USGS

Quality-Control Results for Ground-Water and Surface-Water Data, Sacramento River Basin, California, National Water-Quality Assessment, 1996-1998

By Cathy Munday, and Joseph L. Domagalski

U.S. GEOLOGICAL SURVEY

Water–Resources Investigations Report 02-4201

Sacramento, California 2003



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Abstract

     Evaluating the extent that bias and variability affect the interpretation of ground- and surface-water data is necessary to meet the objectives of the National Water-Quality Assessment (NAWQA) Program. Quality-control samples used to evaluate the bias and variability include annual equipment blanks, field blanks, field matrix spikes, surrogates, and replicates. This report contains quality-control results for the constituents critical to the ground- and surface-water components of the Sacramento River Basin study unit of the NAWQA Program. A critical constituent is one that was detected frequently (more than 50 percent of the time in blank samples), was detected at amounts exceeding water-quality standards or goals, or was important for the interpretation of water-quality data. Quality-control samples were collected along with ground- and surface-water samples during the high intensity phase (cycle 1) of the Sacramento River Basin NAWQA beginning early in 1996 and ending in 1998.
     Ground-water field blanks indicated contamination of varying levels of significance when compared with concentrations detected in environmental ground-water samples for ammonia, dissolved organic carbon, aluminum, and copper. Concentrations of aluminum in surface-water field blanks were significant when compared with environmental samples. Field blank samples collected for pesticide and volatile organic compound analyses revealed no contamination in either ground- or surface-water samples that would effect the interpretation of environmental data, with the possible exception of the volatile organic compound trichloromethane (chloroform) in ground water.
     Replicate samples for ground water and surface water indicate that variability resulting from sample collection, processing, and analysis was generally low. Some of the larger maximum relative percentage differences calculated for replicate samples occurred between samples having lowest absolute concentration differences and(or) values near the reporting limit.
     Surrogate recoveries for pesticides analyzed by gas chromatography/mass spectrometry (GC/MS), pesticides analyzed by high performance liquid chromatography (HPLC), and volatile organic compounds in ground- and surface-water samples were within the acceptable limits of 70 to 130 percent and median recovery values between 82 and 113 percent. The recovery percentages for surrogate compounds analyzed by HPLC had the highest standard deviation, 20 percent for ground-water samples and 16 percent for surface-water samples, and the lowest median values, 82 percent for ground-water samples and 91 percent for surface-water samples. Results were consistent with the recovery results described for the analytical methods.
     Field matrix spike recoveries for pesticide compounds analyzed using GC/MS in ground- and surface-water samples were comparable with published recovery data. Recoveries of carbofuran, a critical constituent in ground- and surface-water studies, and desethyl atrazine, a critical constituent in the ground-water study, could not be calculated because of problems with the analytical method. Recoveries of pesticides analyzed using HPLC in ground- and surface-water samples were generally low and comparable with published recovery data. Other methodological problems for HPLC analytes included nondetection of the spike compounds and estimated values of spike concentrations.
     Recovery of field matrix spikes for volatile organic compounds generally were within the acceptable range, 70 and 130 percent for both ground- and surface-water samples, and median recoveries from 62 to 127 percent. High or low recoveries could be related to errors in the field, such as double spiking or using spike solution past its expiration date, rather than problems during analysis. The methodological changes in the field spike protocol during the course of the Sacramento River Basin study, which included decreasing the amount of spike solution added to volatile organic compound samples and changing the method of spike delivery, had no apparent effect on recovery results.

CONTENTS

Abstract

Introduction

Quality-Control Sample Types

Blank Samples

Field Blanks

Equipment Blanks

Trip Blanks

Source Solution Blanks

Ambient Blanks

Spiked Samples

Replicate Samples

Analysis

Quality-Assurance and Quality-Control Design

Ground Water

Blank Samples

Major Ions

Dissolved Organic Carbon

Nutrients

Trace Elements

Arsenic

Aluminum

Copper

Chromium

Cadmium

Barium

Pesticides in Filtered Water Analyzed by Gas Chromatography/Mass Spectrometry

Pesticides in Filtered Water Analyzed by High Performance Liquid Chromatography

Volatile Organic Compounds

Replicate Samples

Surrogate Recovery

Field Spiked Samples

Pesticides in Filtered Water Analyzed by Gas Chromatography/Mass Spectrometry

Pesticides in Filtered Water Analyzed by High Performance Liquid Chromatography

Volatile Organic Compounds

Surface Water

Blank Samples

Major Ions

Dissolved Organic Carbon

Suspended Organic Carbon

Nutrients

Trace Elements

Aluminum

Chromium, Copper, Manganese, Nickel, Zinc, and Iron

Total Mercury

Methylmercury

Pesticides in Filtered Water Analyzed by Gas Chromatography/Mass Spectrometry

Pesticides in Filtered Water Analyzed by High Performance Liquid Chromatography

Volatile Organic Compounds

Replicate Samples

Surrogate Recovery

Field Spiked Samples

Pesticides in Filtered Water Analyzed by Gas Chromatography/Mass Spectrometry

Pesticides in Filtered Water Analyzed by High Performance Liquid Chromatography

Volatile Organic Compounds

Summary and Conclusion

References Cited


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