Evaluation Of Oils And Grease And Total Petroleum ...The Uniform & Textile Service Association...
50
EVALUATION OF OILS AND GREASE AND TOTAL PETROLEUM HYDROCARBONS IN INDUSTRIAL LAUNDRY EFFLUENTS AND DETERGENTS Prepared for: Uniform & Textile Service Association 1730 M Street Suite 610 Washington, DC 20036 202/296-6744 202/296-2309 (Fax) Prepared by: ETS Analytical Services, Inc. Roanoke, VA June 25, 1994 6/94
Transcript of Evaluation Of Oils And Grease And Total Petroleum ...The Uniform & Textile Service Association...
’ / , P. .. I 1
2, ,. . I
..
EVALUATION OF OILS AND GREASE AND TOTAL PETROLEUM HYDROCARBONS
IN INDUSTRIAL LAUNDRY EFFLUENTS AND DETERGENTS
Prepared for:
Uniform & Textile Service Association 1730 M Street Suite 610 Washington, DC 20036
202/296-6744 202/296-2309 (Fax)
Prepared by:
ETS Analytical Services, Inc. Roanoke, VA June 25, 1994
6/94
SECTION
1.
.. 11.
... 111.
1 1.1 1.2 1.3 1.4 1.5 1.6 1 .I
2 2.1 2.2
3 3.1 3.2 3.3 3.4 3.5
4 4.1 4.2 4.3
> > TABLE OF CONTENTS < <
CONTENTS
Foreword
Executive Summaly
Introduction
STUDY OBJECTIVES AND DESCRIPTION Objectives Wastewater Collection and Shipment Detergent Products Shipment Wastewater Sample Receipt and Initial Processing Gravimetric Analysis Infrared Analysis Quality Assurance/Quality Control
ANALYTICAL DATA Gravimetric Analysis Infrared Analysis
STATISTICAL DATA Mean, SD, and RMSD Results Silica Gel Treatment Results Correlation of Alternative Solvents to Freon@ Contribution of Detergents to O&G and TPH Correlation of Gravimetric and IR Data
QAIQC RESULTS Blanks Calibration Other QA Results
PAGE61
1
2
3
4-10 5
5 6 6
6-7 7-8 8
8-9
11-15 12 12
16-27 17 17 17 18 18
28-30 29 29 29
6 / 9 4
>>TABLES < <
- No. 1 2 3 4 5 6 I 8 9 10 1 1 12 13 14 15 16 17
Detection Limits for Detergent Testing Wastewater Gravimetric Results Detergent Gravimetric Results Wastewater IR Results Detergent IR Results WW O&G Mean, SD, and RMSD by Gravimetric WW TPH Mean, SD, and RMSD by Gravimetric WW O&G Mean, SD, and RMSD by IR WW TPH Mean, SD, and RMSD by IR Wastewater O&G vs. TF'H Detergent O&G vs. TPH Correlation of Solvent Types for O&G Correlation of Solvent Types for TPH Detergent Contribution to O&G and TPH in WW Comparison of Gravimetric and IR Results Blank Results Calibration Verification Results
> > APPENDIX < <
A-1 Description of Wastewater Samples A-2 Description of Detergent Samples A-3 A-4 EPA Method 413.1 A-5 EPA Method 418.1
Project Chain of Custody Form
PAGEL$) 10 13 14 15 15 19 20 21 21 22
23-24 25 25 26 27 30 30
WP60 \ UTSA. RPT 6 / 9 4
. I .. i. FOREWORD
This report was prepared by ETS Analytical Services (ETSAS) exclusively for the Uniform & Textile Service Association (USTA); formerly the Institute of Industrial Launders OIL). No part of this report may be reproduced without UTSA’s permission.
Any mention of trade names or commercial products within this report does not constitute endorsement or recommendation by USTA or ETSAS.
ETSAS wishes to thank the Uniform & Textile Service Association for its generosity in the funding of this study upon which this report is based.
-1- 6 / 9 4
., ii. EXECUTIVE SUMMARY
Based upon the laboratory testing of 12 industrial laundry wastewaters and 22 commercial detergents it appears that:
1)
2)
3)
4)
The current EPA method use for monitoring oil and grease (O&G) in industrial laundry wastewater discharges (gravimetric analysis by Method 413.1) is also measuring substances that could be classified as non-O&G and, therefore, yields bias high results.
The two alternative solvents proposed as a replacement for Freonm do not alter this situation.
For the samples analyzed in this study, the alternative method being used by some enforcement agencies (IR by Method 418.1) gives higher results for O&G and TPH when compared to the gravimetric method.
A significant portion of the O&G as measured by Method 413.1 in some industrial laundry wastewaters may be attributable to the commercial detergent(s) being used. Depending upon the detergent composition, the use of silica gel as a clean-up step may not be effective in removing these substances.
WP60 \ UTSA.RPT -2- 6/94
I .
iii. INTRODUCTION
The Uniform & Textile Service Association (USTA) believes that the oil and grease (O&G) content in industrial laundry wastewater as measured by the required EPA method (413.1) yields biased results. Since the solvent used in this method (Freona) cannot distinguish between oil and grease and other extractable substances, it is believed that a significant amount of the O&G now being measured in EPA regulated discharges is actually Freona soluable substances from commercial detergents and other sources.
The measurement of oil and grease in discharges is a confusing issue since it is nearly impossible to define what O&G substances are in chemical terms. EPA defines O&G for regulation purposes in terms of its Freon@ solubality rather than individual compound identification and measurement (e.g. gas chromatography). Currently proposed regulations dictate that Freona will no longer be available for laboratory use after 1994. It is unlikely that any of the EPA-proposed replacement solvents will alter this situation if testing continues to use solvent partition and weighing the resulting residue. In addition, none of the proposed alternative solvents can be used for the analysis of O&G and TPH by infrared (EPA Method 418.1).
Because of these issues, UTSA commissioned a laboratory study to provide data based upon the analysis of a variety of industrial laundry wastewaters and selected commercial detergents often used by industrial laundries. This study was performed by ETS Analytical Services, Inc. (ETSAS) at its facility in Roanoke, Virginia.
This report presents 1) the experimental design of this study; 2) the data obtained from the laboratory testing; 3) data analysis in terms of mean, precision , and accuracy, and comparison of the results; 4) and basic data observations and conclusions.
This report does not present an in-depth statistical analysis of the data nor does it attempt to make recommendations on changes in discharge limitations or testing protocol. It is acknowledged that further study of the data will be needed to be performed by UTSA to correlate such factors as the final wastewater treatment at each individual site, the actual detergents used, and the types and mix of products being cleaned on the day of the wastewater samplings. Given the probability of further data analysis no attempt has been made to round numeric answers to normally reported significant figures.
-3- 6/94
i . , I .
SECTION 1
STUDY OBJECTIVES AND DESCRIPTION
-4- 6 / 9 4
_ . 1.1 OBJECTIVES
The objective of this study was to examine the oil and grease content of wastewater using EPA Method 413.1 (gravimetric analysis) from a number of industrial laundry facilities using standard Freon@ extraction and two other possible replacement solvents proposed by the EPA. In addition, a number of commercial detergent formulations were to be analyzed with the same 3 solvents. Duplicate O&G solvent extracts would be subjected to a clean-up step using silica gel to remove polar substances. All Freon@ extracts would be analyzed by infrared spectrophotometry (IR) based upon EPA Method 418.1 to determine the amount of total petroleum hydrocarbons (TPH) present. It was believed that the data would yield specific information as to:
The efficiency of the 2 alternative solvents in relation to the Freona "standard" in extracting industrial laundry wastewater;
The contribution of O&G material from a number of commercial detergents often used by UTSA members as measured by all 3 solvents;
The effectiveness of a sample clean-up step performed on extracts from #1 and #2 above;
The relationship between gravimetrically determined and IR determined O&G and TPH content in selected wastewater and detergent samples; and
Statistical information as to the reproducibility of each solvent type by the use of triplicate extractions on each sample.
1.2 WASTEWATER COLLECTION AND SHIPMENT
Wastewater sample kits were shipped from ETSAS to UTSA designated facilities by United Parcel Service. Samples of the plant's wastewater discharge were collected in 2 one gallon glass wide mouth screw cap bottles fitted with a Teflon lid liner. All materials needed to accomplish the sampling were provided by ETSAS and consisted of the following items:
Ice chest 2 gallon glass bottle with TFE lid 1 liter glass bottle used for dipping sample (if required) Bottle labels Project Chain-of-Custody (COC) form (example in Appendix of this report) Chain-of-Custody seals Sealing tape Plastic bag to seal ice for return shipment
The COC Form contained instructions for sampling as well as the reasons for the sampling effort, contact name and phone number for USTA, and contact person and telephone number at ETSAS for any questions.
The sampling was to be performed by responsible plant personnel. All samples were grabs taken from
WP'SO\LITSA.RPT -5- 6 / 9 4
. . , .
the final plant effluent. The COC was to be fully completed by the person performing the sampling and contains such information as:
0
Type of waste treatment Detergents used and supplier(s)
0
Facility name, location, address, and telephone numbers Name of person performing sampling Date, time, and place of sample collection
Type of product (e.g. mats, uniforms)
All samples were to be placed on ice immediately upon collection. Upon completion the samples were to be shipped on ice (sealed in the provided plastic bag) back to the ETSAS facility the same day of collection via Federal Express.
In all, a total of 12 wastewater samples were received at ETSAS between January and April 1994. All samples were received in good condition and on ice with the COC forms properly completed. A listing of the samples with a description of each is contained in the Appendix of this report.
1.3 DETERGENT PRODUCTS SHIPMENT
USTA made all of the product selections and arranged to have the product formulations shipped to ETSAS for testing. Each supplier was requested to submit information on its products including MSDS sheets and recommended mixing criteria. Seven different suppliers sent a total of 22 products to be tested which were reviewed in good condition. In accordance with requests made by the detergent manufacturers, no information will be given concerning these products.
1.4 WASTEWATER SAMPLE RECEIPT AND INITIAL PROCESSING
Effluent and product samples were received and initially processed at ETSAS in the same manner as USEPA contract samples as specified in the ETSAS document titled Standard berat ing Procedures for Samule Receiut Storage. Tracking. and Documentation (available upon request). This includes the following operations:
0
0
0
Initial inspection by the ETSAS Sample Custodian for completeness, breakage, etc.; Assignment of a sequential ETSAS laboratory ID number; Log-in of all information into the ETSAS Laboratory Information Management System (LIMS) for tracking and reporting; Sample and documentation storage under laboratory internal COC; and Written weekly notification to USTA of the samples received during that week.
Upon receipt each wastewater container was pH adjusted to less than 2 using 1 + 1 sulfuric acid, mechanically shaken and combined into a single container bottle, and refrigerated at 4 degrees centigrade. No sample was held for more that one week before analytical work was begun. Just prior to testing, each sample was mechanically shaken and fractionated by pouring the sample as quickly as possible into 9
WPGO\OTSA.RPT -6- 6/94
separate glass bottles. The liquid level in each bottle was marked for later determination of the sample volume.
Detergent samples were stored as received until laboratory testing was initiated.
1.5 GRAVIMETRIC ANALYSIS
Wastewater samples were analyzed for total oil and grease content using EPA Method 413.1; a copy of this method is contained in the Appendix of this Report. The following is a summary of this method: a measured amount of wastewater (typically 1 liter for low level detection) is placed into a separatory funnel, an aliquot of Freon@ solvent is added, and the funnel is shaken for at least 2 minutes and the layers allowed to separate. The solvent layer is drained through a filter funnel containing sodium sulfate to remove any water and drained into an clean, dry Erlenmeyer flask which has previously been weighed. The procedure is repeated twice more with new portions of solvent. The Freon@ extracts are gently evaporated off on a steam bath, the flask dried in a desiccator, and then weighed on an analytical balance. The difference between the ending and beginning flask weight is the amount of Freon@ extracted material expressed as "Oil and Grease" as per the method (USEPA 413.1).
For purposes of this study, the effluent sample fractions were separated in 3 groups consisting of 3 bottles in each group. Each group was extracted with a different solvent. The 3 bottles per group were used to measure the precision of the measurements, i.e., each was one part of a triplicate measurement. The following solvents were used:
Freona (1,1,2 Trichloro-l,2,2-Trifluoroethane);
n-Hexane; and
Cyclohexane
Each solvent was of ACS (American Chemical Society) grade or higher and each lot of solvent was previously tested for purity prior to sample extractions. All extractions were diluted to 100.0 ml final volume in glass Class A volummetric flasks.
Each detergent was accurately weighed and dissolved into deionized water in 3 different glass bottles. The weight of each product was adjusted to give the lowest detection limit in proportion to the amount of foaming that could he tolerated when shaken in the water matrix. Because of this each detergent had a different detection limit; Table 1 on Page 10 lists the detection limits for each product tested. Each detergent formulation was tested only once with each solvent, Le., no triplicate analysis will be performed.
Each of the 100.0 ml extracts were split into 2 equal portions of 50.0 ml each using a Class A glass pipet. One portion was treated with silica gel as prescribed in EPA Method 418.1 for the determination of Total Petroleum Hydrocarbons VPH). The silica gel treatment is intended to remove polar substances such as fatty materials and chlorinated hydrocarbons, theoretically leaving behind, petroleum residues to be measured. Each lot of silica gel was tested for absorption efficiency prior to use.
The extracts were evaporated to dryness as prescribed in Method 413.1, making allowances for the higher boiling points for n-hexane and cyclohexane. The boiling flask was desiccated overnight and the final
WPfiO\UTSA.RPT -7 - 6/94
. ,
weighing performed on an analytical balance to the nearest 0.1 mg. The amount of extracted material for each extract was calculated on an mg/l basis for the effluent samples and on a mg/kg basis for the detergents formulations.
As a result of the above procedures, each of the 12 wastewater samples were tested a total of 18 times: 3 replicates for each of the three solvents and the process repeated with silica gel clean-up. Thus, a total of 216 gravimetric determinations were made on the wastewater samples.
1.6 INFRARED ANALYSIS
EPA Method 418.1 was used to analyze six of the Freona wastewater extracts by infrared spectrophoto- metry, a copy of this method is contained in the appendix of the report. The following is a summary of the method as it relates to this project: a small portion of the Freona extract of the sample (as the result of the extract described in Section 1.5 above) is put into a quartz cell located in the sample beam side of the IR instrument. A portion of the pure Freona is place in the reference side of the IR. The sample extract and reference solvent are scanned with infrared radiation and the absorbance at about 2930 cm-' is measured. The purpose of the reference solvent is to "blank-out" any minor contributions from the solvent. The sample answer is calculated by comparing the intensity of the signal to laboratory prepared reference standards. The measurement being made by the IR at the selected wavelength is a carbon- hydrogen bond stretch. Thus, any C-H molecule will be likely to produce a detector response.
A portion of each of the six Freon@ extracts was treated with silica gel, resulting in a total O&G and a TPH by IR for each of the wastewater samples. Three of these were triplicate extracts while the remaining three were single extractions only. Of the 3 solvents used, only Freon@ can be used in the R analysis.
A total of 5 detergent samples were also tested by IR with and without silica gel treatment.
1.7 QUALITY ASSURANCElQUALITY CONTROL
The following is a summary of the quality assurance/quality control measures performed to insure data quality.
Each lot of solvent was tested for detectable residue; only below detection limit residue results were to be deemed acceptable. Any solvent not meeting this requirement was either replaced or re-distilled and tested again.
The efficiency of each new lot of silica gel was tested using Wesson oil dissolved in Freon@ at a level of 100 mgll. Only a 100% removal efficiency was acceptable for this study.
The ETSAS laboratory deionized water @IW) used for the detergent preparation was extracted with Freon@ and demonstrated to be free of detectable residue prior to preparation of any samples.
The analytical balances used in weighing residues were serviced within the last year and frequently checked with Class S weights and noted in the balance check notebook.
WP60 \UTSA.RPT -8 - 6 / 9 4
All glassware used in the study was thoroughly cleaned for organic residues as prescribed by the EPA. This included a final solvent rinse and oven drying prior to use. The empty, clean boiling flasks used in the evaporation process underwent the same desiccating and weighing steps used in the final sample analysis steps. All volummetric glassware was of Class A type.
Analytical blanks were performed at a minimum of 10% for all aqueous sample extractions to insure that glassware, reagents, and deionized water was free of residue contamination. Only nondetectable blanks were deemed acceptable. Any detectable blanks would cause all samples contained in that preparation group to be re-analyzed once the problem(s) were identified and corrected.
An external QA standard for O&G analysis was performed at a frequency of 10% of extracted aqueous samples. The acceptable recovery was that which is stated in certified standard documentation. Failure to comply with this objective was to cause ETSAS personnel to correct the problem and to re-analyze the affected samples.
All calculations were performed by the analyst and verified by an ETSAS Data Validation Specialist @VS). The ETSAS Quality Assurance Manager (QAM) performed independent audits of the data results to verify integrity.
Copies of all raw data, calculations, solution preparation logs, analyst notes, DVS and QAM notes have been maintained as required for internal review as well as for final reporting to the UTSA. All documentation conforms to EPA contract standards as set forth in ETSAS Standard Operating Procedure manuals.
-9- 6 / 9 4
Table 1 - Detection Limits for Detergent Gravimetric Analysis for O&G and TF'H
ETS ID Units 152462 mgkg
152463 mg/kg
152509 mglkg
152473 mglkg
152474 mg/kg
152475 mg/kg
152480 mg/kg
152481 mg/kg
152482 mglkg
152591 mglkg
152592 mg/kg
152593 mg/kg
152825 mg/kg
152826 mglkg
152827 mglkg
152828 mg/kg
152930 mglkg
152931 mg/kg
152932 mg/kg
155295 mglkg
155296 mg/kg
155297 mg/kg
Freon 3922
3922
3704
3704
985
1982
3846
3846
1793
3774
4000
3279
3873
7
976
990
790
758
800
528
496
680
n-Hexane 1904
1887
1980
1942
990
396
1980
1960
559
2000
1980
1904
3873
7
396
588
532
450
50 1
990
980
1000
Cyclohexane 2000
1942
1942
1980
980
396
1961
1961
359
961
1961
1980
3873
7
667
917
494
48 1
440
948
817
917
-10- 6/94
SECTION 2
ANALYTICAL DATA
-11- 6 / 9 4
2.1 GRAVIMETRIC ANALYSIS
Table 2 on page 13 presents the results for the oil and grease and total petroleum hydrocarbons gravimetric testing performed on the 12 wastewater samples. All of these results are reported in mg of residue per liter of sample (mgll). The Rep # column is the replicate number of each determination.
Table 3 on page 14 is a listing of O&G and TF’H gravimetric results obtained for the commercial detergents. Because these products were weighed for testing the results appear in mg of residue per kilogram of product tested (mg/kg). As previously stated, these determinations were not replicated, therefore, there is not Rep # column.
2.2 INFRARED ANALYSIS
The results of the measurements for O&G and TPH by IR on the selected wastewater samples appear in Table 4 on page 15. The IR results for the selected commercial detergents appear in Table 5 on that same page.
-12- 6 / 9 4
ETS ID 152149
152150
152151
152604
152672
152705
152736
152737
152865
153110
153111
155896
Table 2 -Wastewater Gravimetric Results As measured by EPA 413.1 (Mcdified)
AU m l t s are reported in mgll
I -------Total Oil and Grease------- I Rep # Freon@ 1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
1 2 3
384 460 421
769 795 813
314 317 317
114 124 119
43 44 44
282 266 272
90 97 116
72 1 790 837
110 111 103
96 86 91
157 176 168
20 18 23
n-Hexane 3 12 3 12 3 15
484 486 464
267 265 266
92 96 82
32 27 34
23 1 244 198
57 64 62
919 833 844
107 98 85
83 85 83
147 130 153
13 10 14
Cyclohexane 351 442 400
640 443 534
3 14 323 282
101 99 109
44 33 37
283 301 230
127 138 136
598 575 592
103 94 105
87 76 90
156 158 148
16 21 16
-13-
I --Total Petroleum Hydrocarbons-- I Freon@ n-Hexane
32 53 52
354 412 469
149 148 129
37 44 34
18 13 7
106 131 119
17 27 25
3 84 43 1 460
40 37 48
4 12 12
71 75 80
4 6 6
36 30 40
379 275 294
138 118 106
30 31 30
8 6 6
104 100 88
24 19 29
49 1 444 458
21 30 29
7 <5 6
64 57 73
2 4 6
Cyclohexane 34 18 23
252 205 280
165 140 162
25 35 35
14 8 14
98 100 117
30 36 37
429 369 369
46 52 55
7 18 9
59 63 63
4 5 8
6/94
Table 3 - Detergent Gravimetric Analysis As measured by EPA 413.1 (Modified)
ETS ID 152462
152463
152509
152473
152474
152475
152480
152481
152482
152591
152592
152593
152825
152826
152827
152828
152930
152931
152932
155295
155296
155297
I --------Total Oil and Grease------- I I ---Total Petroleum Hydrocarbons--- I Units Freon@ n-Hexane mgkg 125490 93333
mgkg 176470 92453
mgkg 81481 27723
mg/kg 196296 108738
mg/kg 66995 36634
mg/kg 30924 12687
mgkg 130769 156436
mg/kg 88461 43137
mgkg 34059 13265
mgkg 143396 <ZOO0
mgkg 116000 71287
mglkg 200000 121904
mg/kg 429940 189793
mg/kg 14 28
mgkg 81951 19406
mg/kg 34653 8235
mgkg 40316 19149
mgkg 26515 9910
mg/kg 35200 9022
mg/kg 158311 109901
mgkg 19802 18627
mgkg 45578 25000
Cyclohexane 172000
112621
44660
158416
26470
30132
156863
35294
20077
70588
58824
130693
240147
32
77333
2477 1
16296
11538
16740
132701
17544
21101
Freon@ n-Hexane 54902
39216
22222
14815
21675
7136
15385
11538
16133
71698
12000
101639
19367
7
6829
9901
2372
2273
6400
4449
445s
4762
< 1904
9434
7921
3883
< 990
< 396
< 1980
< 1960
< 359
< 2000
< 1980
< 1904
11620
< 7
2941
2941
14894
2844
1504
9901
9804
6000
Cyclohexane 22000
7767
7767
75248
12745
14273
33333
54902
717
7843
11765
13861
34860
< 7
8667
5504
< 494
5769
2643
12322
11404
12844
-14- 6/94
Table 4 -Wastewater Infmred Analysis As Measured by EPA 418.1 (Modified)
AU results are reported in mgll
ETS ID Rep# 152149 1
2 3
152150 1
3
152151 1 2 3
152604
152672
152705
O&G Freon@ 485 552 513
1350 1570 1640
440 429 418
121
59
401
TPH Freon@
61 69 61
1280 1190 1380
288 308 305
63
33
326
Table 5 - Detergent Infrared Analysis As Measured by EPA 418.1 (Modified)
O&G TPH ETS ID Units Freon@ Freon@ 152825 mgkg 253703 <9683
152826 mgkg < 17 < 17
152930 mgkg 20158 < 1976
152931 m g k 16288 < 1894
152932 m g k 17200 < 2000
-15- 6/94
. .
WPSO\UTSA.RPT
SECTION 3
Sl'ATISTICAL DATA
-16- 6 / 9 4
3.i MEAN, SD, AND RMSD RESULTS
The testing on watewater samples for O&G and TPH by gravimetric and IR was performed in triplicate to establish precision for each determination and to evaluate precision variations among the three solvents systems.
Table 6 on page 19 lists the Mean, Standard Deviation (SD), and the Root Mean Standard Deviation (RMSD) results for O&G by gravimetric analysis for the three solvents. Table 7 on page 20 lists the same information for TPH by gravimetric analysis. Tables 8 and 9 on Page 21 contain this information on the wastewater samples selected for O&G and TPH analysis by IR.
3.2 SILICA GEL TREATMENT RESULTS
The silica gel treatment is intended to remove polar substances from the solvent extract prior to the final analysis step. The difference between the total O&G result and the TPH result for a sample would be a representation of the non-petroleum extractable portion of the sample. Table 10 on page 22 contains the results for these analyses performed on the wastewater samples. The gravimetric results show that the silica gel removals range from 33.9% to 94.8% and the reduction obtained on each sample is largely unaffected by the solvent used.
UTSA reports that a number of its member laundries are subjected to a 100 mg/l O&G discharge limit. Based upon the test replicates mean, 9 of the 12 wastewaters tested for O&G with Freon@ and cyclohexane would fail this criterion and 7 would fail using n-hexane. If silica gel clean-up were allowed 4 of the 12 would fail using Freon@ and cyclohexane and 3 would fail using n-hexane.
Only 3 wastewater samples were tested by IR for O&G and TPH vable 4). Sample 152149 showed nearly 88 % reduction which was approximately the same percentage removal obtained in the gravimetric testing. Sample 152151 had 30% reduction by 1R and 48% for gravimetric while 152150 had close to 16% reduction with silica gel by IR and 55% by gravimetric analysis.
The silica gel treatment gave widely varying results on the detergent products. In addition, there appeared to be a larger variation of these results between solvent types. The percent removal ranges from a low of 22% to nearly 100%. (Note: an result of -55.6% obtained on one product). The MDSD sheets show that these products have a wide range of chemical compositions. Those products having higher removals by silica gel tend to contain alcohols and other polar substances that would be removed by silica gel treatment while ones that had lower removals contained inorganic silicates and alkali.
3.3 CORRELATION OF ALTERNATIVE SOLVENTS TO FREON@
Table 12 (page 25) presents the extraction efficiency of the 2 alternative solvents as a percentage correlation to Freon@ on wastewater O&G analysis. Table 13 (also on page 25) presents the efficiency on the wastewater samples for TPH analysis. Given that Freon@ is the "standard" solvent, correlation of alternative solvents is an important consideration for setting O&G discharge limitations.
WP60\ UTSA.RPT -17- 6 / 9 4
3.4 CONTRIBUTION OF DETERGENTS TO O&G AND TPH
The detergents data contained in Table 3 were used to estimate the contribution to the O&G and TPH in wastewater. To make these determinations, it was assumed that 2 gallons of water were used for every pound of product being cleaned. If the detergent supplier provided a recommended amount, that number was used in the calculation; otherwise, a value of 3.0 Ibs of detergent was assumed for each 100 lbs of product. The data resulting from these calculations are presented in Table 14 on page 26. It is acknowledged that the actual water to product mix will vary for each facility and these data represent an estimation. Likewise, there are no correlations of detergent contribution to the wastewater samples analyzed for this study.
Using the 100 mg/l discharge limit number (as discussed in Section 3.1), the data in Table 14 indicate that the detergents by themselves would cause permit limits to be exceeded in 10 of the 22 products tested by Freon@ and cyclohexane and 8 if n-hexane was used. Using silica gel the number of detergents exceeding this limit would be 3 using Freon@, 1 using cyclohexane, and 0 using n-hexane.
3.5 CORRELATION OF GRAVIMETRIC AND IR DATA
Table 15 on page 27 presents a simple percentage correlation of IR to gravimetric results for wastewater and detergent samples.
The data shows that the IR result obtained for wastewater was higher than that obtained by gravimetric analysis for both O&G and TPH. For all of the wastewaters, the percentage correlation was higher for TPH than that obtained for O&G.
The percentage correlation for detergent samples was much less that 100% for all samples analyzed. This is probably because the organic compound composition of the detergents products tested by IR are substances other than single bonded carbon-hydrogen molecules for which the infrared spectrophotometer measures.
WP60 \ UTSA.RPT -18- 6/94
ETS 1D
152149 152150 152151 152604 152672 152705 152736 152737 152865 153 110 153111 155896
152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
Table 6 -Wastewater Oil and Grease Results by Gravimetric Analysis Mean, SD and RMSD Calculations
Concentration results are reported in mg/l
SOLVENT
Freon@ Freon@ Freon" Freon@ Freon@ Freon@ Freon@ Freon" Freon@ Freon@ Freon@ Freon@
n-Hexane n-Hexane n-Hexane a-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n - H e x an e n - H e x an e n - H e x an e n-Hexane
Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane
REP1
3 84 769 314 114 43 22 90
721 110 96 157 20
312 484 267 92 32
23 1 57
919 107 83 147 13
351 640 3 14 101 44
283 127 598 103 87
156 16
REP2
460 795 3 17 124 44
266 97
790 111 86
176 18
3 12 486 265 96 27
244 64
833 98 85
130 10
442 443 323 99 33
301 138 575 94 76
158 21
STD DEV = Standard Deviation of the three replicates at n-1.
RMSD = Root Mean Standard Deviation of the three replicates.
REP3
42 1 813 3 17 119 44
272 116 837 103 91 168 23
315 464 266 82 34 198 62 844 85 83 153 14
400 534 282 109 37 230 136 592 105 90 148 16
MEAN
422 792 3 16 119 44
273 101 783 108 91 167 20
313 478 266 90 31
224 61
865 97 84
143 12
398 539 306 103 38 21 1 134 588 101 84
154 18
STD DEV
31.0 18.1 1.4 4.1 0.5 6.6 11.0 47.6 3.6 4.1 7.8 2.1
1.4 9.9 0.8 5.9 2.9 19.4 2.9
38.2 9.0 0.9 9.7 1.7
37.2 80.5 17.6 4.3 4.5
30.1 4.8 9.7 4.8 6.0 4.3 2.4
RMSD
7.4 2.3 0.4 3.4 1.1 2.4 10.9 6.1 3.3 4.5 4.7 10.1
0.5 2.1 0.3 6.5 9.5 8.6 4.8 4.4 9.3 1.1 6.8 13.8
9.4 14.9 5.7 4.2 12.0 11.1 3.6 1.7 4.8 7.1 2.8 13.3
WP601UTSA.RPT -19- 6/94
ETS ID 152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
Table 7 -Wastewater Total Petroleum Hydrocarbons Results by Gravimetric Analysis Mean, SD and RMSD Calculations
Concentration results are reported in mgll
SOLVENT Freon@ Freon@ Freon@ Freon@ Freon" Freon" Freon@ Freon@ Freon" Freon@ Freon@ Freon@
n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane
Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane
REP 1 32
354 149 31 18
106 17
384 40 4
71 4
36 379 138 30 8
104 24
49 1 21 7
64 2
34 252 165 25 14 98 30
429 46 7
59 4
REP2 53
412 148 44 13
131 21
431 37 12 75 6
30 215 118 31 6
100 19
444 30 <5 57 4
18 205 140 35 8
100 36
369 52 18 63 5
STD DEV = Standard Deviation of the three replicates at n-1
RMSD = Root Mean Standard Deviation of the three replicates.
-20-
REP3 52
469 129 34 7
119 25
460 48 12 80 6
40 294 106 30 6
88 29
458 29 6
73 6
23 280 162 35 14
117 37
369 55 9
63 8
MEAN 46
412 142 38 13
119 23
425 42 9
75 5
35 3 16 121 30 7
97 24
464 27 4
65 4
25 246 156 32 12
105 34
389 51 11 62 6
STD DEV 9.7
46.9 9.2 4.2 4.5 10.2 4.3
31.3 4.6 3.8 3.7 0.9
4.1 45.2 13.2 0.5 0.9 6.8
4.1 19.7 4.0 1.9 6.5 1.6
6.7 30.9 1.1 4.7 2.8 8.5 3.1
28.3 3.7 4.8 1.9 1.7
RMSD 21.2 11.4 6.5 10.9 35.5 8.6
18.8 7.4 11.1 40.4 4.9 11.7
11.6 14.3 10.9 1.6
14.1 7.0 17.0 4.2 15.1 37.3 10.1 40.8
26.7 12.6 7.2 14.9 23.6 8.1 9.0 1.3 7.3
42.2 3.1
30.0
6 / 9 4
Table 8 -Wastewater Oil and Grease Results by Infrared Spectroscopy Analysis Mean, SD and RMSD Calculations
Concentration results are reported in mg/l
ETS ID SOLVENT REP 1 REP2 REP3 MEAN STDDEV Rh4SD 152149 Freon@ 485 552 513 517 27.5 5.3 152150 Freon@ 1350 1570 1640 1520 123.6 8.1 152151 Freon@ 440 429 418 429 9.0 2.1
STD DEV = Standard Deviation of the three replicates at n-1.
RMSD = Root Mean Standard Deviation of the three replicates
Table 9 - Wastewater Total Petroleum Hydrocarbons Results by Infrared Spectroscopy Analysis Mean, SD and RMSD Calculations
Concentration results are reported in mgll
ETS ID SOLVENT REP1 REP2 REP3 MEAN STDDEV RMSD 152149 Freon@ 61 69 61 64 3.8 5.9 152150 Freon@ 1280 1190 1380 1283 77.6 6.0 152151 Freon@ 288 308 305 300 8.8 2.9
STD DEV = Standard Deviation of the three replicates at n-1.
RMSD = Root Mean Standard Deviation of the three replicates.
WP60\ UTSA.RPT -21- 6/94
Table 10 -Wastewater Gravimetric Analysis O&G vs. TPH
ETS ID 152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
SOLVENT Freon@ Freon@ Freon@ Freon@ Freon@ Freon@ Freon@ Freon@ Freon@ FreonQ Freon@ Freon@
n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane n-Hexane
Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane
MEAN O&G 422 792 3 16 119 44 273 101 783 108 91 167 20
313 478 266 90 31 224 61 864 97 84 143 12
398 539 306 103 38 27 1 134 588 101 84 154 18
MEAN TPH 47 412 142 38 13 119 23 425 42 9
75 5
35 316 121 30 7 97 24 464 27 4 65 4
25 246 156 32 12 105 34 3 89 51 11 62 6
PERCENT REDUCTION'
88.9 48.0 55.1 67.8 71.0 56.6 77.2 45.7 61.4 89.7 54.9 73.8
88.7 33.9 54.6 66.3 78.5 56.6 60.7 46.3 72.4 94.8 54.9 67.6
93.7 54.4 49.2 69.3 68.4 61.3 74.3 33.9 49.3 86.6 60.0 67.9
I Percent reduction obtained by the addition of silica gel as compared to total oil and grease.
-22- 6/94
ETS ID 152462 152463 152509 152473 152474 152475 152480 152481 152482 152591 152592 152593 152825 152826 152827 152828 152930 152931 152932 155295 155296 155297
152462 152463 152509 152473 152474 152475 152480 152481 152482 152591 152592 152593 152825 152826 152827 152828 152930 152931 152932 155295 155296 155297
Table 11 - Detergent Gravimetric Analysis O&G vs. TPH
SOLVENT FIWn" Freon@ Freon@ Freon@ Freon@ Freon@ Freon@ Freon" Freon" Freon@ Freon@ Freon@ Freon@ Freon@ Freon@ Freon" Freon" Freon@ Freon@ Freon@ Freon@ Freon@
n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane n-hexane
MEAN O&G
125490 176470 81481
196296 66995 30924
130769 88461 34059
143396 116000 200000 429940
14 81951 34653 40316 26515 35200
158311 19802 45518
93333 92453 21723
108738 36634 12687
156436 43137 13265
< 2000 71287
121904 189793
28 19406 8235
19149 9910 9022
109901 18621 25000
MEAN TFJH
54902 39216 22222 14815 21615 7136
15385 11538 16133 71698 12000
101639 19367
I 6829 9901 2372 2273 6400 4449 4455 4762
< 1904 9434 7921 3883 c 990 < 396
< 1980 < 960 c 359
< 2000 < 1980 C 1904 11620
c 7 2941 2941
14894 2844 1504 9901 9804 6000
PERCENT REDUCTION'
56.2 77.8 72.7 92.5 67.6 16.9 88.2 87.0 52.6 50.0 89.7 49.2 95.5 50.0 91.7 71.4 94.1 91.4 81.8 97.2 77.5 89.6
298 89.8 71.4 96.4 2 91 2 97 2 99 298 2 97 NC 2 97 298 93.9 275 84.8 64.3 22.2 71.3 83.3 91.0 47.4 76.0
I Percent reduction obtained by the addition of silica gel as compared to total oil and grease. NC = Not Calculatable
WP60 \ UTSA.RPT -23- 6 / 9 4
ETS ID 152462 152463 152509 152473 152474 152475 152480 152481 152482 152591 152592 152593 152825 152826 152827 152828 152930 152931 152932 155295 155296 155297
Table 11 - Detergent Gravimetric Analysis O&G vs. TPH
(continued)
SOLVENT cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane cyclohexane
MEAN O&G
172000 112621 44660
158416 26470 30132
156863 35294 20077 70588 58824
130693 240147
32 77333 24771 16296 11538 16740
132701 17544 21101
MEAN TPH
22000 1767 7761
75248 12745 14273 33333 54902
717 7843
11765 13861 34860
<7 8667 5504 < 494 5769 2643
12322 11404 12844
PERCENT REDUCTION'
87.2 93.1 82.6 52.5 51.9 52.6 78.8 -55.6 96.4 88.9 80.0 89.4 85.5 278 88.8 77.8 2 97 50.0 84.2 90.7 35.0 39.1
' Percent reduction obtained by the addition of silica gel as compared to total oil and grease. NC = Not Calculatable
WP601UTSA.RPT -24- 6 / 9 4
Table 12 - Correlation of Alternative Solvents to Freon for Wastewater O&G Analysis Expressed as a Percentage to Freon Result
ET^ m 152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
% CORRELATION TO FREON n-Hexane Cyclohexane
74.2 94.3 60.3 68.0 84.2 96.9 75.6 86.6 71.0 87.0 82.1 99.3 60.4 132.3 110.6 75.2 89.5 93.2 91.9 92.1 85.8 92.2 60.7 86.9
Table 13 - Correlation of Alternative Solven$ to Freon for Wastewater TPH Analysis Expressed as a Percentage to Freon Result
ETS ID 152149 152150 152151 152604 152672 152705 152736 152737 152865 153110 153111 155896
96 CORRELATION TO FREON n-Hexane Cyclohexane
77.4 54.7 76.8 59.7 85.0 109.6 79.1 82.6 52.6 94.7 82.0 88.5
104.3 149.3 109.3 91.5 64.0 122.4 46.4 121.4 85.8 81.9 75.0 106.3
WPGO\VTSA.RPT -25- 6/94
ETS ID 152462
152463
152473
152474
152475
152480
152481
152482
152509
152591*
152592'
152593*
152825
152826
152827
152828
152930*
152931'
152932'
155295*
15 5 2 9 6 * 155297*
Table 14 - Detergent contribution to O&G and TPH in Wastewater
All results in mg of Detergent Residue per Liter of Wastewater
Freon@ 226
317
980
517
42
98
66
22
122
258
209
360
193
<1
86
43
73
48
63
285
36
82
n-Hexane Cvclohexane 168
166
543
283
17
117
32
8
42
< 4
128
219
85
< 1
20
10
34
18
16
198
34
45
309
203
791
204
41
118
26
13
67
127
106
235
108
<1
81
31
29
21
30
239
32
38
I -----Total Petroleum Hydrocarbons---- I Freon@
99
71
74
167
10
12
9
10
33
129
22
183
9
<1
7
12
4
4
12
8
8
9
n-Hexane < 3
17
19
< 8
<1
<1
<1
<1
12
<4
<4
<3
5
<1
3
4
27
5
3
18
18
11
* No recommended mixing was given by the detergent supplier; calculations were made using 3.0 lbs of detergent per 100 lbs of product.
WPfiO\UTSA.RPT -26-
Cyclohexane 40
14
376
98
19
25
41
< 1
12
14
21
25
16
<1
9
7
1
10
5
22
21
23
6/94
ETSAS ID 152149 152149
152150 152150
152151 152151
152604 152604
152612 152672
152705 152705
152825 152825
152930 152930
152931 152931
152932 152932
Table 15 - Comparison of Gravimetric and IR Results'
Matrix Wastewater Wastewater
Wastewater Wastewater
Wastewater Wastewater
Wastewater Wastewater
Wastewater Wastewater
Wastewater Wastewater
Detergent Detergent
Detergent Detergent
Detergent Detergent
Detergent Detergent
Test O&G TPH
O&G TPH
O&G TPH
O&G TPH
O&G TPH
O&G TPH
O&G TPH
O&G TPH
O&G TPH
O&G TPH
Mean Gravimetric
422 46
792 412
3 16 142
119 38
44 13
273 119
429940 19367
40316 2372
26515 2273
35200 6400
Mean Infrared
517 64
1520 1283
429 300
121 63
59 33
40 1 326
253703 <9683
< 17 < 17
16288 < 1894
17200 < 2000
' Wastewater results expressed as mgll; detergent results expressed as mgkg.
'as calculated by: (IR ResulttGravimetric Result) X 100
WP60\UTSA.RPT -27-
% Correlation IR to Gravimetric2
122 139
192 311
136 211
102 166
134 254
147 274
59 5 50
5 4 S1
61 S 83
5 49 5 3 1
6 / 9 4
SECTION 4
QAlQC RESULTS
-28- 6 / 9 4
The following is a summary of the quality assurance/quality control results obtained in the analysis of the UTSA wastewater and detergent samples.
4.1 BLANKS
All blanks were below detection for all determinations and therefore no corrective actions were needed. Table 16 on page 30 contains a summary of all blank results.
4.2 CALIBRATION
Each set of analyses was checked with a calibration standard obtained from an outside source. For IR analysis, these standards may be analyzed as a continuing calibration check of the IR calibration curve. All calibration verification standard results were within percent recovery quality assurance objectives (QAO) that were established internally to the laboratory and therefore no corrective actions were needed. A summary of Calibration Verification Standards results is presented in Table 17 on page 30.
4.3 OTHER QA RESULTS
Other QA checks performed included 1) analytical balance checks with Class S weights; 2) glassware contamination checks; and 3) laboratory water (deionoized water) and glassware contamination checks. All balance checks were within acceptable limits and all contamination checks were below detection. In addition, an IPR (Initial Precision and Recovery) Study for Method 413.1 was performed under an EPA contract within six months of the UTSA study.
-29- 6 / 9 4
Analytical Number Silica Gel Solvent Method Analyzed Treated? used
11 Gravimetric I 10 I N I Freon@ I < 1.0 mg/l 11 Data
Results
Gravimetric
Gravimetric
11 Gravimetric I 10 I Y I n-Hexane I < 1.0 mg/l 11
11 Y Freon@ < 1 .O mg/l
11 N n-Hexane < 1 .O mg/l
Gravimetric
Gravimetric
10 N Cyclohexane < 1 .O mg/l
8 Y Cyclohexane < 1 .O mg/l
I Infrared OR) I 3
11 Gravimetric I 10 I Y I Freon@ I 0 1 0 11
Y Freona I <5.0 mg/l
Analytical Method
Gravimetric
11 Gravimetric I 10 I N I Cyclohexane I 85-94 I 70-130 11
Number Silica Gel Solvent % Recovery QAO' Analyzed Treated? used Range' (%)
10 N Freon@ 85-99 70-130
Gravimetric
Gravimetric
10 N n-Hexane 76-93 70-130
10 Y n-Hexane 0 0
' If silica gel treatment is used, an answer of 0% recovery is expected if the removal is effective.
* Quality Assurance Objective
Gravimetric
Infrared OR)
WP60 \ UTSA.RPT
10 Y Cyclohexane 0 0
3 N Freon@ 104- 123 70-130
-30-
Infrared OR) I 3
6 / 9 4
Y Freona 0 70-130
APPENDIX
Appendix: A - l
I .
152149
152150
DESCRIPTION OF WASTEWATER SAMPLES
pH Control, SWECO
pH Control, SWECO
/I /I ETSAS I TYPE OF WASTEWATER TREATMENT LAB ID
152151
152604
pH Control, SWECO
Mixing Tank, DAF, Skimmer, Vac Filter
152737
152865
Shaker Screen, Oil Skimmer, Acid
Screening, Equalization, pH Adj, Polymer
153 110
153111
I( 155896 I Dissolved Air Floatation OAF) II
Shaker Screen
Shaker Screen, Air Flotation
In order to maintain confidentiality no other information is available on the wastewater samples.
Appendix: A-2
152825
152826
DESCRIPT.ION OF DETERGENT SAMPLES
Liquid
Liquid
ETSAS DETERGENT LAB ID MARTIX
155295
155296
152462 Solid
152463 Solid
Solid
Solid
152473 Solid
152475 Solid
152480 Solid
15248 1 Solid
152482 Solid
152509 Solid
15259 1 Solid
152593 Solid
152827 Solid
152828 Solid
152930 Solid
152932 Solid
155297 1 Solid 1 In order to maintain confidentiality no other information is available on the detergents.
ETS Analytical Services, Inc. Appendix: A-3 -
Roudly serving indusfry and govemmcnt since 1973. A USEPA Contract Laboramy
A subsidiary of ETS International, Inc.
SAMPLING INSTRUCTIONS, QUESTIONER, & CHAIN-OF-CUSTODY
Instrumions: Thank you for participating in the this survey sponsored by the Institute of Industrial h m d e r e s (IIL). A sample of your plant ef€luent is to be taken and placed in the 2 gallon glass jar provided m this kit and shipped backed to the laboratory (ETSAS). The following steps for sampie collection and shipment need to be followed: 1) Fa-out the information requested on this form; vital information is indicated in boM type. If necessary, use the reverse side of this form to complete any question. 2) Fill the 2 gallon glass jar within 1-2 inches of the top with the wastewater discharge from the plant; a 1 quart glass jar is provided as a "dippmg" container if needed. 3) Screw the lid onto the sampie jty asjightly as possible in order to avoid leakage (hand tighten only!); be careful not to disturb the Teflon cap line6 4) Place the sample jar back into the ice chest in the same position as it was received using the protective material surrounding the jar. Do not ship back the 1 quart dipping jar (discard). 5) Place at least 5 lbs. of ice into the white plastic bag and tie shut to avoid leakage of water during shipping and place into the ice chest. 5) Retain a photocopy of this (completed) form for your records and place the original back into the envelope in the ice chest. 6) Complete the provided Federal Express form and seal the ice chest shut with the provided shipping tape. 7) Ship the ice chest back to ETS Analytical Services by Federal Express the same day of sample collection.
PROJECT: E L Oil & Grease Study CONTAZNERS: One 2 galon Glass with TFE Cap Liner "PE: Grab MATRM: Wastewater Emuent from Plant SHIPPING: Federal Express to ETSAS
FACILITY NAME: ADDRESS:
cl[Ty: STATE: ZIP:
CONTACX PHONE: -- / FA=--- /
TYPE OF WASTE T R E A " T (e.g. Oil Skimmer):
PRODUCT MIX DAY OF SAMPLING: T d - Mats - Uniforms - Linen - Other
DETEXGENT(S) & SUPPLIER(S) USED DAY OF SAMPLING:
COMMENTS:
RELINQUISHED BY (Signatme): DATE: TIME:
RECEIVED @ ETSAS BY: DATE: TIME:
If'there are any questions regarding the instructions on this form or the sampling please feel free to contact either Chris Southworth, Rob Ledger, or Elizabeth Hetz at ETSAS at 800/767-4016. Comments or questions regarding the nature of this survey should be addressed to the Institute of Industrial Lauderes, C/O david L. Clamplitt, Environmental M a i r s Manager, 1730 M Street, Suite 610, Waslington, DC 20036. Phone 202J296-6744 a FAX 202/296-2309.
1401 btunicipai Road, IW - Roanoke, Virginia 7,4017-I509 - Telzphone: 703-765-0004 - FAX: 703-563-4866
Appendix: A-4
..
OIL AND GREASE, TOTAL, RECOVERABLE
i
.
1.
2.
7 J.
4.
5.
6.
LMethod 413.1 (Gravimetric, Separatory Funnel Extraction)
STORET NO. 00556
Scope and Application 1.1 This method includes the measurement of fluorocarbon-1 13 extractable matter from
surface and saline waters, industrial and domestic wastes. It is applicable to the determination of relatively non-volatiie hydrocarbons, vegetable oils, animal fats, waxes, soaps, greases and related matter. The method is not applicable to measurement of light hydrocarbons that volatilize at temperatures below 70'C. Petroleum fuels from gasoline through $2 fuel oils are completely or partially lost in the solvent removal operation. Some crude oils and heavy fuei oils contain a significant percentage of residue-type materials that are not soluble in fluorocarbon-1 13. Accordingly, recoveries of these materials will be low. The method covers the range from 5 to loo0 mg/l of extractable material.
The sample is acidified to a low pH ( < 2) and serially extracted with fluorochrbon- 1 13 in a separatory funnel. Thcsolvent is evaporated from the extract and the residue weighed.
The definition of oil and grease is based on the procedure used. The nature of the oil and/or grease, and the presence of extractable nonsily matter will influence the material measured and interpretation of results.
A representative sample of 1 liter volume should be collected in a glass bottle. If analysis is to be delayed for more than a few hours, the samp1e.is preserved by the addition of 5 ml HCl(6.1) at the time of collection and refrigerated at 4'C.
sample is impractical. Individual portions collected at prescribed time intervals must be analyzed separately to obtain the average concentration over an extended penod.
Separatory funnei, 2000 ml, with Teflon stopcock.
Flask, boiling, 125 ml (Coming No. 4100 or equivalent). Distilling head, Claisen or equivalent. Filter paper, Whatman No. 40, 11 cm.
Hydrochloric acid, 1: 1. Mix equai volumes of conc. HCl and distilled water.
1.2
1.3
1.4 Summary of Method 2.1
Definitions *
3.1
Sampling and Storage 4.1
4.2 Because losses of grease will occur on sampling equipment, the collection of a composite . I V . -
Apparatus 5.1 5.2 . Vacuum pump, or other source of vacuum 5.3 5.4 5.5 Reagents 6.1
Apprwed for NPDFc Issued 1974 Editorial revision 1978
413.1-1
.. 6.2 6.3 Sodium sulfate, anhydrous crystal.
7. Procedure 7.1
Fiurocarbon-l13,( 1,13-trichloro-l,L2-trifluoroethane), b. p. 4s'C.
Mark the sample bottle at the water meniscus for later determination of sample volume. If the sample was not acidified at time of collection, add 5 ml hydrochloric acid (6.1) to thesample bottle. After mixing the sample, check the pH by touching pH-sensitive paper to the cap to insure that the pH is 2 or lower. Add more acid if necesary. Pour the sample into a separatory funnel. Tare a boiling flask (pre-dried in an oven at 103'C and stored in a desiccator). Add 30 mi fluorocarbon-I13 (6.2) to thesample bottle and rotate the bottle to rinse the sides. Transfer the solvent into the separatory funnel. Extract by shaking vigorously for 2 minutes. Allow the layers to separate, and filter the solvent layer into the flask through a funnel containing solvent moistened filter paper. NOTE: An emulsion that fails to dissipate can be broken by pouring about 1 g sodium sulfate (6.3) into the frlter paper cone and slowly draining the emulsion through the salt. Additional 1 g portions can be added to the cone as required. Repeat (7.4) twice more, with additional portions of fresh solvent, combining all solvent in the boiling flask. Rinse the tip of theseparatory funnel, the filter paper, and then the funnel with a total of 10-20 ml solvent and collect the rinsings in the flask. Connect the boiling flask to the distilling head and evaporate the solvent by immersing the lower half of the flask in water at 70'C. Coilect the solvent for reuse. A solvent blank should accompany each set of sampies.
the distilling head. Sweep out the flask for 15 seconds with air to remove solvent vapor by inserting a glass tube connected to a vacuum source. Immediately remove the flask from the heat source and wipe theoutside to remove excess moisture and fingerprints. Cool the boiling flask in a desiccator for 30 minutes and weigh.
. 7.2 7.3 7.4
7.5
7.6
7.7
7.8 When the temperature in the distilling head reaches 50'C or the flask appears dry remove t
7.9
8.1 mg/l total oil and grease = - 8. Calculation R - B
v
where:
R = residue, gross weight-of extraction tlask minus the tare weight, in milligrams. B = blank determination, residue of equivalent volume of extraction solvent, in
V = volume of sample, determined by refilling sample bottle to calibration line and milligrams.
correcting for acid addition if necessary, in liters.
- 413.1-2
!
'.
9. Precision and Accuracy 9.1 The two oil and grease methods in this manual were tested by a single laboratory (EMSL)
on sewage. This method determined the oil and grease level in the sewage to be 12.6 mg/l. When 1 liter portions of the sewage were dosed with 14.0 mg of a mixture of 42 fuel oil and Wesson oil, the recovery was 93% with a standard deviation of ~ 0 . 9 mg/l.
Bibliography
1.
2.
Standard Methods for .the Examination of Water and Wastewater, 14th Edition, p 515. Method 502A. (1975). Blum, K. A., and Taras, M. J., "Determination of Emulsifying Oil in Industrial Wastewater", JWPCF Research Suppl. 40, - R404 (1968).
c
c
413.1-3
Appendix: A-5 * ,
PETROLEUM HYDROCARBONS, TOTAL RECOVERABLE
Method 418.1 (Spectrophotometric, Infrared)
STORET NO. 45501
I. Scope and Application 1.1
1.2
1.3
This method is for the measurement of fluorocarbon-113 exti-actabie petroleum hydrocarbons from surface and saline waters, industrial and domestic wastes. The method is applicable to measurement of light fuels. although loss of about half of any gasoline present during the extraction manipulations can be expected. The method is sensitive to levels of 1 mg/l and less, and may be extended to ambient monitoring.
The sample is acidified to a low pH ( < 2) and serially extracted with fluorocarbon- 1 13 in a separatory funnei. Interferences are removed with silica gel adsorbant. Infrared analysis of the extract is performed by direct comparison with standards.
As in the case of Oil and Grease, the parameter of Petroleum Hydrocarbons is defined by the method. The measurement may be subject to interferences and the resulk should be evaluated accordingly. Oil and Grease is a measure of biodegradable animal greases and vegerabIe 011s along with the relative non-biodegradable mined oils. Petroleum hydrocarbons is the measure of only the m i n e d oils. Maximum information may be obtained using both methods to measdre and characterize oil hnd grease of all sources.
A representative sample of 1 liter volume should be collected in a glass bottle. Because losses of grease will occur on sampling equipment, the collection of a composite sample is impractical. The entire sample is consumed by this test; no other analyses may be performed using aliquots of the sample. A delay between sampling and analysis of greater than 4 hours requires sample preservation by the addition of 5 mi HCI (6.1). A delay of greater than 48 hours also requires refrigeration for sample preservation.
Separatory funnel. 2000 mi, with Teflon stopcock. Filter paper, Wharman No. 40, 1 1 cm, Infrared spectrophotometer, scanning or fixed wavelength, for measurement around 2950 cm". Cells, 10 mm, 50 mm, and 100 mm pathlength, sodium chloride or infrared grade giass. tMagnetic stirrer, with Teflon coated stirring bars.
Hydrochloric acid, 1: 1. Mix equal voiumes of conc HCI and distilled water.
2. Summary of Method 2.1
3. Definitions 3.1
3.2 ,. t
4. Sampiing and Storage 4.1
- -" L
4.2
5. Apparatus 5.1 5.2 5.3
5.4 5.5
6. Reagents 6.1
i Issued 1978
418.1-1
4 . -, 6.2 ' 6.3. Sodium sulfate. anhydrous crystal. 6.4
6.5 Calibration mixtures:
Fluorocarbon- 1 13.C1.1 .ttrichloro- 1 ,?J-trifluroethane), b.p. 48'C.
Silica gel, 60-200 mesh, Davidson Grade 950 or equivalent. Should contain 1-2% water as defined by residue test at 13WC. Adjust by overnight equilibration if needed.
6.5.1 Reference oil: Pipet 15.0 ml n-hexadecane, 15.0 ml isooctane, and 10.0 ml chlorobenzene into a SO ml giass stoppered bottie. Maintain the integrity of the mixture by keeping stoppered except when withdrawing aliquots.
Pipet 1.0 ml reference oil (6.5.1) into a tared 200 ml volumetric flask and immediately stopper. Weigh akd dilute to volume with fluorocarbon- I 13.
Pipet appropriate volumes of stock standard (6.5.2) into 100 mi voiumetric flasks according to the cell pachlength to be used. Dilute to volume with fluorocarbon- 113. Calculate concentration of standards from the stock standard.
6.5.2 Stock standard:
6.5.3 Working st&dards:
7. Procedure 7.1 Mark the sample bottle at the water meniscus for later determination of sample volume.
If the sample was not acidified at time of collection, add 5 ml hydrochloric acid (6.1) to the sample bottle. After mixing the sample, check the pH by touching pH-sensitive paper to thecap to insure that the pH is 2 or lower. Add more acid if necessary. Pour the sample into a separatory funnel. Add 30 mi fluorocarbon-I13 (6.2) to the sample bottle and rotate the bottfe to rinse the sides. Transfer the solvent into the separatory funnel. Extract by shaking vigorously for 2 minutes. Allow the layers to separate. Filtzr the solvent layer through a funnel containing solvent-moistened filter paper into a 100 ml volumetric fi ask. NOTE 1: An emulsion that fails to dissipate can be broken by pouring about I g sodium sulfate (6.3) into the fdter paper cone and slowly draining the emulsion through the salt. Additional 1 g portions can beadded to the cone as required. Repeat (7.3 and 7.4) twice more with 30 mi portions of fresh solvent, combining all solvent into the volumetric flask. Rinse the tip of the separatory funnei, filter paper, and the funnel wirh a total of 5-10 ml solvent and collect the rinsings in the flask. Dilute the extract to 100 mi. If the extract IS
known to contain greater than 100 mg of non-hydrocarbon organic material, piper an appropriate portion of the sample to a 100 mi volumetric anddilute to volume. Discard about 5-10 mi solution from the volumetric flask. Add 3 g silica gel (6.4) and a stirring bar; stopper the volumetric flask, and stir the solution for a minimum of 5 min on a magnetic stirrer.
7.2 7.3
7.4 . !
, 7.5
7.6
7.7
- 418.1-2
!
7.8 Select appropriate working standards and cell pathlength according to the following table of approximate working ranges:
Pathlength
10 mm 50 mm 100 mm
24 0 mg 0.5-8 mg 0.14 mg
Calibrate the instrument for the appropriate cells using a series of working standards (6.5.3). It is not necessary to add silica gel to the srandards. Determine absorbance directly for each solution at the absorbance maximum at about 2930 cm-'. Prepare a calibration plot of absorbance vs. mg petroleum hydrocarbons per 100 mi solution. After the silica gel has settled in the sample extract, fill a clean cell with solution and determine the absorbance of the extract. If the absorbance exceeds 0.8 prepare an appropriate dilution. NOTE 2: The possibility that the absorptive capacity of the silica gel has been exceeded can be tested at this point by adding another 3.0 g silica gel to the extract and repeating the treatment and determination.
7.10 Determine the concentration of petroleum hydrocarbons in the extract by comparing the response against the calibration plot.
Calculate the petroleum hydrocarbons in the sample using the formula:
7.9
8. Calculations 8.1
mg/l Petroleum Hydrocarbons = -7 R x D
where:
R = mg of Petroleum Hydrocarbons as determined from the calibration plot (7. IO). D = extract dilution factor, if used. V = volume of sample, in liters.
9. Precision and Accuracy 9.1 Precision and accuracy data are nor available at this time.
W8.1-3
