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Wastewater VOC survey, August 5, 6 2002
Phillips San Francisco Oil Refinery (Plant #A0016) Rodeo, California

Intention of the study is to determine VOC emissions from wastewater, ambient air locations, and VOC emissions from ancillary wastewater system process units.

Water Sample procedures: Two methods will be used to collect water samples. A coliwasa sampler is the preferred method. However, If the depth of the wastewater is less than one foot a grab sample method shall be used.

1 Coliwasa sample Sample size = 250 ml glass open mouth jar. (Coliwasa stands for composite liquid waste sampler). A coliwasa is designed to take a composite (from top to bottom) sample. The device used in this study is manufactured in high-density polyethylene with and Teflon coated topper, maximum sample size = 250 ml. (Reference: ASTM method D5495-94 (2001) Standard Practice for Sampling with a Composite Liquid Waste Sampler).
2 Grab sample (Sample size = 1 liter container) A grab sample is designed to collect a liquid samples whose upper surface can be accessed by the suitable device, i.e., manhole. The device used in this study uses a caged, i.e., protected, 1-liter glass sample container. (see ASTM method D6759-02 Standard Practice for Sampling Liquids Using grab and Discrete Depth samplers).
3 Air Sample air ambient air grab sample into a 6 liter Stainless steel Summa® passivated canisters. Canisters begin evacuated and will be allowed to return to ambient in wastewater areas and sewer openings.

Mechanics of Sampling:
Sewer manholes and junction boxes will be sampled via coliwasa or grab container. Process line sampling will be use standard Phillips 66 sampling procedures.

Sample prep and organizational meeting:

Non-Refinery Personnel Damian Breen, Tim Dunn, Matt Gerhardt
Refinery Personnel Dennis Quilici
Phillips 66 Labor: Two (2) technicians with confined space equipment (plus one laborer, if necessary)
Phillips 66 Equipment: LEL meter, equipment to open sewer manholes, fork lift if necessary.
Brown & Caldwell Equipment 1 liter caged bottle sampler, i.e. grab sampler.
BAAQMD & ARB Equipment plastic pipe: (a four foot section of three inch PVC) coliwasa tubes, associated plastic pipe to lower sampling device, measuring tape, plumb bob, 10 Summa® passivated canisters, one ice chest, ice. 24 250-ml sample glass wide mouth bottles, 72 VOA glass 40-ml sampling vials, 40 1-liter glass sampling containers, OVA meter, one (1) thermometer.
Time 30 minutes maximum per wastewater sampling location. Ambient air sampling, 15 minutes maximum per air sample.

Sampling Procedure for coliwasa and grab sampling locations


  1. Confirm if sampling area is a confined space entry using LEL meter and OVA meter. If lowering sampling device is considered a confined space activity, and then use Phillips 66 confined space entry procedures. Monitor for explosive gases using LEL throughout sampling activity, if necessary.
  2. Take a measurement of organic gases at 2 inches below manhole lip using OVA. and record measurement.
  3. Record dimensions of sampling area and piping.
  4. Measure depth of flow
  5. Lower 3-inch pipe containing coliwasa (or grab sampler) into sampling area if flow exist. Sample wastewater using coliwasa or grab device.
  6. Retrieve sampler. Place sample in secure location
  7. Repeat sample collection as necessary. Secure a separate sample for sample temperature measurement and observation of sample visual parameters using a graduated cylinder. Measure and record sample temperature using thermometer
  8. Store sample in wet ice.
  9. Retrieve 3-inch plastic pipe
  10. Place used coliwasa samplers in plastic bag.
  11. Place used 3-inch PVC pipe place in plastic bag.
  12. If no flow, collect air sample using Summa canister using sampling procedure detailed in ARB QA manual Volume II Appendix Q.
  13. Close sampling area

Sampling Locations

All sampling locations are shown on Phillips 66 drawing SFE 46-70-Y-1

Sample Date Sample Point Sample
Location		 Sample Type
8/5/2002 1 Sump near Marine Terminal Air
2 Groundwater extraction Water - tap
3 Box 1272 Water - sample thief
6 Box 1426 Water - Coliwasa
9 Laboratory sump Water - sample thief
8 Box 1056 while Laboratory sump pump was not discharging to box Water - sample thief
30 Dry weather sump Water - tap
25 Box 2410 Water - sample thief
23 Box 2348 Water - Coliwasa
24 Box 2312 Water - Coliwasa
22 Box 2421 Air
21 Box 2173 Water - Coliwasa
31 API Separator feed Water - tap
31B API Separator effluent Water - sample thief
32 DAF outlet Water - sample thief
33 PACT mixed liquor Water - tap
28 Box 1968 Water - sample thief
27 Box 1961 Water - sample thief
8/6/2002 15 Box 1786 Air
16 Box 1848 Water - Coliwasa
17 Coke cutting water Water - tap
19 Salt water cooling Water - sample thief
18 Unicracker east Water - Coliwasa
19C Unicracker west Water - Coliwasa
19D Unit 220 Water - sample thief
19B Box 20036 Water - Coliwasa
13 Box 1723 Water - Coliwasa
14 Box 1752 Water - Coliwasa
12 Box 2041 Water - sample thief
34 Equipment blank Water - Coliwasa

Notes:

  1. Spiking - lab will spike a 1 out of ever ten water samples.
  2. Preservation - Samples will be taken with sample containers supplied by McCampbell Analytical Inc. with preservative. Preserve wastewater samples will be stored in wet ice and transported to lab on same day samples were taken.
  3. Trip/equipment blank prepared using laboratory deionized / low organic water using unused coliwasa.
  4. One duplicate will use a coliwasa (using new coliwasa) a new section of 3-inch PVC pipe.
  5. Sample Labeling Code example: P-1 for Phillips 66 sample point #1.
  6. Field staff will measure the relative volumes of aqueous phase and oil phase using a graduated cylinder. Staff will record phases present in sample (e.g., solids, emulsion, water layer, and oily layer).
  7. Procedure for analyzing the wastewater samples will be EPA method 8015/8020. The wastewater samples are one phase (water). Each wastewater sample will result in two analyses (TPH gasoline & TPH diesel). McCampbell Analytical 110, Second Avenue South, D#7, Pacheco, CA 94553.
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