Methods of Analysis by the U.S. Geological Survey - Usgs Open-File Report 2000-170 (Paperback)

The National Water Quality Laboratory (NWQL) determined ammonium plus organic nitrogen (Kjeldahl nitrogen) by using semiautomated, block digester methods for filtered and whole-water samples from 1986 until October 1, 1991. During that time, phosphorus was determined by a persulfate digestion method. In 1991, projected increases in demand for both tests by the U.S. Geological Survey's National Water-Quality Assessment Program led the NWQL to develop and validate methods for determining both analytes in a common digest. This report describes a rapid and accurate method to determine Kjeldahl nitrogen. The batch, high-temperature (block digester), Hg (II)-catalyzed digestion step used in the new methods I-2515-91/4515-91 is similar to U.S. Geological Survey methods I-2552-85/4552-85 and U.S. Environmental Protection Agency method 351.2 except that sample and reagent volumes are halved. Prepared digests are desolvated at 220 degrees Celsius (oC) and digested at 370oC in separate block digesters set at these temperatures, rather than in a single, temperatureprogrammed block digester. This approach permits 40 calibrants, reference materials, and samples to be digested and resolvated in about an hour. Ammonium ions originally present in samples, along with those released during the digestion step, are determined photometrically by an automated, salicylatehypochlorite Berthelot reaction procedure at a rate of 90 tests per hour. About 100 microliters of digest are required per determination. The upper concentration level is 10 milligrams per liter (mg/L) with a method detection level of 0.05 mg/L. Repeatability for a sample containing about 4.1 mg/L of Kjeldahl nitrogen in a high suspended-solids matrix is 3.1 percent. Between-day precision for the same sample is 4.8 percent. A gas diffusion cell in the air-segmented continuous flow analyzer eliminates particulates and ions that otherwise would interfere in the photometric finish. A singlechannel analyzer can process the resolvated digests from two pairs of block digesters each hour. Statistical analysis of paired data for about 1,500 samples determined by U.S. Geological Survey methods I-2552-85/4552- 85 and I-2515-91/4515-91 during method validation revealed a median concentration difference between the former and the latter methods of about 0.1 mg-N/L. This result was expected because digestion blank concentrations (nearly equal to 0.1 mg/L) were not subtracted from concentrations reported by methods I-2552-85/4552-85. A 10-year record of National Water Quality Laboratory Kjeldahl nitrogen blind blank concentration data also supports a step-change decrease in Kjeldahl nitrogen concentrations of about 0.1 mg/L after methods I-2552-85/4552-85 were replaced by methods I-2515-91/4515-91 on October 1, 1991. Somewhat larger concentration differences between the two methods were observed for a subset of about 350 samples with nitrate plus nitrite concentrations greater than 1 mg-N/L.