EPA 625: Base, Neutral, Acid Semivolatiles in Municipal and Industrial Waste Water by Solid Phase Extraction

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Milton Watson
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1 EPA 625: Base, Neutral, Acid Semivolatiles in Municipal and Industrial Waste Water by Solid Phase Extraction Tom Hall, Fluid Management Systems, Watertown, MA

2 Overview Development of a fully automated extraction system for EPA 8270/625 Establishment of an extraction procedure capable of implementation of various aqueous matrices Participation in ILI SPE Demonstration project for method suitability Implementation of platform across other EPA methodologies

3 Matrices DI and Tap ASTM 5909 synthetic Waste Water TCLP Fluid Pond, River and Reservoir surface water Real world industrial effluents and influents Groundwater

4 SPE Waste Water Study Participation Participated in both Phase I and II Submitted data for all matrices in each respective study 3 rd Party participation using FMS equipment

5 Comparison of LLE/CLE vs. Automated SPE Methods LLE/CLE Open to laboratory background Uses >360mls solvent Shaking / Continuous process Forms emulsions requiring centrifuging Little Selectivity Requires water removal Automated SPE Closed system Uses <60mls solvent Filtration process No emulsions formed Wide Selectivity (adsorbent) In-line water removal Fast and Unattended

6 Comparison of LLE/CLE vs. Automated SPE Methods LLE/CLE No Separation of waste More volume to evaporate Massive solvent emission CLE uses a lot of power Requires lots of solvent for cleaning Automated SPE Separates Aqueous and Organic Waste <60mls solvent to evaporate 6 times less solvent emission Easily Capture Solvent Lower solvent costs Lower Disposal Costs

7 Reduced Solvent Usage

FMS TurboTrace ABN Touch Screen Control SD Card for Storing and Transferring Methods Six Elution and Wash Solvents Positive Pressure Pump for precise, consistent delivery of

8 FMS TurboTrace ABN Touch Screen Control SD Card for Storing and Transferring Methods Six Elution and Wash Solvents Positive Pressure Pump for precise, consistent delivery of Sample and Solvent Sample Size 2 ml to unlimited Automatic Bottle Rinse Real Time Graphical Display of Extraction Steps Automatic Liquid Level Sensor ABN Cartridge Carbon Cartridge

9 Dual SPE Cartridge Extraction Direct to Vial Concentration

10 SuperVap Features 6 (250ml) and 12 (50ml) position models for extractions. Dry bath heating element Independent secondary heater for extract nipple (Can be disabled). Sensor controlled Savable temperature log capability.

11 EPA 625/8270 Procedure Fully automates all processes, not manual steps Capable of delivering up to to 3 independent fractions (or combine as 1) Can elute direct to FMS SuperVap evaporator Automated organic solvent rinse of sample bottle Can elute either cartridge independently or in parallel Modular and Expandable Direct to GC Vial extracts

12 Recoveries by Analyte Class Mean PAH 60 Mean Phthalate 40 Mean Phenols 20 Mean Ion Exchangers 0 TCLP Fluid River Water Influent Waste Water Mean Semi VOAs

13 Data Recoveries for Individual Compounds with specific Analyte Classes

14 Naphthalene 2-Methylnaphthalene 1-Methylnaphthalene 2-Chloronaphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Chrysene Benzo[a]anthracene benzo[a]pyrene Indeno[1,2,3-cd]pyrene Benzo[b]fluoranthene Benzo[k]fluoranthene Dibenzo[a,h]anthracene Benzo[g,h,i]perylene PAHs TCLP Fluid River Water Influent Waste Water River Water Influent Waste Water

15 Phthalates TCLP Fluid River Water Influent Waste Water

16 Phenols TCLP Fluid River Water Influent Waste Water

17 Ion Exchangers TCLP Fluid River Water Influent Waste Water

18 Semi-Volatiles TCLP Fluid River Water Influent Waste Water

19 Method Validation Proficiency Data for Laboratory Validation

20 IDC/IPR Data IDC #1 IDC #2 IDC #3 IDC #4 Entry Identifier ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec EPA Limit 1,4-Dichlorobenzene-d N-Nitrosodimethylamine-d N-Nitrosodimethylamine Pyridine Phenol-d Phenol Aniline Bis(2-chloroethyl)ether-d Bis(2-chloroethyl)ether Chlorophenol-d Chlorophenol ,3-Dichlorobenzene D-172 1,4-Dichlorobenzene ,2-Dichlorobenzene Benzyl Alcohol ,2'-oxybis(1-chloropropane) Methylphenol Methylphenol-d

21 IDC/IPR Data IDC #1 IDC #2 IDC #3 IDC #4 Entry Identifier ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec EPA Limit 3/4-Methylphenol Hexachloroethane N-Nitrso-di-n-propylamine D-230 Naphthalene-d Nirtrobenzene Nitrobenzene-d Nitrophenol-d Isophorone Nitrophenol ,4-Dimethylphenol Bis(2-chloroethoxy)methane ,4-Dichlorophenol-d ,4-Dichlorophenol ,2,4-Trichlorobenzene Naphthalene Chloroaniline-d Chloroaniline Hexachlorobutadiene Acenaphthene-d Methylnaphthalene

22 IDC/IPR Data IDC #1 IDC #2 IDC #3 IDC #4 Entry Identifier ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec EPA Limit 1-Methylnaphthalene Chloro-3-methylphenol Hexachlorocyclopendadiene ,4,6-trichlorophenol ,4,5-Trichlorophenol Chloronaphthalene Nitroaniline ,4-Dinitrobenzene Dimethylphthalate-d Dimethylphthalate D-112 1,3-Dinitrobenzene Acenaphthylene-d Acenaphthylene ,6-Dinitrotoluene ,2-Dinitrobenzene Acenaphthene Nitroaniline ,4-Dinitrophenol D-191 Dibenzofuran ,4-Dinitrotoluene Nitrophenol-d Nitrophenol D-132

23 IDC/IPR Data IDC #1 IDC #2 IDC #3 IDC #4 Entry Identifier ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec EPA Limit 2,3,4,6-Tetrachlorophenol ,3,5,6-Tetrachlorophenol Fluorene-d Fluorene Chlorophenyl phenyl ether Diethylphthalate D Nitroaniline Phenanthrene-d ,6-Dinitro-2-methylphenol-d ,6-Dinitro-2-methylphenol D-181 Diphenylamine Azobenzene Bromophenyl phenyl ether Hexachlorobenzene D-152 Pentachlorophenol Phenanthrene Anthracene-d Anthracene Carbazole Di-n-butylphthalate Fluoranthene Pyrene Benzyl butyl phthalate D-152

24 IDC/IPR Data IDC #1 IDC #2 IDC #3 IDC #4 Entry Identifier ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec EPA Limit Benzidine Chrysene-d Benzo[a]anthracene Chrysene Bis(2-ethylhexyl)adipate ,3-Dichlorobenzidine D-262 Bis(2-ethylhexyl)phthalate Di-n-octyl phthalate Perylene-d Benzo[a]pyrene-d Benzo[a]pyrene Benzo[b]Fluoranthene Benzo[k]fluoranthene Indeno[1,2,3-cd]pyrene D-171 Dibenz[a,h]anthracene D-227 Benzo[g,h,i]perylene D-219

25 MDL MDL #1 MDL #2 MDL #3 MDL #4 MDL #5 MDL #6 MDL #7 MDL #8 STD Entry Identifier ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec EPA Limit DEV MDL EPA 1,4-Dichlorobenzene-d N-Nitrosodimethylamine-d N-Nitrosodimethylamine Pyridine Phenol-d Phenol Aniline Bis(2-chloroethyl)ether-d Bis(2-chloroethyl)ether Chlorophenol-d Chlorophenol ,3-Dichlorobenzene D ,4-Dichlorobenzene ,2-Dichlorobenzene Benzyl Alcohol ,2'-oxybis(1-chloropropane) Methylphenol Methylphenol-d /4-Methylphenol Hexachloroethane N-Nitrso-di-n-propylamine D Naphthalene-d Nirtrobenzene Nitrobenzene-d Nitrophenol-d Isophorone Nitrophenol ,4-Dimethylphenol Bis(2-chloroethoxy)methane ,4-Dichlorophenol-d ,4-Dichlorophenol ,2,4-Trichlorobenzene Naphthalene

26 MDL MDL #1 MDL #2 MDL #3 MDL #4 MDL #5 MDL #6 MDL #7 MDL #8 STD Entry Identifier ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec EPA Limit DEV MDL EPA 4-Chloroaniline-d Chloroaniline Hexachlorobutadiene Acenaphthene-d Methylnaphthalene Methylnaphthalene Chloro-3-methylphenol Hexachlorocyclopendadiene ,4,6-trichlorophenol ,4,5-Trichlorophenol Chloronaphthalene Nitroaniline ,4-Dinitrobenzene Dimethylphthalate-d Dimethylphthalate D ,3-Dinitrobenzene Acenaphthylene-d Acenaphthylene ,6-Dinitrotoluene ,2-Dinitrobenzene Acenaphthene Nitroaniline ,4-Dinitrophenol D Dibenzofuran ,4-Dinitrotoluene Nitrophenol-d Nitrophenol D ,3,4,6-Tetrachlorophenol ,3,5,6-Tetrachlorophenol Fluorene-d Fluorene Chlorophenyl phenyl ether Diethylphthalate D Nitroaniline n.d. < Phenanthrene-d

27 MDL MDL #1 MDL #2 MDL #3 MDL #4 MDL #5 MDL #6 MDL #7 MDL #8 STD Entry Identifier ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec ug/l % Rec EPA Limit DEV MDL EPA 4,6-Dinitro-2-methylphenol-d n.d. < ,6-Dinitro-2-methylphenol D Diphenylamine Azobenzene Bromophenyl phenyl ether Hexachlorobenzene D Pentachlorophenol Phenanthrene Anthracene-d Anthracene Carbazole Di-n-butylphthalate Fluoranthene Pyrene Benzyl butyl phthalate D Benzidine Chrysene-d Benzo[a]anthracene Chrysene Bis(2-ethylhexyl)adipate ,3-Dichlorobenzidine D Bis(2-ethylhexyl)phthalate Di-n-octyl phthalate Perylene-d Benzo[a]pyrene-d Benzo[a]pyrene Benzo[b]Fluoranthene Benzo[k]fluoranthene Indeno[1,2,3-cd]pyrene D Dibenz[a,h]anthracene D Benzo[g,h,i]perylene D

28 Expanded Methodology

29 EPA Methods (examples) EPA 8082 EPA 8081 EPA 1694 EPA 1664 EPA 1613 EPA 8151 EPA 1614 EPA 8310 EPA 8290 EPA 8330 EPA 8141 Any EPA 500 series SPE method

30 Examples Extraction Cartridge Clean-up Cartridge

31 Examples Validated Protocols with inline drying/cleaning PAH s with drying and/or Silica Gel clean-up Organochlorine Pesticides with drying and/or Florisil Organophosphorus Pesticides with Drying

32 Typical mid level OCP Recoveries LCS LCS LCS LCS Mean Analyte #1 #2 #3 #4 Rec RSD α-bhc 102.5% 106.8% 106.3% 107.9% 106% 2.2% γ-bhc (Lindane) 102.1% 105.9% 105.5% 107.0% 105% 2.0% β-bhc 96.3% 98.0% 100.9% 100.0% 99% 2.1% δ-bhc 107.7% 110.6% 113.0% 111.8% 111% 2.1% Heptachlor 86.1% 106.4% 107.2% 101.6% 100% 9.8% Aldrin 68.7% 80.2% 79.6% 77.0% 76% 6.9% Heptachlor Epoxide 99.5% 100.0% 102.1% 103.6% 101% 1.9% γ-chlordane 95.5% 88.7% 92.8% 91.3% 92% 3.1% Endosulfan I 93.2% 93.4% 96.8% 96.2% 95% 2.0% α-chlordane 98.9% 97.2% 100.7% 101.8% 100% 2.0% 4,4'-DDE 91.8% 92.3% 97.1% 94.5% 94% 2.6% Dieldrin 101.2% 99.3% 103.0% 104.3% 102% 2.1% Endrin 108.2% 107.6% 112.9% 113.3% 111% 2.7% 4,4'-DDD 104.6% 97.2% 105.5% 104.3% 103% 3.7% Endosulfan II 102.5% 97.7% 102.7% 104.1% 102% 2.7% Endrin Aldehyde 85.4% 77.6% 89.4% 84.1% 84% 5.8% 4,4'-DDT 105.2% 97.5% 106.9% 105.9% 104% 4.1% Endosulfan Sulfate 104.3% 99.1% 104.5% 106.2% 104% 3.0% Methoxychlor 104.8% 90.9% 101.2% 103.4% 100% 6.3% Endrin Ketone 102.7% 93.1% 101.6% 101.8% 100% 4.5% Surrogate TCMX 66% 73% 75% 75% 72.3% 5.7% PCB % 69% 74% 84% 78.7% 11.2%

33 Typical mid level OPP Recoveries Compound Position #1 Position #2 Mean Rec RSD Compound Position #1 Position #2 Mean Rec RSD Alachlor % 2.4% Mevinphos % 4.2% Ametryn % -0.9% MGK % 14.0% Atraton % 7.5% Molinate % 6.6% Atrazine % 1.6% Napropamide % 4.8% Bromacil % -19.2% Norflurazon % 1.5% Butachlor % -0.2% Pebulate % 14.5% Butylate % 2.2% Prometon % -3.3% Carboxin % 16.6% Prometryn % -3.8% Chlorophram % 10.0% Pronamide+* % 2.3% Cycloate % 5.2% Propazine % 3.7% Dichlorvos % 7.9% Simazine % -0.9% Diphenamid % -9.7% Simetryn % 1.3% Disulfoton* % 19.3% Stirofos % -1.6% EPTC % 9.2% Tebuthiuron % 4.2% Ethoprop % 4.4% Terbacil % -10.3% Fenamiphos % -18.5% Terbufos+* % 2.0% Fenarimol % 8.9% Terbutryn % -8.4% Fluridone % 8.5% Triademefon % 16.6% Hexazinone % 3.6% Tricyclazole % 5.9% Methyl Paraoxon % -3.8% Vernolate % 4.5% Metolachlor % 2.0%

34 Typical mid level PAH Recoveries Compound LCS LCSD RPD Naphthalene 92.0% 86.0% -6.7% 2-Methylnaphthalene 93.6% 86.8% -7.5% Acenaphthylene 97.8% 85.2% -13.8% Acenaphthene 96.3% 107.2% 10.7% Fluorene 101.6% 109.6% 7.6% Phenanthrene 97.6% 106.8% 9.0% Anthracene 107.2% 109.6% 2.2% Fluoranthene 108.0% 106.8% -1.1% Pyrene 110.0% 108.4% -1.5% Benzo[a]anthracene 110.0% 108.0% -1.8% Chrysene 108.8% 108.4% -0.4% Benzo[b]fluoranthene 109.2% 106.8% -2.2% Benzo[k]fluoranthene 108.8% 106.4% -2.2% Benzo[a]pyrene 110.0% 108.0% -1.8% Indeno[1,2,3-c,d]pyrene 98.0% 94.4% -3.7% Dibenzo[a,h]anthracene 101.6% 105.2% 3.5% Benzo[g,h,i]perylene 109.6% 106.4% -3.0%

35 Summation Fully Automated 625/8270 extractions Expandable to meet any SPE method Capable of performing in line extract drying and/or Cartridge extract clean-ups In-line evaporation with direct to GC vial tubes.

36 Questions?

Diffusion Results for Rigid Porous Polyethylene Samplers

Diffusion Results for Rigid Porous Polyethylene Samplers Table 1: Metals 21-day Deployment Metals (mg/l)* (mg/l) * (mg/l)* (mg/l) * Antimony 0.0878 0.0810 92 0.0847 0.0799 94 Arsenic 0.0840 0.0768 91 0.0853