The Reston Groundwater Dating Laboratory

Analytical Procedures for Dissolved Gasses N2 / Ar

Preparation

Septum Bottles

The filled septum bottles are weighed. The total volume of water in samples and standards is determined by the difference between the full weight and the empty weight of the bottle. After the samples and standards are allowed to equilibrate to room temperature, 10-12 mL of water are removed from each bottle to create a headspace. This is accomplished by inserting a syringe needle, attached to a vacuum pump, into the stopper and withdrawing water. The headspace volume is determined from the difference in weight between the full bottle and the bottle with the headspace.

Analysis

Photo of N2 / Ar instrument

Samples and QA/QC standards are analyzed using a Hewlett Packard model 7890B GC (see schematic). Helium is used as the carrier gas. The headspace gas pressure is measured with a transducer. The gas is then introduced simultaneously into 2 sampling loops. One sampling loop is injected into an Alltech CTR-III column at 55°C to separate the Argon, Nitrogen, and Oxygen. These gases are quantified with a thermal conductivity detector (TCD). Chromatogram The second sampling loop is injected into an Alltech CTR-I column at 30°C to separate methane and carbon dioxide from the other constituents. After separation, the gas stream is passed through a Nickel methanizer converting the CO2 to methane and the two gases are quantified with a Flame Ionization Detector (FID). Minimum Reporting Levels (MRL) in milligrams per liter are summarized in the table below.

Analyte MRL mg/l
Precision +/- mg/l
Nitrogen 0.001 0.001
Argon 0.003 0.003
Carbon Dioxide 0.04 0.04
Methane 0.001 0.0005
Oxygen 0.002 0.002

 

Calibration

The GC is calibrated with four gravimetric gas standards and one NOAA air standard. The GC is calibrated at the beginning of each day. The calibration is checked again at the end of each day. Instrument drift is generally less than 1% for Ar, N2, and O2 and 1-2% for CH4 and CO2. The composition of the standard gases is given in the table below.

COMPOSITION OF STANDARDS (percent)

Standard

O2

CH4

CO2

N2

Ar + O2

Ar

AIR

20.946

-

-

78.084

21.88

0.934

C1 Std-3

-

4.95

10.007

85.043

-

-

C1 Std-4

-

1

.9995

98.0005

-

-

C3 Std-3

10.02

-

-

87.97

12.03

2.010

C3 Std-4

20.99

-

-

78.006

21.994

1.004

QA/QC

Standard samples for QA/QC are prepared in the laboratory using three temperature controlled water baths set at 8°, 16°, and 24° C. Water is equilibrated with lab air by slow stirring at these temperatures for a minimum of 48 hours before sampling. Empty serum bottles with stoppers are weighed. Samples of the water baths are collected by placing a tube to the bottom of each bath, starting a siphon flow, and following the procedure for field sample collection. The bottles are stored in a refrigerator at about 4°C and are prepped and analyzed with submitted samples.

Standard deviations of the water bath QA/QC samples are typically ±0.3°C or less of the air / water equilibrium temperature. Three check samples are analyzed daily. The analyst must have a deviation of ±0.5 degrees before sample analysis commences.

The current year's QA/QC samples are depicted on the graph as deviation in degrees of the analyzed / calculated temperature from the equilibrated water bath temperature.