DETERMINATION OF OIL AND GREASE IN WATER BY HEADSPACE-MASS SPECTROMETRY

Universidad de Salamanca

Mara Esther Fernndez Laespada, Yolanda Gonzlez Martn, Jos Luis Prez Pavn, Carmelo Garca Pinto and Bernardo Moreno Cordero
Departamento de Qumica Analtica, Nutricin y Bromatologa; Universidad de Salamanca. 37008 Salamanca. ESPAA.

Introduction
Different analytical procedures have been proposed for the determination of the conventional pollutant oil and grease, related with hydrocarbons, vegetable oils, animal fats, waxes, soaps, greases and related matter in waters. As a result of the complexity of the samples the definition of oil and grease is based on the procedure used, which can alter the amount and composition of the material extracted. Standard protocols in polluted waters propose gravimetric or infrared spectrometric procedures, with previous liquid-liquid extraction or solid-phase extraction. In this work we propose the use of Headspace-Mass Spectrometry, which has a series of advantages because the sample preparation steps are eliminated and no solvent is needed. A three component synthetic oil (n-hexadecane, isooctane and benzene) has been used as the calibration standard.

GERSTEL ChemSensor 4440 (Headspace-Mass Spectrometer)

Box-Behnken experimental design

Experimental plan
Variable
HS generation time (min) (A) HS generation temp. (C) (B) Salt content (g/L NaCl) (C) Experiment* 1 2 3 4 5 6 7 8 9 10 11 12 Centre Var. A 10 40 25 25 10 40 25 25 10 10 40 40 25 Var. B 50 50 50 50 80 80 80 80 65 65 65 65 65 10 50 2

Experimental conditions
Response surfaces
Response m/z = 57
Temperatures HEADSPACE SAMPLER Oven Loop Transfer line Time Head space generation Injection 80 C 120 C 130 C 40 min 1 min

Regression coefficients and P-values

Level Term Intercept A B C AxB AxC BxC AxA BxB CxC m/z=57 Coefficient P-value 7.78e+6 1.87e+4 7.02e+4 9.51e+3 1.57e+5 -4.67e+4 1.70e+4 -1.17e+4 -1.71e+5 -3.73e+5 m/z 57 71 78 85 99 0.000* 0.024* 0.000* 0.268 0.147 0.661 0.873 0.934 0.230 0.012* m/z=78 Coefficient 2.93e+6 1.87e+4 1.52e+4 2.04e+3 4.88e+4 -1.96e+4 7.52e+3 -5.03e+4 -6.49e+4 -1.34e+5 Lack of fit 0.584 0.236 0.832 0.216 0.608 P-value 0.000* 0.000* 0.000* 0.342 0.074 0.464 0.778 0.160 0.073 0.001* High
40 80 30 Var. C 16 16 2 30 16 16 30 2 30 2 2 30 16

Low

40 25 10 50 65 Temperature (C)

Ti m
Response 40

80
MASS SPECTROMETER Data acquisition time 1.0 min 49-150 da

e (m
25

in ) Ti m e (m in

m/z = 78

Mass range

Statistical Packages
80 65 10 50 Temperature (C)

The Unscrambler v7.6 SR-1 Pirouette v 3.0

* Most significant variables and interaction effects (P-value <0.05)

* All experiments were made in triplicate

Signals obtained
Calibration samples
25
Found (ppm)

Quantification: Oil and grease in water by PLS

PLS Calibration (UHQ water samples)
Found (ppm)

PLS Prediction (tap water samples)

25 15 5 5 15
Added (ppm)

Error analysis
SEP r Slope 5 25 Intercept 1.330 0.993 0.935 0.109

Signal(E+06)

80

15

60

5
40 Found (ppm)

PLS Prediction (river water samples)

5 25
Added (ppm)

20 r

Error analysis
SEP 1.238 0.997 0.915 0.242

5
20

15

10 5 0 10 20
Added (ppm)

Error analysis
0 44 84 124

Slope 0.767 0.995 0 Intercept

SEC m/z rCal

0.648 0.997

SEV rVal

Samples spiked with the synthetic oil mixture

Quantification: Gasoline in water by PLS

Signals: gasoline in water samples
Signal (E+06)

Recovery in gasoline spiked water samples

Without calibration transfer
Added(ppm) Found (ppm) 4.77 9.18 14.9 River water samples 5.83 11.7 17.5 5.83 11.7 17.5 4.89 9.41 14.0 Tap water samples 4.84 9.41 13.7 83.0 80.4 78.3 5.83 11.7 17.5 83.9 80.4 80.0 5.83 11.7 17.5 %* 81.8 78.5 85.1 UHQ water samples

Future Research
Determination of different types of oils
Diesel fuel, Kerosene Crude oil, Engine oil

With calibration transfer

Added(ppm) 5.83 11.7 17.5 Found (ppm) 5.43 9.89 15.7 River water samples 5.18 9.85 14.7 Tap water samples 5.14 9.80 14.3 88.2 83.8 81.7 88.8 84.2 84.0 %* 93.1 84.5 89.7 UHQ water samples

120

5.83 11.7 17.5

80

Determination in different water matrices

Sea water Waste water

40

Study of other calibration standard mixtures

n-Hexadecane, isooctane and chlorobenzene n-Hexadecane, pristane and toluene n-Hexadecane and stearic acid

0 84 124

m/z

*Results obtained as a mean of three determinations

The prediction of the gasoline spiked samples was carried out with the model built with the synthetic oil mixture

Conclusions
A method based on Headspace-Mass Spectrometry has been developed for the determination of oil and grease in water, involving minimum sample treatment. The analytical signals were the sum of the intensities of the ions measured at m/z: 57, 71, 78, 85 and 99. A Box Behnken design for screening/optimising the significant variables was applied. A multivariate PLS calibration model built in UHQ water was used to predict oil in tap and river waters with satisfactory results. Additionally, samples spiked with three different spike levels of gasoline were analysed using the three component synthetic oil mixture as the calibration standard and the oil content was correctly predicted.