Chapter 4

Volume 2 Start Chapter 1 Chapter 2 Chapter 3 Chapter 4

 

4        Sampling

 

4.1        General

 

4.1.1          Purposes of sampling

General
Sampling and subsequent analysis shall answer questions regarding spills’ origin as well as their properties and effects. To accomplish this, samples should be taken for several different purposes, which are dealt with in this Chapter.

Some spills may involve contacts and co-ordination with other countries regarding sampling and analysis. Occasionally, foreign agencies should be contacted to exchange samples, analysis results, examination reports, etc.

The following list describes eight purposes of sampling after incidents or accidents involving hazardous substances or packaged dangerous goods. Most often only a few of them are appropriate in a specific case.
 

1.

Occupational safety
When necessary, the spill should be examined (analysed) to establish whether there are any health risks for the response personnel. The substance may be flammable and cause fire and/or explosion, or may be toxic and cause danger to health if inhaled or exposed to skin.
 

2.

Penal liability
The responsible polluter should, if possible, be identified and be charged for the spill. This can be done by comparing chemical analyses of samples from the spill with samples from suspected sources. If identity is established between the spill and a suspected source, this can help to identify the polluter.
 

3.

Polluter’s economical liability
The results of sampling have often been used as a basis for compensation claims against the polluter. These claims may concern costs associated with response and cleanup measures, or damage to property, fishery, recreational areas, etc. Above all, it is important to tie the suspected polluter to the damage in order to confirm the claims.
 

4.

Spill response planning
On some occasions, special analyses can give important information that can support planning of response and cleanup work. It is important to study chemical and physical property data of the substance when selecting equipment and methods as well as safety routines for the response operation.
 

5.

Short term environmental protection
The substance’s acute deleterious effects on the environment can vary considerably depending on its properties. Many chemicals show acute toxic effects to the marine life and some substances have a tendency to smear beaches, plants and animals. Besides identifying the substance it may be necessary to sample and analyse the water column, sediment, organisms, etc.
 

6.

Long term environmental protection
Certain substances may cause long term deleterious effects on the environment, and some species may be knocked out, or the environment be polluted for a long time. Assessment should be made to judge how the environment can be restored. It may be necessary to sample and analyse the substance itself, as well as water, sediment, organisms, etc.
 

7.

Information service
Many and sometimes tricky questions are asked about the substance’s properties and effects, especially when facing a large or hazardous spillage. In such cases it is important to give rapid and correct information in order to reduce anxiousness and circulating of rumours. Sampling and analysis can thereby provide the basis for information to be given and for the choice of  information channels. When informing the public, and those who are directly affected by the spill, it is important to account for certain data, for example: 

w

the spill’s origin and extension

w

the substance’s properties and spread in the environment

w

effects on human and environment

w

consequences for various parties and bodies

w

ongoing work regarding response, cleanup and disposal
 

8.

Disposal
The selection of techniques for the subsequent disposal is based on the type of substance and its properties, and the spill’s volume. Many disposal plants are specialized for certain hazardous materials and cannot process other types.
 

4.1.2.         Responsibilities during sampling

Spills occur every day in the marine as well as inland aquatic environment. Although most of the spills are very small, they still often require sampling to get a chance of linking them to the responsible polluters and assess the damage to environment. It is therefore important to trace all conceivable polluters as soon as possible. There is a great need for co-ordination as the sampling activities for spills and suspected sources may go on simultaneously at different places. This work may very well be performed by a permanent Sampling Co-ordinator within the environmental response organisation. This Co-ordinator should be subordinated to the District Chief of the Environmental Response Organisation. During the Organisation’s everyday work the Sampling Co-ordinator keeps record of spill samples from various sites and initiates sampling on board suspected sources when overlooked by the field officers.

The sampling activities may increase considerably during more significant accidents involving spills of hazardous materials. Many different samples may be taken for several different purposes. Many authorities and institutions may be involved in the sampling activities and a confusing situation may arise where different bodies work, perhaps without being aware of each other. On such occasions, it is crucial to co-ordinate the activities to avoid duplication of work, as well as to avoid missing chances of important sampling. Such co-ordination could also promote prevention of anxiousness and circulating of rumours which often happen during major and hazardous spill accidents. In this situation, the Environmental Response Commander should appoint an ad hoc Sampling Co-ordinator to be responsible for the overall co-ordination of all sampling work during the run of the response operation.

If co-operation starts, during a major spill accident, between two or more different national response services, an agreement should be settled on a joint ad hoc Sampling Co-ordinator. The Sampling Co-ordinator should be responsible for the overall co-ordination of all sampling on land and at sea during the run of the response operation. When the accident response phase is finished, and the long-term cleanup work has started, the responsibility for sampling is normally handed over to the local Municipality. However, it is convenient that the original ad hoc Sampling Co-ordinator maintains the duty for sampling concerning the polluter’s penal and economic liabilities.

The contact network for the Sampling Co-ordinator and various bodies is shown in Figure 4 - 1


Figure 4 - 1

 

4.1.3          The duties of the Sampling Co-ordinator
 

1.

Establish a plan for documentation of the sampling work.
 

2.

Make arrangements for appropriate sampling if health risks are liable to occur.
 

3.

Make sure that necessary samples are taken concerning extent and accuracy of both spill and contaminated items as well as suspected sources.
 

4.

Judge if special examinations of the spill are needed to facilitate spill response measures.
 

5.

Judge if short term and/or long term environmental impact may be expected. In such a case, contact appropriate agencies.
 

6.

Judge if special examinations and analyses are needed when providing for general and specific needs for information.
 

7.

Contact responsible bodies for transport and disposal. Check what special information is needed in this context and make arrangements for relevant analyses.

 

4.1.4         General checklist for sampling

1.

Sampling actions on unknown materials should be taken on a “worst possible case basis”, i.e. if nothing is known whatsoever about the substance it should be considered as extremely hazardous and due safety precautions should be taken.
 

2.

All spills encountered and all potential sources of spills should be sampled. It is important to take samples from both spill and source even on such occasions where it seems quite clear from where the spill originates. Use at first hand the type of sampling equipment and routines described in this Chapter.
 

3.

Sampling procedures, which are connected to liability investigations, must be performed with great care and accuracy concerning spills as well as suspected sources. Every action should be taken to prevent a decrease in the samples’ value as evidence.
 

4.

If a spill has scattered on the water surface and only thin sheens remain, yet every possible effort should be made to take at least a small sample. No sample volume is too small to be shipped to the laboratory. The laboratory can often analyse very small samples, for example water samples that seemingly consist of pure water or sample pads that do not show any trace of substance.
 

5.

Assistance should be received from appropriate expertise on occasions of hesitation. All sampling of chemicals on board vessels or in other sources should, if possible, be left to the crew or staff, or should be carried out in close co-operation with the crew/staff. Special safety precautions must be taken during sampling activities in atmospheres that might be explosive.
 

6.

Samples and sampling equipment should be handled and stored so that the samples cannot be manipulated, mixed up, or else be contaminated by strange substances. Samples should be handled as legal evidence and should be kept in a “chain of custody” until identification and possible legal procedure has been completed. Therefore, always use a type of sealable and individually numbered safety bags described later in this Chapter.
 

7.

A bottle containing a sample should not be placed in the sampling kit together with the clean equipment. Reusable sampling equipment should always be very carefully cleaned, and put into clean plastic bags, before restoring in the sampling kit case. Used sample bottles must not be used again - not even after careful washing.
 

8.

Make notes of all relevant information about samples and sample sites. Use a miniature camera or a video camera to record observations which are considered important for the investigation.
 

9.

The samples should be immediately sent to the Sample Co-ordinator. Quick handling of samples is important. If the transmittal is delayed the samples should be kept under a temperature of less than +4°C
 

10.

Consumed equipment should be replaced as soon as possible so that the sampling kit case always is fit for use and so that new samples can always be quickly taken, packed and sent away.
 

4.1.5         Handling of spill information
A whole chain of activities leads to the information to be presented about the spill.
This chain consists of:
 

Sampling

Sample keeping and transmittal

Identification, labelling, documentation

Chemical, physical and biological analyses

Judgement of the analysis results

Presentation of the analysis results
 

Each step must be taken with care and accuracy. This is a prerequisite for a compilation of an information report which is as capable as the circumstances allow. Points to be observed during sampling and subsequent handling of samples, are for example:
 

Several samples must be taken from spills covering large areas or divided in several locations.
 

Sampling in a suspected source must be performed in such a careful way that the suspected polluter with certainty can be tied to, or cleared of, the spill.
 

All samples must be labelled so that they can be unmistakably referred to the sampling points.
 

Sample containers must be labelled, closed and kept in such a way that any supposition on confusion or manipulation can be excluded.
 

All sampling documentation, as well as other evidence, must be available during the investigation, but also be protected from loss, confusion and manipulation.
 

Continuing record-keeping must be made regarding all transmissions of samples, other evidence and documentation between officials.
 

The Sampling Co-ordinator is responsible for transmission of samples to the appointed laboratories.
 

4.2        Sampling chemical spills
             on the water surface      


4.2.1         
Thick waterborne layers, small globules and balls

If possible, focus the sampling on thick parts of the spill. If the spill is large it is important to take samples in several positions of the spill to get a representative sample selection.

Globules, balls and thick parts can often be sampled directly by a sample bottle. Fill the bottle with as many balls as possible or skim substance from the surface by repeated sweeps with the bottle. Remove the water which has entered the bottle (see Section 4.8.2 item 2). Then continue to skim substance and try to get as much as possible of dewatered chemical (a few millilitres are better than nothing).
 

Floating films (thickness greater than appr. 1 mm) or balls on the water surface can with advantage be sampled by a polyethylene cornet (cf. Figure 4 - 2). The cornet should have a wide hem into which a metal ring could be threaded. First cut off the tip of the cornet as shown in the picture.

A holder is fitted onto the ring and by means of this holder the device can be fastened to a boathook or the like.


Polyethylene cornet


Metal ring

 


Holder
 

 

Figure 4 - 2
 

The assembled device is swept through the spill so as to skim as much substance as possible.

Figure 4 - 3

 

Figure 4 - 4


Figure 4 - 5

The water in the cornet is slowly let out and the drainage is stopped when the last drop of water has escaped. Then the substance in the cornet is filled into a 100 ml wide-neck sample bottle. The same procedure is then repeated once or several times until the bottle is approximately three-quarters full of dewatered substance.

N.B. Do not fill the bottle to a higher level than up to 2 cm below the lower edge of the lid.


Figure 4 - 6

 

 

4.2.2         Thin waterborne films (sheens)
A special teflon pad may be used if the substance film on the water surface is very thin (thickness less than appr. 1 mm). The pad material should be teflon because other materials may interfere with the succeeding analytical process in the chemical laboratory.

A practical arrangement for handling a pad is shown in Figure 4 - 7. Great care must be taken during sampling to avoid contamination of the sheen by traces of substances from the sampling vessel or from other sources. The pad should be swept in the spill many times until reasonable assurance is gained that the pad has absorbed at least an amount of substance enough for the analysis.


rod and line

 


clothes peg


teflon pad

 

Figure 4 - 7

 

After a sufficient number of sweeps the teflon pad is carefully put into a sample bottle. The peg can be used to push the pad into the bottle. Another clean wooden peg of any kind can, if necessary, be used to assist in the procedure. It is important to avoid contact with any item that could possibly contain traces of strange substances.

 


Figure 4 - 8

4.3        Sampling chemical spills
             in the water column

Chemical spills that disperse or dissolve in the water column can be sampled by ordinary water sampling equipment. There exist a great variety of such equipment. Bottles mounted in holders (Figure 4 - 9) may be used for sampling the upper 0-30 m water layers. Other sophisticated, more or less automatic devices (Figure 4 - 10) may be more suitable for taking samples at greater depths.

Picture source: HYDRO-BIOS GmbH

Figure 4 - 9

Figure 4 - 10

 
4.4        Taking samples from sunken chemicals
 

Sunken chemicals lying on the seabed are most often sparingly soluble or at least of rather low solubility. Sampling can be performed in various ways. In shallow water a SCUBA diver might be able to do the job with a sample bottle. However, due consideration must be given to the level of hazard of the substance and the diver’s safety. See item 1 under Section 4.1.4 above.

An alternative sampling method on the seabed is to use a sediment sampler (Figure 4 - 11) of which there are many various types also for deep waters.

Figure 4 -  11   A Ponar sampler
(its width is appr. 20 cm)

 
 
4.5        Taking samples on beaches
             and from smeared animals
 

Take samples in every continuous slick. In a spill which is scattered over a long coastline as many samples should be taken to enable a mapping of the substance distribution on the shores.

The substance should be scraped off smeared items and transferred into sample bottles. Avoid, if possible, contamination in the bottles by sand, grass and other debris. In exceptional cases when it is difficult to obtain clean substance samples, it is acceptable to place small contaminated items (pebbles, small pieces of wood, etc.) in the bottles.

Never take whole animal samples, body tissues, etc. which may become rotten during shipment. Try to cut off small parts of smeared feathers, fur, etc. Put the material directly into a sample bottle.

 
 

4.6        Taking samples from packages

Different scenarios may arise that justify different approaches. Taking samples from damaged leaking containers with unknown contents require much higher safety levels than if the containers do not leak.

To draw hazardous samples from various types of containers require specialized skill and training. Emergency response personnel should not try to perform such sampling but call for assistance from chemical institutes or plants with special expertise.

 
 

4.7        Taking samples on board vessels

 
4.7.1             General

Samples must be taken on board ships observing appropriate caution in accordance with current safety regulations. During sampling on board ships the recommendations under Section 4.7.2 below should be followed carefully.

It is often difficult to obtain relevant samples on board suspected sources. Yet, it must be emphasised that it is of the utmost importance for a spill investigation that suspected sources of the spill are traced as far as possible and that reference samples are taken. Sometimes during sampling on board a vessel it is necessary to get assistance by the crew under control. However, it is quite wrong to accept unknown samples straight off which are handed over by representatives from the ship or the shipping company.

Use a miniature camera or a video camera to record observations which are judged to be valuable for the investigation.

 

It may be difficult to obtain samples from tanks on board ships without opening manhole covers or drawing off pipes or pumps. However, it is often possible to use sounding pipes with a sample collector and glass tubes according to Figure 4 - 12. It is used with a steel measuring tape equipped with a carbine hook and a ground wire.

A clean, unused glass tube is put into the sample collector which is hooked onto a steel measuring tape which must be grounded before starting the sampling. The sample is collected through a sounding pipe and transferred to a 100 ml sample bottle. The glass tube is discarded and the sample collector must be thoroughly cleaned!

Figure 4 - 12

 

4.7.2          Advice and directions for safety routines

Directions must be acquired from the ship's officers regarding how sampling should be performed considering the current safety regulations on board the ship. Sampling in tanks and spaces within the ship’s Hazardous Areas should in the first place be carried out by the ship’s own crew. If the ship has sampling equipment of its own, this should be used on first hand. The sampling should be performed under supervision of the personnel which is responsible for the sampling. If this is not possible, sampling should be performed by means of external equipment only after approval by the ship’s officers or by a ship-surveyor.

When samples are taken in tanks containing volatile noxious the following advice shall be observed:

 

Level A protection shall be used (cf. Annex 5).

 

Only one hatch at a time should be opened.

 

One person should perform the sampling and another should supervise the sampler (safety guard). The latter shall observe the sampler’s condition and see to that he or she is taken away to a safe place if influenced by noxious gases (intoxication symptoms).

 

Explosion proof equipment (EEx-marked) only, should be used.

 

The sampler must not have loose items in the pockets. They might fall down into the tank.
 

During loading

 

Equipment made of metal for sampling and ullage-sounding must not be brought into the tank, or be left in the tank, during loading and within 30 minutes after loading has stopped. Examples of such equipment are steel measuring tapes and steel measuring sticks. Non-conducting equipment without metal parts may generally be used at any time. Cords, however, used for lowering equipment into tanks must be made of natural fibres (not synthetic materials).

 

 

After loading

 

Equipment made of metal for sampling and ullage-sounding can be used 30 minutes after loading has stopped. However, it is important that the equipment is firmly grounded to the ship’s hull before it is brought into the tank. The equipment must remain grounded until it has been removed from the tank.

 

 

Miscellaneous

Sounding and sampling by means of pipes, designed for this purpose, is allowed at any time.

 
 

4.8        Handling of samples

4.8.1          Sample custody and documentation

Samples and sampling equipment should be handled and stored so that the samples cannot be manipulated, mixed up, or else be contaminated by strange substances. Samples should be handled as legal evidence and should be kept in a “Chain of Custody” until identification and possible legal procedure has been completed. Such a Chain of Custody can be maintained by means of  durable (approved) sealable and individually numbered safety bags with e.g. three detachable adhesive number labels (see upper part of Figure 4 - 13) with identical number and the same as on the bag.

Each safety bag number is unique for one specific sample. The number is the identification of the sample. One of the detachable number labels shall be affixed onto the glass sample bottle label (Figure 4 - 14). The next number label shall be placed on the outer plastic jar (Figure 4 - 16) and the third label on the Letter of Request (cf. Subchapter 4.9).


Figure 4 -
13

 

A sample label (cf. Figure 4 - 14) shall be affixed to each sample bottle.

 

 

Sampling date.

 

(Space for a number label from an

Judged date for spill:

 

individually numbered safety bag)

Sampling site:

 

 

oSpill

oRef.sample (e.g. from a ship)

Suspected source:

TEMP.  

Water  oC:        Air  oC:

Spill information (volume, extension, judged substance type etc.)

SAMP-

Name:

 

Field unit:

 

 

   LER

Phone:

 

Alt. phone:

 

 

 

 

 

 

 

 

Figure 4 - 14
 

The following documentation is important when samples are taken and shipped:

 

A Letter of Request with a specification of the request and information on enclosed samples (cf. Subchapter 4.9) . Necessary information in the Letter of Request and/or in the sample bottle label is the following:

          - District,  sampler, unit

          - Date and position (or sampling site on board vessel) of sampling

          - Spill’s volume/appearance, substance type

          - Suspected source

 

Sample labels (cf. Figure 4 - 14) shall be affixed onto all sample bottles.

 

Number labels from individually numbered safety bags (cf. Figure 4 - 13) shall be affixed onto all sample bottles.

 

4.8.2           Filling and labelling of sample bottles

1.

As sample containers use 100 ml thick-walled wide-neck high quality glass bottles (Figure 4 - 15). A suitable inner neck diameter is 30 mm. The lid tightening should be of high quality. Use a new (unused) 100 ml sample bottle for each sampling site.

Figure 4 - 15

2.

If possible, avoid getting water into the bottle. One method to remove water from the bottle is to screw on the lid and hold bottle upside down for a minute. Then let the substance float upwards to the bottom of the bottle so that the water can be drained by opening the lid carefully.

3.

Do not fill the bottle to a higher level than to 2 cm below the lower edge of the lid. If the bottle is completely filled of cold substance it may later leak when the substance volume increases at room temperature.

 

4.

Check that the bottle lid gasket is undamaged and that the lid fits tight. Carefully wipe excess substance and water from the outside of the bottle.

 

5.

Affix a filled-in sample label (cf. Figure 4 - 14) onto each bottle.
 

4.8.3           Packing of samples

1.

A sample must be packed appropriately before it could be shipped to a laboratory for analysis. The sample is usually in either of the following forms:

          w Free substance

          w Sample pad containing substance from spill

          w Smeared item (feather, piece of wood, stone, etc)

 

2.

Allow excess water to drain off from the sample. Check that the sample does not contain animal tissue which might rotten during transport. Insert the sample into a sample bottle. The insertion of a sample pad can be facilitated by pushing the pad with the used clothes peg or a clean peg of any kind. Perform this without touching with fingers or contact with items that might contain disturbing contaminants.

 

3.

Affix a sample label (Figure 4 - 14) onto the sample bottle (Figure 4 - 15) and a number label from an individually numbered safety bag (Figure 4 - 13).

 

4.

Insert the bottle into the safety bag and seal the bag according to the bag’s instruction.

 

5.

Put the bottle package into a 600 ml plastic jar (Figure 4 - 16) which is used as an outer container. Affix the second number label onto the outside of this jar. Keep the third number label for the Letter of Request (cf. Subchapter 4.9).

 

 

 

Figure 4 - 16

Plastic jar used as an outer container for the sample bottle which is enclosed in a safety bag.
 

 

Figure 4 - 17

Cardboard box (with approval inscription) for shipment of the sample.

6.

The samples should be sent immediately to the Sample Co-ordinator. A quick handling of samples is important. If the transmittal is delayed the samples should be kept under a temperature of less than +4°C. The Sample Co-ordinator watches the continued shipping of the samples.
 

 

The plastic jar with its content of a sample bottle inserted in a sealed safety bag (Figure 4 - 13) should be placed in a cardboard box, before shipment, as shown in Figure 4 - 17.
 

7.

The whole packaging must be type approved for transport of dangerous goods and the cardboard box must wear an inscription which shows this approval (cf. Figure 4 - 18)
(cf. also Sections
6.1.2 and 6.2.2.1).



Figure 4 - 18

 
The following table shows the meaning of the codes in Figure 4 - 18:
 

The United Nations packaging symbol.

4

Type of packaging (4 = box).

G

Type of packaging material (G = corrugated fibreboard).

X

Intended for packing groups I, II and III.

1

The maximum gross in kilograms for packagings intended to contain solids or inner packagings.

S

Intended for the transport of solids or inner packagings or, for packagings (other than combination packagings) intended to contain liquids, the hydraulic test pressure which the packaging was shown to withstand in kPa, rounded down to the nearest 10 kPa.

02

The last two digits of the year during which the packaging was manufactured.

S

The State authorising the allocation of the mark (S = Sweden).

SP

The name of the manufacturer or other identification of the packaging specified by the competent authority.

319509

Approval Certificate No.

 

4.8.4          Shipping of samples

The Sample Co-ordinator collects all samples and fills in a Letter of Request which is sent to the laboratory together with the samples.
 

The Sample Co-ordinator should also call in special expertise if required from external institutes or laboratories to assist in the sampling activities.
 

Samples of many chemicals are to be considered as dangerous goods when they are shipped. However, if contained and packaged as described above, they can often be shipped as “limited quantities” which means simpler shipping requirements than for normal dangerous goods. IMDG Code rules as well as local regulations should always be followed.

 

 

4.9        Example of a form for Request for Analysis

 

 


Logo-

type

Sending Unit

 

Commanding Officer

Date

 

 

 

 

 

 

 

 

 

 

 

 

To:   Laboratory name and address

 

Request for analysis

 

Request analysis of the samples listed below

 

Sampling date:

 

 

No. of samples:

 

 

No. of pages:

 

 

General information

(Occurred incident, weather, spill size, suspected source, judged substance type, etc.)

 

 

Number label from safety bag

 

Information which
is not given on
the sample bottle
*

 

 

 

 

 

 

 

 

 

*Information:

Sampler: Name/field unit

Spill : Latitude & longitude, and sampling site’s geographical name

Ship: Ship name and sample site on board the ship

 

 

 

 

 

 

 

 

 

 

Signature

 

Name in block letters

 

Rank

 

 

 
     
 

End of Chapter 4