1



# ASTM D7575 

#  ̳ Green ‘ Solventless Infrared Oil and Grease Method Orono Spectral Solutions Carl Tripp, Ph. D. President, OSS; Prof. Chem., UM Luke Doucette Dean Smith Vice President VP for Engineering Tom Schwarz Eric Roy, Ph. D. Research Technician Research Scientist

Email: carl.tripp@ossmaine.com Website: www.ossmaine.com USEPA Visit to OSS 2/23/112 

# OIL AND GREASE MEASURMENT

SUMMARY3 

# OIL AND GREASE MEASUREMENT
OIL AND GREASE MEASUREMENT: • One of the five conventional pollutants covered by the 1974 Clean Water Act • Second most
- enforced
- against parameter, second only to pH. • Measurement included in all: NPDES permits, pre
-treatment permits, Industrial Effluent Guidelines. • Millions of oil and grease analyses each year in the US alone . MEASUREMENT HISTORY: • Montreal Protocol in 1989 • EPA moved from a Freon extraction method (EPA 413) to a n
- Hexane extraction mass
-based determination method (EPA 1664 in ‘95 / EPA 1664a in ’99 allowing LLE and SPE = CURRENT METHOD ) • ISSUES: • personal exposure, handling, and transportation of a hazardous, flammable liquid is required, • n- Hexane is a known neurotoxin, 

### • analytical time is significantly increased, and • millions of liters/year of n - Hexane (not to mention other method solvents) for disposal. • methodology inconsistent with the intent of the Clean Air Act and Clean Water Act that considers n - Hexane a hazardous pollutant. • ASTM D7575 ‘solid phase infrared amenable extractor’ technology will remedy the issues listed above by eliminating solvents from oil and grease analysis

– all while providing a more economical and accurate solution.4 

# Oil and Grease Method Evolution EPA 413.2 (Freon Extraction - Infrared)

 ̳ dirty‘ water Freon extract
Extract in Cuvette

Cuvette in Spectrometer Absorbance (a.u.)

Wavenumber (cm - 1 )



## Peak height corresponds to hydrocarbon concentration Time for analysis ~ minutes LLE5 

# Oil and Grease Method Evolution EPA 1664
 ̳dirty‘ water Hexane extract

Extract in drying pan

Evaporate Hexane 

## Mass

corresponds to 

## concentration of extractables Time ~ 3 - 4 hours LLE
n - Hexane use introduces four issues: 1. Flammable solvent 2. Known neurotoxin 3. Analytical time increased significantly 4. Large amount of solvent for disposal to atmosphere or hazardous waste 

# Total Hexane Usage: Millions of Liters/year6 

# Oil and Grease Method Evolution EPA 1664A
 ̳dirty‘ water Hexane extract

Extract in drying pan

Evaporate Hexane 

## Mass 

## corresponds to concentration of extractables Time ~ 3-4 hours LLE SPE

Extract in drying pan 1. Sample run through SPE disk 2. Disk Eluted with Hexane

Evaporate Hexane7 Federal Register /Vol. 64, No. 93 / Friday, May 14, 1999 /Rules and Regulations 26317 C. Use of Solid
-Phase Extraction (SPE) ...A detailed description of the SPE technique was provided at proposal (61 FR 1730). Even prior to proposal of Method 1664, vendors of SPE devices had requested that SPE be an allowed technique in the Method. Proposed Method 1664 allowed use of SPE, but required a demonstration that SPE produced results equivalent to results produced by the separatory funnel liquid
- liquid extraction technique (LLE) written in Method 1664. Vendors and other commenters objected to this requirement, claiming that SPE provided sufficient advantages in solvent reduction, reduced analysis time, reduced emulsion formation, and other advantages so that its use should be allowed without prior demonstration of equivalency. EPA discussed the issue extensively at proposal and in public workshops and meetings, and specifically solicited data demonstrating equivalency of results produced by SPE and LLE. Data received were mixed, with some data demonstrating that results produced are equivalent and other data demonstrating that results produced are significantly different. EPA reopened the comment period (61 FR 26149) to allow submission of further data, and EPA provided a notice of availability (62 FR 51621) of these and other data so that EPA could consider these data for today’s final rule. Discussions of the detailed issues on SPE are summarized in Section VI of this preamble and given in the detailed comments and responses included in the Docket. Based on comments received and supporting data, EPA is allowing the use of SPE in the version of Method 1664 being approved today without a prior demonstration of equivalency. However, EPA has added a note at the beginning of the extraction procedure (Section 11.3) in Method 1664 to indicate that it is the discharger/ generator’s responsibility to assure that the results produced are equivalent. If there is doubt about this equivalency, liquid/liquid extraction is definitive for the measurement. EPA also acknowledges that if a Region, State, or other permitting authority has concerns about the difference in results produced by SPE and LLE, that authority may specify in the permit the use of one of the two techniques 

### EPA allows SPE Option for 1664 without prior demonstration of equivalency!



### (Because of advantages in solvent reduction, etc.)8 

# Oil and Grease Method Evolution New OSS Method: ASTM D7575 – Standard Test Method for Solvent- Free Membrane Recoverable Oil and Grease by Infrared Determination Absorbance (a.u.)

Wavenumber (cm - 1 ) 

## Peak height corresponds to 

## hydrocarbon concentration Time ~ minutes Sample run through 

## new IR -amenable oil and grease Extractor created by OSS 

### Extractor placed in spectrometer9 

# ASTM D7575 VALIDATION10



## ASTM D7575 DEVELOPMENT MILESTONES

• Initial ASTM D 19 committee presentation of technology Denver, CO (June 2008 ) • Updated presentation of technology Cocoa Beach, FL (January 2009 ) • USEPA presentation to Dick Reding , Lem Walker, Marion Kelly, Richard Englert, Richard Engler (Green Chemistry) o When Dick was asked specifically about his thoughts on the OSS method and data he commented:  Anything that gets rid of use of separatory funnels is a winner  Pluses: no solvent/co
- solvent issues, good for environment, good environmental argument to move the method forward, ASTM approva l will be a bonus.  Difficulties that we may be up against – no one wanting to change, issues with current method, another method defined parameter  Pull from the Green Chemistry office could be a key to helping this move forward – with a key point of a new method being solventless . o When asked about potential inclusion in the update rule Dick commented:  He would be comfortable putting this method out for comment  Finishing the single - lab validation study will be a good starting point  Completion of a multi - lab would not be required in order to get into the update rule – however – a multi - lab plan would be helpf ul o There was general agreement around the table that the matrices we have tested or are planning to test encompassed a sufficien tly broad range of matrices. 

### • ASTM single lab validation study

– technology gives same results as current EPA 1664 method with 95% confidence across spectrum of wastewater matrices (June 2009) • Present single lab results at ASTM D19 Meeting in Las Vegas (June 2009) • single lab results approved • Multilab study plan approved by EPA (Reding , Walker) and ASTM D19.06 members • ASTM multilaboratory validation study

– 12 independent labs (August 2009) • ASTM D7575 method assignment (December 2009) 

### • ASTM D7575
- 10 Final Approval (January 2010)11 

# ASTM D7575 Validation

• New technology and method validated through ASTM process per direction of Dick Reding (ret., Dir. EAD - OST- OW- EPA at the time)


# • Two step process:

– Single lab validation to show preliminary precision as well as comparability to 1664

– Multi - lab validation to show precision across laboratories and establish QC limits12 

# ASTM D7575 Development Exceeds EPA Tier III Requirements13 

# Comparison to EPA 1664

Line represents the 1:1 correlation line between the two methods; Not a best fit line


## (OSS method tested by OSS, 1664A tested at independent lab) ASTM D7575 Concentration (mg/L)14



# Matrices Tested During Development Set 1 Set 2 Set 3 Set 4 Gulf A Stormwater Runoff Cleaning Co. POTW Gulf B Food Processor A Bakery Dairy Food Processor Food Processor B Prison Fish Processor Prison Food Processor C Hospital A Auto Salvage POTW - Primary Effluent POTW - Primary Effluent Hospital B Auto Garage Paper Mill Prison Hospital C Machinist Paper Mill Hospital D Gunsmith Hospital E Gunsmith Stormwater Runoff 

## (Tested by OSS, compared to 1664A, LLE and/or SPE)15 

# Single Lab Validation

• Completed Single Lab Validation – (June  ̳09) 

# • Performed at independent lab
• Key purpose:

– Method Comparability 

# • Compared Results to EPA 1664
• Balloted ASTM Single - Lab Validated Method16 Measured Result in mg/L for Real - World Matrices 

### Replicate # 

## Publicly Owned Treatment Works Gunsmith 1 31.3 76.1 2 29.2 73.3 3 24.7 75.3 4 30.7 78.3 5 34.1 74.5 6 29.7 91.2 7 27.4 89.4 

## Average Recovery (mg/L) 29.6 79.7 Average Recovery by EPA 1664 (mg/L) 32.2 78.9 Average Recovery as % of EPA 1664 92% 101% Standard Deviation (mg/L) 3.0 7.4 Relative Standard Deviation as % 10% 9.3% 

# Single Lab Validation Data

(2 Matrices, 7 Replicates)17 ** Not tested 

### Measured Result mg/L as Oil and Grease Replicate # 

## Auto

Garage Dairy Machine

Shop Auto Salvage

Yard Fish

Processor 1 21.0 89.5 74.0 5.8 50.5 2 19.9 91.4 69.9 4.8 54.1 3 18.4 103.8 98.4 5.8 50.9 Average Recovery (mg/L) 19.8 94.9 80.8 5.5 51.8 Average Recovery by EPA 1664 (mg/L) 21.1 108.8 89.4 6.6 54 Average Recovery as % of EPA 1664 94% 87% 90% 84% 96% Standard Deviation (mg/L) 1.3 7.8 15.4 0.6 2.0 

### Relative Standard Deviation as % 6.7% 8.2% 19% 10% 3.8% Matrix Spike Recovery % 101% ** 96% 94% 94% 

# Single Lab Validation Data (cont.) (5 Matrices, 3 Replicates)18 

## Seven samples of one matrix over 1 month period: POTW Measured Result mg/L as Oil and Grease Replicate # Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 1 22.6 25.6 21.7 23.2 19.6 28.8 1.1 * 2 19.5 29.9 14.8 20.8 19.5 25.7 1.3* 3 23.7 28.6 21.2 25.1 25.9 22.6 0.9 * Average Recovery (mg/L) 21.9 28.0 19.3 23.0 21.7 25.7 1.1 * Average Recovery by EPA 1664 (mg/L) 

### 17.0 28.9 20.9 22.9 30.0 29.8 1.2 * Average Recovery as % of EPA 1664 129% 97% 92% 101% 72% 86% N/A** Standard Deviation (mg/L) 2.2 2.2 3.8 2.1 3.7 3.1 N/A** Relative Standard Deviation, % 10% 8% 20% 9% 17% 12% N/A** Matrix Spike Recovery % 96% 96% 88% *** *** *** 110% * Below recommended reporting limit ** Not calculated – date below recommended reporting limit *** Not performed 

# Single Lab Validation Data (cont.)

(ASTM D7575 vs. EPA 1664 Average Recovery = 96.2%)19 

# • EPA Method Comparability Statistics

– NO DIFFERENCE IN RESULTS at 95% CONFIDENCE!

* ASTM E178 Outliers Removed 

# Single Lab Validation Summary20 

# SINGLE LAB METHOD COMPARABILITY RESULTS2122232425 

# Conclusion The analysis presented here shows that the ASTM D7575 Solventless Oil and Grease method is statistically equivalent to EPA Method 1664A when considered in light of previous well - known precision data reported for EPA Method 1664A. In my interest as a concerned citizen I would hope that that, given equivalence, EPA can provide users a solventless / greener alternative to the use of environmentally unfriendly and hazardous n - hexane as specified in Method 1664. Especially since the current solid - phase extraction version of EPA 1664 was adopted WITHOUT ANY comparability data because of the positive attributes it would provide (time savings, solvent use) over the liquid – liquid extraction procedure of EPA 1664. 

# Supplemental Data and Statistical Analysis in Support of Method Equivalence of ASTM D7575 Solventless Oil and Grease and

EPA Method 1664A Barrett P. Eynon 

## Statistician 

# Introduction I am a professional statistician with over 30 years of experience in applying statistics to the environmental and biotechnology fields. In the early 1990s. I was a statistical consultant to the US EPA Office of Water and provided statistical and data analyses of laboratory measurement data for Oil and Grease in the EPA Freon Replacement studies, including the Phase 1(US EPA, 1993), Phase 2(US EPA, 1995) and Validation (US EPA, 1995) studies that led to EPA Method 1664A (US EPA, 2000), in work done through SRI International and Dyncorp /VIAR (EPA Sample Control Center).26



# MULTI - LAB TESTING27 

# Multi - Lab Validation of ASTM D7575

• Key Purpose – Method Precision and Bias

• Completed – 12 Independent Labs (Aug./Sep.  ̳09)

• Designed according to ASTM D2777

– approved by ASTM D19.06 committee / EPA Office of Water personnel ( Reding , Walker)



# • Youden Pair analyses of three matrices - POTW (10ppm), DAIRY (60ppm), BILGE WATER (100ppm)2829 

## Results\Matrix POTW 1 POTW 2 Dairy 1 Dairy 2 Bilge 1 Bilge 2 True Value (mg/L) 

## 10.8 9.3 58.8 51.6 91.8 86.6 # Sample Results 11 11 12 11 12 10 Average Recovery (mg/L) 

## 11.0 9.1 60.0 53.1 94.8 84.3 Minimum Recovery (mg/L) 8.3 6.6 47.9 43.1 76.5 67.3 Maximum Recovery (mg/L) 13.6 12.4 68.7 62.8 107.1 95.3 Relative Overall Standard Deviation,% 16.8% 19.6% 11.6% 10.5% 10.2% 10.2% Relative Single Operator Standard Deviation, % 16.5% 7.3% 5.2% # Matrix Spike Results 10 10 9 10 11 9 Average Matrix Spike Recovery % 109% 117% 91% 108% 87% 87% 

# Round - Robin Results

(AVERAGE RECOVERIES = TRUE VALUES)30 

## Results\Matrix POTW 1 POTW 2 Dairy 1 Dairy 2 Bilge 1 Bilge 2 True Value (mg/L) 10.8 9.3 58.8 51.6 91.8 86.6 # Sample Results 11 11 12 11 12 10 Average Recovery (mg/L) 11.0 9.1 60.0 53.1 94.8 84.3 Minimum Recovery (mg/L) 8.3 6.6 47.9 43.1 76.5 67.3 Maximum Recovery (mg/L) 13.6 12.4 68.7 62.8 107.1 95.3 Relative Overall Standard Deviation,% 

## 16.8% 19.6% 11.6% 10.5% 10.2% 10.2% Relative Single Operator Standard Deviation, % 16.5% 7.3% 5.2% # Matrix Spike Results 10 10 9 10 11 9 Average Matrix Spike Recovery % 109% 117% 91% 108% 87% 87% 

# Round - Robin Results

(AVERAGE OVERALL RELATIVE STANDARD DEVIATION = 13.1%) (WATER SAMPLE EXPERIENCED LABS = 9.2%)31 

## Results\Matrix POTW 1 POTW 2 Dairy 1 Dairy 2 Bilge 1 Bilge 2 True Value (mg/L) 10.8 9.3 58.8 51.6 91.8 86.6 # Sample Results 11 11 12 11 12 10 Average Recovery (mg/L) 11.0 9.1 60.0 53.1 94.8 84.3 Minimum Recovery (mg/L) 8.3 6.6 47.9 43.1 76.5 67.3 Maximum Recovery (mg/L) 13.6 12.4 68.7 62.8 107.1 95.3 Relative Overall Standard Deviation,% 16.8% 19.6% 11.6% 10.5% 10.2% 10.2% Relative Single Operator Standard Deviation, % 

## 16.5% 7.3% 5.2% # Matrix Spike Results 10 10 9 10 11 9 Average Matrix Spike Recovery % 109% 117% 91% 108% 87% 87% 

# Round - Robin Results

(AVERAGE SINGLE OPERATOR RELATIVE STANDARD DEVIATION = 9.7%) (WATER SAMPLE EXPERIENCED LABS = 7.5%)32 

## Results\Matrix POTW 1 POTW 2 Dairy 1 Dairy 2 Bilge 1 Bilge 2 True Value (mg/L) 10.8 9.3 58.8 51.6 91.8 86.6 # Sample Results 11 11 12 11 12 10 Average Recovery (mg/L) 11.0 9.1 60.0 53.1 94.8 84.3 Minimum Recovery (mg/L) 8.3 6.6 47.9 43.1 76.5 67.3 Maximum Recovery (mg/L) 13.6 12.4 68.7 62.8 107.1 95.3 Relative Overall Standard Deviation,% 16.8% 19.6% 11.6% 10.5% 10.2% 10.2% Relative Single Operator Standard Deviation, % 16.5% 7.3% 5.2% # Matrix Spike Results 10 10 9 10 11 9 Average Matrix Spike Recovery % 

## 109% 117% 91% 108% 87% 87% 

# Round - Robin Results

(AVERAGE SPIKE RECOVERY = 99.8%)33 

# Range / QC Acceptance Limits

All labs were able to meet QC performance spec. within 1 (most) or 2 attempts

Analyte MDL (mg/L) Reporting Range (mg/L) Oil and Grease 

# 1.0 5 - 200 Method Detection Limit and Reporting Range

Analyte Initial Precision and Recovery Lab Control Sample Matrix Spike Test Concentration (mg/L) Recovery (%) Precision Recovery (%) Recovery (%)

Lower limit Upper limit Maximum RSD (%) Lower

limit Upper limit Lower limit Upper limit Oil and Grease 

# 40 88 105 10.5 79 113 69 127

QC Acceptance Criteria34 

# YOUDEN PAIR STATISTICS:
• Overall relative standard deviation (RSD) 13.1% (across all labs, samples, operators)

– Water sample EXPERIENCED labs overall RSD 9.2%

• Within - lab Operator RSD 9.7% (across all samples)

– Water sample EXPERIENCED labs within - lab RSD 7.5% 

# Round - Robin Results35



# Parameter MDL Amount Spiked (mg/L) 4 # Results 12 Pooled MDL (mg/L) 1.0 Standard Deviation of MDL (mg/L) 0.26 

# Pooled Method Limit (mg/L) 3.181 * * NOTE: EPA 1664 Method Limit = 5 mg/L 

# Round - Robin Results (MDL,ML)

(Method Detection Limit = 1.003 ppm ) (Method Limit = 3.181 ppm )

All labs were able to meet MDL performance spec. within 1 (most) or 2 attempts36



# Parameter IPR Mean Recovery Precision Amount Spiked (mg/L) 40 40 # Results 12 12 

## Average Recovery % 96% Standard Deviation of Recovery 5.07% Average RSD 7.53% Standard Deviation of RSD 2.24% 

# Round - Robin Results (IPR)

(Average Recovery = 96%) (95% Confidence Recovery Range Limits = 84% - 107%)

All labs were able to meet IPR performance spec. within 1 (most) or 2 attempts37 

# Parameter LCS Amount Spiked (mg/L) 40 # Results 12 Average % 100% Standard Deviation of LCS (mg/L) 8.0% 

# Round - Robin Results (LCS)

(Average Recovery = 100%) (95% Confidence Recovery Range Limits = 81% - 118%)

All labs were able to meet LCS performance spec. within 1 (most) or 2 attempts38



# ASTM D7575 Published January 2010 and available for purchase at ASTM website39 

# ASTM D7575 METHOD PROCESS40 

# ASTM Method D7575 Video41 

# Calibration Standard Devices Calibration of infrared instrumentation performed with  ̳Standard Devices‘, which contain a known amount of material 

## SOLID STATE DEVICES – Nothing to make up!

Calibration Verification also performed daily using 

## one of the Standard Devices42 

# ASTM D7575 Method

Real Sample

- acidified



## - cooled
1 ) Homogenize (e.g. sonicate , mechanical shake, or hand shake) ( 1 - 20 minutes) 

## 2) Fill Sterile Disposable Syringe43



# Method (con‘t)

Attach OSS Device to Syringe 

## Use Syringe Pump to Force Sample through Device (3 minutes) Use Air Pump to Aid Drying (2 - 45 minutes)44



# Method (con‘t)

Examine with IR Spectrometer

(1 minute) Process Spectrum with Software... ( < 1 minute) 

# ...To Determine Oil and Grease Content = 101 mg/L Absorbance (a.u.)

Wavenumber (cm - 1 )45 

# OSS Extractor Part #1018SPE46 

## FTIR Syringe Pump Drying Manifold

Ultrasonic Bath Small Air Compressor (in back) 

## OSS Extractors OSS CSDs 10cc Syringes 

# ASTM D7575 Oil and Grease System

Cart 36x32x2447 

# ASTM D7575 vs. EPA 1664 METHOD COMPARISON48 

## EPA 1664 METHOD STEPS49 6.1 Sampling equipment. 6.1.1 Sample collection bottles—Glass, approximately 1 - L, with PTFE - lined screw cap. NOTE: In those instances necessitating collection of a sample known or suspected to contain >500 mg/L of HEM (Section 8.1.2), a smaller sample container may be used. 6.1.2 Cleaning. 6.1.2.1 Bottles— Detergent water wash, tap water rinse, cap with aluminum foil, and bake at 200–250EC for 1 h minimum prior to use. Solvent rinse may be used in place of baking. 6.1.2.2 Liners for screw caps— Detergent water wash, tap water and solvent rinse, and bake at 110–200EC for 1 h minimum prior to use. Method 1664 4 February 1999 6.1.3 Bottles and liners must be lot- certified to be free of artifacts by running laboratory blanks according to this method (per Section 9.4). If blanks from bottles and/or liners without cleaning or with fewer cleaning steps than required above show no detectable materials, the bottle and liner cleaning steps that do not eliminate these artifacts may be omitted. 6.2 Equipment for glassware cleaning. 6.2.1 Laboratory sink with overhead fume hood. 6.2.2 Oven —Capable of maintaining a temperature within ± 2EC in the range of 70–250EC. 6.3 Equipment for calibration. 6.3.1 Analytical Balance—Capable of weighing 0.1 mg. 6.3.2 Volumetric flask —Glass, 100- mL. 6.3.3 Vials—Assorted sizes, with PTFE - lined screw caps. 6.3.4 Volumetric pipette—Glass, 5 - mL. 6.2 Equipment for sample extraction. 6.4.1 Balance (optional)—Top loading, capable of weighing 500–2000 g within ± 1% 6.4.2 Glass stirring rod. 6.4.3 Separatory funnel —Glass, 2000- mL, with PTFE stopcock. 6.4.4 Funnel — Large, glass, for pouring sample into separatory funnel. 6.4.5 Centrifuge (optional)— EXPLOSION PROOF , capable of spinning at least four 100 - mL glass centrifuge tubes at 2400 rpm minimum. 6.4.6 Centrifuge tubes (optional)— 100- mL glass. 6.5 Equipment for removal of water, sodium sulfate, and silica gel fines. 6.5.1 Funnel —Analytical, glass. 6.5.2 Filter paper—Whatman No. 40 (or equivalent), to fit funnel. 6.6 Equipment for solvent distillation. 6.6.1 Water bath or Steam bath — EXPLOSION - PROOF , capable of maintaining a temperature of at least 85EC. 6.6.2 Flask

— Boiling, 125 - mL (Corning No. 4100 or equivalent). 

## EPA 1664 EQUIPMENT LIST (page 1 of 3) ASTM D7575 EQUIPMENT50 6.6.3 Distilling head —Claisen (VWR Scientific No. 26339-005, or equivalent), includes Claisen -type connecting tube and condenser. 6.6.4 Distilling adaptor (attached to the distilling head and to the distillate collection flask for recovery of solvent). 6.6.5 Distillate collection flask (attached to the distilling adaptor for collection of the distilled solvent). 6.6.6 Ice bath or recirculating chiller (to aid in the condensation and collection of the distilled solvent). 6.6.7 Vacuum—Vacuum pump or other source of vacuum. 6.6.8 Tongs, for handling the boiling flask (Baxter Scientific Products No. T5007-2, or equivalent). 6.6.9 Desiccator—Cabinet- or jar-type, capable of keeping the boiling flask (Section 6.6.2) dry during cooling. 6.6.10 Hood - EXPLOSION - PROOF , capable of accommodating the equipment used for solvent distillation (Section 6.6.1 -6.6.5). 6.7 Equipment for removal of adsorbable materials. Method 1664 February 1999 5 6.7.1 Magnetic stirrer. 6.7.2 PTFE - coated magnetic stirring bars. 6.7.3 Graduated cylinder—500- mL, capable of measuring ± 5 mL. 6.7.4 Pipettes—Assorted sizes, calibrated to within ± 0.5 percent. 7.0 Reagents and Standards 7.1 Reagent water—Water in which HEM is not detected at or above the minimum level (ML) of this method. Bottled distilled water or water prepared by passage of tap water through activated carbon have been shown to be acceptable sources of reagent water. 7.2 Hydrochloric acid or sulfuric acid—ACS. Mix equal volumes of concentrated HCl and reagent water or 1 part H2SO4 and 3 parts reagent water to produce an approximately 6N solution. 7.3 n - Hexane—85% minimum purity, 99.0% min. saturated C6 isomers, residue less than 1 mg/L. 7.4 Acetone—ACS, residue less than 1 mg/L. 7.5 Sodium sulfate—ACS, granular anhydrous. Dry at 200 -250 EC for 24 h minimum and store in a tightly sealed container until use. NOTE: Powdered sodium sulfate should not be used because traces of water may cause it to solidify. 7.6 Boiling chips—Silicon carbide or fluoropolymer . 7.7 Silica gel —Anhydrous, 75 - 150 micrometers, Davisil Grade 923 (Supelco 21447-7A, or equivalent). Dry at 200–250EC for 24 h minimum and store in a desiccator or tightly sealed container. Determine the n - hexane soluble material content of the silica gel by extracting 30 g of silica gel with n - hexane and distilling the n - hexane to dryness. The silica gel must contain less than 5 mg of n - hexane soluble material per 30 g (< 0.17 mg/g). 

## EPA 1664 EQUIPMENT LIST (page 2 of 3)51 7.8 Hexadecane—98% minimum purity. 7.9 Stearic acid—98% minimum purity. 7.10 Hexadecane/

stearic acid (1:1) spiking solution — Prepare in acetone at a concentration of 2 mg/mL each. 7.10.1 Place 200 ± 2 mg stearic acid and 200 ± 2 mg hexadecane in a 100 - mL volumetric flask and fill to the mark with acetone. NOTE: The solution may require warming for complete dissolution of stearic acid. 7.10.2 After the hexadecane and stearic acid have dissolved, transfer the solution to a 100– 150 mL vial with fluoropolymer- lined cap. Mark the solution level on the vial and store in the dark at room temperature. 7.10.3 Immediately prior to use, verify the level on the vial and bring to volume with acetone, if required. Warm to redissolve all visible precipitate. NOTE: If there is doubt of the concentration, remove 10.0 ± 0.1 mL with a volumetric pipet , place in a tared weighing pan, and evaporate to dryness in a fume hood. The weight must be 40 ± 1 mg. If not, prepare a fresh solution (Section 7.10.1). Method 1664 6 February 1999 7.11 Precision and recovery (PAR) standard — Using a pipet , spike 10.0 ± 0.1 mL of the hexadecane/stearic acid spiking solution (Section 7.10) into 950– 1050 mL of reagent water to produce concentrations of approximately 20 mg/L each of hexadecane and stearic acid. The PAR standard is used for the determination of initial (Section 9.2.2) and ongoing (Section 9.6) precision and recovery. 7.12 The spiking solutions should be checked frequently for signs of degradation or evaporation using the test noted in Section 7.10.3, and must be replaced after six months, or sooner if degradation has occurred. 

## EPA 1664 EQUIPMENT LIST (page 3 of 3)5253 

# GREEN ASPECT OF ASTM D7575 (Toxic Issues with EPA 1664)54 

# ASTM D7575 – Green!5556 U.S. Environmental Protection Agency; EPA Docket Center (EPA/DC) Water Docket MC 28221T 1200 Pennsylvania Avenue, NW Washington, DC 20460 Docket ID No. EPA- HQ- OW - 2010 - 0192 

### The letter presents three key points: 1 ) n - Hexane is a well - documented occupational health hazard; 2 ) Health effects from exposure to n - hexane can occur at exposure levels several orders of magnitude below the federal Occupational Safety and Health Administration’s Permissible Exposure Limit of 1,800 mg/m 3 

### (500 ppm ); 3 ) Reducing the commercial circulation of n - hexane by allowing methods that use solvent free technologies would help mitigate worker exposures to n - hexane throughout its life cycle; this approach is consistent with EPA’s commitment to the principles of green chemistry.57 

## Hexane Mentioned 38 times!!! Cases of direct health issues Cases of explosions Air- reactive substances - These substances may cause fires or explosions, and may generate toxic gases, or vapors.

Flammable air- reactives - include hydrocarbon solvents (such as hexane , toluene, naphtha) and fuels (such as gasoline).5859 

# OIL IN WATER TECHNOLOGIES MATRIX60



## Infrared Based 

# OSS TECHNOLOGY FEATURES61 

## HEXANE EXPLODES OHIO STATE UNIVERSITY LABORATORY62 • Danger of serious health damage • Irritating to skin, eyes, lungs • Risk of impaired fertility • Toxic to aquatic organisms 

### Hexane Issues:

Hazardous Materials Transport / Disposal: 

# OSS METHOD:

NO SOLVENTS NO TOXIC SUBSTANCES 

### DISPOSABLE FAST, EASY PROCESS 

# MEETS OR EXCEEDS EPA 1664 PERFORMANCE 

# CURRENT EPA 1664 METHOD:

Millions of Liters/Year of Hexane evaporated into atmosphere 

### Pollution: 

# Summary63 

# SUPPORT FOR ASTM D7575 INCLUSION IN METHOD UPDATE

RULE64 

### Here are some points for you all to keep in mind: 1) A comparison study between 1664 and D7575 was carried out in accordance with the procedures in EPA's Phase II Freon Replacement Study. 2) On page 5 of the EPA Freon Replacement Study, the Agency states that infrared techniques/methods would be evaluated in the Phase III Replacement Study. Obviously, infrared was under consideration by the Agency. 3) For D7575, a side - by- side comparison was carried out, in triplicate, by a single, independent laboratory. And this was also the case with the EPA Phase II Study. Again, in D7575, thirty samples are covered in the ASTM Report. Also three (or four) additional samples were analyzed, and the results sent to the Agency-- separately. 4) The EPA Phase II Freon Replacement Study analyzed 34 samples. The ASTM D7575 Study analyzed 33 samples. We did not sample a more diverse collection of industries because we did not have 308 Authority—the device EPA employed for its collection efforts. Note that the volunteer industries that we employed for the D7575 ASTM Study were approved by EPA (Dick Reding ). 

# Bill Telliard Points of Note re. ASTM D7575

Development65 

# ASTM Formal Request to EPA to Include D7575 in Rule66 

## ―I was thoroughly impressed with the ease of use and the speed of this method. Even with minimal training, I felt comfortable and confident when asked to use the method without assistance. It only took a couple hours to process an MDL and several samples. With our current system, this could take as much as a full day to run. As the Health and Safety Officer, I was very glad to see that this is a solvent -free method. Any way to reduce hazardous materials in the lab is great. It‘s safer and helps save money. Another of my responsibilities is disposal of hazardous waste. We currently collect 2 X 1 liter ambers for Oil and Grease Analysis. It seems more than likely, that with this method, as long as it doesn‘t 

## affect reporting limits; a smaller volume could be collected. ―

MULTILAB STUDY – USER SURVEY EXAMPLES:

―One large cost- and health - saving advantage of this method is that it does not use any solvent. It can also be a space - saving advantage, since it does not need to be performed in a fume hood, allowing other analyses to be performed in the hood while the Oil and Grease analysis is also being performed. ―67 1) Comment attachment submitted by Andrea Rex, Massachusetts Water Resources Authority Comments Due Dec 22, 2010 11:59 PM ET Public Submission Massachusetts Water Resources Authority EPA - HQ - OW - 2010 - 0192 - 0091.1 11/22/2010 ―For oil and grease, this section explicitly DOESN‘T propose for approval ASTM method D7575 - 10, which is based on solid phase extraction using a membrane and quantitation by infrared absorption of the membrane. We had occasion to try this method out with the method developer (OSS) and found it to be simple yet elegant. It worked well on method detection limit and precision and accuracy samples ,..‖ 2) Comment attachment submitted by Willie R. Taylor, Director, Office of Environmental Policy and Compliance, U.S. Department of the Int eri or Comments Due Dec 22, 2010 11:59 PM ET Public Submission EPA - HQ - OW - 2010 - 0192 - 0108.1 12/01/2010 Proposed Revisions to Method Modification Provisions at 40 CFR 136 ―We are in agreement that regulatory authorities should al low analysts the flexibility to modify CW A methods without prior approval provided the user has documented equivalent or better performance of the method in that particular matrix type. In instrumental analyses. analysts may need to modify approved methods in order to combat matrix in terferences and these modifications should not require extensive review. The Department agrees that acceptable reasons for these modifications should include lower detection limits, improved precision, less spectral interference, lower laboratory cost and the reduction of laboratory waste . ― 3) Comment submitted by Andre Brousseau , President, Maine Wastewater Control Association (MWWCA) Comments Due Dec 22, 2010 11:59 PM ET Public Submission Maine Wastewater Control Association (MWWCA) EPA - HQ - OW - 2010 - 0192 - 0109 ― Method 1664 for Oil& Grease: Hexane In the Federal Register of September 23, 2010, EPA seeks to approve new technologies for other test parameters as part of its ch anges to 40 CFR 136, yet falls short of being able to accept new methods that include new technologies for Oil & Grease. NfWWCA finds that the EPA's reasoning for not approving alternative test methods for Oil & Grease is contradictory to the Agency's "Summary" statement that these regulations will "provide increased flexibility to the regulated community and laboratories in their selection of analytical methods (test procedures) for use in Clean Water Act programs." Further, approving the new methods would be more consistent with the EPA's mission and purpose to "ensure that all Americans are protected from significant risks to human health and the environment where they live learn and work. ― EPA has previously app roved hexane extractable methods for Oil & Grease, then reversed that decision because hexane was a hazardous solvent and required use of Fre on extractable methods for Oil & Grease. Then EPA reversed that decision and went back to hexane, because Freon was considered more harmful to human health and the environment than hexane. However, hexane remains a dangerous solvent. n - Hexane has a flashpoint of - 22 degrees Celsius, so most n - hexane waste is considered a RCRA hazardous waste by characteristic. According to the u.s . Department of Labor, Occupational Safety and Health Administration (OSHA) Guideline for n - Hexane (2008) discussion on toxicology to animals, "n - Hexane is a neurotoxin, a narcotic, and an irritant of the eyes, skin, and mucous membranes [Hathaway et al. 199 I]. n - Hexane also causes (re)productive and embryo toxic effects an d is cytotoxic in mammalian and human test systems [NIOSH 1991]." OSHA also found that n - Hexane is toxic to humans, and recommends extensive medical surveillance for persons working with n - Hexane. EPA must consider the goals of the Clean Water Act when approving test procedures for Clean Water Act permittees in 40 CFR 136. NJWWCA believes that the fats, oils and greases that may be toxic to aquatic organisms, or interfere with sewer collection systems and wastewater treatment, are primarily petroleum, animal or vegetable in origin. These fats, oils and gre ases are not exclusively "hexane extractable" compounds. In fact, other technologies and methods may be better at measuring these compound s, and may be used to better quantify how much fat, oil or grease is toxic to aquatic life or interferes with wastewater treatment. EPA should not specifically and uniquely endorse a solvent specific method for "Oil & Grease." The NJWWCA requests that EPA reve rse its decision that only n - hexane extractable Oil & Grease methods are acceptable. We understand that, to further that reversal, EPA must re -write its current definition of oil and grease so that new technologies and test methods can be approved.



## CURRENT METHOD UPDATE RULE (EPA- HQ - OW- 0192) 9 INDEPENDENT ASTM D7575 PUBLIC COMMENT EXAMPLES *** Note these are comments even though ASTM D7575 was NOT PROPOSED68 4) Comment submitted by David N. Speis , Chair, Environmental Laboratory Advisory Board (ELAB) Comments Due Dec 22, 2010 11:59 PM ET Public Submission Environmental Laboratory Advisory Board (ELAB) EPA - HQ - OW - 2010 - 0192 - 0120 12/20/2010 ― Comment: Flexibility in the Use of Methods for Different Analytes . There is a need for flexibility in adding analytes to EPA-approved methods as long as the supporting quality assurance (QA) and QC based on data quality objectives (DQOs) demonstrates acceptable data quality . As water quality criteria are adopted for new analytes , this type of method flexibility would facilitate more defensible and reliable monitoring of these analytes . Where feasible for a given technology, EPA should allow current EPA approved methods to be used to analyze compounds/analytes in addition to those listed in the methods as long as QA/QC demonstrates acceptable data quality. The development of DQOs for individual programs would facilitate this flexibility and reduce the need for new method s. ELAB recommends that EPA consider providing this flexibility in the final rule. Comment: Method Validation and Approval Process. EPA has proposed numerous changes to the methods in the MUR simply by approving different editions of Standard Methods for us e. This is significant because the method approval process for Standard Methods is not the same as that for EPA or other standards - setting organization s. Additionally, changes are being made by vendors to methods previously deemed to be equivalent to 40 CFR Part 136 methods (e.g., Lachat Methods for total kjeldahl nitrogen ammonia); the acceptability or approval of these changes or updates is not clear. Based on these observations, it appears that many changes to the methods approved for use in this rule, given the information provided by EPA, are occurring without a systematic review, validation, and approval process. 5) Comment submitted by Ellen R Campbell, Nitrate Elmination Co Inc Comments Due Dec 22, 2010 11:59 PM ET Public Submission Nitrate Elmination Co Inc EPA- HQ - OW - 2010 - 0192 - 0121 12/20/2010 ―General Comment The methods approval process at the EPA under the Clean Water and Safe Drinking Water Acts is geared toward old, established ana lytical methods in use before 1960. The EPA seems willing to accept new methods that require high - cost equipment. This mindset is detrimental to in novative companies here in the US. It is time for the EPA to start considering and approving new methods based on reduction of hazardous or toxic reagents AND on methods that are proven to work, . Advances in biotechnology and materials science may simplify and reduce costs for many analytes of interest to the EPA. This How can a new mindset at the EPA toward green and cost -effective methods be established? ‖ 6) Anonymous public comment Comments Due Dec 22, 2010 11:59 PM ET Public Submission University of Maine EPA - HQ - OW - 2010 - 0192 - 0129 12/21/2010 General Comment As an individual who has performed both the previous Freon method as well as the n - hexane method I have been exposed to these dangerous fumes. I read your documentation for why this specific method ASTM D7575 was not chosen as a viable alternative to EPA 1664 based on the fact that all oil and grease sampling techniques require an organic solvent. This breakthrough in the measuremen t of oil and grease should be adopted and the rationale that the method doesn't include a solvent is not in the best interest of science o r t he environment. 

## CURRENT METHOD UPDATE RULE (EPA- HQ - OW- 0192)

9 INDEPENDENT ASTM D7575 PUBLIC COMMENT EXAMPLES (continued)69 7) Comment attachment submitted by Paul Wiegand , Vice President, Water Quality, National Council for Air and Stream Improvement, Inc. (NCASI) Comments Due Dec 22, 2010 11:59 PM ET Public Submission EPA - HQ - OW - 2010 - 0192 - 0166.1 12/27/2010 ― As detailed in the attachment, NCASI’s primary concern is that EPA is proposing adoption of many methods despite the absence of validation data, both in general and specifically using real -world matrices . The absence of appropriate method validation data in the docket is of concern because without such data not only is it impossible to verify the performance of methods proposed as part of this rule, but i t a lso suggests that EPA is proposing methods absent the data to bootstrap even basic quality control (see Comment #2 in the attachment). Similarly, EPA proposes addition of several EPA methods (e.g., 1614A, 614.1, 632, 1664 Rev. B, 622.1, and 619) but has not provided any validation data demonstrating the capabilities of the methods to meet the testing requirements for the NPDES program, nor has it conducted a pe er review and made the result available for public comment.‖ 8) Comment attachment submitted by Joe Boyd, Environmental Express Comments Due Dec 22, 2010 11:59 PM ET Public Submission EPA - HQ - OW - 2010 - 0192 - 0181.112/27/2010 ―The EPA has decided not to include ASTM method D7575 - 10 in Table IB mainly due to the fact that this method does not use the so lvent n - hexane in the determination of oil & grease. Methods that are currently listed in Table IB (EPA 1664B, SM 5520B - 2001, and SM 5520F - 2001) d o indeed list n hexane as the solvent to use for extraction. However, all three of these methods reference ―oil & grease‖ as a method defined pa rameter based on the use of hexane as the extraction solvent. This makes the analytes of interest ―hexane extractable material‖, or HEM rather than ―oil & grease‖. While both ―HEM‖ and ―oil & grease‖ can be construed as method defined analytes , HEM is much more specific in that the name itself implies that the analytes of interest must be extractable using hexane. ―Oil & grease‖, however, is a broader term and does not limit itself to any specific type of extraction. One must understand that no matter what extraction procedure is employed, the analytes of interest will always be a method defined parameter as the term ―oil & grease‖ is truly indefinable. The continued use of the term ―oil & grease‖ in Table IB for Parameter 41, however, leads to so me confusion and brings into question the reasoning behind the EPA‘s decision to limit the measurement of this parameter to hexane extractable material. The EPA‘s decision to abandon methods 413.1 and 418.1 to eliminate the use of the fluorochlorohydrocarbon Freon® has been widely accepted as a step in the positive direction to reduce the amount of pollution generated by the laboratory. While n - hexane is an improvement over Freon®, it is still a highly flammable solvent and has the potential to be highly toxic to the user. Environmental Express, Inc. does not specifically endorse the product created by Orono Spectral Solutions Inc. (OSS) used in ASTM method D7575 - 10, however we would ask that the EPA continue to look at products that can make various analyses ―greener‖. The supportin g data provided by OSS does seem to indicate an equivalent option for the determination of the parameter ―oil & grease‖ and eliminates the risks created by the use of n - hexane. While ASTM method D7575 - 10 does not lead to the analyte of interest as HEM, it does provide an alternative extraction technique to determine ―oil & grease‖. The EPA has already demonstrated that it is willing to alter the definition of the end analyte of interest for the parameter of ―oil & grease‖ by moving from Freon® to nhexane , creating HEM. The EPA should keep the spirit of this philosophy alive in the move to greener methodologies and reconsider it’s stance on ASTM D7575- 10. ‖



## CURRENT METHOD UPDATE RULE (EPA- HQ - OW- 0192) 9 INDEPENDENT ASTM D7575 PUBLIC COMMENT EXAMPLES (continued)70 9) Comment submitted by Peter Halpin , Caltest Analytical Laboratory Public Submission Caltest Analytical Laboratory EPA- HQ - OW - 2010 - 0192 - 0187 12/30/2010 ―In the spirit of the March 207 Method Update Rule that applied to Clean Water Act analyses and sampling procedures we are requesting that you include flexibility to reduce costs where feasible and where the changes do not result in a reduction of data quality . Specifically in allowing alternate extraction procedures, addition of an analyte , and the use of mass spectrometer detectors for all semivolatile analytes where the mass spectrometer is capable of providing sufficiently sensitive detection limits for the purpose of the analysis. For example, where extractable organics can be demonstrated to be adequately extracted from the target water by solid phase e xtraction, we advocate allowing the solid phase extraction. This would result in much less use of the toxic methylene chloride solvent, and generate less waste. Some methods explicitly allow solid phase extraction, some are too old to make reference to the technique. In addition to solid phase extraction, other green chemistry approaches that minimize solvent waste, hazard, and analyst time include stir bar sorptive extraction, and solid phase microextraction . When these approaches can be shown to meet the monitoring objective it would be helpful to be able to use them for compliance purposes...‖



## CURRENT METHOD UPDATE RULE (EPA- HQ - OW- 0192) 9 INDEPENDENT ASTM D7575 PUBLIC COMMENT EXAMPLES (continued)71 

### • Office of Management and Budget (OMB) Circular A- 119 (1998)



### – Encourages federal agencies to benefit from the expertise of the private sector

– Promotes agency participation in standards development activities

– Seeks to reduce reliance on government unique standards

– Section 6 of the OMB Circular requires head of agencies to provide an explanation of the reason(s) for using government - unique standards in lieu of voluntary consensus standards

– Annual report prepared by NIST for OMB on government use of standards and participation in standards activities 

### • National Technology Transfer and Advancement Act (NTTAA) of 1995

– Directs federal agencies to use ―technical standards developed or adopted by the voluntary consensus standards bodies‖ as a means to carry out policy objectives or activities determined by the agencies or departments72 

# ASTM D7575 FIELD EXPERIENCE73 

## Tom 

## Schwarz Dean 

## Smith 

# Blog at http://www.ossmaine.com/ OSS GULF OIL DISASTER FIELD TESTING

JUNE 201074



# GULF FIELD TESTING HIGHLIGHTS :

• Set up equipment and train personnel at Alpha Test Site (Petroleum Laboratories, Lafayette, LA) on ASTM METHOD 

# D7575

• Perform side - by- side comparisons against EPA 1664a

• Perform field sampling around Louisiana coast: • Unaffected areas in the west • Hard - hit areas in Grand Isle • Surface, subsurface, and sediment samples • 100+ samples taken and processed

• Perform real -time field analysis of ASTM D757 using only a generator for power.75 

# Alpha Test Site: Petroleum Laboratories Lafayette, LA

Thousands of samples/year Support of offshore industry76 

# Field Sampling Areas77



# Field Sampling: Grand Isle (surface grab)78



# Real -Time, Portable, Field Analysis79



# Analysis of Ocean Floor
SAMPLE

HOMOGENIZE

PROCESS80



# Identify oil/dispersants DISPERSANT COREXIT 9527 on ZnSe

OTHER OIL AND GREASE MATRICES

• STATISTICAL SIGNAL PROCESSING TO CHARACTERIZE / QUANTIFY DISPERSANTS IN OIL AND GREASE MATRICES??

• CURRENTLY WORKING ON THIS.8182



# AP Article 2/19/1183 

# OSS ASTM D7575 Technology: USM Gulf Study Objective: To study long -term effects of Deepwater Horizon disaster on marine mammals Cruise #1: July 17 - November 8 Cruise #2 (pending): Spring/summer 2011 OSS High Sensitivity Extractor

– Range: 0.2 - 40 ppm

– ML (As defined by EPA)= 200 ppb ~75 Samples collected and processed through high - sensitivity OSS extractor

– Current results between non - detect and 0.6 ppm84 

# OSS visit to NAVSEA Ship Systems Engineering Facility

 OSS sucessfully demonstrated the potential of ASTM Method D 7575 for shipboard bilgewater applications at the NAVSEA facility in Philadelphia, PA .85 

# On - going Field Testing / Tier I Study: Cleveland Ohio86



# MISCELLANEOUS87 

# HOMOGENIZATION EXAMPLE (motor oil in water - sonication)

T = 0 min T = 10 min T = 20 min88 OIL IN WATER CLUB Dr. Ming Yang TUVNEL 

# OSS OIL IN WATER INTERACTIONS

ASTM INTERNATIONAL D19 SUBCOMMITTEE PRODUCED WATER SOCIETY Dr. Colin Tyrie Dr. Dan Caudle
PITTCON WEFTEC MAINE PRETREATMENT Tom Wiley NEW ENGLAND ITLA

ACS / GREEN CHEMISTRY CONFERENCE INVITED PAPERS 2009, 20110

AMERICAN PETROLEUM INSTITUTE Roger Claff EPA INDUSTRIAL STAKEHOLDERS GROUP NAVSEA Ray Morales

PETROLEUM LABORATORIES Charlie Voinche CLEVELAND SANITARY DISTRICT NEW ENGLAND PRETREATMENT CONFERENCE EPA Justin Pimpare TEST AMERICA Dr. Mark Bruce

MISC. ORGANIZATIONS / CONFERENCES

NELAC PETROBRAS89 983 Stillwater Avenue ~ Old Town ME 04468 Tel: 866 -269- 8007 Fax: 866

- 660-4759 Email: info@ossmaine.com Web: www.ossmaine.com



### • Incorporated 2004
• Spun out of University of Maine
• DoD Contractor (CBD -Army) for Chem/Bio Detection
• Actively Pursuing Commercial Opportunities