Pittsburgh Conf. on Anal. Chem.

, Orlando, FL Paper # 2210-1

A High Sensitivity Portable GC for VOCs & Sulfur Compounds #Pittcon

Dr. John N. Driscoll PID Analyzers, LLC Sandwich, MA 02563 http://www.hnu.com

Abstract
A new Model 312 portable GC has been developed for the analysis of volatile organic compounds. The GC uses a touch screen display thus making it easy for operator control and familiarity. The GC weighs 27 pounds and can be battery or line operated. The PID has been redesigned to minimize the dead volume. The electronics have been modified to provide a constant current output for the PID that reduced noise significantly. The electronics uses an integral Pentium PC with Windows XP and PeakWorks software for chromatography. A 16 bit ADC with autoranging is used for signal processing. With these changes and system optimizations, we have achieved nearly an order of magnitude improvement in the detection limit for organic compounds. The detection limit for benzene with no preconcentration is < 0.5 ppb with a dynamic range of nearly 8 orders of magnitude for the PID. The GC uses wide bore (0.53 mm) and narrow bore (0.32 mm) capillary columns up to 50 meters in length. PLOT and micropack columns are also used for gases. Applications include VOCs in factories, fenceline measurements, hospitals Typical analyzes involve solvents (aromatics, ketones, chlorinated hydrocarbons, ETO, ) and levels well below current OSHA PELs.

312 Portable GC

Presentation Objectives
Describe:
Features of GC312 Detectors available PeakWorks Software Applications with various detectors

What are the features?

Integral Pentium PC (350 MHz) with embedded Windows XP (2 GB Smart Card) 7 Color VGA display with Touch screen Windows XP Operating System with PeakWorks Chromatography Software (32 bit) Detectors- new & improved On-board carrier gas >16 hours Weight- < 17 pounds Dimensions- 16 L x 12 W x 6 H Battery, 12 VDC (30-75 C oven)- >4 hours or or 8 hoursvext battery; line operation (30-175 C)

312 Portable GC
Integral Pentium PC with embedded Windows XP and PeakWorks Chromatography SW 2 GByte smart card- no hard drive Six detectors to choose from: Specific to Universal: FPD, PID, FID, COD, FUV, TCD Battery (oven= 35-75 C) or 12 VDC/line operation (35-175 C) Syringe or optional automatic sampling module

GC Detectors
PID- hydrocarbons (>C4), inorganic species H2S, NH3, PH3, etc. at ppb to ppm levels (ppb-%) FID- specific for hydrocarbons (ppm-%) FPD- specific for S or P (ppb) COD- HC, H2, NH3 (high ppm to 100%) FUV- nearly universal detector (ppb to%) TCD- universal detector ( ppm to %)

What Improvements have been Made to the GC Detectors

PID
Mechanical, chromatographic, electronic & software-results: improved detection limits from 2 ppb to < 0.5 ppb

FUV
Electronic, chromatographic, & softwareresults: improved detetion limits from 1-2 ppm to 25-100 ppb

FID
Electronic, chromatographic, & softwareresults: from 100 ppb to 25-50 ppb

Photoionization Detector
Process
R + h = R + + e where R= molecule h = a photon with an energy > IP of R R+ = positive ion e- = electron

PID Characteristics
Linear dynamic range > 5 x107 Detection limit <0.5 ppb benzene Non destructive; other detectors can be run in-series 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 The PID is more sensitive than the FID; >200 x more sensitive for aromatics, 80 times for olefins, & 30 times for alkanes > C6 Non destructive detector; other detectors can be run downstream Concentration sensitive detector

FUV Characteristics
Measures absorbance @ 124 nm-log signal Nearly Universal Response Linear (Log) Range > 105 Low dead volume < 40 uL- fast response Non- destructive Concentration sensitive detector Environmental applications: freons, landfill gases, O2, CO2, CH4 at same detection limit as FID (0.1 ppm), VOCs

FID characteristics
Linear dynamic range > 2 x 106 Detection limit 50 ppb Sensitivity increases as the carbon number increases (carbon counter) Sensitivity to substituted species depends on the mass of carbon present and the ability to break the carbon bonds The FID is most sensitive to hydrocarbons Detector is destructive since sample is burned; mass flow rate Requires the use of zero grade (high purity) hydrogen and air to produce the flame

Detectors and Characteristics

PID FUV Y Y Y Y 1 x 10exp5 FID Y Y Y Y 1 x 10exp6

Species
C1-C4 alkanes C5+ alkanes Alkenes Aromatics Dynamic Range Detection Limits Air aromatics alkenes alkanes Water < 0.5 ppb <5 ppb < 10 ppb 25-100 ppb 25-100 ppb 25-100 ppb 50-100 ppb 50-100 ppb 50-100 ppb N Y Y Y 5 x 10exp7

aromatics
alkenes alkanes

< 0.1 ppb

0.1 ppb 1 ppb

2.5-10 ppb
2.5-10 ppb 2.5-10 ppb

2.5-10 ppb
2.5-10 ppb 2.5-10 ppb

GC Signal Schematic
ADC 16 bit
Touch Screen Display Diagnostics

Detector

AMP

PC

RS232

Digital I/O- valves

Time clock, data calc & storage on Smart Card or USB Memory Stick

Std TBM & THT in CH4

PID

LNG Stream with TBM &THT

PID

100 ppb BTEX

*10000 25 20 3 15 1

PID
10 5 0 2 4 6 5 7

min -5 0:00 1:00 2:00 3:00 4:00 5:00 6:00 7:00 8:00 9:00

5 ppb BTEX
*1000 30 25 20 1 2 5 34

PID

15 10 5 0 -5 -10

min -15 0:00 1:00 2:00 3:00 4:00 5:00 6:00 7:00 8:00 9:00

Low Level (ppb) Linearity of PID

Low Level Linearity of Benzene & Ethyl Benzene
25000 20000

Peak Counts

15000 10000 5000 0 0

y = 972.99x - 16.272 R2 = 0.9999

y = 389.31x - 8.112 R = 0.9999

2

10

15

20

25

ppb Benzene/Ethyl Benzene

Cl2 plant effluent-TCD

TCD

H2S in Cement Plant Effluent

PID

Solvents

FID

PID 10.6 eV

On-screen keyboard

Method

PID 10.6 eV- 3 ppb

Detector Parameters

Calibration

Summary
The Model 312 is:
Compact- weighs 27 lbs Sensitive- ppb levels for PID, FUV, COD, FID, FPD Has application to the analysis of ppb levels of aromatics, VOCs, sulfur compounds, chlorinated HCs, hydrides, inorganics Has easy to use PeakWorks chromatography software Can provide rapid lab type results in the field