This article was downloaded by: [University of California Santa Cruz]On: 09 October 2014, At: 09:41Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registeredoffice: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Soil and Sediment Contamination: AnInternational JournalPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/bssc20

Is Method 1664A Silica Gel Treated N-Hexane Extractable Material (SGT-HEM:Non-Polar Materials) a Measure of TotalPetroleum Hydrocarbons?MICHAEL W. MILLER a , MICHAEL S. WRIGHT b , ALEXANDER M. ALLENc & BOGUSLAW DUDEK ca NJ DEP Office of Quality Assurance , Trenton, New Jerseyb TRC Omni Environmental Corporation , Princeton, New Jerseyc ConocoPhillips Bayway Refinery , Linden, New JerseyPublished online: 17 Aug 2006.

To cite this article: MICHAEL W. MILLER , MICHAEL S. WRIGHT , ALEXANDER M. ALLEN & BOGUSLAWDUDEK (2005) Is Method 1664A Silica Gel Treated N-Hexane Extractable Material (SGT-HEM: Non-Polar Materials) a Measure of Total Petroleum Hydrocarbons?, Soil and Sediment Contamination: AnInternational Journal, 14:2, 105-113

To link to this article: http://dx.doi.org/10.1080/15320380590911724

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the“Content”) contained in the publications on our platform. However, Taylor & Francis,our agents, and our licensors make no representations or warranties whatsoever as tothe accuracy, completeness, or suitability for any purpose of the Content. Any opinionsand views expressed in this publication are the opinions and views of the authors,and are not the views of or endorsed by Taylor & Francis. The accuracy of the Contentshould not be relied upon and should be independently verified with primary sourcesof information. Taylor and Francis shall not be liable for any losses, actions, claims,proceedings, demands, costs, expenses, damages, and other liabilities whatsoever orhowsoever caused arising directly or indirectly in connection with, in relation to or arisingout of the use of the Content.

This article may be used for research, teaching, and private study purposes. Anysubstantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-and-conditions

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

Soil & Sediment Contamination, 14:105–113, 2005Copyright © ASPISSN: 1532-0383 print / 1549-7887 onlineDOI: 10.1080/15320380590911724

Is Method 1664A Silica Gel Treated N-HexaneExtractable Material (SGT-HEM: Non-Polar

Materials) a Measure of Total PetroleumHydrocarbons?

MICHAEL W. MILLER,1 MICHAEL S. WRIGHT,2

ALEXANDER M. ALLEN,3 AND BOGUSLAW DUDEK3

1NJ DEP Office of Quality Assurance, Trenton, New Jersey2TRC Omni Environmental Corporation, Princeton, New Jersey3ConocoPhillips Bayway Refinery, Linden, New Jersey

Total Petroleum Hydrocarbons (TPH) is a non-specific parameter defined by EPAMethod 418.1. The method is simple, inexpensive and straightforward. Freon 113is used to extract petroleum from the matrix. The Montreal Protocol precludes theproduction and importation of Freon 113 into the United States. The search for acost–effective replacement is underway. US EPA method 1664A Silica Gel Treated N-Hexane Extractable Material (SGT-HEM; Non-Polar Materials) has been consideredas a replacement for Method 418.1 by some persons. No comparison data has beenprovided.

The Tosco Corp. Bayway Refinery has a wastewater discharge permit for PetroleumHydrocarbons (Oil & Grease) that specifies the use of Method 418.1. The intent ofthis study was to determine if Method 1664A could replace Method 418.1. Method418.1 is a direct instrumental measurement of the dried extract. Method 1664A isa gravimetric measurement that requires heating the extract to remove the solvent.Also, a key question to be answered is what carbon range petroleum hydrocarbonsdoes heating the extracts lose? Several evaporation procedures and temperatures werestudied.

The study showed that the recovery of petroleum hydrocarbons by method 1664Ais temperature dependent and that under the study conditions the method 1664A SilicaGel Treated N-Hexane Extractable Material (SGT-HEM; Non-Polar Materials) can bea replacement for method 418.1.

Keywords Discharge permit, Method 418.1, Method 1664A, non–polar materials,silica gel treated n-hexane extractable material, solid phase extraction, total petroleumhydrocarbons.

Introduction

Environmental laboratories have used Freon 113 and the infrared spectroscopic U.S. EPAMethod 418.1 (Method 418.1) since the early 1980s to evaluate petroleum hydrocarbon

Address correspondence to Dr. Michael Miller, Research Scientist, Office of Quality Assurance,New Jersey Department of Environmental Protection, P.O. Box 424, Trenton, NJ 08625, USA. E-mail:Michael.W.Miller@dep.state.nj.us

105

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

106 M. W. Miller et al.

contaminated water and soil (USEPA, 1983). Petroleum Hydrocarbons are a class of chem-icals that contains thousands of specific compounds with a wide range of molecular weightsand solubility. The term Total Petroleum Hydrocarbons is defined as the material extractedand determined by Method 418.1. Laboratories were able to analyze samples with a mod-erate investment in equipment and labor. The method was very useful in estimating thecontamination from leaking underground storage tanks. The method determined the con-centration of diesel fuel, and fuel oil numbers 2 through 6. The high volatility of gasolineprevented an accurate determination by the method (Miller et al., 1997). The cost per sampleto the environmental engineer was in the range of 35 dollars. Freon 113, a Class 1 chlo-rofluorocarbon (CFC), is used as the extraction solvent. The United States is committedto discontinuing the use of CFCs as a party to the Montreal Protocol on Substances thatDeplete the Ozone Layer and as required by the Clean Air Act Amendments of 1990. Ef-fective January 1, 2002, laboratories are no longer allowed to purchase Freon 113 thatwas produced or imported after December 31, 2001 for laboratory analyses (USEPA,2001). The use of recycled Freon will be allowed until December 31, 2005; howeverMethod 418.1 requires a quality of Freon 113 that may not be readily available in recycledform.

The search for improved analytical methods to determine petroleum hydrocarbon con-tamination resulted in the development of several gas chromatography (GC) methods, whichcan determine the type of petroleum contamination (Miller and Stainken, 1990; USEPA,1997). Miller presented a paper at the 12th Annual International Soils Conference discussingMethod 1664A and a GC method that covers petroleum with carbon numbers C8–C40(Miller et al., 1997). GC methods also determine gasoline contamination (USEPA, 1997).The USEPA evaluated replacement solvents for Freon 113 used in the determination of oiland grease by USEPA Method 413.1 and determined that n-hexane had similar extractionproperties (USEPA, 1993). This resulted in the development of a method with a gravimetricdeterminative procedure, USEPA Method 1664A n-Hexane Extractable Materials (HEM)(USEPA, 1999). The method contains a liquid-liquid and a solid phase extraction procedure(HEM-SPE). Additionally, by treating the n-hexane extract with silica gel, Method 1664ASilica Gel Treated n-Hexane Extracted Material (SGT-HEM) was developed. The productof the extraction is called Non-Polar Material. The extraction procedure is similar to theMethod 418.1 process (USEPA, 1983). Because changing both the extraction solvent andchanging the determinative step in the respective method changes the result, Non PolarMaterial does not equal Total Petroleum Hydrocarbons.

The New Jersey Department of Environmental Protection has over 400 wastewaterdischarge permits of various types that specify Method 418.1. ConocoPhillips BaywayRefinery (Bayway) in Linden, New Jersey is one of these permitees and is where theexperimental procedures for this paper were performed. To comply with the requirements ofits permit, Bayway must perform compliance monitoring of wastewater discharge locationsas defined in the permit. Bayway’s permit includes discharge limitations of 10 parts permillion (ppm), as a Monthly Average, and 15 ppm (Daily Maximum) for oil and grease. Thepermit requires that Method 418.1 (Total Petroleum Hydrocarbons) be used for the analysisof oil and grease.

One objective of this study is to determine if results generated by SGT-HEM-SPEportion of method 1664A are comparable to those determined by Method 418.1. This side-by-side study is designed to investigate equivalency between the methods based on theAnalytical Method Guidance for EPA Method 1664A Implementation and Use (40 CFRpart 136) (USEPA, 2000). In addition to the method comparison, a study was conducted toinvestigate the effect of temperature on the gravimetric recovery of lower weight (C8, C10,

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

Total Petroleum Hydrocarbons Defined by EPA Method 107

C12 and C14) non-polar hydrocarbons and diesel fuel using modifications to the evaporationprocedure detailed in Method 1664A (USEPA, 1999).

Experimental

Reagents

ACS reagent grade Freon 113 and pesticide grade n-hexane was used to prepare standardsand samples. The reagents were obtained from J. T. Baker (Phillipsburg, NJ) and Burdick& Jackson (Muskegon, MI) chemical companies, respectively.

Standards

Method 1664A QC standard, stearic acid and hexadecane was obtained from Horizon Cor-poration. The Method 418.1 Reference Oil is prepared from ACS reagent grade chemicals,obtained from J.T.Baker, by pipeting 15 ml of n-hexadecane, 15 ml of isooctane, and 10 ml ofchlorobenzene into a 50 ml Teflon septum sealed vial. The Reference Oil is made fresh eachtime it is needed and kept capped except when drawing aliquots. Method 418.1 calibrationstandards were prepared by diluting the Reference Oil in Freon 113.

The hydrocarbon standards were prepared at Bayway from ACS reagent grade n-octane (C8), n-decane (C10), n-dodecane (C12), and n-tetradecane (C14) supplied bydifferent manufacturers. The standards were prepared individually at a concentration of0.4 mg/ml.

Diesel fuel standard, (Winter Blend #2), utilized by ASTM, ASTM (2002) in the Inter-laboratory Crosscheck Program (Sample ID: DL0202), was obtained from ASTM Interna-tional, West Conshohocken, PA. The standard was diluted in n-hexane to a concentrationof 0.4 mg/L.

Equipment

Horizon SPE-DEX©R 3000XL Automated Solid Phase Extractor System was usedfor the analysis of SGT-HEM-SPE (Horizon Technology, 2001a). The Horizon SPEED –VAPTM II 9000 Solvent Evaporation System, (Horizon Technology, 2001b) was used toevaporate the hexane from the SGT-HEM-SPE extracts. The SPE disks used were 47 mmWhatman©R SPE Oil & Grease (VWR catalog # 28454-644). The Method 418.l, liquid-liquidextraction, was accomplished using separatory funnels. A Nicolet Impact 410 FTIR spec-trophotometer was used to analyze the Method 418.1 Freon 113 extract. For the evaluationof Method 1664A SGT-HEM protocol, as written, evaporation of the extracts was completedusing a Claisen distillation apparatus via a Lauda Ecoline 019 hot water bath controlledat 85◦C.

Data Collection and Analysis

Before conducting the side-by-side comparison between Method 1664A SGT-HEM-SPEand Method 418.1, the laboratory determined method detection limits (MDL) for HEM andSGT-HEM-SPE in accordance with Section 9.2.1 of Method 1664A. The laboratory alsocompleted an evaluation of Initial Precision and Recovery (IPR) for HEM and SGT-HEM-SPE in accordance with Section 9.2.2 of Method 1664A.

The EPA guidance document requires that before Method 1664A SGT-HEM-SPE canbe used all performance criteria for Method 1664A HEM must be met. The laboratory

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

108 M. W. Miller et al.

achieved a mean recovery of 87.5% and a relative standard deviation (RSD) of 15% for theMethod 1664A HEM IPR. The method limits are mean recovery 83–101% and RSD 11%.The laboratory achieved a HEM MDL of 1.1 mg/l vs. 1.4 mg/L. The laboratory achieved amean recovery of 94% and a RSD of 9.5% for the Method 1664A SGT-HEM-SPE IPR. Themethod limits are mean recovery 84–116% and RSD 28%. The laboratory achieved a SGT-HEM-SPE MDL of 0.91 mg/l vs. 1.4 mg/L. These studies determined that all performancecriteria were met for the demonstration of laboratory capability for the use of Method 1664Ain regulatory analysis.

The side-by-side comparison of EPA Method 418.1 and EPA Method 1664A SGT-HEM-SPE was conducted using samples collected during November and December of2002 on eight separate days over a seven-week period. Because detectable concentrationsare required to complete the evaluation, three split samples were obtained from the Baywaywastewater prior to treatment (Biox Influent) and analyzed for petroleum hydrocarbons. Thislocation is assumed to provide samples with an organic profile similar to the final permitteddischarge location. The laboratory analyzed reference materials of known concentrationsand field samples collected for matrix spiking in duplicate. In order to provide sufficientdata in case of breakage, or other circumstances that would reduce the quantity of availablesamples, a total of eight sets of replicates were collected and analyzed as compared to theseven sets required in the EPA guidance document. The samples were analyzed in threebatches and the results of the study are displayed in Table 1. Each batch included qualitycontrol samples, as required by the respective methods, and samples of known concentrationsupplied by a NIST accredited vendor (APG Inc.).

U.S. EPA Method 418.1 (USEPA, 1983) was followed as written, using separatoryfunnel liquid-liquid extraction. The Nicolet infrared spectrophotometer was calibrated fol-lowing the manufacture’s instructions. USEPA Method 1664A SGT-HEM-SPE extractionas automated by Horizon Corporation was followed (Horizon Technology, 2001a). TheHorizon Corporation also automated the solvent evaporation procedure using an evapo-ration temperature of 45◦C (Horizon Technology, 2001b). In an attempt to improve theefficiency of recovering lower molecular weight HEM, the evaporation step was performedat 28◦C.

In order to obtain a better understanding of the effect of evaporation temperature onrecovery of lower molecular weight hydrocarbons, standards were prepared and subjectedto evaporation using the Horizon SPEED-VAPTM II 9000 Solvent Evaporation System. Re-covery standards: n-octane (C8), n-decane (C10), n-dodecane (C12), n-tetradecane (C14)and a diesel fuel were prepared in reagent grade n-hexane. The diesel fuel used in thisstudy was Winter Blend #2. A winter blend was chosen because this mixture contains alower mean distillation temperature than the summer blend and therefore should repre-sent a “worse case” standard for gravimetric recovery. Seven (7) individual aliquots of50 mls of each set of standards (a total of 35 samples) were subjected to the evaporationprocedure at 28◦C used during the study, and at the 45◦C evaporation temperature spec-ified in the Horizon SPEED-VAPTM procedure manual (Horizon Technology, 2001b). Ablank of reagent grade n-hexane was also analyzed with each of the sets of standards.The recovery of each aliquot was quantified, and a summary of this data is presentedin Table 2.

Seven samples of Winter Blend #2 were analyzed using Method 1664A SGT-HEM-SPE. The n-hexane solvent was removed from the extracts following the 1664A HEMprotocol, using a Claisen distillation apparatus via a hot water bath controlled at 85◦C toachieve a vapor temperature of 70◦C. The extract residue was dried for one hour at 70◦C ina drying oven. The recovery of Winter Blend #2 was determined under these conditions.

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

Total Petroleum Hydrocarbons Defined by EPA Method 109

Table 1Side-by-side comparison of US EPA methods 418.1 and 1664A SGT-HEM-SPE

1664A SGT-HEM 418.1 PHCDate Data set ‘i’ Data set ‘j’

Raw data (ppm)11/15/02 4.5 3.7 4.0 8.4 8.0 7.911/18/02 5.0 4.9 5.5 7.6 7.5 8.411/19/02 4.0 4.1 3.9 6.7 5.4 5.412/05/02 9.2 9.8 10.1 3.5 4.3 4.312/06/02 4.0 3.5 4.0 3.1 2.5 3.012/09/02 2.0 2.2 2.4 3.2 3.2 3.012/12/02 11.0 12.8 12.8 13.4 13.6 15.212/16/02∗ 14.6 6.5 11.8 3.6 3.7 6.3

Log transformation11/15/02 1.50 1.31 1.39 2.13 2.08 2.0711/18/02 1.61 1.59 1.70 2.03 2.01 2.1311/19/02 1.39 1.41 1.36 1.90 1.69 1.6912/05/02 2.22 2.28 2.31 1.25 1.46 1.4612/06/02 1.39 1.25 1.39 1.13 0.92 1.1012/09/02 0.69 0.79 0.88 1.16 1.16 1.1012/12/02 2.40 2.55 2.55 2.60 2.61 2.72

Triplicate meansStandard Standard Mean

Mean deviation Mean deviation TM “i”, TM “j”

11/15/02 1.40 0.08 2.09 0.13 1.7511/18/02 1.63 0.02 2.06 0.02 1.8511/19/02 1.39 0.01 1.76 0.01 1.5712/05/02 2.27 0.26 1.39 0.26 1.8312/06/02 1.34 0.05 1.05 0.05 1.2012/09/02 0.79 0.01 1.14 0.01 0.9612/12/02 2.50 0.01 2.64 0.01 2.57

Method specific mean for data set ‘i’ = 1.62; Method specific mean for data set ‘j’ = 1.73;Mean-square error = 0.007; Root mean square deviation = 0.25; Method by sample interaction= 0.428; Fcalc ratio = 64.83.

∗This data not used in the log transformation calculations.

Results

The side-by-side comparison data of Method 1664A SGT-HEM-SPE and Method 418.1were evaluated using the statistical approach in Section 2 and Appendix A of the EPA guid-ance document (USEPA, 2000). The first seven sets of replicates obtained were subjected tothe statistical evaluation. Table 1 presents the raw data and the data from the statistical stepsin the guidance document. The mean square error (MSE) and root mean square deviation(RMSD) were calculated for the study results obtained from Method 1664A SGT-HEM-SPEand the current required methodology, Method 418.1. The maximum RMSD to determinea significant difference between the methods (RMSDmax) was determined using the cal-culated MSE and the 95th percentile F value with 7 degrees of freedom in the numerator

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

110 M. W. Miller et al.

Table 2Effect of temperature on the recovery of low molecular weight TPH

Recovery (%)

C8 C10 C12 C14 Diesel

Test #1 28◦C 1.40 28.84 68.81 91.08 87.94Test #2 28◦C 1.40 25.12 90.10 88.33 85.47Test #3 28◦C 0.93 11.16 74.26 91.08 88.44Test #4 28◦C 0.47 18.60 77.23 88.79 83.99Test #5 28◦C 0.47 21.40 77.72 88.33 82.51Test #6 28◦C 0.93 26.98 75.74 91.08 84.98Test #7 28◦C 0.93 16.74 75.25 86.50 86.96Mean 28◦C 0.93 21.26 77.02 89.31 85.76Standard dev 28◦C 0.38 6.25 6.47 1.80 2.15

Test #1 45◦C 0.49 2.01 52.09 87.27 84.49Test #2 45◦C 1.48 9.53 57.99 91.56 84.49Test #3 45◦C 0.49 3.51 57.99 92.99 84.98Test #4 45◦C 0.49 16.56 61.92 91.56 82.51Test #5 45◦C 1.48 12.04 58.48 90.61 83.50Test #6 45◦C 0.49 2.01 64.37 89.18 83.99Test #7 45◦C 1.48 2.51 60.93 92.99 83.00Mean 45◦C 0.91 6.88 59.11 90.88 83.85Standard dev 45◦C 0.53 5.85 3.90 2.08 0.89

s2 0.211 36.639 28.543 3.776 2.708sx1−x2 0.245 3.235 2.856 1.039 0.880t value 0.065 4.445 6.271 1.510 2.166Significant difference between No Yes Yes No No

two sample means at5% level of significance

(representing the number of sample sets per method) and 28 degrees of freedom in the de-nominator. The calculated RMSD (0.25) is greater than the RMSDmax (0.10), and thereforeaccording to EPA guidance document the difference between the methods is significant.Because the difference between the methods is significant it is necessary to determine if thedifference is constant by calculating the mean squares attributable to a method by sampleinteraction (MSINT). The calculated MSINT for this study (0.428) is divided by the MSEfor this study (0.007) to determine the Fcalc ratio. Because the Fcalc ratio of the study data(64.8) is greater than the corresponding 95th percentile F value (2.45), there is a significantinteraction between method and sample and therefore the bias between methods variessignificantly from sample to sample. The methods are not equivalent for these samples.This result is not unexpected because examination of the raw data in Table 1 indicates thatsome concentration values obtained from method 1664A SGT-HEM-SPE are greater thanthe values obtained for the corresponding samples analyzed via Method 418.1; however,other sample sets exhibit the opposite trend. It should also be noted that any combination ofseven sets of results from the available eight sets of data produce an Fcalc ratio of the studydata that is greater than the 95th percentile F value. Because the bias between methods

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

Total Petroleum Hydrocarbons Defined by EPA Method 111

varies significantly from sample to sample, the application of a conversion factor is notappropriate for the samples obtained in support of Bayway’s permit.

Additionally, statistical analysis was also used to evaluate the effect of evaporationtemperature on the recovery of the low molecular weight hydrocarbon standards (Fisherand Yates, 1974). The data are presented in Table 2. The data for recovery at 28◦C wascompared to data recovery at 45◦C using the two-tailed test for means. The two-tailedtest for means entails the establishment of a null hypothesis or an alternative hypothesis.The null hypothesis is established when the difference between the mean of the baseline(recovery at 45◦C), and the mean of the experiment (recovery at 28◦C), is statistically equalto zero at a defined significance level. The alternative hypothesis establishes that the twomeans are statistically different.

To test the null hypothesis, the t statistic was determined:

t = µ1 − µ2

sµ1−µ2

(1)

where µ1 is the mean of baseline data and µ2 is the mean of the experimental data, wheres µ1− µ2 is the estimated standard error of the difference between the two means:

sµ1−µ2 = s

√1

n1+ 1

n2(2)

where n1 and n2 sample sizes and s is the pooled estimate of common standard deviationas determined by:

s =√

(n1 − 1) s21 + (n2 − 1) s2

2

n1 + n2 − 2(3)

where s1 and s2 are the standard deviations of the respective sample pools.The t value, from Equation 1, is calculated and compared to the critical t value found in

the t-distribution table that is based on the degrees of freedom and the percentage significancelevel. The five percent significance level was used for all tests, and calculated based on 12degrees of freedom (six from each set of observations). If the t value from Equation 1 isless than the value from the critical t-distribution table the null hypothesis is accepted (theresults are not significantly different). The critical t value for this study is 2.18. A summaryof the results for these experiments is detailed in Table 2.

The mean recovery of C8 was negligible, less than 10%, at each of the two evaporationtemperatures (28◦C, 45◦C). The results of the two-tailed t test for means show significantdifference for recovery of C10 and C12 at the two different evaporation temperatures withhigher mean recoveries observed at 28◦C. The results of the two-tailed t test for means fromthis study shows no significant difference for recovery of C14. The mean recovery of C14was greater than 70% at each of the two evaporation temperatures.

The recovery of Winter Blend #2 from the n-hexane extract by distillation, with thewater bath set at 85◦C to achieve a vapor temperature of 70◦C, resulted in a mean recoveryof 84.3% with a RSD of 5.3%.

Conclusions

Total Petroleum Hydrocarbons is an empirical method designed to measure a mixture ofcompounds. Several processes that inherently eliminate lower weight organic compounds,

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

112 M. W. Miller et al.

including biological oxidation and extended aeration, are used to treat the Bayway wastewa-ter prior to discharge at the location regulated in the NJPDES permit. The discharge from theregulated location is expected to contain only higher weight organic compounds, thereforethe gravimetric procedure (EPA1664A SGT-HEM-SPE) should be considered suitable forquantification of these compounds. At an evaporation temperature of 28◦C, the mean recov-ery of the modeled discharge material (using the diesel fuel standard) was 85.8%. A directcorrelation was not established between the results from Method 418.1 and method 1664ASGT-HEM-SPE. While each method is prone to produce higher or lower results based onsample conditions, either method is anticipated to provide results suitable for reporting ofoil and grease in Bayway’s wastewater for compliance with the NJPDES permit.

This study shows that the recovery of petroleum hydrocarbons by U.S. EPA Method1664A SGT-HEM-SPE is temperature-dependent. Petroleum compounds with carbon num-bers as low as C12 can be successfully recovered using an evaporation temperature of 28◦C.Under this condition the Method 1664A Silica SGT-HEM-SPE Non-Polar Materials can bea replacement for Method 418.1. At 45◦C method 1664A SGT-HEM-SPE is not suitable forpetroleum hydrocarbon containing compounds with carbon numbers less than C14. If thewater bath is controlled at 85◦C to obtain a vapor temperature of 70◦C, the Method 1664ASGT-HEM-SPE distillation procedure for recovering the petroleum hydrocarbons from then-hexane extract can be use, for materials with molecular weights similar to greater thandiesel fuel or #2 fuel oil. Since every discharge has, different composition, a comparisonstudy should be performed between Method 418.1 and Method 1664A SGT-HEM-SPE.

Acknowledgements

The NJDEP has not subjected this manuscript to internal review. Therefore, the researchresults presented herein do not necessarily reflect Departmental policy. Mention of tradenames of commercial products does not constitute endorsement or recommendation for use.The authors wish to thank Ms. Barbara J. Andrukiewicz, ConocoPhillips Bayway RefineryLaboratory Manager, for conducting the project at the facilities laboratory. The authors alsowish to thank Ms. Denise Scangamor of the TRC Omni Environmental Corporation stafffor formatting the paper and Dr. Bernie Wilk, and Marty Hackman of NJDEP-OQA fortheir technical and editorial suggestions.

References

ASTM. 2002. Committee D-2 Interlaboratory Crosscheck Program #2 Diesel Fuel Sample ID:DL0202. Final report, ASTM International, West Conshohocken, PA.

Fisher, R.A. and Yates, F. 1974. Statistical Tables for Biological, Agricultural and Medical Research,6th ed., Oliver and Boyd, London.

Horizon Technology. 2001a. SPE-DEXR 300XL Series, Automated Solid Phase Extractor SystemUser’s Guide, rev. 4. Atkinson, NH.

Horizon Technology. 2001b. SPEED-VAPTMII 9000, Solvent Evaporation System User’s Guide, rev.6. Atkinson, NH.

Miller, M.W., Appleby, C., Wright, D., and Skelton, P. 1997. A Gas Chromatography Method toReplace Method 418.1 for the Determination of Total Petroleum Hydrocarbons. The 12th AnnualInternational Conference on Soils, Sediments and Water, Amherst, MA.

Miller, M. W., and Stainken, D. M. 1990. An Analytical Manual for Petroleum and Gasoline Productsfor New Jersey’s Environmental Program. In: Petroleum Contaminated Soils, Volume 3, pp.383–398. (Kostecki, P. T. and Calabrese, E.J., Eds.). Lewis Publishers, Inc., Michigan.

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014

Total Petroleum Hydrocarbons Defined by EPA Method 113

USEPA (U.S. Environmental Protection Agency). 1983. Petroleum Hydrocarbons, Total Recoverable,(Method 418.1), Environmental Monitoring Support Laboratory, EPA 600/4-79-020, revised.

USEPA (U.S. Environmental Protection Agency). 1993. Preliminary Report of EPA Efforts to ReplaceFreon for the Determination of Oil and Grease, Office of Water, Washington, DC. EPA-821-R-93-009.

USEPA (U.S. Environmental Protection Agency). 1997. Non Halogenated Organics Using GC/FID,Method 8015B. In: Test Methods for Solid Waste, SW846, 3rd Edition, Volume 1B.

USEPA (U.S. Environmental Protection Agency). 1999. Method 1664, Revision A: N-Hexane Ex-tractable Material (HEM; Oil and Grease) and Silica Gel Treated N-Hexane Extractable Material(SGT-HEM; Non-Polar Material) by Extraction and Gravimetry, Office of Water, Washington,DC. EPA-821-R-98-002, PB99-12949.

USEPA (U.S. Environmental Protection Agency). 2000. Analytical Method Guidance for EPAMethod 1664A Implementation and Use (40 CFR part 136 Office of Water),Washington, DC.USEPA/821-R-00-003.

USEPA (U.S. Environmental Protection Agency). 2001. Protection of the Stratospheric Ozone: DeMinimuis Exemption for Laboratory Essential Uses for Calendar Year 2001, 40CFR Part 82,Office of Air, Washington, DC. FR Vol. 66, No 49, March 13, 2001.

Dow

nloa

ded

by [

Uni

vers

ity o

f C

alif

orni

a Sa

nta

Cru

z] a

t 09:

41 0

9 O

ctob

er 2

014