Detailed Briefing Document: Environmental Sampling and Water Quality

I. Local Environment: Tampa Bay (Source: "Local Environment and Regulatory Scope.pptx.pdf")

• Overview: Tampa Bay is highlighted as the "largest open water estuary in Florida" and is home to over 2.4 million people. Despite being considered impaired, its water quality has "drastically improved" from historical conditions. It also features the "second largest ebb tide delta in Gulf of Mexico."

• Formation and Characteristics: The bay's formation is linked to Florida's geological history, including volcanic activity, sedimentation over millions of years forming the Florida carbonate platform, and karst topography. During the ice age, it was a Savannah, with its current morphology resulting from sea-level rise. The bay's average depth is "12 feet with dredged channels reaching 43 feet deep."

• Watershed: The total freshwater influx into Tampa Bay is significant, ranging "between 1,200 and 2,200 million gallons per day." Florida's porous limestone geology is also noted.

• Salinity and Tidal Circulation: Tampa Bay is classified as a "Partially mixed system" with "Semidiurnal tides to diurnal at times." Tidal height is influenced by winds. Exchange with the coast occurs primarily at Egmont Key, following the shipping channel.

• Residence Times: The overall residence time for water in Tampa Bay ranges from "75 to 150 days," while in the shipping channels, it's shorter, "15 to 30 days."

• Habitats: The bay supports diverse habitats including "Mangrove Forests," "Salt Marshes," "Salt Barrens," "Oyster Bars," "Hard Bottom," "Tidal Rivers and Tributaries," "Artificial Habitats," "Open Bay," and "Barrier Islands."

• Mangrove Forests: Consist of four species (red, black, white mangrove, and buttonwood), which are "Facultative halophytes: grow in freshwater too." Climate change and decreased freshwater are causing a transition from salt marshes and flats to mangroves.

• Salt Marshes: Can be "oligohaline (2-15 ppt)" and are important for the reproduction of various fish species. Dominant plant species include black needle rush, saltmeadow cord grass, smooth cord grass, and sawgrass.

• Organisms: The bay is home to a wide array of organisms from "Phytoplankton" to "Manatees" and "Dolphins." Phytoplankton groups include picoplankton, chlorophytes, cryptophytes, cyanobacteria, dinoflagellates, and diatoms, each with different responses to nutrient availability.

• Species of Commercial Interest: Recreational and commercial saltwater fishing contribute significantly to the economy. Top commercially important species in the Tampa Bay area (as of the provided data) include "Stone Crabs: $23,708,871," "Pink Shrimp: $15,154,929," and "Blue Crab: $9,676,374."

• Invasive Species: Several invasive species pose threats to the bay's ecosystem, including "Brazilian Pepper," "Green Mussels" (which "Displace oysters"), and "Lion Fish." Introduction pathways include "Released Pets," "Ballast water," "Panama Canal," and "Shipping containers."

II. Regulatory Scope: FDEP Standard Operating Procedures (SOPs) (Source: "EVR2892C Midterm Study Guide.docx.pdf" and "Local Environment and Regulatory Scope.pptx.pdf")

• Importance and Purpose: FDEP SOPs are crucial for ensuring "appropriate, reliable, and sound scientific procedures for data collection" across chemical, physical, biological, microbiological, and toxicological analyses. They "Assures appropriate, reliable, and sound scientific procedures for data collection."

• Regulatory Use: All parties producing data for the FDEP are "required to use SOPs."

• SOP Categories: The FDEP SOPs are organized into categories denoted by two-letter codes:

• FA: Administrative & Quality Systems (includes intent, purpose, and regulatory use of SOPs).

• "FA 1200 Regulatory use: All parties producing data for FDEP required to use SOPs."

• FC: Cleaning/Decontamination Procedures

• FD: Field Documentation

• FM: Field Planning and Mobilization

• FQ: Field Quality Control

• FS: Field Sampling (includes general procedures and specific procedures for aqueous, surface water, groundwater, drinking water, wastewater, soil, and sediment sampling).

• FT: Field Test Measurements (covers various field parameters like pH, specific conductance, salinity, temperature, dissolved oxygen, and turbidity).

• Documentation Considerations: Proper documentation is emphasized, including sample collection details, holding times, and ambient field conditions.

• Training: While FA 5000 (Field Training) is listed, it's noted as "Listed only for biological procedures" in the provided excerpts. However, training SOPs exist for specific biological assessments like the stream condition index (FS 7420) and stream habitat assessment (FT 3000).

• Sample Collection Matrices: FDEP SOPs categorize sample collection matrices into:

• Aqueous Environmental Matrices (e.g., potable water, groundwater, surface water).

• Aqueous Waste Matrices (e.g., aqueous chemical waste, industrial wastewater).

• Non-Aqueous Environmental Matrices (e.g., soil, sediment).

• Non-Aqueous Waste Matrices (e.g., non-aqueous liquid industrial sludge, solid chemical waste).

• Biological Tissue Matrices (e.g., finfish, shellfish, plants).

• Air Matrices (e.g., remedial treatment system exhaust, soil vapor).

• Substrates (e.g., contaminated surfaces).

• Analyte Groups: SOPs also define analyte groups for both aqueous and non-aqueous matrices, influencing sampling and analytical methods. Examples include:

• Aqueous: Volatile organics, extractable organics (PCBs, PAHs), petroleum hydrocarbons, metals, inorganic non-metallics (nutrients), aggregate organics (BOD, TOC), microbiological (bacteria, protozoa, viruses), volatile inorganics, and physical/aggregate properties (pH, turbidity, salinity).

• Non-Aqueous: Similar categories to aqueous, with some differences like "Biologicals: benthic macroinvertebrates and periphyton" and "Physical and aggregate properties: particle size."

III. Water Quality Concepts (Source: "EVR2892C Midterm Study Guide.docx.pdf" and "Water Quality Concepts- - Copy.pptx.pdf")

• Properties of Water: Water's polarity and hydrogen bonding are fundamental properties that contribute to its role as a "universal solvent," enabling it to carry dissolved chemicals, minerals, and nutrients essential for life.

• pH:Defined as "- log [H+]," indicating the concentration of hydrogen ions.

• Scale ranges from acidic (low pH, high [H+]) to alkaline (high pH, low [H+]), with 7 being neutral.

• Logarithmic scale where a change of one pH unit represents a tenfold change in [H+].

• Example: If "[H+] = 1.0 x 10-3," then "pH = - (-3) = 3."

• Importance: Affects the "Solubility (amount of metals... that can be dissolved in the water)" and "Biological availability (amount of nutrients... that can be utilized by aquatic life)." Metals tend to be more toxic at lower pH due to increased solubility. pH also influences aquatic organism health and the suitability of water for various uses (taste, corrosion, disinfection). Buffers resist pH changes.

• Oxygen Levels:Dissolved Oxygen (DO) is the amount of gaseous oxygen dissolved in water, crucial for aerobic respiration of aquatic life.

• Oxygen enters water through diffusion, aeration, and photosynthesis. It is consumed through respiration and decomposition.

• Factors affecting DO: temperature (higher temp = lower DO), salinity (higher salinity = lower DO), barometric pressure (lower pressure = lower DO), altitude (higher altitude = lower DO), organic waste (high BOD reduces DO), and turbidity (high solids can hinder oxygen dissolution).

• Classifications: "Hypoxic- low DO (2 mg/L) Anoxic- no DO (0 mg/L)."

• Biochemical Oxygen Demand (BOD) measures the oxygen required to degrade organic matter. High BOD leads to lower DO.

• Temperature: Impacts chemical (e.g., DO concentration) and biological (e.g., metabolic rates) characteristics of water. Riparian vegetation helps regulate temperature and thus DO.

• Salinity: Dissolved salt content, measured in parts per thousand (ppt). Influences the types of organisms that can survive (halophytes, halophiles, euryhalines, stenohalines).

• Nutrients (Nitrogen, Phosphorus, Potassium):Essential macronutrients for plant growth and biological processes.

• Nitrogen (Total Nitrogen (TN) = Organic-N + NH3-N + NO2 + NO3; TKN = Organic N + NH3-N) is a component of proteins, enzymes, and chlorophyll. Sources include animal waste (ammonia nitrogen) and plant tissue (organic nitrogen). Nitrite and nitrate are other inorganic forms.

• Phosphorus (Total Phosphorus (TP), Orthophosphate (PO4)) is involved in photosynthesis, energy transfer, and plant maturation. Sources include phosphoric acid and trisodium orthophosphate. Polyphosphates in detergents can convert to orthophosphate in water. Phosphate mining is also a source.

• Potassium aids in drought resistance, disease resistance, starch production, root growth, and stomata regulation.

• Excess nutrients can lead to eutrophication and harmful algal blooms, depleting DO.

• Standards for Quality of Water:BOD (Biochemical Oxygen Demand): Amount of oxygen consumed by microorganisms in decomposing organic matter. Higher BOD indicates more organic pollution.

• DO (Dissolved Oxygen): Concentration of oxygen in water, essential for aquatic life.

• Turbidity: Measure of water clarity, affected by suspended particles. High turbidity reduces light penetration. Measured in Nephelometric Turbidity Units (NTU).

• Trophic State Index (TSI): Classification system for rating lakes based on biological productivity, often calculated using chlorophyll-a, total nitrogen, total phosphorus, or clarity (Secchi disk). Ranges from oligotrophic (low productivity, good quality) to hypereutrophic (high productivity, poor quality).

• Other mentioned standards include pH and specific conductance (salinity).

• Analyte Chemistry:VOCs (Volatile Organic Compounds): Low boiling points, evaporate easily (e.g., fuel components, solvents). Typically analyzed using a "2-step procedure" involving "Separation/Extraction" and "Detection." EPA Method 8260B (GC/MS) involves sparging VOCs from the sample with helium, trapping them on a desorption tube, separating them in a capillary column, and identifying them by their mass spectra.

• SVOCs (Semi-volatile Organic Compounds), PCBs (Polychlorinated Biphenyls), PAHs (Polynuclear Aromatic Hydrocarbons): SVOCs have higher boiling points. PCBs and PAHs are examples of extractable organic compounds, often analyzed by GC-MS. PAHs form from incomplete combustion of hydrocarbons, are "Highly toxic and carcinogenic," and "Poorly soluble in water" (e.g., anthracene, chrysene, fluoranthene).

• Petroleum Hydrocarbons: Include oil & grease and Total Recoverable Petroleum Hydrocarbons (TRPH). Analytical tests categorize them by carbon range (e.g., Gasoline Range Organics (GRO), Diesel Range Organics (DRO)). Can be aliphatic (straight/branched chains) or aromatic (contain benzene rings).

• ICP (Inductively Coupled Plasma): Technique used for metal analysis. Plasma (ionized gas at high temperature) ionizes the sample, and the resulting ions are measured to determine metal concentrations. ICP-MS measures ions by their mass-to-charge ratio, while ICP-AES (or ICP-OES) measures the light emitted at specific wavelengths. FIAS (Flow Injection Analysis System) enhances metal separation but is not an analytical method itself.

• Inorganic Non-Metallic Constituents: Nutrients (nitrogen, phosphorus), chloride, sulfate, silica, residual chlorine, and dissolved oxygen.

• Metals: Can be measured as total or filtered (passing through a 0.45 µm filter). "Clean-hands" techniques are needed for ppt levels. Examples include mercury, chromium VI, antimony, cadmium, copper, lead, nickel, selenium, silver, and zinc.

• Sampling Design:2-step procedure for VOCs: Separation/extraction and detection.

• Steps for Planning Sampling Design: Involves defining objectives, target and sampled populations, sampling units, and determining the number, type, and location (spatial/temporal) of samples.

• SOPs needed prior to sampling: FA 1000 (Administrative Procedures), FC 1000 (Cleaning), FD 1000-9000 (Documentation), FM 1000 (Field Planning), FQ 1000 (Field QC), FS 1000 (General Sampling), FS 2000 (General Aqueous Sampling), etc.

• Quality Assurance/Quality Control (QA/QC): QA ensures the reliability of the entire process, while QC involves specific checks to monitor data quality.

• Types of Sampling:Judgemental: Based on expert opinion.

• Simple Random: Each sampling unit has an equal chance of selection. Provides unbiased estimates but can be difficult to implement geographically.

• Stratified Sampling: Population divided into strata (sub-populations) based on prior information. Can increase precision.

• Systematic Sampling (including Grid): Samples collected at regular intervals (spatial or temporal). Useful for identifying hotspots and ensuring uniform coverage.

• Ranked Set Sampling: Two-phase design using field screening to select representative samples, effective for soil contamination.

• Sediment and Soil Sampling:Distinguishing characteristics: Sediment is submerged in aquatic environments, while soil is unconsolidated material on the Earth's surface supporting land plants and is not submerged. Dirt is commercially worthless material.

• Soil Horizon Profile: O (organic), A (organic-rich), E (leached), B (subsoil), C (weathered parent material).

• Texture-by Feel Analysis: Protocol for determining soil texture.

• VOC sampling vs. Composite soil sampling: VOC sampling often uses soil core samplers (EPA Method 5035) to minimize loss of volatiles. Composite sampling involves mixing multiple subsamples to obtain an average representation.

• Sediment and Soil Collectors: Various types including coring devices (core barrel, split-spoon), grab samplers (Ekman, Ponar, Petersen, Shipek, Orange-Peel, Smith-McIntyre), shovels, and augers. Table FS 4000-1 summarizes bottom sampling equipment, outlining their uses, advantages, and disadvantages (e.g., Ekman for soft sediments, Ponar for various substrates, potential for sample loss or contamination with some devices).

• Surface Water Sampling:Methods: Direct grab, intermediate vessels (cone and churn splitters for subsampling or creating homogeneous composites), Kemmerer and Van Dorn samplers (depth-specific), double-check valve bailers, and weighted grab samplers (can be depth-integrated using Equal Width Increment Sampling).

• Preservation: Dechlorinate/filter if needed, preserve according to FS 1000-4 to FS 1000-8 tables immediately (within 15 minutes), chill to 4-6°C, and check pH of pH-preserved samples. Avoid dipping pH paper into the sample.

• Compositing: Can be discrete time aliquots or flow/stage proportional. Automatic samplers can be used, except for oil and grease/TRPH samples.

• Special Handling for TPH: Avoid skimming, pre-rinsing bottles, and automatic samplers. Preserve with acid and chill.

• Surface Water Classification (FAC 62-302.400): Class I (Potable), Class II (Shellfish), Class III (Fish consumption/recreation), Class III Limited, Class IV (Agricultural), Class V (Navigation/industrial). Each class has specific water quality criteria for various constituents (e.g., arsenic, cyanide, mercury).

• Stage and Streamflow:Stage (Gauge Height): Height of water surface above a datum (e.g., NAVD88), accurate to 0.01 foot. Used in stage-discharge relations. Measured with staff gauges.

• Stage-Discharge Relation: Empirical relationship between stage and streamflow (discharge).

• Discharge (Streamflow): Volumetric rate of flow (volume/time). Site selection for measurement requires uniform flow, avoiding turbulence, bends, sandbars, and vegetation.

• Field Equipment for Measurement: Marsh-McBirney and Sontek flowtrackers (electromagnetic and acoustic Doppler), Price current meter (mechanical), acoustic Doppler current profilers (sonar), V-notch weirs and Parshall flumes (engineered structures). Logistics include wading rods, tag lines, cable cars, and sounding weights.

• Velocity Measurement: Two-point method (0.2 and 0.8 depth) for depths > 2.5 ft, one-point method (0.6 depth) for shallower depths.

IV. Quality Control (QC) (Source: "EVR2892C Midterm Study Guide.docx.pdf" and "Sampling Design.pptx.pdf")

• Purpose: QA/QC samples verify the integrity of the entire sampling process, assess bias (accuracy), and variability (precision).

• Types of QC Samples:Equipment blanks: Check cleaning procedures.

• Trip blanks (VOCs only): Check for leaks during shipment.

• Field blanks: Assess contamination from the onsite environment.

• Field duplicates: Assess lab and field repeatability.

• Split samples: Assess repeatability between laboratories.

• Laboratory blanks: Check for lab contamination.

• Spike samples (Lab/Field): Assess bias and matrix effects by adding a known concentration of analyte.

• Reference samples: Prepared samples with known concentrations to measure bias and variability over time.

• FDEP Requirements: FDEP requires a minimum of 5% QC samples.

• Data Quality Objectives (DQOs) and Quality Assurance Plans (QAPs): Guide the amount and type of QC needed based on the study's objectives and required data quality.

• Pointers for QC Data: Define acceptable contamination levels beforehand. Surrogate and recovery data are critical for interpreting organic results. Precision data strengthens conclusions, and blank data provides confidence in methods. Publishing QC data is good practice.