October 20, 1997

**Protocols For Collecting NRDA Samples SPILL SOURCE**

# Sampling Objectives

-   To obtain a sample(s) of the original product(s) involved in the
    incident, for characterization, fingerprinting, predicting fate and
    effects (via bioassays) of the spilled oil.

-   To maintain the integrity the spill source sample(s) during
    sampling, transport, and storage.

## Sample Volume

-   Ideally, collect a minimum of 1 liter per source sample. That is,
    for each location sampled (e.g., per tank, hold, etc.), one 1-L
    sample should be taken. If there are many different holds or tanks,
    take a small sample (250 ml) from each.

## Sampling Equipment/ Containers

-   Source samples can be collected directly into the sample container,
    minimizing risks of contamination. Use a device which holds the
    container, such as a Wheaton grab sampler (holds a 1-L bottle
    strapped to a metal rod with the ability to unscrew the cap
    remotely) or a Volskom sampler (frame which holds the container is
    lowered on a rope). For black oils, these methods can be messy,
    coating the device and container with oil.

-   Other types of samplers for transferring to a container include:
    drum thief; coliwasa (narrow tube with positive end seal); bailer;
    bomb sampler; and air-driven metallic pumps.

-   Sampler material, in order of preference: Teflon (there are
    inexpensive disposable models); PVC (may contribute phthalates, but
    should not interfere with interpretation); and glass.

-   Under emergency conditions, a new metal (preferred) or plastic (a
    last resort) bucket can be used after cleaning with soap and water.

-   Use glass containers, certified-clean as organic-free (i.e., solvent
    rinsed), with Teflon-lined lids. Wide-mouth containers are easier to
    fill. As a last resort, use clean \"mason\" jars.

-   Paper, metal, or plastic funnels are useful when transferring
    samples. Clean prior to use.

### **Sample Collection Methods**

-   Safety is of greatest concern. Be aware of physical and chemical
    hazards at the site. Get a safety briefing before entering the area.
    Do not enter confined spaces unless they have been determined to be
    safe. Use recommended safety equipment and procedures.

-   Collect the source sample as soon as possible, even for potential
    releases. Collect the freshest sample of the spilled material even
    if it is from the water, shoreline, etc.

-   Decon equipment after unique tank or hold is sampled with rinses of
    acetone or methanol, then

-   Methylene chloride. Collect all rinsate for proper disposal.

-   Give the source sample used for NRDA purposes a name other than just
    the spill name, since there could be multiple \"source\" samples
    collected for different purposes.

-   Label each sample container uniquely and sequentially, whether it is
    a replicate or from different storage tanks on a vessel. For
    example, Spill Name NRDA Source Oil No. 1-2P-rep 1 would be the
    first sample collected, from #2 port hold, replicate #1.

-   Fill out the chain-of-custody form, noting where each source sample
    was collected from, sampling device used, time/date of collection,
    size and container type, and sampler name.

-   Make special notation on the chain-of-custody form about any
    problems or observations during sampling, such as visual differences
    in samples from different tanks, presence of water in the sample,
    etc.

-   Maintain strict chain of custody during sample storage and
    transportation.

-   Ship source samples separately from environmental samples to reduce
    risk of cross contamination

## Preservation/Holding Times

-   Immediately place all samples in cooler and keep at 47C (do not
    freeze).

-   Use packing material, such as bubble wrap, around containers to
    prevent breakage.

-   Petroleum samples can be held at 4°C in the dark for up to 3-4
    months without *loss* of sample integrity, as long as there is no
    organic material or water present to serve as nutrients for
    bacterial growth.

**[Analytical Methods:]{.underline}**

-   **Petroleum products** are usually analyzed for fingerprinting
    purposes, so that the spilled oil can be differentiated from other
    petroleum sources. Chemical analyses for this purpose includes:\
    **Saturated Hydrocarbons (SHC)**. These compounds include n-alkanes
    and saturated isoprenoids. They are contained in the fl fraction
    obtained after column chromatography and measured by GC-FID
    analysis. The chromatographic trace can be used to differentiate
    among oils and is valuable for predicting the short-term weathering
    and fate of the oil\
    **Polynuclear aromatic hydrocarbons (PAH)**. PAHs are used to
    fingerprint the spilled oil, monitor weathering, and predict
    toxicity. If PAHs are to be measured, it is important that the
    analytes include the alkyl-substituted PAH homologs, in addition to
    the standard PAH \"priority pollutants." This method is referred to
    as Modified EPA Method 8270, because the list of PAHs is expanded to
    include the alkylated homologs, using GC/MS in the selected ion
    monitoring mode.\
    **Steranes and triterpanes**. These compounds are highly resistant
    to degradation and have a unique distribution for each oil type.
    Thus, they are valuable for differentiating among different sources
    of hydrocarbons. However, few laboratories have the ability for this
    analysis, which is a specialized method using GC/MS in the selected
    ion monitoring mode.

-   There are no general analytical guidelines for chemical products
    because of their variability.

# Other Considerations

-   There may be different products loaded in different compartments or
    tanks, even when only one type of product is involved (e.g., two
    different types of No. 2 fuel oil could be loaded). Before sample
    collection, get a loading diagram and as much data as possible on
    the products. Slight differences in product properties, such as
    specific gravity, may indicate different products. Each unique
    product should be sampled.

-   Make sure that the source sample(s) collected represent the material
    actually released. Again, product in intact holds may not be the
    same as the released product.

-   Be aware of sources of contamination or mixing of products onscene,
    such as transferring of product between holds, dilution with
    fire-fighting water, or application of a foam blanket.

**[Key References]{.underline}**:

NOAA, 1993. Sampling and analytical methods of the National Status and
Trends Program, National Benthic Surveillance and Mussel Water Projects,
1984-1992. Volume IV, Comprehensive descriptions of trace organic
analytical methods. Lauenstein, G.G. and A.Y. Cantillo (eds.). NOAA
Tech. Memo NOS ORCA 71, Silver Spring, MD. 181 pp.

Sauer, T.C. and P.D. Boehm. 1995. Hydrocarbon chemistry for analytical
methods for oil spill assessments. Marine Spill Response Corporation
Technical Report Series 95-032, Washington, D.C. 114 pp.

USEPA, 1979. Methods for chemical analysis of water and wastes.
EPA-600/4-79/020. USEPA Environmental Monitoring Systems Laboratory,
Office of Research and Development, Cincinnati, Ohio.

USEPA, 1986. Test methods for evaluating solid waste. SW 846 Third
Edition (and updates).