SBSE & “in liner” derivatization, for the analysis of ...apinternationalsbsemeeting.com/2013/SBSE2013... · Spent caustics = Petrochemical wastewaters ... •Biological treatment

)20/02/2013 Veolia Environnement Recherche & Innovation

SBSE & “in liner” derivatization, for the analysis of polar substances in petroleum matrices

Christophe Tondelier

Introduction : SBSE at Veolia

Analytical support for Veolia R&D :

• Method developments

Disinfection By-Products / Taste & Odor in drinking water

French regulation (RSDE, DCE…) - COFRAC

• Treatment processes evaluation

Waste water treatments (municipal, industrial, Oil & Gas…)

Drinking water production

• Passive sampling tools

ARISTOT / PLATON

POCIS

• Characterizations (technical assistances)

Targeted (contaminants database) & untargeted screening

Rivers / Waste / Sea waters / Soil

LC-HRMS / GC-MS / GCxGC-MS

2/20/2013 Veolia Environnement Recherche & Innovation 2GCxGC-TOF(MS) chromatogram

LECO – Pegasus IV

Water taste & Odor

Refinery waste water

ARISTOT sampler

)20/02/2013 Veolia Environnement Recherche & Innovation

SBSE & “in liner” derivatization, for the analysis of polar substances in petroleum matrices

20/02/2013 Veolia Environnement Recherche & Innovation 4

Outline

1. Context1. Spent caustics in refinery plants

2. Naphthenic acids

2. Analytical development1. Naphthenic acids characterization

2. SBSE & spent caustics

3. Analytical configuration

4. In liner derivatization - theory

3. Applications1. Spent caustics analysis

2. A Naphthenic Acids Index

4. Conclusion / perspectives


Outline


2. Naphthenic acids









Context – Spent caustics in refinery plants

Spent caustics = Petrochemical wastewaters

• Sulfidic SC � hydrocarbon wash for H2S removal

Loaded in sulfurous compounds

• Phenolic SC � cracked gasoline treatment

Recycled � small volume

Highly loaded in phenols and naphthenic acids (>80% TOC)

pH # 14 - TOC ~ 100 g/L

�� High toxicity

Removal pathways

• Biological treatment non available (toxicity)

• Incineration in treatment plants for hazardous waste

High costs & environmental impact

• Veolia R&D studies for alternative treatments

Analytical methods for rapid treatments evaluation


Naphthenic acids

NA structures where R is an alkyl chain, Z describes the hydrogen deficiency, and m is the

number of CH2 units.

Major contributors to the toxicity of refinery wastewaters [1]

Complex mixture of alkyl-substituted acyclic and cycloaliphatic carboxylic acids [2]

[1] Fedorak et al. Chemosphere 50 (2003) 1265–1274

[2] Fedorak et al. Chemosphere 60 (2005) 585–600

plenty of molecules

/ formula


Outline


2. Naphthenic acids









Naphthenic acids characterization

Literature :

GC (or LC) separation – FID, MS… (Fedorak et al.)

Extraction with CH2Cl2 at pH 2

Silylation derivatization

Commercial standard mixture

• Mixture of Napht. Acids (NA) containing pentacarbonated cycles (1, 2 & 3)

Preparation of standard solution in dichloromethane (100 ppm)

Derivatization : 1mL solution + 50 µL BSTFA � 30 min @ 80°C

• GC/MS - 1/50 split injection

Groups of unknown NA

MS : Intense ions, Ø Mol. ions

Low sensitivity (injector degradation ?)

• COC injection + Negative CI (CH4)

Identification of NA groups

Cx H2x+1

Cy H2y

COOSi(CH3)3

Cx H2x+1

Cy H2y

COOSi(CH3)3

6.00 8.00 10.00 12.00 14.00 16.00 18.00

2000

4000

6000

8000

10000

12000

Time (min)

Abundance

6.00 8.00 10.00 12.00 14.00 16.00 18.006.00 8.00 10.00 12.00 14.00 16.00 18.00



+ 14

CH2



17.00 18.00 19.00 20.00 21.00 22.00 23.00 24.00 25.00 26.00 27.000

200000

600000

1000000

1400000

1800000

2200000

Time (min)

Abundance

m/z = 215 � C12H22O2

m/z = 229 � C13H24O2

m/z = 243 � C14H26O2

m/z = 257 � C15H28O2

m/z = 271 � C16H30O2

m/z = 285 � C17H32O2

6 main mono-cyclic NA – Reconstituted Ion Chromatogram



17.00 18.00 19.00 20.00 21.00 22.00 23.00 24.00 25.00 26.00 27.000

20000

40000

60000

80000

100000

120000

Time (min)

Abundance

m/z = 241 � C14H24O2

m/z = 255 � C15H26O2

m/z = 269 � C16H28O2

m/z = 283 � C17H30O2

m/z = 297 � C18H32O2

m/z = 311 � C19H34O2

6 main di-cyclic NA – Reconstituted Ion Chromatogram


SBSE & spent caustics ?

Spent caustics high TOC : Dilution required � low ppm level

SBSE suitability for NA ?

• Example : a monocyclic NA

C12H22O2 � 198 g/mol

Log ko/w = 4.74

SBSE recoveries for 100 mL water extraction

pKa ~ 5 � Extraction in acid condition (3 drops of 37% HCl)

• SBSE (at pH 2) is suitable for NA extraction

For GC analysis :

• Carboxylic acids function � DERIVATIZATION required

Idea : Post-extraction derivatization step named “in liner derivatization”

CH3

OH

O

Twister recovery calculator :


Analytical configuration

MPS 2Gerstelized System :

• Agilent 6890 GC

• Agilent 5973 MS

• MultiPurpose Sampler

• TDU

Twister desorption

• Gripper

Automated Tube Exchange

TDU Liquid injections

• CIS 4 PTV inlet

Cryo-cooling

• Restek Rxi-5Sil MS Column

30m x 0.25mm x 0.25µm


In Liner derivatization - theory

GerstelTDU

Cooled Zone(-70°C)

Helium

Split ventCIS liner

Liner option(PDMS foam)

AnalytesGerstel

TDU

Helium

Analytical column

Twister

TDU liner

Thermal Desorption

Cryo-focalisation

Constant cryo-cooling

GerstelCIS 4

STEP 1STEP 2



GerstelTDU

Cooled Zone(-70°C)

Helium

Split vent


GerstelTDU

Helium

Analytical column

Cryo-focalisation


STEP 3



GerstelTDU

Cooled Zone(-70°C)

Helium

Split vent


GerstelTDU

Helium

Analytical column

1 µL BSTFA

ATEX

BSTFA injection

Cryo-focalisation


STEP 3


GerstelTDU

Cooled Zone(-70°C)

Helium

Split vent


GerstelTDU

Helium

Analytical column

Cryo-focalisation



TDU desorption

BSTFA volatilization

STEP 4


GerstelTDU

Heated Zone(300°C)

Helium

Split vent

GerstelTDU

Helium

Analytical column

CIS desorption (slow)

� BSTFA vaporization

� Analytes derivatization


STEP 5



GerstelTDU

Heated Zone(300°C)

Helium

Split vent

GerstelTDU

Helium

Analytical column

TMS derivatives

vaporization

& separation

STEP 6


Outline


2. Naphthenic acids









Spent caustic analysis

GC/MS Total Ion chromatograms

12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.000

4000000

8000000

1.2e+07

1.6e+07

2e+07

2.4e+07

2.8e+07

3.2e+07

3.6e+07

4e+07

4.4e+07

4.8e+07

5.2e+07

Time (min)

Abundance

Spent caustic sample

NA mixture 500 ppb

D3

D4


Time-->

13.00 15.00 17.00 19.00 21.00 23.000

1000000

2000000

3000000

4000000

13.00 15.00 17.00 19.00 21.00 23.000

200000

400000

600000

800000

1000000

GC/MS Reconstituted Ion chromatogramsNaphthenic acids distribution

Sample 1

NA mixture 500 ppb


Ion 215.00 � C12H22O2

Ion 229.00 � C13H24O2

Ion 243.00 � C14H26O2

Ion 257.00 � C15H28O2

Ion 271.00 � C16H30O2

Ion 285.00 � C17H32O2

Hexacarbonated cycles

Pentacarbonated cycles



GC/MS Reconstituted Ion chromatogramsPhenolic compounds distribution

13.00 14.00 15.00 16.00 17.00 18.00 19.000

200000

400000

600000

800000

1000000

1200000

1400000

1600000

1800000

Time (min)

Abundance

Si

O m/z = 165 � C1 - Phenols

Si

O

m/z = 179 � C2 - Phenols




A Naphthenic Acids « INDEX »

Calibration in SIM mode

• Target ion m/z = 117 : O

O CH3

CH3

CH3

Si

+

m/z = 117

TMS-carboxylic acids

12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00

4000000

8000000

1.2e+07

1.6e+07

2e+07

2.4e+07

2.8e+07

3.2e+07

3.6e+07

4e+07

4.4e+07

4.8e+07

5.2e+07

Time (min)

Abundance

Sample TIC

Sample RIC : m/z = 117


A Naphthenic Acids « INDEX »

• RIC (m/z = 117) integration

Global quantification of all TMS naphthenic acids

Internal Standard : 2,3,5-trichlorophenol (TMS derivative)

• Calibration

ResultsTreatments evaluation

Total Area

y = 0,3296x + 2,9868R2 = 0,9817

0,0

20,0

40,0

60,0

80,0

100,0

0 50 100 150 200 250 300

NA conc. (ppb)

To

tal N

A /

IS a

rea

Treatment

time0 x hours y hours

NA conc. 43.6 g/L 21.9 g/L 7.0 g/L

Elimination - 50% 84%


Conclusion & perspectives

SBSE - In liner derivatization - TD-GC/MS

• ☺ Simple, rapid & solventless extraction protocol

• ☺ Automated in line derivatization GC method

• � High amount BSTFA injection

BSTFA venting before analytes desorption

For spent caustic analysis

• A Naphthenic Acids index

• Treatments evaluation

Perspectives

• ☺ SBSE for polar compounds analysis

• Other applications :

Halogenated phenols in drinking water (medicinal taste)

Endocrine disruptors (hormones) in municipal waste waters


Documents

SBSE & “in liner” derivatization, for the analysis of ...apinternationalsbsemeeting.com/2013/SBSE2013... · Spent caustics = Petrochemical wastewaters ... •Biological treatment