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Standard Operating Procedure (SOP) for Hazardous Waste Sampling

 Standard Operating Procedure (SOP) for Hazardous Waste Sampling, incorporating detailed guidance on collecting representative samples from various sources, including tote tanks (wastewater), solid waste from bulk piles drums and bags. The SOP retains the original structure and integrates the new content seamlessly, ensuring compliance with U.S. EPA, RCRA, and SW-846 guidelines. The focus is on methods to ensure representativeness, tailored to specific waste types and containers, while maintaining brevity where possible.

 Standard Operating Procedure (SOP) for Hazardous Waste Sampling

1. Purpose

This SOP outlines procedures for collecting, preserving, and handling hazardous waste samples to ensure compliance with U.S. EPA regulations under RCRA (40 CFR Part 261) and to produce representative, defensible data for waste characterization, identification, and disposal. Emphasis is placed on obtaining representative samples from tote tanks (wastewater), solid waste in bulk piles, drums, and bags.

2. Scope

This SOP applies to sampling solid, liquid, and semi-solid hazardous waste streams at facilities generating, treating, storing, or disposing of hazardous waste. It covers sampling equipment, containers, preservation, chain of custody (COC), quality assurance/quality control (QA/QC), and methods for ensuring representative sampling from various sources.

3. References

- U.S. EPA. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods (SW-846), Chapters 9 and 10.

U.S. EPA. RCRA Waste Sampling Draft Technical Guidance (August 2002).

40 CFR Part 261, Identification and Listing of Hazardous Waste.

ASTM Standards (e.g., D5679-95a, D5680-14, D5743-97, D6063-11, D5088-15a).

 U.S. EPA. Laboratory Operations and Quality Assurance Manual (2015).

 U.S. EPA. Guidelines for Preparing Sampling Analysis Plans (SAPs).

4. Definitions

Hazardous Waste: Waste listed under 40 CFR Part 261 or exhibiting characteristics of ignitability, corrosivity, reactivity, or toxicity.

Representative Sample: A sample reflecting the average physical and chemical properties of the waste stream or batch, accounting for heterogeneity.

Chain of Custody (COC): A record documenting sample possession and handling from collection to analysis.

TCLP: Toxicity Characteristic Leaching Procedure (SW-846 Method 1311).

5. Responsibilities

Sampling Personne: Collect representative samples, label, preserve, and document as per this SOP.

Project Manager: Develops Sampling and (SAP), ensures RCRA compliance, and reviews COC.

Laboratory: Analyzes samples per SW-846 methods and maintains COC.

QA/QC Officer: Implements QA/QC protocols and verifies data integrity.

6. Safety

Wear PPE (gloves, safety glasses, steel-toed boots, respirators if needed).

Review Safety Data Sheets (SDSs) for waste hazards.

Follow OSHA guidelines (OSHA Technical Manual, Section II: Chapter 1).

 Decontaminate equipment to prevent cross-contamination (ASTM D5088-15a).

7. Sampling Equipment

Equipment is selected based on waste type and container:

Solid Waste:

 Trier: For soft solids or sludges (ASTM D5680-14).

 Scoop/Spatula: For granular or powdery solids.

 Coring Device: For consolidated solids (ASTM D5679-95a).

 Shovel: For bulk piles.

Liquid Waste (e.g., Tote Tanks):

Coliwasa: For multilayered liquids (ASTM D5743-97).

 Bailer: For drums or tanks.

Peristaltic Pump: For wastewater or low-viscosity liquids (USEPA 1996b).

 Dipper: For shallow liquids.

General:

  Stainless steel or Teflon-coated tools.

  Pre-cleaned containers (glass or HDPE).

 Decontamination supplies (deionized water, detergent, 10% nitric acid).

 Field notebook, labels, indelible markers, GPS device.

8. Sampling Containers and Preservation

Containers and preservation depend on analyte and waste type (SW-846, 40 CFR Part 261).

8.1 Solid Waste Containers

Glass Jars (250 mL–1 L, wide-mouth, Teflon-lined caps):

For VOCs, semi-volatiles, metals.

HDPE Bottles (500 mL–1 L):

For non-volatile inorganics, TCLP.

Polypropylene Bottles(1 L):

 For layered or composite solids.

8.2 Liquid Waste Containers

Amber Glass Bottles(40 mL–1 L, Teflon-lined caps):

For VOCs, semi-volatiles, pesticides (no headspace for VOCs).

Clear Glass Bottles (1 L):

 For metals, cyanide, sulfide.

HDPE Bottles (250 mL–1 L):

 For pH, corrosivity, inorganics.

 8.3 Preservation

VOCs: 4°C, no headspace, analyze within 7 days (14 days with HCl).

Metals: HNO₃ to pH <2, 4°C, 6 months (mercury: 28 days).

Cyanide: NaOH to pH >12, 4°C, 14 days.

pH/Corrosivity: Measure within 24 hours, 4°C.

TCLP Extracts: Analyte-specific preservation.

8.4 Container Preparation

 Use pre-cleaned, laboratory-supplied containers.

Label with sample ID, date, time, and sampler’s initials.

9. Sampling Methods for Representative Samples

Representative sampling ensures the sample reflects the waste’s average properties, accounting for heterogeneity (SW-846 Chapter 9, RCRA Guidance). Methods vary by waste type and container.

9.1 General Principles for Representative Sampling

Assess Heterogeneity: Evaluate waste for physical (e.g., layering, particle size) and chemical variability (e.g., concentration gradients).

Use Systematic Sampling: Follow a Sampling and Analysis Plan (SAP) specifying locations, frequency, and number of samples.

Composite vs. Grab:

 Grab Sampling: Single sample for homogeneous or small batches.

Composite Sampling: Combine multiple subsamples for heterogeneous wastes to average variability.

Statistical Approach: Use EPA’s systematic or random sampling strategies (SW-846 Chapter 9) to achieve 95% confidence in representativeness.

Avoid Bias: Sample all phases, layers, or sections of the waste

9.2 Wastewater from Tote Tanks

Characteristics: Liquids in tote tanks (e.g., 275–330 gallons) may have settled solids, oil layers, or chemical gradients.

Equipment: Coliwasa, peristaltic pump, or bailer.

Procedure:

  1. Inspect Tank: Check for layering, settling, or floating phases via inspection port or dipstick.

  2. Mix if Possible: If safe and permitted, stir tank contents using a mechanical mixer or paddle to homogenize (avoid for VOCs to prevent volatilization).

  3. Coliwasa Sampling (preferred for multilayered liquids, ASTM D5743-97):

 Lower a clean Coliwasa slowly to the tank bottom.

Seal the top to capture a vertical column of all layers.

Transfer to a composite container (e.g., 1 L amber glass for VOCs).

  4. Peristaltic Pump Sampling (for large volumes or continuous sampling):

 Insert tubing to multiple depths (top, middle, bottom).

 Pump equal volumes from each depth into a composite container.

  5. Bailer Sampling (for smaller tanks or grab samples):

Lower a bailer to specific depths, collecting subsamples from each layer.

Combine subsamples in a composite container.

  6. Composite Sampling:

Collect 3–5 subsamples from different depths or locations.

Mix in a clean stainless steel or glass container before transferring to sample bottles.

  7. Label and Preserve: Fill containers per Section 8, preserve immediately (e.g., 4°C for VOCs, HNO₃ for metals).

Frequency: Minimum one composite sample per tank; additional samples for large or variable tanks (per SAP).

QA/QC: Collect duplicates (10% of samples) and trip blanks for VOCs.

9.3 Solid Waste from Bulk Piles

Characteristics: Bulk piles (e.g., soil, sludge, ash) are often heterogeneous with varying particle sizes, moisture, or contaminants.

Equipment: Trier, scoop, shovel, coring device.

Procedure:

  1. Map the Pile: Divide the pile into a grid (e.g., 1 m² sections) or zones (surface, middle, core) using stakes or markers.

  2. Determine Sampling Points: Use systematic random sampling (SW-846 Chapter 9):

Select 5–10 points across the grid, covering all zones (surface, 0.5 m depth, 1 m depth).

For large piles (>100 tons), increase points per SAP (e.g., 1 sample per 25 m³).

  3. Collect Subsamples:

 Surface Sampling: Use a scoop or trier to collect 100–500 g from the top 10 cm.

 Depth Sampling: Use a coring device or shovel to collect from 0.5–1 m depths (ASTM D5679-95a).

 Remove large debris (e.g., rocks >2 cm) unless specified in the SAP.

  4. Composite Sampling:

 Combine subsamples in a clean stainless steel or glass bowl.

Mix thoroughly with a stainless steel spoon to homogenize.

Transfer 500 g–1 kg to a glass jar or HDPE bottle.

  5. Grab Sampling (if homogeneous): Collect a single 500 g sample from a central location.

  6. Label and Preserve: Store at 4°C, analyze within holding times (e.g., 7 days for VOCs).

Frequency: Minimum one composite sample per 100 m³ or as specified in SAP.

QA/QC: Collect field duplicates and equipment blanks to verify decontamination.

9.4 Solid or Liquid Waste from Drums

Characteristics: Drums (e.g., 55-gallon) may contain liquids, sludges, or solids with layering or settling.

Equipment: Coliwasa (liquids), trier or scoop (solids), bailer (liquids).

Procedure:

  1. Inspect Drum: Check for leaks, labels, or phase separation (e.g., oil, water, sludge).

  2. Liquid Sampling:

     Coliwasa (ASTM D5743-97):

 Insert Coliwasa to drum bottom, seal to capture all layers.

 Transfer to a 1 L amber glass bottle (VOCs) or HDPE bottle (inorganics).

    Bailer:

     Collect subsamples from top, middle, and bottom.

    Combine in a composite container.

  Mixing: If safe, gently roll drum to homogenize (avoid for VOCs).

  3. Solid/Sludge Sampling:

    Trier or Scoop:

Collect 100–500 g subsamples from top, middle, and bottom (ASTM D5680-14).

Combine in a stainless steel bowl and mix for composite sample.

       Transfer to a 500 mL glass jar.

     Core Sampling (consolidated solids):

 Use a coring device to collect a vertical core (ASTM D5679-95a).

  4. Composite Sampling:

Combine 3–5 subsamples from different depths or locations.

M Mix thoroughly before transferring to sample containers.

  5. Label and Preserve: Follow Section 8 for container and preservation requirements.

Frequency: One composite sample per drum; sample 10% of drums for large batches (per SAP).

QA/QC: Collect duplicates and trip blanks (for VOCs).

9.5 Solid Waste from Bags

Characteristics: Bags (e.g., 50 kg sacks) may contain powders, granules, or mixed solids with variable composition.

Equipment: Scoop, trier, or spatula.

Procedure:

  1. Select Bags: Randomly select bags (e.g., 10% of total or per SAP) using a random number generator or systematic selection.

  2. Inspect Bags: Check for tears, moisture, or segregation of contents.

  3. Collect Subsamples:

Open bag and use a trier or scoop to collect 100–200 g subsamples from top, middle, and bottom.

For small bags, collect from multiple locations (e.g., corners, center).

  4. Composite Sampling:

Combine subsamples from multiple bags or locations in a stainless steel bowl.

   Mix thoroughly to homogenize.

  Transfer 500 g to a glass jar or HDPE bottle.

  5. Grab Sampling (if homogeneous): Collect a single 500 g sample from the center.

  6. Label and Preserve: Store at 4°C, analyze within holding times.

Frequency: One composite sample per 10–20 bags or as specified in SAP.

QA/QC: Collect duplicates and field blanks.

9.6 Sampling Plan

Develop an SAP per EPA guidelines, specifying:

 Sampling objectives (e.g., TCLP, waste classification).

 Number and location of samples (e.g., grid for piles, random for drums).

  Composite vs. grab sampling strategy.

 Statistical confidence level (e.g., 95% for representativeness).

  QA/QC measures (e.g., duplicates, blanks).

10. Chain of Custody (COC)

COC Form: Document sample ID, date, time, location, sampler’s name, analytes, preservation, and custody transfers.

Procedure:

  Seal containers with custody seals.

  Store in locked coolers during transport.

 Transfer to laboratory with signatures.

  Retain COC copy for records.

11. Quality Assurance/Quality Control (QA/QC)

11.1 QA Measures

Train personnel in representative sampling techniques.

Use validated SW-846 methods (e.g., Method 1311 for TCLP).

Document deviations in field notebook.

11.2 QC Measures

Field Blanks: One per day to check contamination.

Trip Blanks: For VOC samples to detect transport contamination.

Duplicates: 10% of samples to assess precision.

Equipment Blanks: Verify decontamination.

Holding Times: Adhere to analyte-specific limits.

11.3 Data Validation

Verify COC completeness.

Compare results against QA/QC criteria.

Report anomalies to QA/QC officer.

12. Decontamination

 Rinse equipment with deionized water, detergent, and 10% nitric acid (for metals).

Final rinse with deionized water.

 Collect equipment blanks to verify cleanliness (ASTM D5088-15a).


13. Documentation

Record in field notebook:

 Sampling date, time, location (GPS coordinates).

  Waste type, container, and heterogeneity.

 Sampling method, equipment, and number of subsamples.

Preservation and COC details.

Retain records for 3 years per RCRA.

14. Regulatory Compliance

Comply with 40 CFR Part 261 for waste identification.

Use SW-846 methods for testing (e.g., Method 1010A for ignitability).

Ensure timely analysis within holding times.

 15. Waste Characterization

 Analyze for RCRA characteristics (ignitability, corrosivity, reactivity, toxicity).

Classify as listed (F, K, P, U) or characteristic waste.

16. Shipping and Handling

Package samples in coolers with ice packs (4°C).

Use leak-proof containers with secure lids.

Label as “Hazardous Waste Sample” if required.

Follow DOT regulations.

17. Training

Train personnel annually on:

 Representative sampling techniques.

 RCRA, SW-846, and safety protocols.

 COC and QA/QC procedures.

18. Revision History

 [Insert revision history]

19. Attachments

COC Form

SAP Template

Sampling Checklist

- QA/QC Checklist


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## Notes

- **Representativeness**: The key to representative sampling is addressing heterogeneity through systematic or random sampling, compositing subsamples, and following the SAP. For highly variable wastes, consult EPA’s RCRA Sampling Guidance (2002).

- **Customization**: Adjust the number of subsamples or sampling points based on waste volume, variability, and regulatory requirements.

- **Further Assistance**: If you need a specific SAP template, detailed calculations for sampling points, or additional guidance for a particular waste stream, let me know!


This SOP provides comprehensive guidance for representative sampling across tote tanks, bulk piles, drums, and bags while maintaining compliance with EPA and RCRA standards. Let me know if you need further clarification or additional details!

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