Photoionization Chapter 10

1.0 INTRODUCTION This chapter is written from the perspective of an environmental professional. It focuses on those aspects of photoionization that aid in the understanding and selection of portable instrumentation and their relationship to laboratory methods. In addition, it should be a useful resource for anyone who is responsible for interpreting data collected in the field. By the late nineteen seventies, Love Canal was one of the world's first recognized hazardous waste sites. As a result of the attendant publicity, and the discovery of a multitude of additional sites throughout the US, this led to the Comprehensive Environmental Response Compensation and Liability Act (CERCLA), now known as Superfund which has been used to clean up hazardous waste sites. The most serious problems with hazardous waste sites involve contamination of the soil and migration of toxic organics into the surrounding groundwater. The HNU Model PI101 and HNU GC detector Model PI52 (laboratory GC detector using photoionization) were used extensively at this site by the State of New York to determine the extent and nature of the contamination. This led to the choice of the HNU PID for the first Rapid Response Team assembled by the EPA in the late nineteen seventies. The passage of the Resource, Conservation and Recovery Act (RCRA) in 1976 and the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA or Superfund) in 1980 also led to an expansion of the list of hazardous chemical compounds under EPA regulation. There are in excess of 250,000 gasoline stations in the United States. It is estimated that 30 to 40 % of these stations have leaking fuel storage tanks contributing significantly to the
John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

problem of groundwater contamination. The leaking underground storage tank (UST) program was initiated in the nineteen eighties to deal with this problem. Many of the stations have had tanks replaced along with a cleanup but there are still a number of problem "tanks" and areas that have to be cleaned up. For the Superfund program, the large number of contaminants or "priority pollutants" resulted in the emphasis of analytical methods with multianalyte capabilities such as gas chromatography/mass spectrometry (GC/MS) for organic analysis and subsequent laboratory analysis. EPA and its regional Superfund contractors e.g. Field Investigation Teams (FIT) and Technical Assistance Teams (TAT) (1) saw a need for and developed faster, lower cost field screening methods to supplement, and in some cases replace, the laboratory analytical methods, depending on how the data was to be used (2). Answers were needed quickly and 15-30 day turnaround was just not acceptable for the many critical and timely decisions that had to be made in the field. This led to the evolution of field screening and analysis methods in the 1980's by the EPA and the FIT and TAT teams. In order to support these new methods, portable versions of analytical laboratory instruments were needed to provide similar, if not identical, analytical capabilities in the field environment. The star performers of these Superfund methods for hydrocarbons were portable field instruments such as the total volatile organics analyzer and gas chromatographs. Some rapid and simple methods for screening organics in water and soil using photoionization analyzers will be described in this chapter. 2.0 Structures of Selected Organic compounds at Hazardous Waste Sites The most common organic compounds found at hazardous waste sites are gasoline hydrocarbons,
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Photoionization Chapter 10
chloroalkanes such as tri and tetrachloroethylene and polychloro biphenyls (PCB's). These compounds are from leaking underground storage tanks (gasoline stations), solvent usage and transformer insulation (PCB's). The chlorinated compounds are from dry cleaning and other industrial operations. In Table I, the most common organic compounds are given along with their frequency at 546 Superfund sites. The structures for some hydrocarbons and common toxic organic compounds are shown in Figures 1 and 2. Table I Most Frequently Found Organic Compounds in Air at Superfund Sites
Compound Ionization Potential (eV) 9.25 13.79 14.01 12.98 14.54 13.61 Response

Fig. 2 Structures for Organic Compounds

Substituted

Benzene Carbon dioxide Carbon monoxide Methane Nitrogen Oxygen Trichloroethylene Water

High None None None None None High None

12.35

Fig. 1 Structures Organic Compounds

Gasoline, for example, is a complex mixture of aromatic, aliphatic (alkanes), and olefinic (alkenes) compounds that may contain 200 or more compounds produced by distillation of crude oil. It is not surprising then that benzene and toluene, which were added to gasoline to replace lead compounds are among the most common organic compounds found in Table I. Other compounds such as oxygenated species may be blended into gasoline to produce more efficient combustion. Recent studies have shown that methyl tert butyl ether (MTBE) is being detected in water

John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

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Photoionization Chapter 10
supplies. This compound will migrate faster than benzene or toluene and can be an early warning indicator of a leaking gasoline tank. Diesel fuel, a higher boiling mixture than gasoline, contains alkanes and many cyclic compounds. It is necessary to use a gas chromatograph (GC) to differentiate these two fuel types (see for example Chapter on Gas Chromatography). 3.0 Photoionization In 1974, the first commercial photoionization instrument (PID) was described by HNU Systems, Inc. (3). The process of ionization which occurs when a photon of sufficient energy is absorbed by a molecule and results in the formation of an ion plus and electron: R + hν ⇒ R+ + e where:
R = an ionizable species hν= a photon with sufficient energy to ionize species R

A list of some of the major

In the ion chamber, the ions (R+) formed by absorption of the UV photons are collected by applying a positive potential to the accelerating electrode and measuring the current at the collection electrode. A PID consists of an ion chamber, a UV lamp with sufficient energy to ionize organic and inorganic compounds, a voltage source for the accelerating electrode, an amplifier and a readout. A schematic of a PID is shown in Fig. 3. A photo of two of the HNU photoionization instruments are shown in Fig. 4 a & b. The PI101 (Fig. 4a) was used at the Love Canal site in 1975 and thousands of hazardous waste sites worldwide since that time. It is still being produced today because of its simplicity and rugged design. Many of the instruments produced 15-20 years ago are still in use today. Fig. 3 Schematic of a PID
John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

constituents in air, ionization potentials (IP's) along with some of the toxic components at a hazardous waste site are shown in Table II. The IP is the amount of energy required to move an electron to an infinite distance from the nucleus thus creating a positive ion plus an electron. Note that all of the major components of air have IP's above 12 eV. As a result, they will not be ionized by the Fig. 4 Photo of HNU PID

10.2 or 11.7 eV lamps. The response for the photoionization analyzer will then be the sum of the organic and inorganic compounds in air that are ionized by the appropriate lamp (9.5, 10.2, or 11.7 eV). A list of ionization potentials and responses for 9.5, 10.2 and 11.7eV lamps are given in Table III.

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Photoionization Chapter 10
What compounds will the 10.2 eV lamp respond to? Generally, the response will extend to compounds with IP’s up to 0.3 eV higher than 10.2 or 10.5 eV. The 10.2 eV lamp will respond to H2S which has an IP of 10.5 eV. While most of the measurement with a PID can be done with a 10.2 eV lamp, the 9.5 eV lamp does provide more selectivity (responds to fewer compounds) and the 11.7 eV lamp will respond to more compounds as shown in Fig. 5. The chloroalkanes, in particular, are of interest to measure at a hazardous waste site since these compounds do not have a very high response on the FID. A list of the ionization potentials, and response factors for the 9.5, 10.2 and 11.7 eV lamps are given in Table III. Table II Ionization Potentials of Major and Minor components in Air Compound Ionization Potential (eV)
9.25 13.79 14.01 12.98 14.54 13.61

Response

Fig. 5 Effect of Lamp energy on Response . Some characteristics on the PID are given in Table IV. Note that the PID is a carbon counter (molar response increases with carbon number) like the FID. There are several differences in that the PID is non destructive (the sample is burned in the FID) and the PID has no response to ambient methane. The methane background measured on the FID is 3-5 ppm. Thus, the PID is an order of magnitude more sensitive than the FID since it can measure down to 0.1 ppm that is the background in clean air. Table IV PID Characteristics
Sensitivity increases as the carbon number increases (carbon counter) For 10.2 eV lamp, responds to carbon aliphatic compounds > C4, all olefins and all aromatics; the PID also responds to inorganic compounds such as H2S, NH3, Br2, I2, PH3, AsH3, e.g. any compound with an ionization potential of < 10.6 eV For 9.5 eV lamp, the response is more selective; higher response to aromatic hydrocarbons and less response to aliphatic hydrocarbons For 11.7 eV lamp, responds to more compounds like carbon tetrachloride, chloroform, methanol, formaldehyde, etc. which have ionization potentials > 10.6 and < 11.7 eV Non destructive- sample (tube or bag) can be collected downstream of the detector

Benzene Carbon dioxide Carbon monoxide Methane Nitrogen Oxygen Trichloroethyl ene Water

High None None None None None High None

12.35

Table III List of Response Factors for Various Lamps

John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

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Photoionization Chapter 10
Concentration sensitive- relatively insensitive to flowrare over a wide range

A schematic of the PID probe is shown in Fig. 6. As a result of the level of contamination around a hazardous waste site, it is not unusual for the ion chamber to require cleaning on a regular basis. The instrument was designed so that the ionization chamber is removable and easy to clean. The lamp is also removable (no wires to attach/detach) and the window is easy to clean. If the sensitivity of the PID is low (determined by the isobutylene reading), one of the first things to do is to clean the lamp. This process takes only a few minutes to complete. The PI101 is extremely rugged and has only three controls: zero, span and range selection switch. The DL101 is under microprocessor control but has a survey mode that is similar in performance and ease of use to the PI101. These instruments are designed for a long lifetime and ability to be used by personnel with a minimum of training. Fig. 6 Probe Assembly for PID

Fig. 7 EPA Levels of Investigation

4.0 Screening and Analysis Levels The framework of the EPA methodology involves five levels of investigative screening or analyses with held analyzers (EPA protocol specifies a photoionization detector like HNU Model PI or DL101) shown in Figure ?? and other site characterization equipment such as an oxygen meter, explosimeter, radiation survey equipment and chemical testing tubes. Level I effort is designed to determine the real time total level of contaminants present (i.e., total volatile organics) which allows determination of the appropriate level of on site respiratory protection and evaluation of air quality for existing or potential threats to surrounding populations (4). Additional benefits include more efficient and cost effective sampling and analysis and assistance in guiding quick and suitable cleanup efforts. A summary of the precision and accuracy expected for the various Levels is shown in Table V. Examples of tools for Level II (and sometimes Level III) screening are the HNU GC311 and XRF instruments.
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John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

Photoionization Chapter 10
• Table V Precision & Accuracy Requirements for Various EPA Methods
Level I Precision +/- 10% Accuracy +/- 50% Requirement Screening (1000 ppm det. limit) Eval. of Human Exposure (detection limit, low ppm) Litigation & Regulatory Enforcement (det. limit, ppb)

protecting the health of workers involved in the investigation and remedial work

II

+/- 10%

+/- 15%

III

+/- 5%

+/- 10%

The second level (Level II) involves field analysis with more sophisticated instrumentation to provide identification (as far as possible) of specific components present. The final level discussed, Level III, uses laboratories located "off site" and frequently involves CLP analysis (2). Levels IV & V will not be discussed in this paper. 4.1 Level I Screening The purpose of Level I field screening is to find total contaminant levels (i.e., total volatile organics). Using a screening/survey instrument, such as the HNU Model PI or DL101 (see Fig. 4) for example, it is possible to accomplish the following during Level I screening: • Identification of contamination sources • Monitoring soil vapor wells to determine the extent of the pollutant plume (headspace) • Measuring the total concentration profile in a borehole to determine contaminant migration on the groundwater
John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

4.2 Level II Screening Once a Level I screening identifies a contaminated area and delineates its extent, a Level II screening can establish the identity of the compound(s) and relative concentrations. In the nineteen eighties, this was done predominantly by sending samples to a laboratory for detailed analysis. In the nineteen nineties, many of these measurements are done in mobile laboratories. The intermediate Level II analysis was introduced by EPA in order to reduce both the time required to start remedial actions and the high costs associated with laboratory analysis and keeping trained personnel in the field waiting for results. Field analytical equipment is currently used for on site detection and identification of organic and inorganic contaminants in air, water and soil. Portable GCs (i.e., HNU (Model 311, see Figure 1) are used for characterization of volatile organic compounds, semivolatile organics, polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Methods for Level II screening are described in more detail in the Chapter on Gas Chromatography. 5.0 Total Hydrocarbon Measurement Techniques 5.1 Calibration 5.1.1 Air Samples One of the first things to do after calibration with a span gas and a preliminary survey of the "hot spots" is to develop a set of calibration curves for the PID if some new or toxic compounds are found and a direct reading value for these compounds inambient air is required. A very useful tool for this application is a 1 or 2 liter Hamilton syringe. This device
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Photoionization Chapter 10
has a number of uses from calibration to sample collection. The syringe is made of plexiglass and some caution should be observed with sample preparation or collection at high (%) levels. In general, ppm levels can be prepared or sampled with no difficulty. A method for sample preparation was described by Becker et. al . (5). To prepare a gas sample with a liquid, one needs a liquid syringe (10 µL) and the 1 or can measure the level in the 1 or 2 liter syringe. The final value should be adjusted for the volume of dilution air. 5.1.2 Headspace Samples Soil or water samples can be prepared on either a volume or weight basis. Liquid samples are generally prepared on a volume basis (ppm v/v) and soil samples are prepared on a weight basis (mg/Kg). To prepare a 1 ppm sample by volume in water, measure 1 µL of liquid (using a 10 µL syringe) and dissolve in 1L of water (in a volumetric flask). To prepare a soil sample, use a 10 µL syringe (multiply by the density of the liquid to get the weight) and weigh 1000 g of soil on a balance with a readability of 0.1 g. Mix thoroughly to ensure that the volatile hydrocarbon standard is evenly dispersed in the soil. 5.2 Industrial Hygiene and Survey Measurements One of the primary uses of the PID at hazardous waste sites is for worker protection. The air at the site is initially screened and if values above a specified level are observed, the teams are required to wear self contained breathing apparatus. Then areas are screened for high levels in the soil, surface or groundwater by measuring the concentrations a short distance above the source. At this point, a sample could be taken for analysis by a Level II method or further measurements can be made with the PID. Clearly, the latter measurements can be made more quickly. 5.3 Soil Gas Measurements Although headspace analyses (6) are common for volatile hydrocarbons, one of the most commonly used field analysis technique for site characterization is soil gas analysis (7) where the sample is collected by in-situ pumping of a well using a probe such as that shown in Fig. 4. In many cases, such as with an PI101 or DL101. This type of Level I screening could be used to
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2 liter syringe. The formula for calculation of the values produced is given below:

A calibration curve can be prepared by using 5-6 injections of various volumes to cover the range desired and recording the values produced by the PID. This is a fairly easy method to prepare a calibration curve. The measurements should be within 5-10% provided that the user can accurately deliver the known values of the liquid. This will be the largest error in the method. This procedure does work best with volatile liqiuids but the syringe can be mildly heated with a hair dryer to help a less volatile liquid evaporate. One of the most frequent problems with collecting vapors out of a stack or out of the ground involves the condition of the sample e.g. saturation with water at ambient (soil gas) or elevated temperatures (stack). Many VOC’s are soluble in water to a greater (acetonemiscible) or lesser extent (benzene). Condensation in the sampling line can lead to losses from a few % to as great as 100 % for an organic compound that is miscible with water. Any losses greater than a 5 % are clearly unacceptable. If the syringe is half filled with clean dry air prior to sampling, the water content will be reduced by 1/2. If this is insufficient, then a larger quantity of dry air should be used to prevent condensation. The Model 101's
John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

Photoionization Chapter 10
determine the extent of contamination of the soil ("total" but not individual hydrocarbons) and groundwater which occurred. Site characterization is done rapidly and in "real time". 5.4 Headspace The headspace method is easy to perform, requires a minimum of equipment, and requires only that the sample and standards be at equilibrium to obtain accurate results. A typical procedure involves weighing (or measuring) 1 g of soil into a weighing boat which is placed in a container of about 100 cc volume which can be sealed (a series of half pint clean paint cans could suffice), placed in an oven at 60 C for 15 minutes, cooled to room temperature (6). The sample can be left at ambient (in a trailer on site, for example) for a specified period of time (approximately 1 hour). Standards bracketing the samples should be run at the same time and under exactly the same conditions. For a total hydrocarbon measurement, the vessel top is removed and a reading (maximum) is taken and recorded. The concentration can then be determined by comparison to a calibration curve generated from standards. Liquid samples can be prepared by making solutions as described in 5.1, placed in a sealed bottle (250 ml) and allowed to equilibrate. Then, the bottle is uncapped and the maximum reading is observed (and recorded) on the PID. A typical calibration curve for toluene in water is shown in Fig. 8. Note the linear response and sensitivity of this method. Robbins (8) described a headspace method using a polyethylene bag where samples are collected in a modified one quart bag. Twenty five grams of soil are added to the bag and the bag is inflated until taut. After three or four minutes of agitation, the bag is ready to be sampled. The method will also work with water samples. Fig. 8. Calibration Curve for Toluene in Water (headspace)
John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

If the determination of individual hydrocarbons is required, then a portable GC is the instrument of choice. Here, the vessels should be modified to include a Swagelock connector which incorporates a septum. A gas syringe is used to remove a sample (1 cc) and inject it into the GC (see also the chapter on Gas Chromatography). 6.0 Reporting Data After developing and demonstrating the ability of field screening and analytical methods to supplement or replace laboratory analytical methods, EPA and its contractors then had the task of developing "Field Analyses." These results were to be reported as a "tentative identification" rather than a definitive identification as field analysis was not meant to replace laboratory analysis using greater sophistication and analytical controls (i.e., CLP analysis). Field analytical data seemed to best supplement laboratory methods when laboratory analysis had already identified the contaminants present at a site. Field analytical methods could be used to set worker safety levels, determine the extent of contamination, the placement of monitoring wells, to optimize sampling grids, to establish cleanup levels, during treatability studies, and to identify critical samples for CLP confirmatory analysis (2). Generally, at least 10% of the samples analyzed in the field are returned for laboratory analysis unless one uses a
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Photoionization Chapter 10
GC in a mobile laboratory where Level II or Level III methods are used. 7.0 Conclusions EPA has shown that field methods and laboratory methods can yield similar results for volatile hydrocarbons. It was determined that when very little is known about a site or its contaminants, it is generally more cost effective to use the CLP (or an equivalent like a state certified lab) as a screen than to conduct extensive field analyses designed for analyzing a limited number of target compounds. Field analytical methods were determined to be most useful when the contaminants of concern have already been identified, so that appropriate methods, dilutions, calibration ranges, etc. can be employed (2). It was also found that credibility could be lent to field data by using quality control techniques similar to laboratory methods (i.e., duplicates, standards run at regular intervals, % of samples sent back to the lab, etc.). EPA has published a field screening methods catalog as a reference (see reference no. 7). Field screening and analytical methods have been extensively developed through the 1980's and into the 1990's thanks in large part to the Superfund Program. These methods have been used to obtain real time data for health and safety considerations during site investigations, and determine the presence or absence of contamination. They are also used to obtain qualitative data relative to a primary calibration standard if the contaminants being measured are unknown, or obtain quantitative data if a contaminant is known and the instrument is calibrated to that contaminant. A final use is to identify soil, water, air and waste locations that have a high likelihood of showing contamination through subsequent CLP confirmatory analysis (2). The PID has been shown to be a useful tool for industrial hygiene, soil gas monitoring, finding contaminated areas, and screening soil and water by
John N. Driscoll Handbook of Environmental Instrumentation Wiley 2005- Chapter 10

headspace. The PID is easy to use and by changing the lamp can be a selective or more general detector (11.7 eV lamp) for chloroalkanes (dichloro ethane, chloroform, carbon tetrachloride, etc.). In this chapter we have described a number of basic aspects of photoionization and portable instruments in order to provide the reader with a basic understanding of field methodology.

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Photoionization Chapter 10
REFERENCES 1.Williams, L. R. "Guest Editorial, " American Environmental Laboratory. October 1990. p. 6. 2. Data Quality Objectives for Remedial Response Activities, USEPA, Development Processes, PB 88-131370, March 1987 3. Driscoll, J. N. and F.F. Spaziani, Anal. Inst. (Oct. 1974) 4. Morin, J.O. "Development and Application of an Analytical Screening Program to Superfund Activities, "Proceedings of the National Conference on Management of Uncontrolled Hazardous Waste Sites. Hazardous Materials Control Research Institute. Silver Springs, MD. 1985. p. 97 5. Becker, J.H., J. N. Driscoll, D. Renaud, and P. Tiffany, Instrument Calibration with Toxic and Hazardous Materials, Ind. Hyg. News, July 1983 6. Driscoll, J. , and J. H. Becker, “Rapid Screening Techniques for Determination of Residual Organics in Food, Polymers and Soil,” Pitt. Conf. Paper # 603 (1981) 7. Field Screening Methods Catalogue ) Users Guide. EPA/540/2)88/005 (Hazardous Site Evaluation Division, U.S. E.P.A. Office of Emergency and Remedial Response, Washington, D.C. 1988). 8. Robbins, G., Groundwater Monitoring Review (1989)

The replacement instrument for a PI101 or DL101 is a DL102 manufactured by:
PID Analyers, LLC 2 Washington Circle Sandwich, MA 02563 1 774 413 5281 URL: http://www.hnu.com Follow us on Facebook: http://on.fb.me/qX0kWl Blogs: follow us at: http://gasanalysis.blogspot.com http://gcdetectorguy.blogspot.com http://analyzersource.blogspot.com

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