This report describes the quality of volatile organic compound (VOC) data collected from October 1996 to December 2008 from groundwater and surface-water sites for the U.S. Geological Survey's National Water-Quality Assessment (NAWQA) Program. The VOC data described were collected for three NAWQA site types: (1) domestic and public-supply wells, (2) monitoring wells, and (3) surface-water sites. Contamination bias, based on the 90-percent upper confidence limit (UCL) for the 90th percentile of concentrations in field blanks, was determined for VOC samples from the three site types. A way to express this bias is that there is 90-percent confidence that this amount of contamination would be exceeded in no more than 10 percent of all samples (including environmental samples) that were collected, processed, shipped, and analyzed in the same manner as the blank samples. This report also describes how important native water rinsing may be in decreasing carryover contamination, which could be affecting field blanks.

The VOCs can be classified into four contamination categories on the basis of the 90-percent upper confidence limit (90-percent UCL) concentration distribution in field blanks. Contamination category 1 includes compounds that were not detected in any field blanks. Contamination category 2 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is about an order of magnitude lower than the concentration distribution of the environmental samples. Contamination category 3 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is within an order of magnitude of the distribution in environmental samples. Contamination category 4 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is at least an order of magnitude larger than the concentration distribution of the environmental samples.

Fifty-four of the 87 VOCs analyzed in samples from domestic and public-supply wells were not detected in field blanks (contamination category 1), and 33 VOC were detected in field blanks. Ten of the 33 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than the concentration distribution in environmental samples (contamination category 2). These 10 VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative of the sources of contamination bias affecting the environmental samples for these 10 VOCs. Seven VOCs had a 90-percent UCL concentration distribution of the field blanks that was within an order of magnitude of the concentration distribution of the environmental samples (contamination category 3). Sixteen VOCs had a 90-percent UCL concentration distribution in the field blanks that was at least an order of magnitude greater than the concentration distribution of the environmental samples (contamination category 4). Field blanks for these 16 VOCs appear to be nonrepresentative of the sources of contamination bias affecting the environmental samples because of the larger concentration distributions (and sometimes higher frequency of detection) in field blanks than in environmental samples.

Forty-three of the 87 VOCs analyzed in samples from monitoring wells were not detected in field blanks (contamination category 1), and 44 VOCs were detected in field blanks. Eight of the 44 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than concentrations in environmental samples (contamination category 2). These eight VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative. Seven VOCs had a 90-percent UCL concentration distribution in field blanks that was of the same order of magnitude as the concentration distribution of the environmental samples (contamination category 3). Twenty-nine VOCs had a 90-percent UCL concentration distribution in the field blanks that was an order of magnitude greater than the distribution of the environmental samples (contamination category 4). Field blanks for these 29 VOCs appear to be nonrepresentative of the sources of contamination bias to the environmental samples.

Fifty-four of the 87 VOCs analyzed in surface-water samples were not detected in field blanks (category 1), and 33 VOC were detected in field blanks. Sixteen of the 33 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than the concentration distribution in environmental samples (contamination category 2). These 16 VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative. Ten VOCs had a 90-percent UCL concentration distribution in field blanks that was similar to the concentration distribution of environmental samples (contamination category 3). Seven VOCs had a 90-percent UCL concentration distribution in the field blanks that was greater than the concentration distribution in environmental samples (contamination category 4). Field-blank samples for these seven VOCs appear to be nonrepresentative of the sources of contamination bias to the environmental samples.

The relation between the detection of a compound in field blanks and the detection in subsequent environmental samples appears to be minimal. The median minimum percent effectiveness of native water rinsing is about 79 percent for the 19 VOCs detected in more than 5 percent of field blanks from all three site types. The minimum percent effectiveness of native water rinsing (10 percent) was for toluene in surface-water samples, likely because of the large detection frequency of toluene in surface-water samples (about 79 percent) and in the associated field-blank samples (46.5 percent).

The VOCs that were not detected in field blanks (contamination category 1) from the three site types can be considered free of contamination bias, and various interpretations for environmental samples, such as VOC detection frequency at multiple assessment levels and comparisons of concentrations to benchmarks, are not limited for these VOCs. A censoring level for making comparisons at different assessment levels among environmental samples could be applied to concentrations of 9 VOCs in samples from domestic and public-supply wells, 16 VOCs in samples from monitoring wells, and 9 VOCs in surface-water samples to account for potential low-level contamination bias associated with these selected VOCs. Bracketing the potential contamination by comparing the detection and concentration statistics with no censoring applied to the potential for contamination bias on the basis of the 90-percent UCL for the 90th-percentile concentrations in field blanks may be useful when comparisons to benchmarks are done in a study.

The VOCs that were not detected in field blanks (contamination category 1) from the three site types can be considered free of contamination bias, and various interpretations for environmental samples, such as VOC detection frequency at multiple assessment levels and comparisons of concentrations to benchmarks, are not limited for these VOCs. A censoring level for making comparisons at different assessment levels among environmental samples could be applied to concentrations of 9 VOCs in samples from domestic and public-supply wells, 16 VOCs in samples from monitoring wells, and 9 VOCs in surface-water samples to account for potential low-level contamination bias associated with these selected VOCs. Bracketing the potential contamination by comparing the detection and concentration statistics with no censoring applied to the potential for contamination bias on the basis of the 90-percent UCL for the 90th-percentile concentrations in field blanks may be useful when comparisons to benchmarks are done in a study.