ENVIRONMENTALENVIRONMENTALANALYSISANALYSISI. Solid Phase ExtractionI. Solid Phase Extraction

ENVIRONMENTALENVIRONMENTALANALYSISANALYSISI. Solid Phase ExtractionI. Solid Phase Extraction

resin-based sorbents

Resin vs. Silica SorbentsResin vs. Silica SorbentsResin vs. Silica SorbentsResin vs. Silica Sorbents

* Methacrylate - ester hydrolyzes at high pH

Silica Resin

Stability (pH) limited (2-8) broad (0-14) *

Interactions multiple primarily hydrophobic

Capacity 1-5% up to 50%

Selectivity high low

Conditioning required sometimes required

Why Use Resin-Based Sorbent?Why Use Resin-Based Sorbent?Why Use Resin-Based Sorbent?Why Use Resin-Based Sorbent?

Increased surface area ( ~ 1100 m2/g )

Decreased bed size

Extract a wide range of polarities

Resistant to pH extremes

Types of ISOLUTE ResinsTypes of ISOLUTE ResinsTypes of ISOLUTE ResinsTypes of ISOLUTE Resins

ISOLUTE ENV+Hydroxylated Polystryrene Divinylbenzene

OH

CH-CH2 -

-CH-CH2-CH-CH2

-

C-CH2-CH-CH

2-CH-CH2

--CH-CH2-

HO

OH

OH

OH

HO

C-CH2-

CH-CH2 -

-CH-CH2-CH-CH2

-

CH-CH2-

CH-CH2--CH-CH

2-

ISOLUTE 101Polystryrene Divinylbenzene

HO

PolyvinylpyrrolidonePolyvinylpyrrolidonePolyvinylpyrrolidonePolyvinylpyrrolidone

N

CH - CH2

O

N

CH - CH2

O

Polyamide (Nylon)Polyamide (Nylon)Polyamide (Nylon)Polyamide (Nylon)

R NH

R’

NH

R NH

R’

NH

O O O O

MethacrylateMethacrylateMethacrylateMethacrylate

C=O

CH2 - CH

O

CH3

CH2 - CH

O=C

O

CH3

WettabilitiesWettabilitiesWettabilitiesWettabilities

Name Wettabilitysinks (5-10 sec)sinks (5-10 sec)sinks (5-10 sec)sinks (20-30 sec)sinks (20-30 sec)sinks (>1 min)sinks (<5 sec)floats (5-10 sec) floats (5-10 sec)floats (5-10 sec)floats (>1 min)floats (<5 sec)floats (<5 sec)floats (5-10 sec)

ISOLUTE® ENV+ (Hydrox PSDVB)Lichrolut EN (Hydrox PSDVB)MCI CQP (methacrylate)ISOLUTE® 10Y (Polyamide)Tosohaas HW (methacrylate)Spe-ed RP105Reillex HP (Polyvinylpyrrolidone)ISOLUTE® 10Z (PSDVB)Bond-Elut ENVISOLUTE® 101 (PSDVB)Oasis HLB (divinylbenzene co)ISOLUTE® 10W (PSDVB)Bond-Elut PPL (PSDVB bromin)ISOLUTE® 10X (PSDVB)

SwellingSwellingSwellingSwelling

Swelling (acetone)none observednone observed20-30%none observed20-30%5-10%20-30%5-10%5-10%5-10%5-10%20-30%10-20%none observed

Name

ISOLUTE® ENV+ (Hydrox PSDVB)Lichrolut EN (Hydrox PSDVB)MCI CQP (methacrylate)ISOLUTE® 10Y (Polyamide)Tosohaas HW (methacrylate)Spe-ed RP105Reillex HP (Polyvinylpyrrolidone)ISOLUTE® 10Z (PSDVB)Bond-Elut ENVISOLUTE® 101 (PSDVB)Oasis HLB (divinylbenzene co)ISOLUTE® 10W (PSDVB)Bond-Elut PPL (PSDVB bromin)ISOLUTE® 10X (PSDVB)

Physical CharacteristicsPhysical CharacteristicsPhysical CharacteristicsPhysical Characteristics

Name Avg Particle Size Surface AreaName Avg Particle Size Surface Area

ENV+Lichrolut ENMCI CQP (methacrylate)ISOLUTE 10YTosohaas HW (methacrylate)Spe-ed RP105Reillex HP (PVP)ISOLUTE 10ZBond-Elut ENVISOLUTE 101Oasis HLBISOLUTE 10WBond-Elut PPLISOLUTE 10X

9070373545

>100300

54125

6030

125125

35

11601200

90500700500831

500510

Capacity versus Surface AreaCapacity versus Surface AreaCapacity versus Surface AreaCapacity versus Surface Area

0

100

200

300

400

500

0 500 1000 1500Surface Area (m2)

Caf

fein

e C

apac

ity

mg

/g

Reillex HP (PVP)

10 Z

BondElut PPL

10 X

101

ENV+

Lichrolute

BondElut Env

Oasis HLB

ISOLUTE ENV+ SorbentISOLUTE ENV+ SorbentISOLUTE ENV+ SorbentISOLUTE ENV+ Sorbent

Polystyrene Divinylbenzene Polymer

High Surface Area ( ~ 1100 m2/g )

Highly Crosslinked

Narrow Particle Size DistributionReproducible flow characteristics

High sample flow rates

Fines Free (trouble-free analysis)

Problem AnalytesProblem AnalytesProblem AnalytesProblem Analytes

Polar

Water soluble

Unretained on non-polar silica

based sorbents

Applications requiring “salting out”

PhenolsPhenolsPhenolsPhenols

Average recovery of phenols on C18(EC)...

< 50 % !

Extraction of PhenolsExtraction of PhenolsExtraction of PhenolsExtraction of Phenols

1. Sample pre-treatment

2. Column solvation

3. Column equilibration

4. Sample application

5. Interference elution

6. Analyte elution

pH = 2

Methanol

Water at pH = 2

One liter

Deionized water

Methanol

ISOLUTE ENV+, 150 mg / 3 mL and 200 mg/6 mL

Recovery of PhenolsRecovery of PhenolsRecovery of PhenolsRecovery of Phenols

Flow Rate

Analyte

Phenol 95.1 100.1

2-Chlorophenol 100.1 100.1

2,4-Dichlorophenol 100.8 100.4

2,4,6-Trichlorophenol 96.8 97.4

15 mL / min 60 mL / min (150 mg/3 mL) (200 mg/6 mL)

Extraction of ExplosivesExtraction of ExplosivesExtraction of ExplosivesExtraction of Explosives

Sample pre-treatmentSample pre-treatment

Column conditioningColumn conditioning

Column equilibrationColumn equilibration

Sample applicationSample application

Interference elutionInterference elution

Analyte elutionAnalyte elution

NoneNone

THF THF ( 2 mL soak 4 min, then 4 mL)( 2 mL soak 4 min, then 4 mL)

4 mL water4 mL water

30 mL/min + Bottle Rinse30 mL/min + Bottle Rinse (10 mL MeOH, 10 mL water)(10 mL MeOH, 10 mL water)

10 mL water, 10 mL water, 1010 min N min N2 2 or COor CO22

Two x Two x 1.51.5 mL mL ACNACN

Recovery of ExplosivesRecovery of ExplosivesRecovery of ExplosivesRecovery of Explosives

1,3-DinitrobenzeneTetryl

NitrobenzeneTNT

2-Nitrotoluene4-Nitrotoluene3-Nitrotoluene

Average

98102

98106

949191

97Sample volume: 1 liter Analyte conc: 0.04 ppb

Recovery of HerbicidesRecovery of HerbicidesRecovery of HerbicidesRecovery of Herbicides

RecoveryRecovery Std DevStd DevDicambaDicamba 8282 33DichloropropDichloroprop 8484 44ChlorambenChloramben 7373 66Dacthal, MADacthal, MA 6969 55NorflurazonNorflurazon 7373 66SilvexSilvex 9090 55DinosebDinoseb 7272 14 14MCPAMCPA 8080 33AcifluorfenAcifluorfen 7171 44BentazonBentazon 8989 332,4-D2,4-D 8383 33

AVGAVG 7878 55

Conc: 500 pptConc: 500 pptVolume: 1 LiterVolume: 1 Liter

ISOLUTE ENV+(500 mg, 6 mL)on AutoTrace

Recovery of Carbamates Recovery of Carbamates and Urea Pesticidesand Urea PesticidesRecovery of Carbamates Recovery of Carbamates and Urea Pesticidesand Urea Pesticides

Conc: 500 pptConc: 500 pptVolume: 1 LiterVolume: 1 Liter

ISOLUTE ENV+(500 mg, 6 mL)on AutoTrace

RecoveryRecovery Std DevStd Dev

MethiocarbMethiocarb 8484 77FluometuronFluometuron 9090 99LinuronLinuron 7979 11PropoxurPropoxur 8585 44NeburonNeburon 7575 55CarbarylCarbaryl 9292 99BarbanBarban 85 85 13 13CarbofuranCarbofuran 8888 44DiuronDiuron 8585 66

AVGAVG 8585 66

C8 / ENV+ Layered ColumnsC8 / ENV+ Layered ColumnsC8 / ENV+ Layered ColumnsC8 / ENV+ Layered Columns

A layered column approach has been applied to the extraction of a broad range of organic pollutants from

drinking water and surface water (EEC directives 80/778 and 75/440) to form an efficient multiresidue

extraction approach. Analyte classes extracted:Base neutral herbicides

Acidic herbicidesPhenols

PAHsPhthalate esters

Ref: Davi et al, Intern. J. Environ. Anal. Chem 74 (1-4) 155-166

Multiresidue SPE MethodMultiresidue SPE MethodMultiresidue SPE MethodMultiresidue SPE Method

1. Sample pre-treatment

2. Column solvation

3. Column equilibration

4. Sample application

5. Interference elution

6. Analyte elution

10 ml methanol

10 ml water

1L sample – 60 ml / min

Dry 10 mins under vacuum

10 ml acetone / ethyl acetate

(1:1, v/v)

Acidify to pH2 with HClAdd 10 ml methanol

C8 / ENV+ layered column700 mg / 6 ml

Base-Neutral HerbicidesBase-Neutral HerbicidesBase-Neutral HerbicidesBase-Neutral Herbicides

Compound % Recovery % RSDmetribuzin 90 4atrazine 92 3desethylatrazine 89 7ametrine 90 2desisopropylatrazine 85 5terbutyline 95 2alachlor 82 4metolachlor 95 3propachlor 80 4molinate 75 15propanil 75 5oxadiazon 85 3tiobencarb 75 6

Acidic Herbicides and Acidic Herbicides and PhthalatesPhthalatesAcidic Herbicides and Acidic Herbicides and PhthalatesPhthalates

Compound % Recovery % RSDAcidic herbicides2,4D 86 8MCPA 95 6MCPB 94 5MCPP 92 5bentazone 88 3Phthalate estersdiethylhexyl phthalate 92 3dibutyl phthalate 95 3benzylbutyl phthalate 96 2diethyl phthalate 98 2dimethyl phthalate 98 2dioctyl phthalate 94 5

Phenolic CompoundsPhenolic CompoundsPhenolic CompoundsPhenolic Compounds

Compound % Recovery % RSDphenol 84 102-chlorophenol 90 82-methylphenol 96 53-methylphenol 96 44-methylphenol 96 62-nitrophenol 87 72,4-dimethylphenol 95 62,4-dichlorophenol 90 102,6-dichlorophenol 90 84-chloro-3-methylphenol 86 72,4,6-trichlorophenol 85 112,4-dinitrophenol 87 104-nitrophenol 90 74,6-dinitro-2-methylphenol 90 6pentachlorophenol 85 10

PAHsPAHsPAHsPAHs

Compound % Recovery % RSDnaphthalene 87 4acenaphthalene 90 3acenaphthene 90 4fluorene 92 4phenanthrene 94 4anthracene 95 3fluoranthene 95 2pyrene 96 2benzo(a)anthracene 96 3chrysene 96 5benzo(a)fluoranthene 98 3benzo(k)fluoranthene 95 3benzo(a)pyrene 95 2indeno(1,2,3 cd)pyrene 93 3dibenzo(a,h)anthracene 95 4benzo(ghi)perylene 96 4

ENV+ vs. CarbopackENV+ vs. CarbopackENV+ vs. CarbopackENV+ vs. Carbopack

RecoveryRecovery Std DevStd Dev

DichlobenilDichlobenil 7676 33

ChlorothalonilChlorothalonil 5757 44

Conc: 500 pptConc: 500 ppt

Volume: 1 Liter Volume: 1 Liter NOT RETAINED ON CARBOPACK!NOT RETAINED ON CARBOPACK!

ISOLUTE ENV+(500 mg, 6 mL)on AutoTrace