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Comparison of Headspace and Direct Injection Techniques for the Determination of Low Levels of VOCs in Water
John N. Driscoll, PID Analyzers LLC, 2 Washington Circle, Sandwich, MA 02563, USA
Introduction The determination of VOCs at a process discharge poses several analytical problems. Manufacturing processes most frequently have mixtures of polar and non polar hydrocarbons. Thus, two different techniques are required for removing the VOCs from the aqueous discharge namely purge and trap approach for non polar VOCs (benzene, hexane, etc.), and headspace for the polar VOC species. In addition, if grab samples are collected for laboratory analysis there is a delay of several hours to several weeks depending upon the urgency of the analysis and whether an in-house or outside laboratory is used. The approach preferred by EPA is reduction of VOC emissions by pollution minimization. Here, one should be able to quickly monitor the effluent and its sensitivity to process variables. A near process or on-line technique is required. With an automatic GC, it is possible to employ a sparging approach to replace purge and trap and a direct injection technique to replace the headspace technique that is used in the laboratory. The added advantages of this approach is that with these on-line methods, the time frame can be reduced, process minimization could be accomplished and the manual labor (and cost) of the analysis can be reduced significantly. We will describe some laboratory results using both static headspace (1) and direct injection methods and compare these results to a continuous sparging technique. The ultimate goal was to determine the feasibility of developing automatic analyzers for low (ppb) levels of polar and non polar hydrocarbons in water. Description of Approach An HNU Model 311 GC with a photoionization detector (PID) and Peakworks for Windows integration software was used for the analyses. The carrier gas was prepurified nitrogen at a flowrate of 17 ml/min and a temperature of 80C. The column was a Restek 30 meter by 0.53 mm MXT1 column. Samples were injected into a heated on-column injector with a 1 L liquid syringe or a 1 ml gas syringe. A capped test tube with a septum and minimum headspace was used for the direct injection samples. A 125 mL sealed flask with a 50 mL head space and a septum was used for the static headspace measurements. Samples were prepared by dissolving known quantities of the various organic compounds in deionized water that had been run through a carbon bed to remove organic compounds. A water bath was used to equilibrate the samples. The number of replicate injections was a minimum of three and a maximum of five. For direct injection, samples between 0.1-0.5 L were used since with samples larger than 0.5 L the quenching from the water peak would reduce any improved sensitivity with the early eluting (prior to toluene) peaks. With the static headspace approach, samples varied between 0.5-1 ml. Larger volume samples did not improve the detection limits for the static headspace method. We used an HNU Model 650 Sparging system with a Model 301-A Automatic GC for the tests with dynamic headspace (sparging). A photo of the sparging system is shown in Figure 1.

Fig. 1 Photo of Sparging System

Discussion Effluents from chemical plants and manufacturing processes contain VOCs that are both polar and non polar. Purge and trap and sparging techniques are generally applied to the latter group of compounds that can be easily

Published in American Environmental Laboratory, Dec. 1998

PID Analyzers, LLC


purged from the solution. For the polar compounds, an extraction approach was applied. The static headspace approach with GC-PID was developed by Stuart and Robbins (1) as a field method ( to replace the purge and trap) for use in the measurement of VOCs at contaminated well sites. The advantage of this technique was that a minimum of equipment (EPA VOC vial and a gas syringe) was needed and the results obtained were comparable to purge and trap as shown in Table I below. The correlation coefficient (r2) between the two methods was 0.99 for benzene and 0.89 for toluene. Table I Comparison of Static Headspace & P&T for Analysis of VOCs (2)
Detection Limit ppb Static Purge & headspac trap e 12.7 17.3 40.5 709 2170 330 2800 61.8 1144 4320 496 3180

Comparison of the Direct Injection and Static Headspace


Type of Injection Static Headspace Manual Species CV % benzen e toluene isoprop anol ethanol acetone benzen e toluene isoprop anol ethanol acetone 14.4 16.6 -15.0 11.7 12.3 11.6 14.0 11.0 8.2 Detectio n Limit 15 ppb 20 ppb 0.5 ppm 0.4 ppm 0.01 15 ppb 20 ppb 0.5 ppm 0.75 ppm 0.05

Direct injection manual

Sampl e# 1

Comp. benzen e toluene benzen e toluene benzen e toluene

dynamic headspace rather than a static one. The basis of the sparging approach (3) is through the application of Henrys Law which states that, at equilibrium, the solubility of a gas in a liquid is proportional to the partial pressure of a gas in contact with a liquid as given below: Benzene (aq) K PBenzene where Benzene (aq) is the concentration of benzene in the liquid phase, K is the Henrys Law constant which governs the solubility of gases in water, and PBenzene is the partial pressure of benzene in the gas phase. As a result of the above equation, it can be seen that if the concentration of benzene in the gas phase and at equilibrium is measured, this is related to the concentration of benzene in the dilute aqueous solution by a proportionality constant (K) that can be determined by calibration. A sample of the temperature controlled headspace above the sample is automatically injected into the GC through a Permapure dryer to remove moisture. The use of the permeation dryer improves the detection limits for the early eluting peaks. During our work on sparging applications (4), we found, to our surprise, that polar compounds also passed through the Permapure dryer but the efficiency was low (several percent). This can be seen in the chromatogram in figure 2. We were only able to detect low or sub ppm levels of polar compounds instead of low or sub ppb levels of the non polar species. When we compare this to the results in Table II, we found that the detection limit for a polar compound such as isopropanol was similar to either the static

The direct injection approach can also be easily accomplished in the field with a minimum of equipment (liquid syringe and a collection bottle). One problem with a direct injection is that some of the more volatile components can be lost during the injection. If we compare the results of the two techniques in Table II, we found that the reproducibility and detection limits for the series of polar and non polar compounds was essentially identical. Even with a simple and compact GC such as the HNU 321, samples can be analyzed faster and near the process with either direct injection or static headspace. The difference in performance compared to the lab is small since the detection limits for laboratory purge & trap GC for aromatic hydrocarbons such as toluene is about 5-10 ppb. Another method that could be used involves the extraction into a non aqueous solvent. This is a more sensitive method (2) but cannot be easily automated to interface with a continuous monitor so we did not consider this approach further. The static headspace method is clearly related to the sparging technique except in the latter the sample flows continuously through the chamber and the headspace is continuously purged. Thus sparging should be considered a Table II

Published in American Environmental Laboratory, Dec. 1998

PID Analyzers, LLC


dynamic headspace approach provides better precision for both polar and non polar hydrocarbons than either of the manual techniques evaluated. In addition, detection limits for non polar aromatic hydrocarbons are improved by nearly two orders of magnitude (see figure 2). The most interesting aspect of these results is that the sparging approach can be used for the determination of both polar and non polar species provided that an effective GC separation can be obtained. Hence, one GC analyzer with a continuous sparger can be used for monitoring of both polar and non polar species. Thus, the sparging technique becomes an efficient tool for on-line monitoring as a result of the range of hydrocarbons that can be detected, rapid analyses and usefulness in developing a pollution prevention approach to emissions. References

Figure 2 Chromatogram of Polar and Non Polar Species on the Model 650

headspace or direct injection technique. The interesting thing to note is that the aromatic hydrocarbon detection limits are improved by two orders of magnitude via the sparging approach with an integral Permapure. On the basis of the results in Table III below, it can be seen that the sparging or Table III Sparging System Test Results
Type of Injection Dynamic Head Space Automatic Species CV % 3.3 Detection Limit 0.1 ppb

1. Roe, V.D. M.J. Lacey, J.D. Stuart, and G.A.

2. 3. 4.

benzene

Robbins, Manual Headspace Method to Analyze for the Volatile Aromatics of Gasoline in Groundwater and Soil Samples, Anal. Chem. 61, 2584-2585 (1989) Anon., Gasoline in Groundwater and Soil, HNU application Note # APN1G, Nov. 1992 Driscoll, J. N., Presented at the Water Environment Federation Meeting, Phil. (Aug. 1997) Driscoll, J. N. unpublished results (1997-98)

toluene isopropanol

2.6 5.8

0.1 ppb 0.5 ppm

Published in American Environmental Laboratory, Dec. 1998