1. ENVIRONMENTAL ANALYSIS I. Solid Phase Extraction
resin-based sorbents

2. Resin vs. Silica Sorbents
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
* Methacrylate - ester hydrolyzes at high pH

3. Why Use Resin-Based Sorbent?
Increased surface area ( ~ 1100 m2/g )
Decreased bed size
Extract a wide range of polarities
Resistant to pH extremes

4. Types of ISOLUTE Resins
C-CH2-
CH-CH2-
-CH-CH2
-CH-CH2-
CH-CH2-
-CH-CH2
-CH-CH2-
C-CH2- HO OH OH HO
ISOLUTE 101
Polystryrene Divinylbenzene
ISOLUTE ENV+
Hydroxylated Polystryrene
Divinylbenzene

5. Polyvinylpyrrolidone
CH - CH2
CH - CH2 N O

6. Polyamide (Nylon) O O O O R’ R’ R N H N H R N H N H

7. Methacrylate
C=O
CH2 - CH O
CH3
O=C

8. Wettabilities Name Wettability ISOLUTE® ENV+ (Hydrox PSDVB)
sinks (5-10 sec)
Lichrolut EN (Hydrox PSDVB)
sinks (5-10 sec)
MCI CQP (methacrylate)
sinks (5-10 sec)
ISOLUTE® 10Y (Polyamide)
sinks (20-30 sec)
Tosohaas HW (methacrylate)
sinks (20-30 sec)
Spe-ed RP105
sinks (>1 min)
Reillex HP (Polyvinylpyrrolidone)
sinks (<5 sec)
ISOLUTE® 10Z (PSDVB)
floats (5-10 sec)
Bond-Elut ENV
floats (5-10 sec)
ISOLUTE® 101 (PSDVB)
floats (5-10 sec)
Oasis HLB (divinylbenzene co)
floats (>1 min)
ISOLUTE® 10W (PSDVB)
floats (<5 sec)
Bond-Elut PPL (PSDVB bromin)
floats (<5 sec)
ISOLUTE® 10X (PSDVB)
floats (5-10 sec)

9. Swelling Name Swelling (acetone) ISOLUTE® ENV+ (Hydrox PSDVB)
none observed
Lichrolut EN (Hydrox PSDVB)
none observed
MCI CQP (methacrylate)
20-30%
ISOLUTE® 10Y (Polyamide)
none observed
Tosohaas HW (methacrylate)
20-30%
Spe-ed RP105
5-10%
Reillex HP (Polyvinylpyrrolidone)
20-30%
ISOLUTE® 10Z (PSDVB)
5-10%
Bond-Elut ENV
5-10%
ISOLUTE® 101 (PSDVB)
5-10%
Oasis HLB (divinylbenzene co)
5-10%
ISOLUTE® 10W (PSDVB)
20-30%
Bond-Elut PPL (PSDVB bromin)
10-20%
ISOLUTE® 10X (PSDVB)
none observed

10. Physical Characteristics
Name Avg Particle Size Surface Area
ENV+ 90
1160
Lichrolut EN 70
1200
MCI CQP (methacrylate) 37
ISOLUTE 10Y 35
Tosohaas HW (methacrylate) 45
Spe-ed RP105
>100
Reillex HP (PVP)
300 90
ISOLUTE 10Z 54
500
Bond-Elut ENV
125
700
ISOLUTE 101 60
500
Oasis HLB 30
831
ISOLUTE 10W
125
Bond-Elut PPL
125
500
ISOLUTE 10X 35
510

11. Capacity versus Surface Area
100
200
300
400
500
1000
1500
ENV+
Lichrolute
10 Z
BondElut PPL
Caffeine Capacity mg/g
10 X
BondElut Env
101
Oasis HLB
Reillex HP (PVP)
Surface Area (m2)

12. ISOLUTE ENV+ Sorbent Polystyrene Divinylbenzene Polymer
High Surface Area ( ~ 1100 m2/g )
Highly Crosslinked
Narrow Particle Size Distribution
Reproducible flow characteristics
High sample flow rates
Fines Free (trouble-free analysis)

13. Problem Analytes Polar Water soluble
Unretained on non-polar silica based sorbents
Applications requiring “salting out”

14. Phenols
Average recovery of phenols on C18(EC)...
< 50 % !

15. Extraction of Phenols 1. Sample pre-treatment 2. Column solvation
Methanol
Water at pH = 2
One liter
Deionized water
1. Sample pre-treatment
2. Column solvation
3. Column equilibration
4. Sample application
5. Interference elution
6. Analyte elution
ISOLUTE ENV+, 150 mg / 3 mL and 200 mg/6 mL

16. Recovery of Phenols Flow Rate Analyte Phenol 95.1 100.1
2-Chlorophenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
15 mL / min mL / min
(150 mg/3 mL) (200 mg/6 mL)

17. Extraction of Explosives
None
THF ( 2 mL soak 4 min, then 4 mL)
Sample pre-treatment
Column conditioning
Column equilibration
Sample application
Interference elution
Analyte elution
4 mL water
30 mL/min + Bottle Rinse
(10 mL MeOH, 10 mL water)
10 mL water, 10 min N2 or CO2
Two x 1.5 mL ACN

18. Recovery of Explosives
1,3-Dinitrobenzene
Tetryl
Nitrobenzene
TNT
2-Nitrotoluene
4-Nitrotoluene
3-Nitrotoluene
Average 98
102
106 94 91 97
Sample volume: 1 liter
Analyte conc: 0.04 ppb

19. Recovery of Herbicides
Recovery Std Dev
Dicamba
Dichloroprop
Chloramben
Dacthal, MA
Norflurazon
Silvex
Dinoseb
MCPA
Acifluorfen
Bentazon
2,4-D
AVG
ISOLUTE ENV+
(500 mg, 6 mL)
on AutoTrace
Conc: 500 ppt
Volume: 1 Liter

20. Recovery of Carbamates and Urea Pesticides
Recovery Std Dev
Methiocarb
Fluometuron
Linuron
Propoxur
Neburon
Carbaryl
Barban
Carbofuran
Diuron
AVG
ISOLUTE ENV+
(500 mg, 6 mL)
on AutoTrace
Conc: 500 ppt
Volume: 1 Liter

21. C8 / 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 herbicides
Phenols
PAHs
Phthalate esters
Ref: Davi et al, Intern. J. Environ. Anal. Chem 74 (1-4)

22. Multiresidue SPE Method
Acidify to pH2 with HCl
Add 10 ml methanol
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)
C8 / ENV+ layered column
700 mg / 6 ml

23. Base-Neutral Herbicides

24. Acidic Herbicides and Phthalates

25. Phenolic Compounds

26. PAHs

27. ENV+ vs. Carbopack Dichlobenil 76 3 Chlorothalonil 57 4 ISOLUTE ENV+
(500 mg, 6 mL)
on AutoTrace
Recovery Std Dev
Dichlobenil
Chlorothalonil 57 4
Conc: 500 ppt
Volume: 1 Liter NOT RETAINED ON CARBOPACK!