1、Designation: F 2059 06Standard Test Method forLaboratory Oil Spill Dispersant Effectiveness Using theSwirling Flask1This standard is issued under the fixed designation F 2059; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the yea
2、r of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the procedure to determine theeffectiveness of oil spill dispersants on various oils in
3、thelaboratory. This test method is not applicable to other chemicalagents nor to the use of such products or dispersants in openwaters.1.2 This test method covers the use of the swirling flask testapparatus and does not cover other apparatuses nor are theanalytical procedures described in this repor
4、t directly appli-cable to such procedures.1.3 The test results obtained using this test method areintended to provide baseline effectiveness values used tocompare dispersants and oil types under conditions analogousto those used in the test.1.4 The test results obtained using this test method areeff
5、ectiveness values that should be cited as test values derivedfrom this standard test. Dispersant effectiveness values do notdirectly relate to effectiveness at sea or in other apparatuses.Actual effectiveness at sea is dependant on sea energy, oil state,temperature, salinity, actual dispersant dosag
6、e, and amount ofdispersant that enters the oil.1.5 The decision to use or not use a dispersant on an oilshould not be based solely on this or any other laboratory testmethod.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibil
7、ity of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Summary of Test Method2.1 Dispersant is pre-mixed with oil and placed on water ina test vessel. The test vessel is agitated on a moving ta
8、bleshaker. At the end of the shaking period, a settling period isspecified and then a sample of water taken. The oil in the watercolumn is extracted from the water using a pentane/dichloromethane mixture and analyzed using gas chromatog-raphy.2.2 The extract is analyzed for oil using a gas chromato-
9、graph equipped with a flame ionization detector, (GC-FID).Quantification is by means of the internal standard method.Effectiveness values are derived by comparison with a cali-brated set of effectiveness values obtained at the same time andby the same method.3. Significance and Use3.1 A standard tes
10、t is necessary to establish a baselineperformance parameter so that dispersants can be compared, agiven dispersant can be compared for effectiveness on differentoils, and at different oil weathering stages, and batches ofdispersant or oils can be checked for effectiveness changeswith time or other f
11、actors.3.2 Dispersant effectiveness varies with oil type, sea energy,oil conditions, salinity, and many other factors. Test resultsfrom this test method form a baseline, but are not to be takenas the absolute measure of performance at sea. Actual fieldeffectiveness could be more or less than this va
12、lue.3.3 Many dispersant tests have been developed around theworld. This test has been developed over many years usingfindings from world-wide testing to use standardized equip-ment, test procedures, and to overcome difficulties noted inother test procedures.4. Interferences and Sources of Error4.1 I
13、nterferences can be caused by contaminants, particu-larly residual oil or surfactants in solvents, on glassware, andother sample processing apparatus that lead to discrete artifactsor elevated baselines in gas chromatograms. All glasswaremust be thoroughly cleaned. The cleaning process includesrinsi
14、ng with dichloromethane to remove the oil, followed byrinsing three times each with tap water, purified water (reverseosmosis), and acetone. Once cleaned, precautions must betaken to minimize contact of the glassware with surfactants toprevent undesired interferences.4.2 Dispersant effectiveness is
15、very susceptible to energylevels. Table top shakers generally start and stop slowly.Shakers that start motion rapidly and stop suddenly impart a1This test method is under the jurisdiction of ASTM Committee F20 onHazardous Substances and Oil Spill Response and is the direct responsibility ofSubcommit
16、tee F20.13 on Treatment.Current edition approved Oct. 1, 2006. Published October 2006. Originallyapproved in 2000. Last previous edition approved in 2000 as F 2059 00.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.high energy to the
17、 system and thus cause more dispersion thanwould be the case with a normal shaker. Furthermore, thisvariation would not be repeatable. The shaker table usedshould be observed for rapid movements or stops to ensure thatit is usable for these tests. The rotational speed of the shakershould be checked
18、with a tachometer every week.4.3 The Erlenmeyer flasks used in this test are tapered andthe energy level varies with the amount of fill.4.4 The output is highly sensitive to the volume of oil,water, and extractant delivered. All pipets and dispensersshould be calibrated frequently and verified daily
19、.4.5 The use of positive displacement pipets is mandatory forall controlled volumes of microlitre quantities. Use of volumedisplacement pipets will result in erroneous results due to theviscosity of the dispersants and oils, the variable viscosity ofthe oils to be tested (some semi-solid), and the d
20、ensity ofdichloromethane.4.6 The order of addition of the dispersant and oil haseffects on the accuracy of results, as the dispersant may interactwith the vessel walls if added first, thereby reducing thequantity available in the premix. It is therefore important to addoil to the vessel first, and a
21、dd the dispersant directly to the oil.Asecond addition of oil is suggested simply because it is easierto control a large volume of oil than a minute volume ofdispersant when attempting to achieve a specific ratio of 25:1.4.7 Following surfactant addition, vigorous mixing is re-quired to thoroughly h
22、omogenize the sample. Sharp, manualstrokes are suggested for light oils, while very heavy oils mayrequire stirring with a clean glass rod or spatula.4.8 There are indications that the results for some premixeddispersant/oil combinations change over time. It is necessary totake precautions against th
23、is potential source of variation. Thetesting should be concluded as soon as possible after thepremix is prepared, generally within a few hours. Results fromsamples stored for periods as long as a week should not beconsidered reliable.4.9 Since the performance of the dispersant is affected bysalinity
24、, thorough mixing of the salt water is required. Careshould also be observed to avoid evaporation from opencontainers of salt water. Over a period of days and weeks, theloss of water can significantly increase the salinity. An airtightclosure is recommended to maintain salinity levels at 3.3 %.4.10
25、Temperature is a factor in dispersion, so it is importantthat all components (salt water, pre-mix, and temperaturecontrolled chamber) are stable at 20C before starting.4.11 Extreme care should be taken when applying the oil tothe surface so that mixing does not occur. The oil should gentlyglide acro
26、ss the water to form a slick. If the oil streams out intothe water, the agitation can disperse the oil, increasing theamount of oil dispersed and erroneously raising the finaldispersion result.4.12 A slick may form at the water surface in the spout ofthe swirling flask during mixing and settling. It
27、 is importantthis oil does not enter the water sampled for analysis. Thereforeit is important to drain the contents of the spout (about 3 mL)prior to sampling, and ensure any adhering droplets do notenter the sample.4.13 The procedure is time critical for the elements ofmixing, settling, and samplin
28、g. Care should be taken to adhereto the times indicated in the procedure for both the mixing andsettling element, as variations in energy input, and especiallytime allowed for droplet creaming, can impact results. Sincethe water samples cannot be sampled simultaneously, this stepmust be performed wi
29、th as much careful haste as possible, toreduce the difference in settling times experienced by thesamples in the test run.4.14 Analysis of the gas chromatograph-detectable TotalPetroleum Hydrocarbon (TPH) content is subject to variabilityin GC operation and repeatability. Therefore, it is imperative
30、that a rigorous quality assurance program is in place to ensurethe GC is functioning properly and valid results are obtained.4.15 Care should be taken to determine the baseline in avalid and repeatable manner for both samples and calibrationsets.4.16 The accuracy and repeatability of the test can be
31、verified and compared using standard oil and dispersantsamples5. Apparatus5.1 Modified 120-mL Erlenmeyer Flask, used as the testvessel. A side spout is added to a standard Erlenmeyer flask toenable sampling from the water column with minimal distur-bance of resurfaced oil. This vessel is illustrated
32、 in Fig. 1.5.2 Moving-Table Shaker, with an orbital motion of 1 in.(25.4 mm) and fitted with flask holders. Ideally such shakersshould be constructed inside temperature-controlled chambers.If such an enclosed chamber is not used, the measurement mustbe conducted inside temperature-controlled rooms.F
33、IG. 1 Flask with Side SpoutF20590625.3 Gas Chromatograph (GC), equipped with a flame ion-ization detector is used for analysis. The column is a fusedsilica column.5.4 The following is a list of other necessary supplies.Suppliers of suitable units are footnoted. Equivalent suppliesare acceptable in e
34、very case. Quantities of supplies are given toconduct a full set of six samples and calibration set:5.4.1 Eighteen Crimp Style Vials, with aluminum/PTFE(polytetrafluoroethylene) seals, 12 by 32 mm,5.4.2 Twelve Erlenmeyer Flasks, 125 mL Glass, modifiedwith the addition of a drain spout attached to ba
35、se,25.4.3 Six Graduated Mixing Cylinders and Stoppers, 25 mLglass,5.4.4 Six Separatory Funnels and Stoppers, glass, 125 mL,5.4.5 Six Graduated Mixing Cylinders and Stoppers, glass,100 mL,5.4.6 Six Separatory Funnels and Stoppers, glass, 250 mL,5.4.7 Six Graduated Cylinders, glass, 50 mL,5.4.8 Six Di
36、spenser or Glass Graduated Cylinders, 5to25mL,5.4.9 Positive Displacement Pipet, 10 to 100 L,5.4.10 Positive Displacement Pipet, variable volume, 1 mL,5.4.11 Two Digital Timers,5.4.12 Dispenser or Graduated Cylinders, 20 mL to 100mL, and5.4.13 One Plastic Carboy, 20 L.6. Reagents6.1 ReagentsWater pu
37、rified by reverse osmosis or equiva-lent means is used for the test water. Dichloromethane andpentane are distilled-in glass grades. Fine granular sodiumchloride or table salt, non-iodized, is used for making the saltwater. The chemical dispersant is used as supplied by themanufacturer. Oil is used
38、as received.7. Procedure7.1 Crude Oil and Dispersant Sample Collection andStorageThe bulk oil is mechanically mixed for 2 to 4 h priorto obtaining a working sample. Working samples are stored in2-L high-density polyethylene bottles with polypropylenescrew closures. The working sample is mechanically
39、 shakenfor 30 min at 20C prior to removing a sub-sample for testing.When not in use, all samples should be stored in a temperaturecontrolled room at 5C. The dispersant is manually shaken,vigorously, prior to sampling.7.2 Premix Sample PreparationA small amount of oil(approximately 1.0 mL) is weighed
40、 into a 5-mL amber vialwith PTFE-lined cap. Approximately 100 mg of dispersant isadded to the oil. Oil is added until a 1:25 ratio (by weight) ofdispersant to oil is achieved. The sample is well mixed bymanual shaking or stirring.7.3 Salt-Water PreparationGranular salt is weighed andadded to water f
41、rom reverse osmosis (RO) filtration to obtaina 3.3 % (w/v) solution. The water temperature is stabilized to20C before use.7.4 Swirling Flask PreparationThe 120 mL of salt wateris placed into a 125-mL modified Erlenmeyer flask. The flaskis inserted into the flask holders on the oscillating table of t
42、heshaker. A 100-L volume of pre-mix solution is carefullyapplied onto the surface of the water using a positive displace-ment pipet. The tip of the pipet is placed at the water surfaceand the dispersant/oil mixture gently expelled. Extreme careshould be taken when applying the oil to the surface suc
43、h thatmixing does not occur. The oil should gently glide across thewater to form a slick. If the oil streams out into the water, theagitation can disperse the oil, increasing the amount of oildispersed and erroneously raising the final dispersion result.Herding of the oil and some creeping of the mi
44、xture up thevessel wall is normal but can be minimized.7.5 Shaking of Swirling FlasksThe flask and contents aremechanically mixed on the shaker in a temperature controlledchamber at 20C, immediately after applying the oil to thesurface of the water. A rotation speed of 150 r/min and amixing time of
45、20 min are used to agitate the samples followedby a 10-min settling period. The flasks should be removed fromthe table-mounted holders prior to the settling period to limitthe agitation between settling and sampling.7.6 Sample CollectionAfter the settling time is complete,3 mL of oil-in-water phase
46、from the spout of the flask aredrained and disposed of to remove any oil residing in the spoutand to obtain a representative sample. A 30-mL aliquot of thedispersed oil in water sample is collected in a graduatedcylinder and transferred to a 125-mL separatory funnel. The oilis extracted three times
47、with 5 mL of a 70:30 dichloromethane-:pentane solvent mixture, shaken vigorously for at least 1 min,and the extract collected in a 25-mL graduated mixing cylinder.The final extraction volume is adjusted to 15 mL. Care is takento ensure that water is not taken along with the solvent. Duringextraction
48、, vigorous shaking is required to achieve full extrac-tion. It is best to shake each separatory funnel individually toachieve consistent results.7.7 Sample AnalysisAnalysis consists of gas chromato-graphic analysis using a flame ionization detector (GC/FID) todetermine the concentration of oil in so
49、lvent. A 900.0-Lportion of the 15-mL solvent extract and a 100.0-L volume ofinternal standard (200 ppm 5-a-androstane in hexane) arecombined in a 12 by 32 mm crimp-style vial with aluminum/PTFE seals and shaken well. Petroleum hydrocarbon content isquantified by the internal standard method, with the averagehydrocarbon relative response factor (RRF) determined overthe entire analytical range in a separate run. The petroleumcontent is determined by integrating the total peak area by thefollowing equation:TPH 5AinitAis1RRF20g! 150.912030(1)which simplifies to:TPH 5A
