charleston Harbor to NOAA Pier Romeo. Pre- and post- calibration data obtained at the first location are presented in Section 6.1 of this report; however, no additional data from that location are available. The saltwater test lasted for 31 days, during which time the Ocean Seven 316s monitored the naturally occurring range of the target parameters 24 hours a day, while dockside reference measurements were made, and reference samples for turbidity were collected. The Ocean Seven 316s were mounted on iron posts that were driven into the river bed. The instruments were approximately 0.5 meters apart (Figure 3-4) in the shallows of the Cooper River. Samples were collected in rotation during the morning, afternoon, and evening hours throughout the test. More intense sampling occurred at the beginning (Days 1 and 2) and the end (Days 29 and 30) of the sampling period, when samples were taken at 15-minute intervals for eight hours, except on Day 29, when only four hours of sampling occurred because of weather conditions. For the duration of the test, the Ocean Seven 316s were deployed at depths between approximately three and 10 feet, varying according to the tide. Table 3-3 shows the times and numbers of samples taken throughout the saltwater test period. Aside from the initial setup days (July 11 through 14), the Ocean Seven 316s were deployed and collecting data approximately every 15 minutes on the days indicated in Table 3-3. 7 ------- Table 3-3. Schedule for Saltwater Sample Collection Test Day of # Reference # Field # Duplicate Day Week Date Samples Blanks Samples Location Thu 11 -Jul-02 Pier Romeo Fri 12-M-02 Pier Romeo Sat 13-M-02 Pier Romeo Sun 14-M-02 Pier Romeo 1 Mon 15-M-02 16 Pier Romeo 2 Tue 16-Jul-02 16 Pier Romeo 3 Wed 17-Jul-02 3 1 1 Pier Romeo 4 Thu 18-Jul-02 Laboratory 5 Fri 19-Jul-02 Laboratory 6 Sat 20-Jul-02 Pier Romeo 7 Sun 21-Jul-02 Pier Romeo 8 Mon 22-Jul-02 2 Pier Romeo 9 Tue 23-Jul-02 Pier Romeo 10 Wed 24-Jul-02 3 1 1 Pier Romeo 11 Thu 25-July-02 2 1 Pier Romeo 12 Fri 26-Jul-02 Laboratory 13 Sat 27-Jul-02 Laboratory 14 Sun 28-Jul-02 Laboratory 15 Mon 29-Jul-02 Laboratory 16 Tue 30-Jul-02 Laboratory 17 Wed 31 -Jul-02 Laboratory 18 Thu 01 -Aug-02 Laboratory 19 Fri 02-Aug-02 1 1 Pier Romeo 20 Sat 03-Aug-02 Pier Romeo 21 Sun 04-Aug-02 Pier Romeo 22 Mon 05-Aug-02 1 1 Pier Romeo 23 Tue 06-Aug-02 2 2 1 Pier Romeo 24 Wed 07-Aug-02 3 1 1 Pier Romeo 25 Thu 08-Aug-02 Pier Romeo 26 Fri 09-Aug-02 Pier Romeo 27 Sat 10-Aug-02 Pier Romeo 28 Sun 11-Aug-02 Pier Romeo 29 Mon 12-Aug-02 7 Pier Romeo 30 Tue 13-Aug-02 16 Pier Romeo 31 Wed 14-Aug-02 Pier Romeo 8 ------- Figure 3-4. Saltwater Deployment 3.3.2 Freshwater Testing Freshwater testing was conducted at Lake Edmunds. Because this site is shallower than Charleston Harbor, samples were taken at only one depth (approximately 0.3 meters). As in the saltwater portion of the verification test, the Ocean Seven 316s monitored the naturally occurring target parameters 24 hours a day, while reference measurements were made and turbidity reference samples collected, again rotating among collection times. More intense sampling occurred at the beginning (Day 3) and the end (Day 23) of the sampling period, when samples were taken at 15- to 30-minute intervals for periods ranging between six and eight hours, as weather permitted. Table 3-4 shows the sampling times and number of samples collected throughout the freshwater test period. The Ocean Seven 316s were tethered with cable ties to large posts driven into the bottom of the lake. 9 ------- Table 3-4. Schedule for Freshwater Sample Collection Test Day of Reference # Field # Duplicate Day Week Date Samples Blanks Samples Location Mon 19-Aug-02 Laboratory Tue 20-Aug-02 Laboratory 1 Wed 21 -Aug-02 Lake Edmunds 2 Thu 22-Aug-02 Lake Edmunds 3 Fri 23-Aug-02 16 Lake Edmunds 4 Sat 24-Aug-02 Lake Edmunds 5 Sun 25-Aug-02 Lake Edmunds 6 Mon 26-Aug-02 4 Lake Edmunds 7 Tue 27-Aug-02 Lake Edmunds 8 Wed 28-Aug-02 2 1 1 Lake Edmunds 9 Thu 29-Aug-02 Laboratory 10 Fri 30-Aug-02 Laboratory 11 Sat 31-Aug-02 Lake Edmunds 12 Sun 01-Sep-02 Lake Edmunds 13 Mon 02-Sep-02 Lake Edmunds 14 Tue 03-Sep-02 Lake Edmunds 15 Wed 04-Sep-02 1 1 Lake Edmunds 16 Thu 05-Sep-02 2 1 1 Laboratory 17 Fri 06-Sep-02 Laboratory 18 Sat 07-Sep-02 Lake Edmunds 19 Sun 08-Sep-02 Lake Edmunds 20 Mon 09-Sep-02 3 1 Lake Edmunds 21 Tue 10-Sep-02 3 1 Lake Edmunds 22 Wed ll-Sep-02 Lake Edmunds 23 Thu 12-Sep-02 12 Lake Edmunds 24 Fri 13-Sep-02 Laboratory 10 ------- 3.3.3 Mesocosm Testing Mesocosm testing was performed according to the schedule shown in Table 3-5. The mesocosm tanks were filled with water and drained twice daily, simulating a semi-diurnal tidal cycle. Reference measurements were made and water samples were collected during each test day throughout the normal operating hours of the facility (nominally 6 a.m. to 6 p.m.). During this period, the mesocosm was manipulated to introduce variations in the measured parameters. The turbidity of the system was varied by operating a pump near the sediment trays to suspend additional solids in the water. Conductivity was varied by adding freshwater to the saltwater during one of the fill-and-drain cycles. Variations in temperature, pH, and DO were driven by natural forces and the changes in the other test parameters. Parameters over the ranges specified in Table 3-1 were monitored by the Ocean Seven 316. Each collected sample was analyzed using a reference method for comparison. Table 3-5. Schedule for Mesocosm Sample Collection Test Day of # Reference # Field # Duplicate Day Week Date Samples Blanks Samples Location Mon 16-Sep-02 Laboratory Tue 17-Sep-02 Laboratory Wed 18-Sep-02 Laboratory 1 Thu 19-Sep-02 2 Mesocosm 2 Fri 20-Sep-02 5a Mesocosm 3 Sat 21-Sep-02 Mesocosm 4 Sun 22-Sep-02 Mesocosm 5 Mon 23-Sep-02 6b Mesocosm 6 Tue 24-Sep-02 6c'd Mesocosm 7 Wed 25-Sep-02 1 1 1 Mesocosm Thu 26-Sep-02 Laboratory Fri 27-Sep-02 Laboratory a Stir sediment. b Turn off aeration pump. c Turn on aeration pump. d Add freshwater. 11 ------- 3.4 Materials and Equipment The reference equipment used in this verification test was selected for the specific parameters, as follows: ¦ DO—National Institute of Standards and Technology (NIST)-traceable, commercially available probe (Orion 83 OA) ¦ Conductivity—NIST-traceable, handheld conductivity meter (Oakton 35631-00) ¦ Temperature—NIST-traceable, handheld thermocouple and readout (Orion 830A) ¦ pH—NIST-traceable, handheld pH meter (Oakton 35631 -00) ¦ Turbidity—Hach Ratio XR turbidity meter (Hach 43900). Reagents were distilled deionized water (for field blanks) and a Hach Ratio XR turbidity standard from Advanced Polymer Systems. Sampling equipment consisted of 0.5- to 1.0-L glass bottles, a Niskin sampling device provided by CCEHBR, and provisions for sample storage. The maximum sample holding times are given in Table 3-6. All sample holding time requirements were met. Table 3-6. Maximum Sample Holding Times Parameter Holding Time DO none(a) Conductivity none Temperature none pH none Turbidity 24 hours (a) "None" indicates that the sample analysis must be performed immediately after sample collection or in the water column at the site. 12 ------- Chapter 4 Quality Assurance/Quality Control Quality assurance/quality control (QA/QC) procedures were performed in accordance with the quality management plan (QMP) for the AMS Center(2) and the test/QA plan for this verification test.(1) 4.1 Instrument Calibration Both the portable and laboratory reference instruments were calibrated by CCEHBR according to the procedures and schedules in place at the test facility, and documentation was provided to Battelle. 4.2 Field Quality Control Field blanks and laboratory duplicate samples were taken at the times shown in Tables 3-3 through 3-5. The field blank was a container of deionized water taken to the field and then brought back to the laboratory. It was analyzed in the same manner as the collected samples. The laboratory replicate samples were collected once each week during a regular sampling period. These replicate samples were the field sample split in the field into two separate samples (containers) and analyzed by the same methods. The results from the replicate analysis were within the expected values shown in Table 4-1. The results for the field blanks were within the expected tolerances. 4.3 Sample Custody Samples collected at the saltwater and freshwater sites were transported to the laboratory in an ice-filled cooler. 13 ------- Table 4-1. Replicate Analysis Results Parameter Anticipated Interval of Results DO ±5% Conductivity ±5% Temp erature ± 1 ° C pH ±0.1 Turbidity ±5 NTU 4.4 Audits 4.4.1 Performance Evaluation Audit A performance evaluation (PE) audit was conducted by the Battelle Verification Test Coordinator once during the verification test to assess the quality of the reference measurements. For the PE audit, an independent standard was used. Table 4-2 shows the procedures used for the PE audit and associated results. Table 4-2. Summary of Performance Evaluation Audits Audited Parameter Audit Procedure Acceptable Tolerance Actual Difference Passed Audit DO Independent monitor ±5% 6.7% No(a) Conductivity Independent monitor ±5% 0.6% Yes Temperature Independent monitor ±rc 0.2°C Yes pH Independent monitor ±0.1 pH 0.04 pH Yes Turbidity Independent turbidity standard ±10% 0.4% Yes (a) Although the measurement recorded during the PE audit was outside the acceptable tolerance, this measurement was repeated 111 times during the verification test. The average agreement during the verification test was 0.2%; therefore, no corrective action was taken. The DO measurement made by the Orion 83OA was compared with that from a handheld DO monitor made by Hanna (94130M). Agreement within 6.7% was achieved. Although this measurement was outside the acceptable tolerance, the measurement was, in fact, repeated 111 times during the verification test, with an average difference of 0.2%, indicating acceptable performance of the reference monitor. A handheld conductivity meter made by Hanna (HI 983 5) was used to perform the conductivity audit. Agreement within 0.6% between the results of the Hanna meter and those of the Oakton reference meter was seen. A NIST-traceable mercury-in-glass thermometer was used for the temperature performance audit. The comparison was made with a sample of collected water, and agreement was within 0.2°C. The handheld pH reference meter from Oakton was compared with a handheld pH meter made by Hanna (991301). 14 ------- A pH tolerance of 0.04% was recorded. The Hach turbidity meter measurements were compared with an independent turbidity standard. Agreement within 0.4% was observed. 4.4.2 Technical Systems Audit The Battelle Quality Manager conducted a technical systems audit (TSA) on August 28, 2002, to ensure that the verification test was performed in accordance with the test/QA plan(1) and the AMS Center QMP.(2) As part of the audit, the Battelle Quality Manager reviewed the reference methods used, compared actual test procedures to those specified in the test/QA plan, and reviewed data acquisition and handling procedures. Observations and findings from this audit were documented and submitted to the Battelle Verification Test Coordinator for response. No findings were documented that required any corrective action. The records concerning the TSA are permanently stored with the Battelle Quality Manager. During the verification test, three deviations from the test/QA plan were necessary. The first was because the manufacturer's instructions required a different calibration frequency than the test/QA plan for pH, conductivity, and turbidity measurements. Because the calibrations were within the specified range during each calibration, it was determined that there was no impact on the verification test. The second and third deviations were that the sampling frequency and total number of samples were different than stated in the test/QA plan. Samples were taken at 15- instead of 30-minute intervals because, in some cases, sampling went faster than anticipated; and weather and environmental conditions required ending the deployment sooner than specified by the test/QA plan, resulting in fewer samples. 4.4.3 Audit of Data Quality At least 10%) of the data acquired during the verification test were audited. Battelle's Quality Manager traced the data from the initial acquisition, through reduction and statistical analysis, to final reporting, to ensure the integrity of the reported results. All calculations performed on the data undergoing the audit were checked. 4.5 QA/QC Reporting Each assessment and audit was documented in accordance with Sections 3.3.4 and 3.3.5 of the QMP for the ETV AMS Center.(2) Once the assessment report was prepared, the Verification Test Coordinator ensured that a response was provided for each adverse finding or potential problem and implemented any necessary follow-up corrective action. The Battelle Quality Manager ensured that follow-up corrective action was taken. The results of the TSA were sent to the EPA. 4.6 Data Review Records generated in the verification test were reviewed within two weeks of generation before these records were used to calculate, evaluate, or report verification results. Table 4-3 summarizes 15 ------- the types of data recorded. The review was performed by a technical staff member involved in the verification test, but not the staff member who originally generated the record. The person performing the review added his/her initials and the date to a hard copy of the record being reviewed. Table 4-3. Summary of Data Recording Process Data to be Recorded Responsible Party Where Recorded How Often Recorded Disposition of Data Dates, times of test events CCEHBR Laboratory record books/data sheets Start/end of test; at each change of a test parameter; at sample collection Used to organize/ check test results; manually incorporated data into spreadsheets - stored in study binder Test parameters Battelle/ CCEHBR Laboratory record books/ data sheets Each sample collection Used to organize/ check test results; manually incorporated data into spreadsheets - stored in study binder Ocean Seven 316 data - digital display - electronic output CCEHBR CCEHBR Data sheets Probe data acquisition system (DAS); data stored on probe downloaded to PC Continuous fifteen- minute sampling; data downloaded to PC Used to organize/ check test results; incorporated data into electronic spread- sheets - stored in study binder Reference monitor readings/reference analytical results CCEHBR Laboratory record book/data sheets or data management system, as appropriate After each batch sample collection; data recorded after reference method performed Used to organize/ check test results; manually incorporated data into spreadsheets - stored in study binder Reference calibration data CCEHBR Laboratory record books/ data sheets/DAS Whenever zero and calibration checks are done Documented correct performance of reference methods PE audit results Battelle Laboratory record books/ data sheets/DAS At times of PE audits Test reference methods with independent standards/ measurements 16 ------- Chapter 5 Statistical Methods The statistical methods presented in this chapter were used to verify the performance parameters listed in Section 3.1. 5.1 Pre- and Post-Calibration Results Pre- and post-calibration of the Ocean Seven 316s was done for each measured parameter according to that vendor's instruction manual. The results from the calibration checks were summarized, and accuracy was determined each time the calibration check was conducted. Calibration check accuracy (A) is reported as a percentage, calculated using the following equation: Where Cs is the value of the reference standard, and Cp is the value measured by the vendor's probe. 5.2 Relative Bias Water samples were analyzed by both the reference method and the Ocean Seven 316, and the results were compared. The results for each sample were recorded, and the accuracy was expressed in terms of the average relative bias (B), as calculated from the following equation: where CP is a measurement taken from the Ocean Seven 316 being verified at the same time as the reference measurement was taken, and Cs is the reference measurement. This calculation was performed for each reference sample analysis for each of the five target water parameters. Readings of pH were converted to H+ concentration, and temperature readings were converted to absolute units (i.e., Kelvin) prior to making this calculation. Relative bias was assessed independently for each Ocean Seven 316 to determine inter-unit reproducibility. a = i- (c, - cpyc, x ioo (i) C -C B= — — x 100 Cs (2) 17 ------- 5.3 Precision The standard deviation (S) of the measurements made during a period of stable operation at the mesocosm was calculated and used as a measure of probe precision: where n is the number of replicate measurements, Ck is the concentration reported for the kth measurement, and C is the average concentration of the replicate measurements. Precision was calculated for each of the five target water parameters. Probe precision was reported in terms of the percent relative standard deviation (RSD) of the series of measurements: 5.4 Linearity For target water parameters with a wide range of variation, linearity was assessed by linear regression, with the analyte concentration measured by the reference method as an independent variable and the reading from the analyzer verified as a dependent variable. Linearity is expressed in terms of the slope, intercept, and coefficient of determination (r2). Linearity for pH was assessed by converting pH results to H+ concentration before comparison. Linearity was assessed separately for each Ocean Seven 316 and for the data generated at each of the saltwater, freshwater, and mesocosm test sites. 5.5 Inter-Unit Reproducibility The results obtained from the two Ocean Seven 316s were compiled independently for each analyzer and compared to assess inter-unit reproducibility. Inter-unit reproducibility was determined by calculating the average absolute difference between the two Ocean Seven 316s. In addition, the two Ocean Seven 316s were compared by evaluating the relative bias of each. —I" (Ct-cf n -1 k=1 1/2 (3) %RSD = = * 100 C (4) 18 ------- Chapter 6 Test Results The results of the verification of the two Ocean Seven 316s (identified as GO 204 and GO 205 in this report) are presented in this section. The Ocean Seven 316 data were recorded at 15-minute intervals throughout the verification test. Figures 6-1 a through e show plots of nearly 6,000 data points that were collected by the Ocean Seven 316s during this verification test and data points for the 132 reference samples that were collected and analyzed. (Figures 6-4 through 6-8 show parameter-specific data for each of the three tests, so much of the same data is presented as in Figure 6-la through e, but over a shorter period and with better time resolution). Reference sample results and corresponding Ocean Seven 316 readings are provided in Appendix A. The entire data set is presented in a graphical format in Figures 6-1 a through 6-1 e to allow several non-quantitative observations. First, a comparison of GO 204 and 205 and the reference measurements shows that, for each condition and parameter, the Ocean Seven 316s generally follow the trend of the reference measurements. A visual inspection of the GO 204 and GO 205 data for DO, conductivity, temperature, pH, and turbidity suggests that the GO 204 and 205 data generally agree with each other and the reference measurements. The DO measurements (Figure 6-1 a) show tidal and daily fluctuations, with the freshwater deployment showing the largest magnitude fluctuations. The conductivity measurements (Figure 6-lb) show that Ocean Seven 316s again track daily fluctuations from the saltwater environment, to the freshwater environment, and back to the mesocosm environment. Figure 6-lb also shows that the mesocosm conductivity measured in the saltwater environment closely agrees with the reference measurement during the transition from saltwater to freshwater on September 24, 2002, and back to saltwater. The temperature (Figure 6-1 c) and pH (Figure 6-1 d) measurements from the GO 204 and 205 are overlaid on their respective charts, and their close agreement makes it difficult to see the individual values. Finally, the turbidity measurements (Figure 6-le) made by the GO 204 and 205 follow the general trends of the reference measure- ments and generally agree with each other. It can be seen that on September 21, 2002, a spike in turbidity corresponded with the activation of the pump in the mesocosm. This increased level in turbidity was captured by both the GO 204 and 205, as well as the reference measurements. This report attempts to quantify the extent of agreement using the various statistical methods described in Chapter 5. 19 ------- Saltwater Freshwater Mesocosm O 204 x 205 ifcti 7/3/02 12:00 7/13/02 AM 12:00 AM 7/23/02 8/2/02 12:00 8/12/02 8/22/02 9/1/02 12:00 9/11/02 12:00 AM AM 12:00 AM 12:00 AM AM 12:00 AM 9/21/02 10/1/02 12:00 AM 12:00 AM Date and Time Figure 6-la. Dissolved Oxygen Data Collected from GO 204 and GO 205 During the Verification Test ------- O 204 x 205 Sa twater Freshwater Mesocosm 7/3/02 12:00 7/13/02 7/23/02 8/2/02 12:00 8/12/02 8/22/02 9/1/02 12:00 9/11/02 AM 12:00 AM 12:00 AM AM 12:00 AM 12:00 AM AM 12:00 AM 9/21/02 10/1/02 12:00 AM 12:00 AM Date and Time Figure 6-lb. Conductivity Data Collected from GO 204 and GO 205 During the Verification Test ------- 9 8 O204 x 205 Mesocosm Saltwater Freshwater 7/3/02 12:00 7/13/02 AM 12:00 AM 7/23/02 8/2/02 12:00 8/12/02 8/22/02 9/1/02 12:00 9/11/02 12:00 AM AM 12:00 AM 12:00 AM AM 12:00 AM Date and Time 9/21/02 10/1/02 12:00 AM 12:00 AM Figure 6-lc. Temperature Data Collected from GO 204 and GO 205 During the Verification Test ------- to LtJ 11 10 x Q. O 204 x 205 Reference M Saltwater Mesocosm Fmshwatpr 7/3/02 12:00 7/13/02 AM 12:00 AM 7/23/02 8/2/02 12:00 8/12/02 8/22/02 9/1/02 12:00 9/11/02 9/21/02 10/1/02 12:00 AM AM 12:00 AM 12:00 AM AM 12:00 AM 12:00 AM 12:00 AM Date and Time Figure 6-ld. pH Data Collected from GO 204 and GO 205 During the Verification Test ------- 200 to 180 160 140 120 ^ 100 ¦g !q Freshwater Mesocosm Saltwater O 204 x 205 Reference 7/3/02 12:00 7/13/02 7/23/02 8/2/02 12:00 8/12/02 8/22/02 9/1/02 12:00 9/11/02 9/21/02 10/1/02 AM 12:00 AM 12:00 AM AM 12:00 AM 12:00 AM AM 12:00 AM 12:00 AM 12:00 AM Date and Time Figure 6-1 e. Turbidity Data Collected from GO 204 and GO 205 During the Verification Test ------- 6.1 Pre- and Post-Calibration Results The Ocean Seven 316s were calibrated at the beginning and end of each deployment period (noted as "in Laboratory" in Tables 3-3, 3-4, and 3-5). The only exception to this was on July 29, 2002, when battery problems prevented a calibration check from being performed on the GO 205. The calibration was checked periodically throughout the deployments to monitor how well the probes held the original calibrations. This operation was performed for pH, conductivity, and DO since only those parameters are adjusted during the calibration. The calibration check levels were selected based on the manufacturer's instructions. Tables 6-1 a, b, and c show the results from these calibration checks for the saltwater, freshwater, and mesocosm tests. Figure 6-2 is a graphical representation of these calibration results. The "Reference Standard" column refers to the listed concentration of the standards used in the calibrations, the "GO 204 and GO 205 Readings" columns give the Ocean Seven 316 results during the calibration checks, and the "GO 204 and GO 205 % Accuracy" columns show the calibration check accuracy using the calculations given in Section 5.1. The accuracy for the pH tests ranged from 99% to 108%, for the conductivity tests from 94% to 104%), and for the DO tests from 82% to 105%. 25 ------- Table 6-la. Results from the Pre- and Post-Calibration Tests for GO 204 and GO 205 in Saltwater(a) Reference Standard GO 204 Readings GO 205 Readings GO 204 % Accuracy GO 205 % Accuracy Date pH"" Con- ductivity (mS/cm) DO (%) PH Con- ductivity (mS/cm) DO (%) PH Con- ductivity (mS/cm) DO (%) PH Conductivity DO PH Con- ductivity DO 6/25/2002 7.00 10.00 100 7.065 9.934 104.5 6.99 10.02 91.4 101 99 105 100 100 91 6/25/2002 10.00 10.1 10.02 101 100 7/11/2002 7.00 10.00 100 7.086 9.917 100.5 7.03 10.04 90.7 101 99 101 100 100 91 7/19/2002 7.00 10.04 100 7.145 9.7 96.5 7.11 9.82 95.7 102 97 97 102 98 96 7/19/2002 10.00 -- -- 10.09 -- -- 10.03 -- -- 101 -- -- 100 -- -- 7/29/2002 7.00 12.88 100 7.061 13.42 98 NA NA NA 101 104 98 NA NA NA 7/29/2002 10.00 -- -- 10.02 -- -- NA -- -- 100 -- -- NA -- -- 8/1/2002 7.00 10.00 100 7.00 10.00 100 7.00 10.00 100 100 100 100 100 100 100 8/1/2002 10.00 -- -- 10.00 -- -- 10.00 -- -- 100 -- -- 100 -- -- 8/20/2002 7.00 12.88 100 6.933 12.52 99.6 7.11 12.56 103.3 99 97 100 102 98 103 (a) Shaded section is from first saltwater deployment. (b) The pH calibration checks were performed at two levels, using two separate solutions, while conductivity and DO were checked at one level. NA= No calibration check was performed because of battery problems. ------- Table 6-lb. Results from the Pre- and Post-Calibration Tests for GO 204 and GO 205 in Freshwater Reference Standard GO 204 Results GO 205 Results GO 204 % Accuracy GO 205 % Accuracy Con- Con- Con- ductivity DO ductivity DO ductivity DO Con- Con- Date PH (mS/cm) (%) PH (mS/cm) (%) PH (mS/cm) (%) PH ductivity DO PH ductivity DO 8/19/2002 7.00 12.88 100 7 12.88 100 7.00 12.88 100 100 100 100 100 100 100 8/19/2002 10.00 -- 10 -- -- 10 -- 100 100 -- -- 100 -- 8/29/2002 7.00 1.41 100 7.22 1.34 87.7 7.01 1.33 103.3 103 95 88 100 94 103 8/29/2002 10.00 -- 10.18 -- -- 10.00 -- -- 102 -- -- 100 -- 9/6/2002 7.00 1.41 100 7.38 1.41 90.8 7.151 1.4 98.1 105 100 91 102 99 98 9/6/2002 10.00 -- 10.3 -- -- 10.09 -- -- 103 -- -- 101 -- 9/17/2002 7.01 1.411 100 7.59 1.41 82 -- -- -- 108 100 82 -- -- 9/18/2002 7.01 1.41 100 — — — 7.32 1.37 102.5 — — — 104 97 103 Table 6-lc. Results from the Pre- and Post-Calibration Tests for GO 204 and GO 205 in Mesocosm Reference Standard GO 204 Results GO 205 Results GO 204 % Accuracy GO 205 % Accuracy Con- Con- Con- ductivity DO ductivity DO ductivity Con- Con- Date PH (mS/cm) (%) PH (mS/cm) (%) PH (mS/cm) DO (%) PH ductivity DO PH ductivity DO 9/25/2002 7.00 1.41 100 7.11 1.42 105 7.17 1.42 97.4 102 101 105 103 100 97 9/25/2002 10.00 -- 9.99 -- -- 10.04 -- -- 100 -- -- 100 -- ------- 40 20 0 6/13/2002 7/3/2002 7/23/2002 8/12/2002 9/1/2002 9/21/2002 10/11/2002 Date Figure 6-2. Percent Accuracy of GO 204 and GO 205 During Calibration Checks 6.2 Relative Bias Relative bias was assessed by comparing the reference measurements with the GO 204 and GO 205 readings. The reading that correlated most closely in time to the reference sample was used. Plots of the GO 204 and GO 205 data, along with the corresponding reference measurements that were used for the relative bias calculations, are shown in Figures 6-3a through e. The relative bias is summarized in Table 6-2. The temperature biases were less than or equal to 0.11% for all deployment settings. Conductivity, pH (reported as FT concentration), and DO biases were between approximately 2 and 36% for both units for all deployment settings. The conductivity bias was consistently positive, indicating that generally, the Ocean Seven 316s reported a higher conductivity than the handheld reference probe. The DO bias was consistently negative for each deployment setting. The bias for turbidity ranged between approximately -44% and 420%. From Figure 6-3e it can be seen that the turbidity measurements follow the trends of the reference measurements for the saltwater and mesocosm tests. The probes, in fact, capture the spike that occurred in the mesocosm test during a period of high turbidity. Inter-unit reproducibility was assessed by comparing the direction and size of the relative biases of the Ocean Seven 316s. In general, the Ocean Seven 316s exhibited close agreement for temperature, conductivity, and DO. ~ GO 204 fc Accuracy pH ¦ GO 204 f> Accuracy Conductivity GO 204 °y f> Accuracy DO X GO 205 °y f> Accuracy pH X GO 205 °y f> Accuracy Conductivity • GO 205 °y f> Accuracy DO 28 ------- A 0 204 « x 205 X Reference i * 0 X — j* o • X A o ft o V X U 8 ft X x *1 X * * 0 « * ** Saltwater Freshwater Mesocosm 7/3/02 12:00 7/13/02 7/23/02 8/2/02 12:00 8/12/02 8/22/02 9/1/02 12:00 9/11/02 9/21/02 10/1/1 12:00 AM 12:00 AM 12:00 AM 12:00 AM Date and Time 12:00 AM 12:00 AM 12:00 Figure 6-3a. Relative Bias Data for Temperature X Xy *s O * 6 * S PA f *. V Saltwater Freshwater Mesocosm O204 x 205 Reference O r\ r\ rv \ r\ # * i * 7/3/02 12:00 AM 7/13/02 12:00 AM 7/23/02 12:00 AM 8/2/02 12:00 AM 8/12/02 12:00 AM 8/22/02 12:00 AM 9/1/02 12:00 AM 9/11/02 12:00 AM 9/21/02 12:00 AM 10/1/02 12:00 Date and Time Figure 6-3b. Relative Bias Data for Conductivity 29 ------- 16 14 12 - 10 Saltwater Freshwater Mesocosm 0 204 x 205 Reference s i * * * „ 5 Ox O « 0 e xx " X X O x IL 8 e 5 x X * x £* x* & * X | V o o V A * X 0 1 7/3/02 12:00 AM 7/13/02 12:00 AM 7/23/02 12:00 AM 8/2/02 12:00 AM 8/12/02 12:00 AM 8/22/02 12:00 AM 9/1/02 12:00 AM 9/11/02 12:00 AM 9/21/02 12:00 AM 10/1/02 12:00 AM Date and Time Figure 6-3c. Relative Bias Data Test for Dissolved Oxygen 2.50E-06 - 1 50E-06 - O204 x 205 Reference 4 b h «~ K 4 0.00E+00 7/3/02 12: AM - t o 00 7/13/02 12:00 AM 7/23/02 12:00 AM 8/2/02 12:00 AM 8/12/02 12:00 AM 8/22/02 12:00 AM 9/1/02 12:00 AM 9/11/02 12:00 AM 9/21/02 12:00 AM 10/1/02 12:00 AM Date and Time Figure 6-3d. Relative Bias Data for pH 30 ------- 200 n 140 _ 120 £ 100 - 20 Saltwater Freshwater Mesocosm X 0 0 204 x 205 Reference o X o *0 0 X s X g t X CO X o o o 9 * oS * j? £ 7/3/02 12:00 7/13/02 7/23/02 8/2/02 12:00 8/12/02 8/22/02 9/1/02 12:00 9/11/02 9/21/02 10/1/02 AM 12:00 AM 12:00 AM AM 12:00 AM 12:00 AM AM 12:00 AM 12:00 AM 12:00 AM Date and Time Figure 6-3e. Relative Bias Data for Turbidity Table 6-2. Average Relative Bias Results for GO 204 and GO 205 Saltwater Freshwater Mesocosm Parameter Units % Rel. Bias 204 % Rel. Bias 205 % Rel. Bias 204 % Rel. Bias 205 %ReL Bias 204 %ReL Bias 205 Temperature K -0.09 -0.06 -0.11 -0.03 -0.07 -0.09 Conductivity mS/cm 21.5 10.6 9.21 15.1 2.62 1.96 DO rng/L -21.9 -24.8 -28.6 -20.4 -6.19 -15.3 H+ mol/L 28.2 28.8 35.5 -23.9 -20.3 -31.2 Turbidity NTU 269 -43.9 318 420 146 111 6.3 Precision Precision, expressed as %RSD, was calculated during periods of stable operation in the mesocosm tank. Periods of stable operation typically corresponded to times during the mesocosm test when the pump was not operating, periods when the freshwater replaced the saltwater, or other periods during which the parameter in question showed no visible change in Ocean Seven 316 measure- ments. Table 6-3 shows the results of these calculations and the period over which the calculations were made. No %RSD was determined for DO or turbidity because data from a period of stable operation were not available for analysis. 31 ------- Table 6-3. Percent Relative Standard Deviation for GO 204 and GO 205 During Periods of Stable Operation Stable Time Period Number of Parameter Start Stop Measurements %RSD 204 %RSD 205 Temperature 9/24/02 2:30 PM 9/24/02 3:45 PM 6 0.05 0.04 Conductivity 9/24/02 4:30 PM 9/24/02 11:00 PM 27 1.08 1.07 DO NA NA NA NA NA PH 9/24/02 5:15 AM 9/24/02 8:45 AM 15 0.07 0.02 Turbidity NA NA NA NA NA The pH and temperature had the lowest %RSD, ranging between 0.02%RSD and 0.07%RSD, and conductivity was 1,08%RSD and 1,07%RSD for the two probes. 6.4 Linearity Linearity was assessed by comparing probe readings against the reference values for each of the parameters at each deployment location. Table 6-4 gives the results of this comparison by showing the slope, intercept, and coefficient of determination (r2) at each condition. Linear response was highest for conductivity and temperature, with slopes between 0.85 and 1.23 and r2 values above 0.85. Correlation coefficient results during the mesocosm deployment were above 0.84 except for DO, which had r2 values of 0.56 and 0.66. 6.5 Inter-Unit Reproducibility Inter-unit reproducibility was assessed by comparing the relative bias of the two Ocean Seven 316s (Section 6.2), as well as by comparing the average differences between the two probe readings for each parameter at each deployment location. Figures 6-4 through 6-8 show the data used for these calculations. In terms of relative bias, the two Ocean Seven 316s exhibited close agreement for temperature, conductivity, and DO; but showed larger differences for pH (freshwater only) and turbidity (see Table 6-2). The results of average difference comparisons between the two Ocean Seven 316s are shown in Table 6-5. The average difference in temperature readings was 0.08°C over a range of 24 to 34°C. The difference in conductivity averaged 0.04 mS/cm over a range of 0.3 to 49 mS/cm (Figures 6-5a-c). The DO difference averaged 0.55 mg/L, while the actual Ocean Seven 316 DO readings varied from 0 to 12 mg/L (Figures 6-6a-c). The average difference in pH readings was 0.12 over a range of 6.6 to 9.6 (Figures 6-7a-c). The average difference in turbidity readings was 8.96 NTU, while the actual turbidity measurement ranged from 0 to 125 NTU (Figures 6-8a-c). The magnitude of the inter-unit reproducibility results was affected by spatial and temporal changes in the sampling environment. For example, the Ocean Seven 316s were sampling in an environment that was changing 8°C over a 24-hour period. Because they were not sampling 32 ------- Table 6-4. Results of Linearity Analysis for GO 204 and GO 205 Saltwater Freshwater Mesocosm GO Parameter Slope Intercept Coefficient of Determination Slope Intercept Coefficient of Determination Slope Intercept Coefficient of Determination 204 Temp 0.93 20.49 0.85 0.96 10.92 0.99 0.97 9.35 0.98 205 Temp 0.94 18.47 0.86 0.91 28.11 0.91 0.85 45.84 0.95 204 Cond 1.17 -1.59 0.92 1.23 -0.05 0.93 1.05 -0.08 0.99 205 Cond 1.17 -1.55 0.92 1.19 -0.01 0.93 1.04 -0.09 1.00 204 DO 0.16 3.15 0.06 0.67 0.33 0.66 0.97 -0.22 0.56 205 DO 0.36 1.95 0.12 0.82 -0.10 0.92 0.63 1.39 0.66 204 PH 0.94 0.00 0.55 0.26 0.00 0.53 0.62 0.00 0.88 205 PH 0.94 0.00 0.55 0.48 0.00 0.78 0.62 0.00 0.84 204 Turb 0.63 7.67 0.05 2.64 10.18 0.14 1.05 5.88 0.88 205 Turb 0.49 0.43 0.12 4.86 0.21 0.32 1.09 5.42 0.85 ------- Table 6-5. Average Difference in GO 204 and GO 205 Readings for Each Parameter at Each Deployment Location Average Difference between GO 204 and GO 205 Temperature Conductivity DO Turbidity Location C (mS/cm) (mg/L) pH (NTU) Saltwater 0.01 0.10 0.34 0.07 8.18 Freshwater 0.11 0.02 0.60 0.24 17.67 Mesocosm 0.13 0.01 0.71 0.06 1.02 Average 0.08 0.04 0.55 0.12 8.96 in exactly the same location, differences in temperature, caused by the 24-hour fluctuations, resulted in some differences in measurement by the Ocean Seven 316s. Similar behavior occurs in any location that experiences dynamic changes in the environment. 6.6 Other Factors 6.6.1 Ease of Use The Ocean Seven 316s were set up to collect data with minimal difficulty, and data were down- loaded without incident using the provided data cable and a PC. The Ocean Seven 316 operators during this verification test included individuals with and without a college education, all of whom had some experience working with monitoring equipment. The monitors were transported to and from the testing sites in a five-gallon bucket, wrapped in wet towels. Battery replacement was necessary every time the Ocean Seven 316s were brought to the lab for the calibration check interval despite the fact that the Ocean Seven 316s were operating in sleep mode between samples to conserve power. 6.6.2 Costs At the time of testing, the Ocean Seven 316, as verified, cost $15,000 per unit. 6.6.3 Data Completeness All portions of the verification test were completed; however, because one period of low battery power resulted in no data being collected on one probe, one day out of a total of 62 sampling days resulted in no data collection. Therefore, data completeness was approximately 98%. 34 ------- 7/6/02 12:00 7/11/02 12:00 AM 7/16/02 12:00 AM 7/21/02 12:00 AM 7/26/02 12:00 7/31/02 12:00 8/5/02 12:00 8/10/02 12:00 8/15/02 12:00 AM AM AM AM AM Date and Time Figure 6-4a. Inter-Unit Reproducibility Data for Temperature During Saltwater Tests 204 205 34 - Reference 8/15/02 12:00 AM 8/20/02 12:00 AM 8/25/02 12:00 AM 8/30/02 12:00 AM 9/4/02 12:00 AM 9/9/02 12:00 AM 9/14/02 12:00 AM Date and Time Figure 6-4b. Inter-Unit Reproducibility Data for Temperature During Freshwater Tests 35 ------- g 27 9/16/02 12:00 AM 9/18/02 12:00 AM 9/20/02 12:00 AM 9/22/02 12:00 AM 9/24/02 12:00 AM 9/26/02 12:00 AM 9/28/02 12:00 AM Date and Time Figure 6-4c. Inter-Unit Reproducibility Data for Temperature During Mesocosm Tests 45 40 E. 35 30 25 - 20 ¦ ¦ ' ¦ ¦ i . i -204 -205 Reference 7/6/02 12:00 7/11/02 12:00 7/16/02 12:00 7/21/02 12:00 7/26/02 12:00 7/31/02 12:00 8/5/02 12:00 8/10/02 12:00 8/15/02 12:00 AM AM AM AM AM AM AM AM AM Date and Time Figure 6-5a. Inter-Unit Reproducibility Data for Conductivity During Saltwater Tests 36 ------- 0.8 shJ- -A- ) -204 -205 Reference 8/15/02 12:00 AM 8/20/02 12:00 AM 8/25/02 12:00 AM 8/30/02 12:00 AM 9/4/02 12:00 AM 9/9/02 12:00 AM 9/14/02 12:00 AM Date and Time Figure 6-5b. Inter-Unit Reproducibility Data for Conductivity During Freshwater Tests -204 -205 Reference 9/16/02 12:00 AM 9/18/02 12:00 AM 9/20/02 12:00 AM 9/22/02 12:00 AM 9/24/02 12:00 AM 9/26/02 12:00 AM 9/28/02 12:00 AM Date and Time Figure 6-5c. Inter-Unit Reproducibility Data for Conductivity During Mesocosm Tests 37 ------- 204 205 Reference 7/6/02 12:00 7/11/02 12:00 7/16/02 12:00 7/21/02 12:00 7/26/02 12:00 7/31/02 12:00 8/5/02 12:00 8/10/02 12:00 8/15/02 12:00 AM AM AM AM AM AM AM AM AM Date and Time Figure 6-6a. Inter-Unit Reproducibility Data for Dissolved Oxygen During Saltwater Tests 204 205 Reference 8/15/02 12:00 AM 8/20/02 12:00 AM 8/25/02 12:00 AM 8/30/02 12:00 AM 9/4/02 12:00 AM 9/9/02 12:00 AM 9/14/02 12:00 AM Date and Time Figure 6-6b. Inter-Unit Reproducibility Data for Dissolved Oxygen During Freshwater Tests 38 ------- 9/16/02 12:00 AM 9/18/02 12:00 AM 9/20/02 12:00 AM 9/22/02 12:00 AM 9/24/02 12:00 AM 9/26/02 12:00 AM 9/28/02 12:00 AM Date and Time Figure 6-6c. Inter-Unit Reproducibility Data for Dissolved Oxygen During Mesocosm Tests 8.6 - 8.4 8.2 7.6 -204 -205 Reference 7^ I I I 7/6/02 12:00 7/11/02 12:00 7/16/02 12:00 7/21/02 12:00 7/26/02 12:00 7/31/02 12:00 8/5/02 12:00 8/10/02 12:00 8/15/02 12:00 AM AM AM AM AM AM AM AM AM Date and Time Figure 6-7a. Inter-Unit Reproducibility Data for pH During Saltwater Tests 39 ------- 204 205 Reference 7.5 6.5 8/15/02 12:00 AM 8/20/02 12:00 AM 8/25/02 12:00 AM 8/30/02 12:00 AM 9/4/02 12:00 AM 9/9/02 12:00 AM 9/14/02 12:00 AM Date and Time Figure 6-7b. Inter-Unit Reproducibility Data for pH During Freshwater Tests 7.5 204 205 Reference 9/16/02 12:00 AM 9/18/02 12:00 AM 9/20/02 12:00 AM 9/22/02 12:00 AM 9/24/02 12:00 AM 9/26/02 12:00 AM 9/28/02 12:00 AM Date and Time Figure 6-7c. Inter-Unit Reproducibility Data for pH During Mesocosm Tests 40 ------- 60 204 205 i- z £ |d E 3 I- 7/6/02 12:00 7/11/02 12:00 7/16/02 12:00 7/21/02 12:00 7/26/02 12:00 7/31/02 12:00 8/5/02 12:00 8/10/02 12:00 8/15/0$ 12:00 \A AM AM AM AM AM AM AM Date and Time Figure 6-8a. Inter-Unit Reproducibility Data for Turbidity During Saltwater Tests 140 120 204 205 100 Reference i- z £ ;o !n 3 I- 8/15/02 2:00 AM 8/20/02 12:00 AM 8/25/02 12:00 AM 8/30/02 12:00 AM 9/4/02 12:00 AM 9/9/02 12:00 AM 9/14/02 12:00 AM -20 Date and Time Figure 6-8b. Inter-Unit Reproducibility Data for Turbidity During Freshwater Tests 41 ------- 140 120 - & 60 - -204 -205 Reference 9/16/02 2:00 AM 9/18/02 12:00 AM 9/20/02 12:00 AM 9/22/02 12:00 AM 9/24/02 12:00 AM 9/26/02 12:00 AM 9/28/02 2:00 AM Date and Time Figure 6-8c. Inter-Unit Reproducibility Data for Turbidity During Mesocosm Tests 42 ------- Chapter 7 Performance Summary Pre-and post-calibration tests showed that pH measurement values were accurate within a range of 99 to 108% of the true values. Except for the first result of 73%, the remaining DO measurement values were accurate within a range of 82 to 105% of the true values. Conductivity measurement values were accurate within a range of 94 to 104% of the true values. No modifications were made to the probes (calibration adjustments, maintenance, etc.) during the testing. The temperature biases were less than or equal to 0.11% for all deployment settings. Conductivity, pH (reported as H+ concentration), and DO biases were between approximately 2 and 36% for both units under all deployment settings. The conductivity bias was consistently positive, indicating that generally, the Ocean Seven 316 probes reported a higher conductivity than the handheld reference probe. The DO bias was consistently negative for each deployment setting. The bias for turbidity ranged between approximately -44% and 420%. Percent RSD was lowest for the pH and temperature, ranging between 0.02%RSD and 0.07%RSD. Precision for conductivity was 1,08%RSD and 1,07%RSD for the two Ocean Seven 316s. DO and turbidity precision estimates were not determined. The linear response for the Ocean Seven 316, expressed in terms of slope, intercept, and coefficient of determination at each condition, was highest for conductivity and temperature. Analysis of inter-unit reproducibility, relative bias of the Ocean Seven 316s exhibited close agree- ment for temperature, conductivity, and DO; but showed larger differences for pH (freshwater only) and turbidity. The average difference in temperature readings between the two Ocean Seven 316s was 0.08°C over a range of 24 to 34°C. The difference in conductivity averaged 0.04 mS/cm over a range of 0.3 to 49 mS/cm. The average difference in readings for DO was 0.55 mg/L, while the actual Ocean Seven 316 DO readings varied from 0 to 12 mg/L. The average difference in pH readings was 0.12 over a range of 6.6 to 9.6. The average difference in turbidity readings was 8.96 NTU, while the actual turbidity measurement ranged from 0 to 125 NTU. The magnitude of the inter-unit reproducibility results was affected by spatial and temporal changes in the sampling environment. For example, the Ocean Seven 316s were sampling in an environment that was changing 8°C over a 24-hour period. Because the Ocean Seven 316s were not sampling in exactly the same location, differences in temperature, caused by the 24-hour fluctuations, resulted in some difference in measurement by the Ocean Seven 316s. Similar behavior occurs in any location that experiences dynamic changes in the environment. 43 ------- The probes were set up to collect data with minimal difficulty, and data were downloaded without incident using the provided data cable and a Windows-based PC. Battery replacement was necessary every time the probes were brought to the lab for the calibration check interval despite the fact that the probes were operating in sleep mode between samples to conserve power. The Ocean Seven 316 verified in this test cost $15,000 per unit. 44 ------- Chapter 8 References 1. Test/QA Plan for Long-Term Deployment of Multi-Parameter Water Quality Probes/Sondes, Battelle, Columbus, Ohio, Version 2.0, May 2002. 2. Quality Management Plan (QMP) for the ETV Advanced Monitoring Systems Center, Version 3.0, U.S. EPA Environmental Technology Verification Program, Battelle, Columbus, Ohio, December 2001. 45 ------- Appendix A Reference Sample and Probe Readings A-l ------- m/d/y hh:mm Temp C Cond. mS/cm 204 GO 205 Reference DO Turb. Temp Cond. DO Turb. Temp Cond. DO Turb. mg/L PH NTU C mS/cm mg/L PH NTU C mS/cm mg/L PH NTU 4.41 7.65 9.35 28.574 27.94 3.99 7.60 1.9 28.550 24.7 4.68 7.62 5.2 4.37 7.63 8.48 28.594 26.72 3.99 7.57 1.85 28.650 24.3 4.79 7.64 5.2 4.22 7.63 8.08 28.617 26.45 3.98 7.57 1.7 28.750 24.2 4.72 7.63 4.4 4.11 7.63 8.78 28.638 26.42 3.86 7.57 1.58 28.750 24.1 4.65 7.64 5.2 4.13 7.63 9.73 28.67 26.43 3.83 7.57 1.6 28.950 24.1 4.81 7.67 4.7 4.07 7.63 10.4 28.686 26.43 3.81 7.57 1.6 29.150 25 4.9 7.65 4 3.81 7.73 13.6 28.678 35.49 3.4 7.68 2.75 29.050 30.7 6.18 7.69 4 3.86 7.74 10.2 28.673 35.56 3.45 7.68 1.75 28.950 29.8 4.9 7.71 3 3.9 7.78 11.8 28.662 38.7 3.52 7.72 2.33 28.850 31.5 4.83 7.67 3.5 3.88 7.79 10.7 28.671 39.13 3.48 7.73 1.85 28.950 32.8 4.76 7.71 3.3 3.78 7.79 11.8 28.658 40.1 3.46 7.73 2.03 29.050 32.8 5.09 7.73 3.4 4.03 7.76 11.5 28.874 35.32 3.62 7.71 1.58 29.150 30.5 5.22 7.78 3.1 3.9 7.77 9.28 28.741 38.94 3.53 7.72 1.8 29.150 34.2 5.19 7.78 3.4 3.91 7.78 8.83 28.87 38.06 3.68 7.72 1.58 29.050 35 5.04 7.8 4.5 4 7.78 7.88 28.9 38.17 3.68 7.72 1.65 29.250 34.3 5.32 7.73 4.4 4.24 7.79 8.83 28.97 37.81 3.8 7.73 1.63 29.250 33.3 5.72 7.83 3.8 4.02 7.66 9.35 28.694 27.6 3.64 7.59 1.9 28.650 24.3 4.73 7.61 4.2 3.93 7.65 8.65 28.722 27.11 3.43 7.58 2.13 28.650 23.9 4.78 7.6 4.1 4.16 7.66 10.5 28.74 27.53 3.77 7.61 2.98 28.750 24.9 4.76 7.67 5.2 4.34 7.63 8.03 28.746 26.35 3.94 7.57 2.15 28.850 23.3 4.75 7.61 4.4 4.18 7.6 8.63 28.77 25.46 3.73 7.55 2.35 28.950 23.2 4.72 7.59 4.5 4.07 7.6 8.53 28.837 25.21 3.62 7.55 2.13 28.950 23.4 4.8 7.64 4.4 3.86 7.6 9.55 28.8 25.71 3.49 7.54 2.33 29.050 23.4 4.8 7.63 4.4 3.87 7.61 9.45 28.852 25.6 3.54 7.55 2.1 29.150 23.3 4.76 7.6 3.7 3.62 7.62 8.43 28.894 26.61 3.19 7.55 2.1 29.050 26.6 4.81 7.54 3.6 3.44 7.63 9.65 28.798 28.26 3.12 7.56 2.43 29.050 27.4 4.81 7.67 5.1 3.31 7.63 11.4 28.783 29.64 2.97 7.56 2.7 29.150 27.2 4.89 7.7 5.5 3.55 7.67 11.5 28.845 28.71 3.29 7.60 2.5 28.950 29 4.68 7.73 3.8 3.53 7.73 10.2 28.841 35.38 2.93 7.65 2.43 29.050 34.3 4.37 7.82 6.1 7/15/02 8:00 AM 7/15/02 8:30 AM 7/15/02 9:00 AM 7/15/02 9:30 AM 7/15/02 10:00 AM 7/15/02 10:30 AM 7/15/02 1:00 PM 7/15/02 1:30 PM 7/15/02 2:00 PM 7/15/02 2:30 PM 7/15/02 3:00 PM 7/15/02 3:30 PM 7/15/02 4:00 PM 7/15/02 4:30 PM 7/15/02 5:00 PM 7/15/02 5:15 PM !:00 AM !:15 AM !:30 AM 7/16/02 9:00 AM 7/16/02 9:30 AM 7/16/02 10:00 AM 7/16/02 10:15AM 7/16/02 10:30 AM 7/16/02 12:30 PM 7/16/02 12:45 PM 7/16/02 1:00 PM 7/16/02 1:30 PM 7/16/02 2:00 PM 7/16/02 I 7/16/02 I 7/16/02 I 28.583 28.598 28.631 28.664 28.673 28.697 28.672 28.671 28.663 28.669 28.663 28.874 28.731 28.832 28.926 28.967 28.701 28.729 28.738 28.755 28.778 28.819 28.805 28.858 28.916 28.800 28.784 28.845 28.841 27.97 26.77 26.34 26.29 26.37 26.5 35.53 35.32 38.74 39.07 40.16 34.95 39.17 38.32 37.89 37.5 27.55 27.01 26.98 26.25 25.5 25.32 25.47 25.4 26.66 28.16 29.15 28.7 35.32 ------- GO 204 GO 205 Reference Temp Cond. DO Turb. Temp Cond. DO Turb. Temp Cond. DO Turb. m/d/y hh:mm C mS/cm mg/L PH NTU C mS/cm mg/L PH NTU C mS/cm mg/L PH NTU 7/17/02 11:15AM 29.411 24.85 3.83 7.58 9.98 29.399 24.96 3.23 7.50 3.2 29.850 23 4.86 7.7 3.9 7/17/02 12:00 PM 29.473 24.8 3.62 7.59 10.8 29.499 24.81 3.13 7.47 3.4 30.050 23.5 4.8 7.66 3.75 7/17/02 1:00 PM 29.335 27.61 3.33 7.6 11.6 29.409 26.64 2.98 7.48 3.75 29.950 24 5.09 7.67 3.65 7/22/02 2:00 PM 30.141 28.31 4.03 7.65 13.7 30.138 28.38 4 7.60 3.9 30.050 25.1 5.32 7.77 5.49 7/22/02 2:30 PM 30.123 28 4.3 7.66 13.7 30.121 28.14 4.18 7.61 3.95 30.150 24 5.09 7.67 4.54 7/24/02 2:30 PM 29.474 30.16 3.5 7.57 14 29.471 30.34 3.78 7.53 4.7 29.450 26.4 4.26 7.63 5.27 7/24/02 2:45 PM 29.447 29.14 3.47 7.55 14.4 29.448 29.31 3.73 7.52 4.85 29.450 26.1 4.76 7.63 4.62 7/24/02 3:30 PM 29.431 27.9 3.36 7.51 15.6 29.433 28.05 3.77 7.51 4.33 29.450 25 4.83 7.61 4.8 7/25/02 2:15 PM 29.795 31.98 4.08 7.62 13.2 29.771 32.35 4.28 7.63 5.75 29.850 28.6 5.78 7.76 5.21 7/25/02 3:00 PM 29.821 30.21 3.96 7.58 15.1 29.818 30.51 4.21 7.60 6 29.850 27.1 5.65 7.73 4.43 8/6/02 2:45 PM 29.761 33.7 4.21 7.64 7.98 29.745 33.53 4.54 7.72 1.85 29.850 30.6 2.98 7.75 3.72 8/6/02 3:00 PM 29.768 33.71 4.09 7.63 7.5 29.744 34.2 4.38 7.72 2.15 29.850 30.7 6.03 7.78 2.8 8/7/02 2:30 PM 29.052 35.36 4.31 7.67 10.9 29.08 35.29 5.22 7.80 1.7 29.050 31.6 5.7 7.83 4.67 8/7/02 3:00 PM 29.076 34.88 4.6 7.67 9.53 29.084 34.63 5.26 7.77 1.55 29.150 31.2 5.74 7.88 3.14 8/7/02 3:30 PM 29.131 34.11 4.6 7.66 8.15 29.156 33.81 5.26 7.76 1.45 29.250 30.3 5.87 7.84 3.11 8/12/02 2:00 PM 27.561 44.84 3.55 7.48 36.7 27.538 42.96 3.85 7.66 4.03 28.150 40.2 5.1 7.82 11.5 8/12/02 2:30 PM 27.561 44.84 3.55 7.48 36.7 27.744 40.61 4.03 7.65 3.85 28.550 36.6 5.33 7.76 6.6 8/12/02 3:15 PM 27.561 44.84 3.55 7.48 36.7 27.76 41.69 3.66 7.65 3.88 28.050 38.1 5.05 7.77 8.7 8/12/02 3:30 PM 27.561 44.84 3.55 7.48 36.7 27.831 40.94 3.85 7.66 3.2 28.250 36.3 5.34 7.8 6.1 8/12/02 3:45 PM 27.561 44.84 3.55 7.48 36.7 28.086 39.77 4.36 7.66 2.85 28.350 35.5 5.53 7.8 7.5 8/12/02 4:00 PM 27.561 44.84 3.55 7.48 36.7 28.224 38.76 4.63 7.67 3.05 28.350 34.3 5.62 7.81 6.9 8/12/02 4:15 PM 27.561 44.84 3.55 7.48 36.7 28.345 37.46 4.86 7.67 3.03 28.450 33.4 5.59 7.8 6.7 8/13/02 8:00 AM 27.561 44.84 3.55 7.48 36.7 27.78 27.97 3.9 7.43 2.8 27.750 25.4 4.52 7.57 5.31 8/13/02 8:15 AM 27.561 44.84 3.55 7.48 36.7 27.782 27.43 3.83 7.42 2.8 27.750 24.9 4.57 7.57 5.14 8/13/02 8:30 AM 27.561 44.84 3.55 7.48 36.7 27.784 27.14 3.59 7.40 2.8 27.850 24.9 4.58 7.54 5.23 8/13/02 8:45 AM 27.561 44.84 3.55 7.48 36.7 27.792 27.04 3.5 7.41 2.9 27.850 25.1 4.58 7.55 5.81 8/13/02 9:15 AM 27.561 44.84 3.55 7.48 36.7 27.766 27.49 3.61 7.40 3 27.950 25.3 4.76 7.57 4.47 ------- GO 204 GO 205 Reference Temp Cond. DO Turb. Temp Cond. DO Turb. Temp Cond. DO Turb. m/d/y hh:mm C mS/cm mg/L PH NTU C mS/cm mg/L PH NTU C mS/cm mg/L PH NTU 8/13/02 1:00 PM 27.561 44.84 3.55 7.48 36.7 27.778 35.64 3.34 7.44 2.8 27.850 31.7 4.54 7.63 5.1 8/13/02 1:15 PM 27.561 44.84 3.55 7.48 36.7 27.771 37.1 3.41 7.49 2.6 27.850 35.1 4.52 7.69 6.6 8/13/02 1:30 PM 27.561 44.84 3.55 7.48 36.7 27.745 39.45 3.23 7.51 2.6 27.850 35.8 4.56 7.71 6 8/13/02 1:45 PM 27.561 44.84 3.55 7.48 36.7 27.755 38.9 3.62 7.54 2.6 27.850 35.6 4.58 7.71 6.3 8/13/02 2:15 PM 27.561 44.84 3.55 7.48 36.7 27.728 40.26 3.55 7.55 2.53 27.850 36.7 4.52 7.67 7 8/13/02 2:30 PM 27.561 44.84 3.55 7.48 36.7 27.721 40.56 3.52 7.56 2.6 27.850 37.6 4.44 7.72 5.5 8/13/02 2:45 PM 27.561 44.84 3.55 7.48 36.7 27.706 41.3 3.56 7.58 2.6 27.850 38.1 4.48 7.74 8.1 8/13/02 3:00 PM 27.561 44.84 3.55 7.48 36.7 27.706 41.3 3.56 7.58 2.6 27.850 38.6 4.55 7.74 7.25 8/23/02 8:30 AM 27.700 0.485 1.32 7.21 15.8 27.794 0.499 1.3 7.01 16.3 27.750 0.456 1.97 6.84 8.02 8/23/02 8:45 AM 27.744 0.484 1.59 7.22 16.2 27.819 0.499 1.38 7.02 15.5 27.350 0.453 1.98 6.78 9.2 8/23/02 9:00 AM 27.740 0.484 1.53 7.22 15.4 27.828 0.499 1.5 7.02 16.9 27.850 0.456 2.51 6.82 8.19 8/23/02 9:15 AM 27.726 0.485 1.61 7.22 14.8 27.907 0.5 1.52 7.05 15.6 27.950 0.449 2.04 6.78 8.45 8/23/02 9:30 AM 27.833 0.486 1.72 7.25 14.8 27.979 0.501 1.79 7.06 15 28.150 0.454 3.1 6.9 8.54 8/23/02 9:45 AM 27.955 0.487 2.12 7.26 14.6 28.054 0.501 2.15 7.07 15.1 28.050 0.451 2.73 6.89 7.59 8/23/02 10:00 AM 28.166 0.489 2.36 7.29 15.5 28.317 0.503 2.31 7.10 14.6 28.450 0.453 3.88 6.94 7.17 8/23/02 10:15AM 28.257 0.49 2.68 7.29 14.8 28.389 0.505 2.41 7.17 16.2 28.450 0.452 3.25 7.01 6.9 8/23/02 1:30 PM 31.529 0.515 7.6 8.55 19.1 31.61 0.53 8.87 8.40 19.6 31.750 0.449 10.3 8.33 7.1 8/23/02 1:45 PM 31.831 0.517 8.87 8.64 15.2 31.964 0.532 8.91 8.50 16.9 32.650 0.447 10.1 8.41 8.63 8/23/02 2:00 PM 32.118 0.519 8.9 8.73 14.9 32.167 0.534 8.87 8.50 16.1 32.550 0.448 10.7 8.3 6.66 8/23/02 2:15 PM 32.538 0.523 8.74 8.74 14.9 32.476 0.537 9.13 8.48 9.33 32.950 0.447 10.7 8.43 6.88 8/23/02 2:30 PM 33.017 0.528 8.8 8.73 15.5 32.814 0.54 9.64 8.51 17.6 32.950 0.447 10.9 8.28 7.13 8/23/02 2:45 PM 33.253 0.532 8.6 8.77 15.7 33.173 0.545 9.48 8.54 15.3 33.250 0.446 11.4 8.39 6.48 8/23/02 3:00 PM 33.349 0.533 8.82 8.82 15.6 33.305 0.546 9.43 8.59 15.3 33.550 0.449 12.1 8.38 8.11 8/23/02 3:15 PM 33.570 0.534 9 8.92 15.1 33.42 0.548 9.38 8.65 16.1 33.450 0.448 11.7 8.42 6.78 8/26/02 2:00 PM 28.257 0.484 3.62 7.48 23 30.576 0.521 7.54 8.10 33.9 30.650 0.44 11.5 8.49 7 8/26/02 2:15 PM 28.257 0.484 3.62 7.48 23 30.597 0.521 8.12 8.19 34.9 30.650 0.447 11.8 8.37 7.3 8/26/02 2:30 PM 28.257 0.484 3.62 7.48 23 30.735 0.521 8.59 8.41 35.5 30.750 0.442 12.3 8.57 8.1 ------- GO 204 GO 205 Reference Temp Cond. DO Turb. Temp Cond. DO Turb. Temp Cond. DO Turb. m/d/y hh:mm C mS/cm mg/L PH NTU C mS/cm mg/L PH NTU C mS/cm mg/L PH NTU 9/5/02 1:15 PM 25.503 0.273 4.97 8.12 12.5 25.596 0.292 5.83 8.10 13.6 25.550 0.261 6.91 7.77 0.95 9/5/02 1:30 PM 25.420 0.273 5.06 8.08 12.6 25.516 0.296 5.84 8.07 12.1 25.450 0.267 6.9 7.73 0.77 9/9/02 1:45 PM 27.787 0.366 6.12 7.82 104 27.829 0.392 5.85 7.40 84.8 27.850 0.341 8.37 7.2 10.5 9/9/02 2:00 PM 27.787 0.366 6.12 7.82 104 27.829 0.392 5.85 7.40 84.8 27.850 0.341 9.2 7.55 10 9/9/02 2:15 PM 27.909 0.368 8.02 8.25 104 27.977 0.393 8.46 7.75 86 27.850 0.342 9.86 7.48 10.5 9/10/02 10:00 AM 25.481 0.355 2.47 7.48 86.3 25.545 0.371 2.75 7.18 125 25.550 0.343 3.35 6.66 9.8 9/10/02 10:15 AM 25.481 0.355 2.47 7.48 86.3 25.545 0.371 2.75 7.18 125 25.650 0.344 3.9 6.76 9.7 9/10/02 10:30 AM 25.546 0.354 3.13 7.52 90.6 25.578 0.371 4.05 7.23 100 25.550 0.342 4.2 6.7 9.85 9/12/02 10:30 AM 27.547 0.373 5.97 7.88 35.5 27.582 0.402 6.41 7.64 61.8 27.550 0.349 7.1 7.07 15 9/12/02 10:45 AM 27.688 0.374 6.3 7.96 35.8 27.601 0.401 6.9 7.67 60.5 27.550 0.348 6.9 7.17 12.7 9/12/02 11:00 AM 27.688 0.374 6.3 7.96 35.8 27.601 0.401 6.9 7.67 60.5 28.050 0.348 8.89 7.32 13.7 9/12/02 11:15 AM 28.109 0.378 7.6 8.22 35.6 28.064 0.404 8.06 7.86 59.6 28.050 0.351 8.45 7.42 16.2 9/12/02 1:45 PM 29.442 0.388 8.84 8.91 42.5 29.41 0.414 9.27 8.45 68 29.750 0.349 12.6 8.53 11 9/12/02 2:00 PM 29.442 0.388 8.84 8.91 42.5 29.41 0.414 9.27 8.45 68 29.450 0.35 11 7.84 12.6 9/12/02 2:15 PM 29.391 0.387 8.97 9.04 40.5 29.45 0.414 10.1 8.75 70.4 29.650 0.349 11.2 8.33 13.7 9/12/02 2:30 PM 29.555 0.388 9.78 9.22 42.2 29.253 0.413 9.98 8.51 67.3 29.450 0.349 10.9 8.62 16.9 9/12/02 2:45 PM 29.555 0.388 9.78 9.22 42.2 29.253 0.413 9.98 8.51 67.3 29.950 0.346 13.4 8.88 18.8 9/12/02 3:00 PM 29.707 0.388 10.3 9.43 43 29.921 0.415 11 9.21 74.5 29.750 0.348 12.4 8.78 14.7 9/12/02 3:15 PM 29.712 0.389 10.3 9.41 41 29.736 0.411 11.1 9.18 75.1 29.850 0.347 12.3 8.75 12.6 9/12/02 3:30 PM 29.712 0.389 10.3 9.41 41 29.736 0.411 11.1 9.18 75.1 29.550 0.348 11.1 8.65 15.6 9/19/02 4:00 PM 28.585 38.86 7.28 7.94 5.05 27.364 37.85 4.96 8.03 2.5 28.650 35.3 7.34 7.97 1.59 9/19/02 4:15 PM 28.585 38.86 7.28 7.94 5.05 28.789 38.94 6.43 8.02 4.23 28.950 35.5 7.31 7.94 2.13 9/20/02 9:00 AM 24.515 36.24 6.85 7.81 4.33 24.641 36.24 6.1 7.87 6.15 24.650 35.2 6.87 7.81 1.51 9/20/02 9:30 AM 24.576 36.28 7.55 7.78 114 24.7 36.28 6.37 7.86 122 24.750 35.8 6.77 7.79 60 9/20/02 11:00 AM 25.153 36.7 7.53 7.83 124 25.275 36.7 5.74 7.91 125 25.350 35.9 6.78 7.8 133 9/20/02 4:00 PM 29.641 40.2 6.54 7.85 33.6 28.048 38.86 5.3 7.94 44 29.150 35.8 6.65 7.84 19.4 ------- m/d/y hh:mm GO 204 GO 205 Reference Temp C Cond. mS/cm DO mg/L PH Turb. NTU Temp C Cond. mS/cm DO mg/L PH Turb. NTU Temp C Cond. mS/cm DO mg/L PH Turb. NTU 9/23/02 11:00 AM 24.958 38.28 5.35 7.88 4.8 25.084 38.29 5.83 7.94 4.6 25.150 37.8 6.94 7.83 2.4 9/23/02 1:45 PM 26.005 39.09 5.45 7.92 4.6 25.959 38.97 5.64 7.97 2.8 26.050 38.3 6.72 7.84 1.45 9/23/02 3:30 PM 27.224 40.05 5.06 7.94 3.3 27.361 40.07 5.45 8.00 2.5 27.450 38.4 6.72 7.88 1.35 9/23/02 4:30 PM 28.642 41.22 5.29 7.85 3.9 27.778 40.43 5.51 7.99 2.6 29.550 38.1 6.5 7.71 2.05 9/24/02 9:30 AM 24.393 38.28 2.77 7.45 4.9 24.513 38.29 3.93 7.49 5.3 24.550 37.7 3.71 7.28 1.9 9/24/02 9:45 AM 24.376 38.27 5.1 7.53 12.5 24.515 38.29 3.89 7.51 5.43 24.550 37.7 4.54 7.36 1.9 9/24/02 11:00 AM 26.967 0.493 5.52 8.72 9.63 27.085 0.511 4.82 8.78 9.4 27.150 0.68 5.96 8.4 6.25 9/24/02 1:30 PM 27.069 1.397 6.11 8.24 5.9 27.116 1.321 5.44 8.33 5.7 27.250 1.304 6.4 7.97 2.46 9/24/02 3:15 PM 27.123 1.516 6.09 8.22 7.4 27.215 1.483 5.56 8.23 5.2 27.250 1.406 6.55 7.89 4.22 9/24/02 4:30 PM 28.311 2.682 6.55 8.19 8.98 28.479 2.691 5.28 8.27 7.23 28.450 2.67 6.22 8.04 3.87 9/25/02 11:00 AM 24.147 3.093 6.78 8.06 6.9 24.265 3.105 6 8.08 7.65 24.350 3.35 6.88 7.63 1.91 ------- |