The free amino acid composition of seawater obtained without desalting and preconcentration

A conventional amino acid analyzer was modified to allow detection of dissolved free amino acids in a direct injection of 0.5 to 2.0 ml of seawater. The amino acids were monitored fluorimetrically by reaction with o-phthaldialdehyde after column chromatography. The accuracies of two commonly employed desalting methods, cation exchange resin and copper Chelex, were determined by comparison with the direct injection method. After correcting the results of the desalting methods for the procedural blank and recovery rate for each individual amino acid, the amino acid compositions on a mole percent basis as determined by these methods resembled approximately the true composition determined by direct injection. However, on an absolute basis the cation resin method overestimates and the copper Chelex method underestimates the total amount of dissolved free amino acids. The reasons for these discrepancies are discussed. Using the direct injection method, the spectra of dissolved free amino acids in surface seawater samples from different locations were determined. As opposed to the relatively uniform patterns reported in most past investigations, the amino acid spectra found were highly variable. In a number of samples, the acidic amino acids dominated the spectra. Valine was also high in many samples. In a depth profile the deep samples were dominated by arginine. Application of the method to real-time shipboard analyses of dissolved free amino acids is discussed.