1、Designation: F2059 06 (Reapproved 2012)1Standard Test Method forLaboratory Oil Spill Dispersant Effectiveness Using theSwirling Flask1This standard is issued under the fixed designation F2059; the number immediately following the designation indicates the year oforiginal adoption or, in the case of
2、revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1NOTEAn editorial change was made to Section 6 in February 2012.1. Scope1.1 This test method covers the proc
3、edure to determine theeffectiveness of oil spill dispersants on various oils in 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
4、cover other apparatuses nor are theanalytical procedures described in this report 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 th
5、ose used in the test.1.4 The test results obtained using this test method areeffectiveness 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 d
6、ependant on sea energy, oil state,temperature, salinity, actual dispersant dosage, 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 The values stated in SI units are to be re
7、garded asstandard. No other units of measurement are included in thisstandard.1.7 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and deter
8、mine 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 tableshaker. At the end of the shaking period, a settling period isspecified and then a sample of
9、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-graph equipped with a flame ionization detector, (GC-FID).Quantification is by means of the inte
10、rnal 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 test is necessary to establish a baselineperformance parameter so that dispersants can be compared,
11、 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 factors.3.2 Dispersant effectiveness varies with oil type, sea energy,oil conditions, salinity, a
12、nd 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 value.3.3 Many dispersant tests have been developed around theworld. This test has been developed
13、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 Interferences can be caused by contaminants, particu-larly residual oil or surfactants in solvent
14、s, on glassware, andother sample processing apparatus that lead to discrete artifactsor elevated baselines in gas chromatograms. All glasswaremust be thoroughly cleaned. The cleaning process includes1This test method is under the jurisdiction of ASTM Committee F20 onHazardous Substances and Oil Spil
15、l Response and is the direct responsibility ofSubcommittee F20.13 on Treatment.Current edition approved Feb. 1, 2012. Published February 2012. Originallyapproved in 2000. Last previous edition approved in 2006 as F2059 06. DOI:10.1520/F2059-06R12E01.1Copyright ASTM International, 100 Barr Harbor Dri
16、ve, PO Box C700, West Conshohocken, PA 19428-2959, United States.rinsing 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 surfacta
17、nts toprevent undesired interferences.4.2 Dispersant effectiveness is very susceptible to energylevels. Table top shakers generally start and stop slowly.Shakers that start motion rapidly and stop suddenly impart ahigh energy to the system and thus cause more dispersion thanwould be the case with a
18、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 with a tachometer every week.4.3 The Erlenmeyer flasks used in this
19、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.4.5 The use of positive displacement pipets is mandatory forall con
20、trolled 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 density ofdichloromethane.4.6 The order of addition of the dispersant
21、 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 add the dispersant directly to the oil.Asecond addition of oil is sug
22、gested 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 homogenize the sample. Sharp, manualstrokes are suggested for light o
23、ils, 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 this potential source of variation. Thetesting should be concluded as
24、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, thorough mixing of the salt water is required. Careshould also be
25、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 Temperature is a factor in dispersion, so it is importantthat all co
26、mponents (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 across the water to form a slick. If the oil streams out intothe water,
27、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 is importantthis oil does not enter the water sampled for analysis.
28、 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 sampling. Care should be taken to adhereto the times indicated in the proce
29、dure 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 with as much careful haste as possible, toreduce the difference in set
30、tling 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 imperativethat a rigorous quality assurance program is in place to ensurethe G
31、C 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 beverified and compared using standard oil and dispersantsamples5. App
32、aratus5.1 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 in Fig. 1.5.2 Moving-Table Shaker, with an orbital motion of 1 in.(
33、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.5.3 Gas Chromatograph (GC), equipped with a flame ion-ization detecto
34、r 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 every case. Quantities of supplies are given toconduct a full set of six samples and calibration set:5.4.
35、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 base,25.4.3 Six Graduated Mixing Cylinders and Stoppers, 25 mLglass,2The sole source of supply of the appa
36、ratus known to the committee at this timeis Pro Science, Inc., 770 Birchmount Road, Unit 25, Scarborough, OntarioM1K5H3. If you are aware of alternative suppliers, please provide this informationto ASTM International Headquarters. Your comments will receive careful consid-eration at a meeting of the
37、 responsible technical committee,1which you may attend.F2059 06 (2012)125.4.4 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
38、Six Dispenser 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 ReagentsWa
39、ter purified 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
40、 used 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 mechan
41、ically 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 w
42、eighed 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 w
43、ater from 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 tabl
44、e of theshaker. 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 surfa
45、ce such 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
46、the mixture 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 ti
47、me of 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
48、phase 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
49、times with 5 mL of a 70:30 dichlorometh-ane:pentane solvent mixture, shaken vigorously for at least 1min, and the extract collected in a 25-mL graduated mixingcylinder. The final extraction volume is adjusted to 15 mL.Care is taken to ensure that water is not taken along with thesolvent. During extraction, vigorous shaking is required toachieve full extraction. It is best to shake each separatoryfunnel individually to achieve consistent results.7.7 Sample AnalysisAnalysis consists of gas chromato-graphic analysis using a flame ionization detector (GC/FID) todetermin
