SAN JUAN BAY ESTUARY PROGRAM

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1 SAN JUAN BAY ESTUARY PROGRAM May, 2008 Water Quality Monitoring Volunteer Program STANDARD OPERATING PROCEDURES P.O. Box 9509 San Juan, PR Tel: (787) Fax: (787) Web site: Revised: 0 APPROVED: Author Date QAPP Manager Date QAPP Quality Assurance Officer Date

2 2 Section TABLE OF CONTENT Page Program Overview... 3 Purpose and Applicability... 4 Summary of Method... 4 Health & Safety Warnings... 5 Cautions... 5 Interferences... 6 Personnel Qualification... 6 Personnel Responsibilities... 6 Equipment & Supplies... 7 Safety Equipment List... 7 Monitoring Equipment list... 8 Procedure... 8 Data and Record Management Quality Control and Quality Assurance Equipment Calibration Field QC check Laboratory QC check Data analysis QC checks ATTACHMENTS Attachment 1 Attachment 2 Attachment 3 Attachment 4 Attachment 5 Hydrolab Quanta Water Quality System Operating Manual Quanta Hydrolab Calibration Sheet Change of Custody (COC) record sheet Field Data Sheet LaMotte Dissolved Oxygen Water Quality Kits Instructions Manual

3 3 Program Overview The San Juan Bay Estuary system is located on the north coast of the Island of Puerto Rico. The System includes the San Juan Bay, the Condado Lagoon, the San José Lagoon, Los Corozos Lagoon, La Torrecilla Lagoon and the Piñones Lagoon, as well as the interconnecting Martín Peña and San Antonio Channel and the Suárez Canal. Fresh water flows into the system from different creeks and rivers in the watershed, being the Puerto Nuevo River the main source. The Atlantic Ocean waters enter the system through three inlets: Boca del Morro at the San Juan Bay, el Boquerón at the Condado Lagoon and Boca de Cangrejos in La Torrecilla Lagoon. The watershed or drainage basin covers approximately 97 square miles, with a population of over 622,000 residents. The SJBE watershed extends above a broad, flat coastal plain and consists of 83 square miles of land and 14 square miles of water. The estuary basin, which is almost completely urbanized, encompasses the territory of eight municipalities. Other natural systems associated with the estuary, but not necessarily located within the transitional mixing zone characteristic of estuaries, are included within the geographic scope of the SJBE system. The SJBE was designated by the EPA as a resource of national importance on As a result, the SJBE Program was created to identify those actions needed to improve and maintain the integrity of the estuary and its designated uses. These efforts are summarized in the Comprehensive Conservation and Management Plan, which was approved and adopted as part of both the Commonwealth and Federal governments public policy. The Program has been involved, since then, in the full implementation of the CCMP and in assuring that any action within the SJBE is consistent with the commitments established in the plan. The proposed study will established a long- term water quality program for the SJBE by collecting water samples in 23 stations within the estuary system and tributaries (See Table 3 and Figure 3 of the QAPP) in order to evaluate the effectiveness of implemented CCMP actions and to evaluate natural and human-induced impacts to the

4 4 system. Annual water quality reports will be provided through the SJBE web page ( Every two (2) years the results will be published in the Estate of the San Juan Bay Estuary report. Efforts will be directed toward transmission of knowledge obtained during this activity to the general public. Furthermore, the data will be used to provide scientifically-based presentations and documentation to communicate the results to the general public, government, and the academia The hands-on involvement of volunteers will serve both to educate the public and enhance interest in the SJBE. Volunteer participation will also supplement existing and future monitoring programs. The program stands in the philosophy that only through knowledge and hands-on experiences, the public will be able to protect and preserve the integrity of the Estuary. It will also help identify several water quality issues in the Estuary that could be harmful for humans, public health and estuarine species. Purpose and Applicability The purpose of these Standard Operating Procedures (SOPs) is to establish a uniform procedure for collecting water samples and measure water quality parameters for the monitoring of the water quality parameters within the San Juan Bay Estuary System. The procedures presented in these SOPs are applicable to all field sampling coordinators and water quality monitoring volunteers as part of the SJBE s Water Quality Monitoring Program. Summary of Method Water (grab) samples will be collected from the surfaces of the San Juan Bay Estuary water bodies. These water samples will be shipped on ice chest to an environmental analysis laboratory (EQlab) for the analysis of nutrients (nitrate + nitrite, ammonium, total phosphate), coliform, enterococcus, oil and grease, BOD, Chlorophyll, total organic carbon, and turbidity. A total of 23 stations will be occupied quarterly for the collection of these samplers. Also, monthly visit to the same 23 stations will be

5 performed for the in-situ determination of dissolved oxygen, specific conductance, ph, temperature, and turbidity using a Hydrolab Quanta Water Quality Monitoring System. A secchi disk will be used for the determination of water transparency. The resultant data will be presented in an annual report. 5 Health & Safety Warnings The monitors will wear protective latex globes during water sample collection. Sampler containers should be handled with care. During precipitations events, extra precautions should be taken due to the possible presence of pollutants coming form stormwater runoff and fecal coliforms from sewage treatment collection system and combined sewer overflows. Particular attention should be place to the detection of bad odors and the presence of floating material. All monitors should wear Personal Flotation Devices (PFD) and follow solar protection indications such as using solar protector and cap/hat during sampling events. All volunteers should familiarize with the use of the first aid kits. The sampling event should be abort in any case where the field sampling coordinator or any volunteers perceive unsafe environmental conditions. Cautions Please follow the following recommendations: 1. Check the television, radio, or Weather Services for current forecast before deciding whether to sample. Consider rescheduling the sampling event if weather/sea conditions are poor. 2. Always maintains all working areas organize and in proper order. 3. Know all sampling procedures and double check instrument calibration before going to the field. 4. Always place the guard cup over the Hydrolab Quanta transmitter before deploying the instrument.

6 5. Some samples containers have preservatives inside thus avoid water overflow during sampler collection (Oil & Grease). 6. Always check for deposits inside the water samples containers. 7. Do not expose Chlorophyll samples to direct sunlight. 6 Interferences Avoid careless handling of samples in order to avoid the introduction of contaminants. Check that preservative and samples containers are free of dirt and other particles. Personnel Qualification Interested individuals that want to become part of the Volunteer Monitoring Program will participate in two (2) training session conducted by the Field Sampling Coordinator/Leader or the QAPP Manager. The first training section will consist of one lecture about water quality basic concepts, explanation of the goals and objectives of the monitoring program, and monitoring techniques. Also, monitoring safety precautions and emergencies general procedures will be discussed. During this section, one copy of the Standard Operating Procedures (SOPs) will be distributed among the attendees and use as training textbook. The second training section will consist in hands-on field exercise. A copy of the Standard Operating Procedures (SOPs) will be available at all time during the monitoring event. Personnel Responsibilities Each monitoring event will consist of an boat captain/operator, the Field Sampling Leader, an at least one volunteer monitor. The Field Sampling Leader is responsible for managing volunteers, equipment, and laboratory needs related to the water quality monitoring program. This include checking that all necessary equipment is on board before the monitoring events, ensuring equipment calibration a, equipment

7 operation and deployment, measurement recording, water sample collection, and taking secchi disk reading. The boat captain is responsible for the safe operation of the boat including boat and engine maintenance, safety equipment, navigation to the station coordinates, and weather/sea state conditions watching. Volunteers interesting in becoming boat captain should complete a safe boating course (US Coast Guard approved, Department of Natural and Environmental Resources, or US Power Squadron navigation safety course certification). Volunteers monitors will assist with the operation of the monitoring equipment, assist with recording measurements, collect water samplers and take secchi readings. Volunteer monitors do not require scientific background or experience. 7 Equipment & Supplies Safety Equipment List Personal Flotation Devices (PFD); US Coast Guard Approved Fire Extinguisher Sound Producing Devices/whistler Visual Distress Signals (flares and orange flag) VHF radio Anchor and anchor lines Oars Scoop bucket as alternate dewatering devices Buoy with 20 meters of rope First Aid Kits Rubber Gloves Cellular phones Emergency Contact Information Sheet Sunblock Insect Repellant Personal Identification Safety goggles Antibacterial soap solution Alcohol Estuary map Flashlight Hat/cap Raingear

8 8 Monitoring Equipment list Hydrolab Quanta Water Quality System Secchi disk ( 20 cm diameter) with calibrated line. Field Data Sheet Pencil and/or all weather pen ( Rite in the Rain ) Distilled water Wash bottle Standard Operating Procedures manual Binoculars Digital camera GPS with digital nautical chart. Sampling bottlers (provided by EQLab) Trip blank Duck tape Kim wipes Ice Coolers Thermometer ( o C) Winkler titration field kit and sample bottles Calibration check solutions Sharpie permanent marker Wildlife identification guides Field weather sensor/gauge Procedure Before leaving the dock: 1. Calibrate the Hydrolab Quanta according to procedures presented in the instrument operating manual (See Attachment 1). Fill the calibration results in the Quanta Calibration Sheet (see Attachment 2). 2. Verify that all sampling station coordinates are loaded in the GPS and in the correct chart datum (NAD 83). 3. Check that all safety and monitoring equipment are complete and on board. 4. Verify that the set of sample bottles send by EQLab are complete and with the Change of Custody (See Attachment 3).

9 5. Fill labels of sample bottlers with the corresponding information (date and site number). 6. Ensure your participation in the on-site review of field procedures and safety issues. 7. Adjust and put a Personal Flotation Device (PFD). 8. Decided according to sea/weather conditions the first station to occupy. 9 Arrival to the First Station: 1. Navigate to the first station using the GPS. 2. The boat should be maintained during sampling inside a radius of 20 meters from the station coordinates. Avoid dropping the anchor since mud may become stirred into the water. 3. If necessary, deploy a buoy in the station as reference point. 4. Place the Cooler Temperature control sample inside the cooler and cover it with ice. Sampling Station procedures 1. Follow these procedures for all sampling stations. 2. Always wear latex gloves. 3. Make sure the boat is still and stable before sampling. 4. Fill data sheet with all visual and weather observations (see Attachment 4). 5. Remove the protective cap from the Quanta Transmitter and replace with the probe guard cup. 6. Lower the probe transmitter to 0.5 meter below surface. 7. Record in the field data sheet instrument reading after the parameters values remains constant. 8. Rinse the probe with distilled water, remove guard cup, and replace with the storage cap filled with distilled water. 9. Take a Secchi reading following these steps: a. The measurement is taken with the sun at your back and without sunglasses.

10 10 b. Lower the disk until it disappears completely. Record the depth shows in the calibrated line. c. Raise the disk until it became visible again and record this depth. d. The average of these depths is the Secchi disk depth. Record this value. e. Have another volunteer repeat the process. Accept the average of these results as the official Secchi Disk Depth for the station. f. If the disk hits the bottom before dropping out of sight, record this observation as bottom depth. 10. Collect the samples for bacteria testing following these steps: a. Stay clear of alga blooms, surface debris, and oil slicks. Avoid agitating the bottom sediments and do not allow the boat propeller to stir up the water. b. Plunge the bottle into the water upside-down. Open the sample water underwater, keeping hands off the mouth and the inside of the cap. Hold the lid. c. Reach down into the water as far as possible, stil holding the bottle with its mouth down. d. In a single motion, rotate the bottle mouth away and sweep the bottle up and out of the water. e. Make sure that the sweeping motion continues until the bottle is fully out of the water. f. Pour enough water to leave about one (1) inch of air space in the bottle. g. Replace the lid, again making sure not to touch the inside of the cap or bottle rim. h. Place the bottle in the cooler. Do not allow water accumulating in the cooler from melting ice to submerge the bottles. i. The samples should be transported to the laboratory within the next six (6) hours. 11. Collect water samples following these steps: a. Uncape the bottle, being careful no to touch the container s mouth.

11 11 b. Rinse the bottlers by pushing it into the water in a forward motion holding the container by the bottom. After filling the bottle, bring it to the surface with the mouth facing up. Pour the water on the down current side of the boat and away from the actual sampling site. Rinse the cap as well. c. Push the bottle back into the water and bring it to the surface with the mouth facing up. d. Leave a small amount of air at the mouth except for the Total Organic Carbon and dissolved oxygen samples. The water sample bottlers for these parameters should be filled completely without leaving any air space. e. Cap the bottlers. f. Add corresponding preservatives. g. Store in the ice cooler. h. Fill all required information in the Change of Custody (See Attachment 3). At 10 % of the monitoring stations (2 stations) selected randomly: 1. Collect a sample to be analyzed for dissolved oxygen (DO) form the same location for which the Hydrolab Quanta was used to quantify DO levels. 2. Fix the sample using the field DO kit (Winkler Titration) provided. 3. Place the fixed sample in the cooler for analysis on shore. 4. Fill the quality control (field duplicate, matrix spike, etc.) container provided by EQLab for QA/QC purposes. After each monitoring event follow these steps: 1. Check the salinity calibration using salinity certified standard according to the instrument manual. 2. Rinse the Hydrolab Quanta with distilled water. 3. Inspect the DO probe membrane for any bubbles, rips, winkles, or looseness.

12 4. Allow the sensor to rest at least four 94) hours before recalibrating. 5. Analyze the dissolved oxygen samples following the instruction provided by the LaMotte kits (see Attachment 5). 6. Compare the results with the reading obtained with the Hydrolab Quanta. If the results deviate by more than 0.5 mg/l, flag the Hydrolab Quanta results and implement procedures presented in Section 16 of the QAPP. 12 Data and Record Management A data summary will be provided by EQLab and will be attached to the annual report. At the end of the monitoring year, the results will be presented into an annual water quality monitoring report. The report will include an executive summary, introduction, material, methods, sampling collection and handling records, analytical logbook, QC sample records, equipment calibration records, assessment reports, tables, graph, discussion of the results and conclusions. The specific routine procedures that will be implemented to access data precision, accuracy and completeness are detailed in Section 8.0 of the QAPP. Original data sheet will be scanned into electronic files before storage in the SJBE volunteer monitoring program files for a period of five years. Quality Control and Quality Assurance Detailed quality control procedures for the San Juan Bay Estuary Water Quality Volunteer Monitoring Program are discussed in the program s Quality Assurance Plan (QAPP). Portions of these procedures are summarized below. Equipment Calibration The Hydrolab Quanta Water Quality Monitoring System Operating Manual (see Attachment 1) presents calibration procedures for the instrument. The Hydrolab Quanta

13 13 will be calibrated before each monitoring event. The dissolved oxygen calibration will be checked through the modified Winkler titration method (see Attachment 5). The salinity calibration will be checked with certified standard and the ph checked with 4, 7, and 10 buffers as stated in the Quanta manual (see Attachment 1). Field QC check Instrumentation will be checked through calibration prior to the sampling day under a controlled environment. Also, the calibration will be performed at the end of the sampling day to ensure less than 5 % instrument drift in one sampling day. If the calibration check indicates that the instrument s calibration has drifted outside the calibration acceptance criteria, the data will be flagged and evaluated following the procedures in Section 16 of this QAPP. When not in use the Hydrolab Quanta will be stored in the field laboratory station. The instruments will be secured, padded and protected during transportation. Instrument dissolved oxygen observations will be checked and calibrated using the LaMotte Field DO kit (EPA modified Winkler titration method). The specific conductance calibration will be checked before and after the monitoring events following the procedures presented in the Quanta manual (See Attachment 1). Certified and dated standard will be used for instruments calibration. A maintenance schedule will be prepared and followed for all instrumentation and recorded in the water-resistances field sheets. No entries will be erased instead the incorrect information will be crossed out with a single line and correct information will be entered and initiated. Sampling equipment will be checked for visual material and mechanical integrity daily. A field dissolved oxygen kit based on the azide modification of the Winkler titration method will be used to validate the instrument s DO calibration on randomlycollected samples from 10 % of the monitoring locations sampled during each monitoring events. A manual for the test kit to be used is presented in Attachment 6. If the Winkler titration and the Quanta results deviate by more than 0.5 mg/l, the Quanta results will be flagged and the procedures presented in Section 16 of the QAPP will be implemented.

14 All field samples collected will be identify with a specific site identifier label. Weather conditions and visual observations of each station will be recorded in the field data sheet. The collected samples along with the temperature control sample supplied by EQ Laboratory will be stored upright in a cooler with ice. The temperature control will be checked to be sure the samples were maintained within the required 2 10 o C. If the temperature control sample is out of this temperature range, the results will be label Results Questionable Temperature Control Exceeded 10 o C. Section 16 presents the procedures the SJBE monitoring program will follow when the temperature control sample exceeds the acceptable limits. All samples will be sent to EQ Lab at the end of the sampling date (before the established holding times). 14 A duplicate sample for bacteria (Fecal Coliform and Fecal Enterococcus), and for nutrients (phosphate, nitrite + nitrate, ammonium), Biochemical Oxygen Demand (BOD), Chlorophyll a, oil & grease, total organic carbon, and turbidity will be collected at 10 % sampling site on days when these parameters are measure. The locations where duplicate samples are to be collected will be selected randomly. Laboratory QC check One distilled water blank (Method Blank) will be included for analysis during each monitoring event to identify any contamination occurring at the laboratory. One Cooler Temperature control blank will be checked to be sure the samples were maintained within the required 2 10 o C in the coolers. If the temperature control sample is out of this temperature range, the results will be label Results Questionable Temperature Control Exceeded 10 o C. Section 16 presents the procedures the SJBE monitoring program will follow when the temperature control sample exceeds the acceptable limits. EQLAB will include all lab control samples (Reagent Blank, Lab. Duplicate, Lab. Matrix Spike, Matrix Spike Duplicate, Lab. Control Sample, Surrogates, and Internal Standards) for each monitoring event. The SJBE program will request the QA/QC data sheets from EQLAB which after examination by the QAPP Coordinator or QA Officer will be included in the SJBE monitoring program records. Laboratory

15 control elements, including spikes and blanks, will be performed according to EQLab protocols and procedures (see Appendix 4 of the QAPP). 15 Data analysis QC checks The QAPP coordinator and/or QA Officer will be present during each monitoring event. They will check the field and laboratory QA/QC data for any deviation from the Data Quality presented in Section 8 of the QAPP. They will calculated the Relative Percent Deviation Difference of any field duplicates and their corresponding samples using the formula presented in Section 8.1 of the QAPP. The QAPP Coordinator and/or the QA Officer will ensure that all field equipment is appropriately maintained and/or calibrated, and inspect data for any measurements indicating equipment or method malfunction.

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