USGS-NWQL: I-4464-01: Organic plus Inorganic Mercury in Unfiltered Natural Water by Cold-Vapor AFS

Summary
Analytes
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Data and Sites

Official Method Name

Methods of Analyis by the U.S. Geological Survey National Water Quality Laboratory - Determination of Organic Plus Inorganic Mercury in Filtered and Unfiltered Natural-Water with CV-AFS

Current Revision

2001

Media

WATER

Instrumentation

Cold Vapor Atomic Fluoresence Spectrophotometer

Method Subcategory

Organic

Method Source

USGS-NWQL

Citation

Garbarino, J.R., and Damrau, D.L., 2001, Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of organic plus Inorganic mercury in filtered and unfiltered natural water with cold vapor--atomic fluorescence spectrometry: U.S. Geological Survey Water-Resources Investigations Report 01-4132.

Brief Method Summary

Concentrations of organic plus inorganic mercury in filtered and unfiltered natural-water samples are determined by using CV-AFS. The method is based on U.S. Environmental Protection Agency (1999) Method 1631 but does not use gold amalgamation for mercury preconcentration. By eliminating the preconcentration procedure, the MDL is at least a factor of 10 greater, yet the method provides the determination of mercury at ambient concentrations. Mercury species in a natural-water sample are oxidized to mercury (II) inside the borosilicate-glass sample bottle by using bromine monochloride; excess oxidant is neutralized with hydroxylamine hydrochloride. Mercury (II) is reduced to elemental mercury by using stannous chloride, and is purged from the solution with ultrapure argon gas into a cell in which the mercury concentration is measured by atomic fluorescence emission at 253.7 nanometers (nm).

Scope and Application

This method is used to determine concentrations of organic plus inorganic mercury in filtered and unfiltered natural-water samples. Bromine monochloride is used to oxidize elemental mercury, mercury complexes, various alkyl- and phenyl-mercury compounds, and other forms of mercury. The upper limit of the linear concentration range is 125 ng/L mercury. The short-term method detection limit is 5 ng/L mercury.

Applicable Concentration Range

5 - 125 ng/L (undiluted)

Interferences

Contamination must be avoided because of the inherently low mercury concentration found in natural water. Gold, silver, and iodide interfere with the determination of mercury by this method. Buildup of condensation in the vapor generator or fluorescence cell will degrade the analytical signal. Ultrapure argon (99.998 percent) must be used for the purge gas to minimize the possibility of fluorescent quenching by impurities.

Quality Control Requirements

Quality-control samples area analyzed at a minimum of one in every ten samples. These QC samples include at least one of each of the following: blanks, quality control samples, third party check solutions, replicates, and spikes. Correlation coefficients for calibration curves must be at least 0.99. QC samples must fall within 1.5 standard deviations of the mean value. If all of the data-acceptance criteria in the SOPs are met, then the analytical data are acceptable.

Sample Handling

Description: 250 mL Glass bottle, acid-rinsed. Treatment and Preservation: Filter through 0.45-um filter, use filtered sample to rinse containers and acidify collected sample with 2 mL of 6N (6 normal) hydrochloric acid (HCl).

Maximum Holding Time

180 days from sampling

Relative Cost

$51 to $200

Sample Preparation Methods

This method has 1 analyte associated with it.

Analyte	Detection Level	Bias	Precision	Pct False Positive	Pct False Negative	Spiking Level
Mercury(7439-97-6) Hg Hydrargyrum Liquid silver Mercury Mercury (inorganic) Quicksilver	5.000 ng/L	100% Rec (SL)	N/A			45.00 ng/L

Precision Descriptor Notes:	The percentage recovery of results for various concentrations of mercury spiked into unfiltered surface water, and unfiltered ground water was used to validate the method. Data were acquired during 7 nonconsecutive days. No more than two sets of data were acquired in 1 day. The range of average percent recovery for all filtered and unfiltered matrices at 20, 45, and 75 ng/L was 89 to 108, 96 to 103, and 94 to 98 percent, respectively. The variability in the recovery of 20 ng/L, a concentration about four times the short-term MDL, was about twice that of higher spike concentrations. In addition, the variability in recoveries at 20 ng/L for the unfiltered matrices was about twice those for corresponding filtered matrices. There was little difference, however, in variability for filtered and unfiltered matrices for spike concentrations of 45 and 75 ng/L.
Detection Level Note:	Method detection limits (MDLs) were determined for this method using the procedures of the U.S. Environmental Protection Agency (1997).

Precision Descriptor Notes:

The percentage recovery of results for various concentrations of mercury spiked into unfiltered surface water, and unfiltered ground water was used to validate the method. Data were acquired during 7 nonconsecutive days. No more than two sets of data were acquired in 1 day. The range of average percent recovery for all filtered and unfiltered matrices at 20, 45, and 75 ng/L was 89 to 108, 96 to 103, and 94 to 98 percent, respectively. The variability in the recovery of 20 ng/L, a concentration about four times the short-term MDL, was about twice that of higher spike concentrations. In addition, the variability in recoveries at 20 ng/L for the unfiltered matrices was about twice those for corresponding filtered matrices. There was little difference, however, in variability for filtered and unfiltered matrices for spike concentrations of 45 and 75 ng/L.

Detection Level Note:

Method detection limits (MDLs) were determined for this method using the procedures of the U.S. Environmental Protection Agency (1997).

Revision	PDF/Link
2001

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USGS-NWQL: I-4464-01: Organic plus Inorganic Mercury in Unfiltered Natural Water by Cold-Vapor AFS

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