Limnol. Oceanogr., 44(7), 1999, 1702–1714

Methods for quantifying total dissolved phosphorus (TDP) were reevaluated. High-temperature ashing/hydrolysis (Ash/Hydrol.) and Acid Persulfate methods were examined for their ability to quantitatively convert a range of organic-P compounds to orthophosphate. The Ash/Hydrol. method recovered on average 99% of organic-P compounds tested, including phosphonates (compounds with C-P bonds). Contrary to concerns voiced in prior studies, we found no P loss due to volatilization in seawater samples. Poor recovery by the Acid Persulfate method was observed for two compound classes: phosphonates and phospholipids. The Ash/Hydrol. method is recommended for routine TDP analyses. The hydrolysis of dissolved organic phosphorus (DOP) during the phosphomolybdate-blue reaction and the subsequent overestimation of dissolved inorganic phosphorus (DIP) have long been a concern. Extent of hydrolysis of standard DOP compounds was evaluated both during this reaction and over long-term acidified (pH 1.0)/refrigerated and unacidified/frozen storage. Eleven of 12 compounds tested hydrolyzed ,2% during the phosphomolybdate-blue reaction. Phospholipid, phosphosugar, and nucleotide monoand diphosphate standards stored acidified/refrigerated over 2.5 months were ,5% hydrolyzed; compounds with higher energy phosphate bonds (e.g., phosphocreatine) hydrolyzed to a greater extent. A natural seawater sample showed no hydrolysis over 80 d, however, suggesting that refrigerated storage of acidified samples is a viable option. Seasonal DOP profiles from the Eel River Shelf quantified by the Ash/Hydrol. and Acid Persulfate methods yielded comparable results, indicating that the DOP pool at this site did not contain significant phospholipids or phosphonates, which are underrecovered by the Persulfate method. Recoveries using a third method, Nitrate Oxidation, were on average 7% lower. Surface-water DOP exceeded DIP in summer and was apparently related to biological productivity, underscoring the need to include organic species when evaluating nutrient limitation and creating nutrient budgets. Despite early studies indicating the potential importance of DOP as a nutrient source to primary producers in marine systems (Redfield et al. 1937; Butler et al. 1979; Jackson and Williams 1985; Rivkin and Swift 1985; Orrett and Karl 1987), many past assessments of nutrient inventories and nutrient limitation have ignored dissolved organic nutrient reservoirs. DOP can be a significant fraction of the TDP pool in surface waters—in some cases, seasonally surpassing levels of DIP (Butler et al. 1979; Orrett and Karl 1987; Cotner et al. 1997; Karl and Tien 1997). Exclusion of DOP may lead to erroneous estimates of the bioavailable P reservoir, negatively affecting assessments of nutrient limitation and nutrient budgets. Two factors account for the lack of routine DOP data collection: (1) lack of appreciation of the role of P as a limiting nutrient in oceanic systems (e.g., Krom et al. 1 To whom correspondence should be addressed.