“1s eatona tgp aed asoedance th aeons scapnad pepe on standndzaton eh the Dc o Puen fo the Design fr Aly Designation: D8193 - 18 is Standard Test Method for Fences sed bye Se re Oration tect Rass to Tse 1 Cane Total Oil and Grease (TOG) and Total Petroleum Hydrocarbon (TPH) in Water and Wastewater with Solvent Extraction Using Non-Dispersive Mid-IR Transmission Spectroscopy’ “Tvs dad fel mde the fie design DELS, he uber snoely following the dewgnan nde he ye of pal ‘lon ease cs, he em ofa evs A un npvemheser nee the Yea fa epoval Sts epg fe stkcnes an en change ace he ast eon 01 appa 1. Scope LU This test method covers the determination of tolal ot! and grease (TOG) that can be extracted from water of waste- ‘water samples by cyclohexane and measured by non-dispersive IR spectioscopy fiom 1370-1380 em! Treating the extract with Flotsil? to remove polar substances prior to the IR ‘measurement enables determination of the total petroleum, cP). 1.2 This method also considers the volatile fraction of petroleum hydrocarbons witch is Tost by gravimetrie methods, ‘hat require solvent evaporation prior (© weighing, as well as, by solventless IR methods that requure drying of the employed sold phase material prior to measurement. Similarly, a more complete fraction of extracted petroleum hydrocarbon is a ‘esse by this method as compared to GC methods that use a time window for quantification, as petroleum hydrocarbons, cluting outside these windows are also quantified 1.3 This method defines total onl and grease in water as ‘material that ean be extracted with cyclohexane and measured, by IR absorption in the region of 1370-1380 ny (7.25-7.3 thm), Similarly, total petroleum hydrocarbon i water 1s defined ‘as material that can be extracted with eyelohexane, remains in the extract after filtration over Plorisil and is measured by IR absorption inthe region of 1370-1380 cnr (7.25-7.3 wm), The. concentration of tolal grease is defined as the difference between the total oil and grease and total petroleum hydrocar- ‘bon concentrations 1.4 This method covers the range of 05 to 1000 mg/L for total onl and grease as well as for total petroleum hydrocarbons and has a method detection limit (MDL) of 0.5 mg/L. The range and method detection limit may be extended to higher or "Ts tet mt ue she eno of ASTM Comme 19 on Wate athe det espn af Succ D198 4 Mato Fox Atal 0) ‘reane Suances Water ‘Gent tea Do. 15,2018 Pulsed Jansary 2019 DOD 10520 Fl dadomak by US Sita Company, edn, MD lower concentrations by adyushng the water or solvent volume cused in the liquid-liquid extraction, 1.5 The values stated in ST onits are to be regarded as standard No other units of measurement are included in this tard, 1.6 This standard does not purport 10 address alt of the safery concerns, if any, associated with us use. I 18 the responsibilty of the user of this standard 10 establish appro- priate safety, health, and environmental practices and deter- ‘nine the applicability of regulatory limitations prior 10 use. LT This international standard was developed in accor dance with miernationally recognized principles on standard ization established in the Decision on Principles for the Development of Internononal Standards, Guudes and Recon ‘mendanons issued by the World Trade Organization Techncat Barriers 19 Trade (TBT) Commuiee 2, Referenced Documents 2.1 ASTM Standards:* 11129 Termmology Relating to Water DIMI Practice for the Preparation of Substitute Ocean ‘Water 11193 Specification for Reagent Water 2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Commuttee DI9 on Water 1D3370 Practices for Sampling Water from Closed Conduits DS847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis i678 Test Method for Total Oil and Grease (TOG) and Total Petroleum Hydrocarbons (TPH) in Water and Waste- water with Solvent Extraction using Mid-IR Laser Spec- ‘woscopy E168 Practices for General Techniques of Infrared Quanti- tative Analysis “Foy sccnced ASTM sd, i the ASTNG weber ana 8 ‘onint ASTM Canine Seve at eres ety For Al Bok of ASTH ‘Stan vue anton othe tna’ Dace! Summa pie cera AST nana 008 Ha Oe, POBox C708, as Caatchacen, PA IHE298 Urs Ses Pumaaroht tes AST tot fall raha reserved), Tie Mar 252139 5OKDT 202] ,fly vs193 - 18 22 180 Standavds:* 180 9377-2 Determination of Hydrocarbon Oil Index 23 Code of Federal Regulatons (CFR) Pubheatrons:* 40 CER Patt 136 Guidelines Establishing Test Procedures for the Analysis of Pollutants 49 CFR Part 172 Hazardous Materials Table, Spectal Provisions, Hazardous Matertals Communteations, Emer geney Response Information, Training Requirements, and Secunty Plans 3. Terminology 3.1 Definmons: 3.1.1 For defintions of terms used in this test method, refer {© Terminology D1129 and Practices E168. 31.2 total oi! and grease (TOG), n—matersal that can be extracted from water or wastewater by this test method and Which can be measured by infrared absorption in the region from 1370 cm to 1380 cm" 3.13 sotal petroleum hydrocarbon (TPH), n—non-polar or zganie material that can be extracted fiom water of wastewater, and which ean be measured by infrared absorption nthe region from 1370 em! to 1380 env 3.2 Definitions of Terms Specific to This Standard 3.2.1 grease, n—the difference between TOG and TPH of & sample, 4. Summary of Test Method 4.1 An acidified 900-mL sample of water or wastewater is extracted with 50 mL of cyclohexane, A part of the extract is measured with infrared spectroscopy to quantify the total oil and grease (TOG) concentration The remaining part of the extract 1s treated by Florsil co emove polar substances, The lueated extract 1 measured with infrared spectroscopy 10 {quantify the total petroleum hydrocarbon concentration (TPH) ‘The diifetence between TOG and TPH provides the amount of ‘arease extracted from the sample 5. Si 5.1 The ptesence and concentration of total peteoleum hydrocarbons, as well as total oil and grease, in damestie and industrial wastewater is of concern to the public because of its deleterious aesthetic effect and us impact on aquatic lie nificance and Use 5.2 Regulations and standards have been established that Fequire momttonng of total petroleum hydrocarbons as well as Total oil and grease m water and wastewater 6, Interferences 6.1 Soaps, detergents, surfactants, and other materials may Form emulsions that could reduce the amount of oil and grease aas well as petroleum hydrocarbons extracted from a sample. "jvalale fom Inno Organzauon tr Sundadoaon ISO) IS Covi Sects HIKC Th, Cem de Blndonet CP, 1214 Yane, Genevs, Saved hep rane nos “avaible won US Geveinmem Pntng Otic, Sapsnmendent of Dcamens, 232.N spiel St NW, Wishngion, DC 2DH01-001, hap ‘This test method contains procedures that can assis the analyst in breaking such emulsions. 62 Orgame compounds and other materials not considered as oul and grease or petroleum hydrocarbons based on their chemical structure (for example, halogenated oF eyelte hydro- carbons) may be extracted and measured by the method 7. Apparatus 7.1 All glassware that wall come in contact with the sample shall be thoroughly cleaned, rinsed with distlled water, and dried at 130°C 72 ‘Temperature conteolled absorption spectrometer with an ‘automatic filling system and a transmission cell The spectvom- eter should use a light souree and an optical interference filter lransmiiting mm the range from 1370-1380 em. The path length of the transmission cell shall be between 11.5 mm. In ‘order for the spectrometer to qualify, the standard deviation of 10 blank measurements should be less than 0.06 mAU 73 Glass wide mouth sample bottle, suggested 1 L, enther with screw cap having a fuoropolymer liner or a wide-necked glass flask with a ground neck with enther glass or fluorapo- Iymer stopper. The sampling bot shall allow direct extraction from the bottle, ‘14 Micro-separator, for example see figure in Annex A2 oF ‘other suitable device for phase separation (optional). 75 Solid phase extraction cartridges containing Florist ‘with PTFE or stainless steel fits (for TPH), 76 Beakers 50-100 mL 7.9 Magnetic stiver, with PTFE-fluorocarbon stirring bar (optional, 7.8 Volumetric flasks, glass, various (50, 100, and 200 mL) 7.9 Teflon spriz bottle, one-piece wash bottle for rinsing, 7 10 Volumetric pipettes, glass, vanous (10, 20, and 40 mi.) TAL Analytical balance 7.12 Graduated glass syringes, 250 yl (optional, 7.13 Benchtop shaker, (optional) 7.14. Glass stitting rod, (optional) 8, Reagents and Materials, 8.1 Purity of Reagents—Reagent grade chemicals shall be sed 1 all fests, Unless otherwise indicate, it is mntended that all reagents shall conform to the specification of the committee ‘on analytical reagents of the American Chemical Society, Where such specifications are avatlable.® Other grades may be used, provided it 1 first aseertamed that the reagent 15 of sufficiently bigh purity to permit its use without lessening the accuracy of the determination "Reagent Choma, Awescan Chena Sets Spetcaions. Ametan CChemeal Soc Washington, DC, wr chem eng Ps sugecion Oh the tesimg a eens ao sted by the Anoean Caetes! Sao eth Und Sater Pharmac aid Natal arnt US. Pharmacope Conver, Ine (USP), Roce AID. hap wp oreGp vo199—18 82 Cyeloherane, nunimum puiity 99 5 4, used for extrac 8.3. Purity of Wates—Unless otherwise indicated, references {o laboratory or reagent water shall be understood 1 mean reagent water conforming to Speetication B1193, Type HL 8.4 m-Ocrane, 99.0 4 minimum purty, for use mn calibre tion, 85. 2,24 Trmerhvlpensane, 99.0 4% mionmum purity, for use in calibration 8.6 1.1 (whw) Minsure of Mineral Oil Type A (Diesel Oi! Without Additives) and Mineral Oil Type B (Lubvicating Oi Without Addinves), for use as laboratory control sample (LCS). readily prepated 1-1 (ww) mixture ofthese oils may be used (for example, BAM KOI0") 8.7 Florisil, grain size 75 ym to 150 ym (100 mesh to 200 mesh), heated to 140°C for 16 h and stored an a desiccator: Florist is uade name for a prepared diatomaceous substance, ‘mainly consisting of anhydrous magnesium silicate 8.8 Sodiwn Sulfate (Na,SO,), anhydrous, granular 89 Sulfur Acid (1+1)—Slowly and carefully add | vole ume of sulfuric acid (H,S0,, sp gr 1.84) to | volume of water, sturing and cooling the solution during addition 810 Hydrochloric acud, ACS, (1 + 1} Mix equal volumes. of concentrated! HCL and water, 8.1L Stearyl stearate (Cl 203), munimnum purity 98.0%, for qualification of Florist used for TPH measurements 9. Hazards 9.1 Normal laboratory safety apples to this method. Ana- lysts should wear safety glasses, gloves and Jab coats Analysts, should review the Safety Data Sheets (SDS) for all reagents used in this method, Additional hazards may be presented by ‘he particular sample being tested so proper care must be taken. 10, Sampling, 10.1. Weigh the dried bottle betore sample collection, Pre: rinse the sample bottle and cap with the solvent (8.2) and dry 1 por to sample collection. Do not rinse the sample botle vith the sample to be analyzed. 10.2 Collect the sample m accordance with the principles escribed in Practiees D3370, using a glass bottle as specified, m3 10.3 Fill the bottle to approximately 80 %. Filling the boctle above 80 % of total volume or allowing the bottle to overflow. will make extraction more difficult and lead to erroneous, resulls 10.4 A sample volume of about 900 mL is recommended for this test Weigh the bottle containing the sample to determine. the actual sampled amount Alternatively, record the sampled German Fee! ost Maes Resse ad ox, Bein you te uae of alonaie spp, pene peovide ths nematen o ASTM ft tnt Headgutee. You comment leave caseload a etn, ‘tthe epome eel comme! whch you may ated nk os ASST To el sit marvel, Ther: 21.39 SOEDT 2001 volume. Use the entire sample because removing 2 portion ‘would not apportion the hydrocarbons that adhere Co the botle surfaces. The high probability that extractable matter may. adhere to sampling equipment and result in measurements that have a low bias precludes the collection of composite samples, for determination of total oil and grease and total peuoleum hydrocarbon, Therefore, samples must be collected as grab, samples, If a composite measurement is required, individual grab samples collected at prescribed time intervals. may be analyzed separately and the concentrations averaged Alternatively, samples can be collected in the field and com. postted in the laboratory. For example, collect three individual 300-mL samples over the couse of a day. Ib the laboratory, ‘extract each 300-mL. sample with 1S mL and combine the extacts a 30-mL, volumetne flask and fill up to mark with solvent prior to measurement (12.2 and 12.3). 10.5 Preserve the sample with a sufficient quantity of sulfur acid (see 8 9) or hydrochloric acid (see 8.10) to a pH ‘of 2 oF lower and refrigerate at [-6°C from the time of collection until extaetion, ‘The amount of acid required will be {dependent upon the pH and buffer capacity ofthe sample atthe time of collection. Ifthe amount of acid required is not known, make the pH measurement on a separate sample that will nt be analyzed, Introduction of pH paper (© an actual sample or ‘sample cap may remove Some oil from the sample, In ease the bottle contanning the sample cannot be weighed before addition of the acid, the volume of acid added to each sample can be recorded and then subtracted from the final measured sample amount. Ifthe sample is to be shipped by commercial carrier US. Department of Transportation regulations limit the pH 0 A mminimum of 1.15 sf H,SO, 18 used and 1.96 if HCL ts used (ce 40 CER Part 136, Table IT Footnote 3 and 49 CFR Part 1m, 10.6 All samples must be reftigerated at 1-6 °C from the time of collection until extraction, AU samples must be analyzed within 28 days of the date and time of collection (40 CER 136, Table ID), Extracted samples can be stored up t0 «wo ‘weeks between 7°C and 10°C. 11. Quality Control 111 To ensure analytical values obtained using this test method are valid and accurate within the confidence limits of the test, the instrument manufacturer's instructions and the following procedures must be followed when performing the {est method. Calibrations made by the mstrument manufacturer may be used for analysis. 1.2 Instrument Cabdbraton: 11.2.1 Bring all solutions to 2 11.22 Calibration Solunon S: 11.221 Prepare a stock solution by weighing in 9.00 a-octane and 100 g 2.24 Trimethylpentane #3. Nowe {A (0. soluwon of 2.24 Tamethylpentine in mOetne ws fount provide representative valves for TOG and TPH fv a broad ange fof samples, ranging fam heavy evade 1 ger condenses lin fils ad tbrcans “ None 2—The calibration standad spoested in ths procedde reflects the objective of he eat to deter secaverble ol a arene and ptely veies - 18 hydocarbon mateeal in water and wastewater wih 4m unknowe comp: sition of o and grease In few etes, the commponton of the eid preset sample al be kaos stich eases, ss pssle to develo calito wth he known tgeto As longa al och steps an hs es method ate followed, such calations may be used for metal mont tng oe maeinal eporting However, ox such eahbaons i 5 ot possible to develop repreirbty sstements and the tepeatabulty statement of ts text method wall not be valid. Ta onder to aba cosisent results between aboitetes, 11 eguted to use the standard ealbation ound 1m Section TT when tepoiting TOG a1 TPIE valves citing the ASTM designed number 11.2.3 Calibraviow Solution A 112.31 Weigh 1.8 g of Calbratton Solution § in a 100 mt. volumetric flask and fill 10 the mark with eyelohexane 1.2.3.2 Calibration Solution A = 18000 mg/l, (1000 mgt. coil an water) 11.24 Calibrarion Solution B. 1.2.4.1 Place 40.0 mL. of Calbration Solution Am a 00-mL. volumetne Mask and AIL to mark with solvent 11.2.4.2 Cahbration Solution B = 7200 mg/l (400 mg/L oil 1m water) 1.2.5 Caltbrarion Solution C: 1.25.1 Phice 200 mL. of Cabbration Solution B in 100-mt. volumetne Mask and fll wo mark with solvent 11.2.5.2 Calsbration Solution C= 1440 mg/l. (80 mg/L oil wn water) {1 2.6 Calibration Solution D: 11.26. Place 10.0 mL. of Calibration Solution Cm a 100-mL. volumetrie Rask ane! fll c mark with solvent. 1.2.6.2 Calibration Solution D = 144 mg/L (@.0 mg/L ol in water). 11.2.7 Caltbration Solunon E: 11.2.7. Weigh 1.35 2 of Cahbration Solution S in a 100 ma, volumetne Mask and fil to the mark with eyelohexane. 1.2.2.2 Cahibration Solution E = 13500 mg/L (950 mg/L oil mn water) 11.28 Calibration Solution F. 1.28.1 Place 20.0 mL. of Calibration Solution E in a 1o0-mL. volumetse flask and fll e mark with solvent. 11 28 2 Calibration Solution F = 2700 mg/L. (150 mg/L oil in water) 11.29 Calibranon Solution G: 1.2.9.1 Place 20.0 mL of Cahbration Solution Fn a 1o0-mL. volumetric Rask and fll wo mark with solvent. 11.2.9.2 Calibration Solution G = 540 mg/l. (20 mg/L cil in water) 1.2.10 Calebration Solution H: 12.401 Place 10.0 mL of Calibration Solution G in a 100-mL. volumetne Rask and fll to mark with solvent 11.2.102 Calibration Solution = 54 mg/L @ mg/L oil in water) L211 Measurement of the Calibration Standards: 1211.1 The cabbration must contain a mummum of 8 non-zero points 11.2.11.2 Use eyelohexane from the same botle used for preparing the calibration samples fo measure a new reference (background), 112,113 Obtain the absorbance values for the calbration standards A to H. Make a new reference measurement belore ‘measuring the next calibration sample 11.2114 Deteumine the constants of a second order poly ‘nomial which, ma least squares sense, represents the best fc 10 the absorbance measured! and the concentration of the calibr tion solutions None 3~Even though solvent ot high panty used fr anal, ean contain small amounis of non-cyclie hydrocubons and even plat oniponenis. Prtherre there wl ration i hs content een wodocton batces (lt numbers), even fran the sane roduc To uvond that vartuvon ar prdet quality affects the results of ts test method Solvent of the same Tot auinber must be wsed Tor reference and simple 113. Calibration Verification: UB. Use the calibration constants obtained in 11.2 11 4 fand the absorbance values measured 1n [1 2 11 3 (@ calculate the predicted concentrations for all calibration samples. The calibration 1s verified if the difference between the actual and predicted concentration 1s smaller than =1.5 % of the mea- sired value or £13 mg/L oil in solvent concentration (0.7 mme)/L oul in water), whichever is greater 11.3.2 If calibration cannot be verified, recalibrate the instrument Non Pero eahbaton veaieavon 1 eared ou by measurement of the 50 mg/l. LCS. Ifthe LCS fas, a measurement of one oF the ‘alibvation standards can be used wo verify the ealibeaion I this ease the result shall fall wr the ts defined 19 113 1 114 Standardization of Sample Cleanup. L141 The sample cleanup procedure required for the mea- surement of total petroleum hydrocarbons uses Florisil solid Phase extraction cartridges. Such cartridges can be bought ready-made or can be prepared in the lab. Each time a new batch of Florisil cartridges is used, the suitability shall be tested. Cartridges may be qualified by the manufacturer and used as delivered 11.4.2 If sold phase extraction cartrdges with plastic hous- ing are used, ensure that the cartridges do not affect the results, Measure a blank using only eyclohexane. ‘The mstrument readiig must be <0.5 migil. and 20.5 mgiL. 11.43 Prepare 1800 mg of Mineral Oil Type A and Type B (:1 (w/w) (8 6) na 100 mL volumetric ask. Fill (0 the mark with cyclohexane 1144 Measure the sofution without any cleanup and note the result on the fask, 11.4.5 Draw the solution through the Flonsil carnidge and perform 4 measurement of the treated extract, The instrument reading shall be at least 95 % of the untreated value obtained in ida 1146 Prepare 65 mg stearyl stearate (8.11) 1m 2 100 mL volumetric Mask, Fill 1 the mark with eyelohexane, 1147 Measure the solution without any cleanup and note the result on the flask, 11.4.8 Dra the solutton through the Flonsil cartridge and perform the measurement of the treated extrac. The instrument reading shall be less than 1/30 of the reading of the original extract obtained in 11.4.7, 11.49 [the signal ss higher, activate the Floris! by heating. it to 140°C for 16 hand repeat the qualification procedure. Nore SMe wse of 90mg Flu! eaudges is suictent 0 clean samples up atleast 70 m/l (tery! semate) Tl Higher eveasefl v8193 - 18 Concentrations ate expect eter werease the amount of Fons ot ‘due de sale 11.5. Preparation of the Laboratory Control Sample (LCS) 11.5.1 Pout 900-mL reagent water into a sample bottle Record exact volume o1 weight 11.5.2 Using a micro-syrimge, add 45,0 mg of Mineral Os) ‘Type A and Type B (1:1 (wiw)) (86) to oblam a nominal conicentratson of 50.0 mg/L. (oil n water concentration) Obtain the exact concentration by difference weighing of the micro- sytinge and the exact water volume Noms 6—A mixtae of 4 Mineral Onl Type A an Type B has been selected as material for stl demonsoaton of labonatry cally and for establishing LCS a sea aaable weld a abo used for elivation of 1$0 9377-2, which determines the hydtocathon oll dex ‘ate! using slventextation and ga» chromatography, aswell as LCS Test Meth! D767 Is therefore sued to vey the eovretpefexmance ofthe test method despite of as difleent chemical compaston to most ‘ude ad condensate el types 11.6 Innal Demonstration of Laboratory Capabuiv 11.6.1 Ifa laboratory has not performed the test before or if there has been a major change i the measurement system, for ‘example, new analyst, new instrument, ete., a precision and bias study must be performed to demonstrate laboratory capability. 11.6.2. Analyze a reagent water (est blank. The cota oil and grease concentration in the blank must be in the range +0.5 igi. f the cotal oil and grease concentration ts outside this range, analysis of samples is halted until the contamination is climinated and the blank gives concentrations in the range 205 moll, 11.6.3 Prepare 7 samples by each weighing in 45.0 mg of a mixture of a Mineral Oil Type A and Type B (8.6) 1n 900 ml (of reagent water, Each sample must be taken through the complete analytical test method ineluding any sample preser- vation and pretreatment stops, 1164 Calculate the mean value and the standard deviation and compare to the acceptable ranges of precision and bias, fbiained through the single laboratory study. The found mean value for TOG shall he between 48.2 and 50.2 mg/L. and the standard deviation shall be below 2.1 mg/L. For TPH the mean value shall lie between 47,7 and $0.1 mg/l. and the standard deviation shall be below 25 mg/L, All values are calculated, based on Practice DS847 at the 99 % level 11.65 This study should be repeated untl the single opera- tor precision and the mean recovery are within the limits given above. 11,7 Laboratory Conurot Sample (LCS): 11.2.1 To ensure that the test method is in control, analyze the LCS contaming 50 mg/L of a Is (ww) mexture of mineral ‘il type A and B with each batch of 20 samples. The selected LCS follows recommendation of Practice DS847 to use an independent reference matcral as the LCS, If farge numbers of samples are analyzed in the batch, analyze the LCS after every 50 samples The LCS must be taken through all of the steps of the analytical method meluding sample preservation and pre- treatment The TOG result obtained for dhe LCS shall fall \within the limits 46.4-51.9 mg/L. The TPH result obtamned for ‘Camorecht hy ASTM Indl (all hts reserved), Th Mar 2521.39 S0EDT 2021 the LCS shall fall within che linus 45.6-52.2 mg/l. These limits ate based on Practice DSR47 evaluation at the 99% level 11.7.2 If the result is not whan these linus, analysis of samples 1s halted until the problem 1 corrected, and eather all, samples in the batch must be reanalyzed, or the results must be qualified with an indication that they do not fall within the performance criteria of the test method 1.8 Method Blank 11.8.1 Analyze a reagent water test blank with each batch of 20 samples ‘The total oil and grease concentration in the blank. ‘must be in the range 205 mg/l. If the total ofl and grease concentration 1s outside this range, analysis of samples 1s halted until the contamination is eliminated aad the bla concentrations a the range 0.5 mgt. 11.9 Matrix Spike (MS) 11.9.1 To cheek for interferences 1» the specific matrix being tested, perform an MS on at least one sample from each bach by sprking.an aliguot of the sample wath a known amount ‘of Mineral Oil Type A and Type B (1+1) and taking it through the analytical method Addition of Mineral Oil Type A and ‘Type B (1+1) shall be carried out using a glass syringe and by difference weighing 11.9.2 The spike concentration plus the background concen- tration of total oil and grease must not exceed 1000 mg/L. The spike must produce a concentration in the spiked sample 2 t0 5 times the background concentration or 10 10 SO times the Uetection limit of the test method, whichever 1s greater 11.93 Cateulate the percent recovery of the spike (P) using the following formula av-av o where: A = concentration of total onl and sample (mg). Concentration of total onl and ‘un-spiked sample (mg/L), amount added during spiking (mg), and volume of sample used (L) ‘erease found an the spuked yease found inthe 11.94 The pescent recovery of the spike shall fall watban the limits 70-130 %. This margin considers difficulties associated \wuth splitting a sample into aliquots of the same concentration due (@ the nature of the analyte which tends to adhere (0 surfaces. Ifthe percent recovery 18 not within these Timuts, a matex interference may be present sn the sample selected for spiking. Under these evrcumstances, ane of the following Femedies must be employed: the matrix interference must be removed, all samples in the bateh must he analyzed by a test method not affected by the matrix interference, or the results must be qualified with an indication that they do not fall within the performance criteria of the test method, 12, Procedure 12.1 Extrachon 12.1.1 Bring the sample € a temperature of 22 © 3°C,(Gy va103~ 18 12.1 2 Add 50 mL of eyclohexane (8 2) to the sample an the original sample bottle, Recap ammediately and shake vigor ously for 2 minutes, Alternatively, add a magnetic stir bar and sr the sample for 30 min on a magnetic stirrer Allow contents to setle and bubbles to disappear 121.3 In the case of formation of add Type nulsions, MgSO, 7H,0 during the luid-iguid extraction step cally an amount of 5-10 g will be sulieret 12.14 Ia miero-exttactor as in Annex A2 is used, remove the cap from the bottle and replace it by the micro-separator Add enough dishilled water to allow withdrawal of the organte phase from the nicro-separator 12.15 If no micro-separator 16 used for phase separauon, add distilled water to the botle to facibiate withdrawing the ‘organic phase (top layer) using a glass pipette or glass syringe 12.16 When transfermng the orgame phase to a beaker, censure that no free water is transfered Free water will imerfere with the measurement of TOG and the cleanup procedure and measurement of TPH, 12.17 If the sample 1s turbid, use an additional Na,SO, drying cartridge to prevent water from interfering with the sample cleanup and measurement 12.1.8 Centrifuge the extract before the measurement if emulsion is still seen un the extiact 12.2 Measurement of Total Oil and Grease (TOG) 12.2.1 Use eyelohexane from the same batch (lot number) used for extraction to measure a reference. 12.2.2 Record the infrared absorbance of the extract ob- tained in 12.1 12.2.3 Determine the concentration of oil and grease in the solvent by applying the calibration constants 12.2.4 Wf the concentration of total ot] and grease exceeds ‘he calibration range, dilute the extract to bring the concentra- tion within the cahbraton range using the same batch of cyclohexane as used for extraction and repeat the measure- ment 12.3 Measurement of Tonal Petroleum Hydrocarbon (TPH) 12.3 | Use a fresh cartridge for each measurement 12.3.2 Draw eyelohexane from the same batch (lot number) used for exttaction through the Florisil sold phase extraction cartridges and perform 4 reference measurement 12.3.3 Draw the extract obtained in 12.1 through the Flonsit solid phase extraction cartridge and record the infrared absor- bance of the treated extract 12.34 Determine the concentration of petroleum hydrocar- bons mn solvent by applying the calibration constants. 12.35 If the concentration of total hydrocarbons exceeds the calibration range, or the difference between TOG and TPH values is larger than 70 mg/L, or if the cartridges. show indication of break-through (colored throughout the cartridge), dilute the extract 10 umes and repeat the measurement 13, Caleutation of Results 13.1 Calculate the total oil and grease (TOG) concentration an the original water sample and report tothe nearest 0.1 mg/L ‘Test Method D8193 TOG (mg/l) = D ay where Roy = measured concentration of total oil and grease mn mg/l. mn extract, D dilution factor (volume of diluted extract £ volume undiluted extract, if any, as utilized in 122.4, and E = enrichment factor (volume of water / volume of solvent) due to the Tiguid-liquid extraction 132 Calculate the total petroleum hydrocarbon (TPH) con- ‘centration in the original water sample report tothe nearest 0 1 mp/L: ‘Test Method D819 Row TPH (mga) = pA o where Rrmyy = measured concentration of total petroleum bydrocar- bons in mg/L in extract after treatment with Floris, D dilaton factor (volume of diluted extract / volume undiluted extract), if any, a8 utilized in 12.3.5, and E = ennchment factor (volume of water / volume of solvent) due to che lguid-tigund extraction. 14, Precision and Bias 4.1 A single laboratory validation study was eartied out with ocean substitute water (Practice DII41) samples. The sample set included 3 crude osls with densities 811 kg/m? (os 1), 839 kg/m? (ol 2) and 896 kgm’ (os 3). Two diferent crude ouls were used per concentration sn the range from 5 to 500 rngit. In addition, the lightest erude oil (ol 1) was used for 900, gil. Each sample was prepared by spiking a given amount of ol mm 900 mL water and extracting with 50 mL. eyelohexane For each extract a single measurement of each TOG and TPH was caried out. For the concentrations where more than one cil type was used, the pooled menn, pooled standard deviation and pooled recovery were calculated. The raw data are shown in Tables ALI and Al 2m Annex Al, For the QC seetion, 8 samples with » mixture of Mineral Oil Type A and Type’ B (BAM KO10) im reagent water (Spectication D1193) at a concentration of 50 mg/L. was taken through the entire analyti- eal method for both TOG and TPH. The results are summarized tm Tables AIL3 and A1.4 mm Annex Al 14.2 Repeatabilin—Based on the single lab study, a pre- luminary repeatability for the diferent concentrations. was estimated based on Practice D2777. ful interlaboratory study will be completed within five years to determine the repeat ability of the method. See ‘Tables 1 and 2. Now 7—The rato of TOG and TPH recovery teflect the amount of ‘poly sbsances tht ae removed hy means of he teatment wth Flos 143. Method Detection Lumut—Eight samples of ocean sub- stitute water spiked with oil 3 at a nominal concentration of 1,7 mg/L. were used to determine the method detecton Tint (MDL) according 10 40 CFR PL. 136, Appendix B. The raw data are shown in Tables AU I and AlL2 in Annes Al. See Table 3fly psi9s - 18 TABLE 1 Repeatabllly Table for TOG Based on the Single Lab shudy Gancantaton 5 a Resa (rat) eau he @ a ea 0 0252 ree oe So ho 8 Cconcemsaton- nora concanvaten as propared Nvurbor of camplea Maan (ng) = mean ae Stingt} Sanda aon fu Ge le standard evan i FRdcovary (8) ao TOG value andthe prepeed conceneaton TABLE 2 Repeatability Table for TPH Based on the Single Lab ‘study “Gonceniaton ean ag Ry —.—UmUrrr~—~—irsS— 5 38 ae 7 2 os 135 a 0 oo oo 220 aa 83 tea CConcriraton- ren cancenlaien as prepared Nena of sanelos Yang) ~ aan ae SFimgl) = stndar devon fa ()~ ave sansa dowaton me Fdcoeny (2) rao of TPA vee an he prepara cancer TABLE 3 Single Laboratory MOL Study Conconraton yy ‘ean “OL Racoon fon (rat) mat) rat)“ Toa 17 bur 016 04a 100 wen 17, 8 om on os ‘anor of eanes aan mat) ~ mom vate Sngt} = stnda denabon MOL fii) = matt detection tl deternned he 99% ve FRecovary (3) rata! mean vl To the prepared coneariaion 144 Reproducibiluy—A full interlaboratory study will be ‘completed wuthin five years to determine the reproducibility of, this test method. 15, Keywords 15.1 oil total oll and grease (TOG); (otal petroleum hydeo- carbon material (TPH) ‘nnuraht by ASTM In all ght reserve), Thu Mar 25 2139 S0 EDT 2021Ay pat 93 18 ANNEXES) (Mandatory Information) AL, SINGL ALA The following tables summarize the raw data from the sangle lab study. Naw. Al 1—The rato of TOG and TPH recovery eect the amount of pol subsanoes tht ae emoved by means othe Weatenent wah Flos AL2 Holding Trme Dato—In total 6 samples of surface water were spiked with 50 mg/L oil ‘Three samples. were spiked with off | and thiee samples wath ot! 3. Te samples swore treated with hydrochloric acid and stored for 9 weeks (63 |AB STUDY. ddays) as desenbed an the method. The samples were extracted and a single TOG measurements was carcied out on each sample ‘The resulls were compared to the upper and lower lint of the 99 % conlidence interval for a single result calculated from the single Tab study 1n Table AI.1. All measurements were found to be within the 99 4% confidence interval implying that the holding time is long compared to the tested time mterval for these samples TABLE At Single Laboratory Study Results for Total Oil and Grease (TOG) m Ocean Substitute Water (OSW) ‘anole no ee cee Os 17 tm ts tents tes tat tat Ott cc rr rr | a ST) ois toate footw tos oa ke ois oa as mr Bo testo aae Olt amas ame ame mae es teva ame amet tant Ott Soo Soot Saga son? rey aoa ates S000 ase mer toe Ott om tors__ boas aoee aoe cost oases (gh) —noraraleoncenvaton as prepares Mean (nat) ~maan value 5 mgt) sandra dowaten Fenovery (2) ra mean TOG vale sd th prepared concenaton eefy psi93 ~ 18 ‘TABLE A1.2 Single Laboratory Study Results for Total Petroleum Hydrocarbon (TPH) in Ocean Substitute Water (OSW) [Nore 1—Becaus the propated sample contains pola substances that ate removed by the Fonsi eatment, the TPH iccovety i lowe than dhe TOG recovery Same ] 1 2 3 4 5 6 7 8 — A are sono gts = a a a a CT oe ee a OW SP ea Se SR oe os es kgs tS ae eek Pt oi: eo igey tse tor eso, fecasuar tei? oi: mart ena oy a er ats ao font © (rat ~ nominal concentration as pope ean (nit) mean vale Slot) slandid dealer Fesoery rao mean TPH vos adhe propired conceniaon TABLE A1.3 Single Laboratory Study Results for Total Oil and Grease (TOG) for the Quality Control Sample (BANKO1O) in Reagent Water eee DB RS Soria igi? (not) . ‘ trot) _¢) Sais 0 sis) aye O78 (ma) - noma conconaton as prepared taaan er) mean va Singh) = slandar deton Recovery (ata f met TOS vali the prepare concntaon ‘TABLE A1.4 Single Laboratory Study Results for Total Petroleum Hydrocarbon (TPH) for the Quality Control Sample (BAMKO10) in Reagent Water a ; 5 zi a . 5 Tam Recovery Sarole gm? impt : . 8 emt toghy “te Boose (mot) — nemo concetaton as papated ean (mg) aan valve mgt} serdar deition Recovery (3) sata mean TPH wave andthe prepared concanaton| TABLE A1.5 Holding Time Experments ‘Sample 1 2 3 acm Conse remot Goat iat art 0 ae we wwe 8 50 O18 80 53 Be su a0 et ¢rg) — vernal cancntenon os popu Gyessnn=thelonec it fhe 9 5: conkenes le fora ale tel cause or the TOG snl hic ess cane othe sa i andcencanrton in‘ "te appar ln of he 90S condone taal for ssn teed eels om tha TOG snl lb tidy ete oem fr the same ot an(fy pete - 18 A2, DEVICE. USED FOR PHAS A2.1 The device can be mounted direcily on a GAS threaded extraction bottle, When mounted on an extcaction bottle, distilled water ean be filed sn the long thi tube 1m order 1 displace the eyelohexane phase ito the thie tube. The small ‘ross section of the tube as compared to the extraction bottle facilitates phase separation See Fig A2.1 FIG, A2.1 Example of a Dovico Used for Phase Separation AST emanates no pasion respecting the wae of any patent rats assorted connecton wh any em mentored ‘nt stand User ofthe sandra ar anpessyadeced a olrmhon oo vane of ary auth patent Pgs and he sk ‘titangement osu nhs, ae ental Pr oat cenit ‘Ths stand suet eusian a any te yh espana lca arena ut Be eewed vey hve yrs ac ‘snot, eta rsiproveso aidan Yourconmonts feed ators rassono hs tana oro acon stands Sana shoul be aatessed@ ASTAY Iematenal Hesaquaren Your comments il aces cae conaderaon aa mee fe ‘espanatie cna! comme, whch jamal you tel hat your conments have ol ecoved nr hosong you shod ‘make your vows known tothe AST Commies on Stand, x fh aos shown boo ‘Ths stand copynged by ASTI nlematona, 100 Bar Harbor Ove, FO Boe C700, We! 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