Elsevier

Marine Chemistry

Volume 78, Issue 4, June 2002, Pages 171-184
Marine Chemistry

A preliminary methods comparison for measurement of dissolved organic nitrogen in seawater

https://doi.org/10.1016/S0304-4203(02)00020-8Get rights and content

Abstract

Routine determination of dissolved organic nitrogen (DON) is performed in numerous laboratories around the world using one of three families of methods: UV oxidation (UV), persulfate oxidation (PO), or high temperature combustion (HTC). Essentially all routine methods measure total dissolved nitrogen (TDN) and calculate DON by subtracting the dissolved inorganic nitrogen (DIN). While there is currently no strong suggestion that any of these methods is inadequate, there are continuing suspicions of slight inaccuracy by UV methods.

This is a report of a broad community methods comparison where 29 sets (7 UV, 13 PO, and 9 HTC) of TDN analyses were performed on five samples with varying TDN and DIN concentrations. Analyses were done in a “blind” procedure with results sent to the first author. With editing out one set of extreme outliers (representing 5 out of 145 ampoules analyzed), the community comparability for analyzing the TDN samples was in the 8–28% range (coefficient of variation representing one standard deviation for the five individual samples by 28 analyses). When DIN concentrations were subtracted uniformly (single DIN value for each sample), the comparability was obviously worse (19–46% cv). This comparison represents a larger and more diverse set of analyses, but the overall comparability is only marginally better than that of the Seattle workshop of a decade ago. Grouping methods, little difference was seen other than inconclusive evidence that the UV methods gave TDN values for several of the samples higher than HTC methods. Since there was much scatter for each of the groups of methods and for all analyses when grouped, it is thought that more uniformity in procedures is probably needed. An important unplanned observation is that variability in DIN analyses (used in determining the final analyte in most UV and PO methods) is essentially as large as the variability in the TDN analyses.

This exercise should not be viewed as a qualification exercise for the analysts, but should instead be considered a broad preliminary test of the comparison of the families of methods being used in various laboratories around the world. Based on many independent analyses here, none of the routinely used methods appears to be grossly inaccurate, thus, most routine TDN analyses being reported in the literature are apparently accurate. However, it is not reassuring that the ability of the international community to determine DON in deep oceanic waters continues to be poor. It is suggested that as an outgrowth of this paper, analysts using UV and PO methods experiment and look more carefully at the completeness of DIN conversion to the final analyte and also at the accuracy of their analysis of the final analyte. HTC methods appear to be relatively easy and convenient and have potential for routine adoption. Several of the authors of this paper are currently working together on an interlaboratory comparison on HTC methodology.

Introduction

Although attempts to measure dissolved organic nitrogen (DON) in seawater extend over a century (at least as far back as Putter, 1909), it could probably be argued that modern methods began with publication of a method based on ultraviolet (UV) light oxidation (Armstrong et al., 1966). Because of apparent problems with incomplete oxidation of recalcitrant organic compounds by UV, use of the strong chemical oxidant, potassium persulfate, was introduced in the 1970s (see Koroleff, 1976) as an alternate method. There was indication that the persulfate oxidation (PO) method gave better recovery of standard chemicals and slightly higher values for DON in natural marine samples than the UV method D'Elia et al., 1977, Solorzano and Sharp, 1980. Similar higher values by PO than UV have been demonstrated for rainwater Cornell et al., 1995, Scudlark et al., 1998. Nonetheless, many laboratories have used some variant of either UV or PO methods for the past 20–30 years. Sometimes, UV methods use higher energy UV sources and different geometry than the original Armstrong et al.'s instrument; however, some current routine methods use essentially the same system as the original.

A high temperature combustion (HTC) method was described in the 1980s that appeared to measure considerably higher concentrations of DON in seawater (Suzuki et al., 1985) than either wet chemical method. While this method created considerable interest, other analysts were not able to reproduce the high DON values using HTC methods (e.g., Koike and Tupas, 1993, Hansell, 1993, Lopez-Vernoni and Cifuentes, 1995) and the method as originally published was eventually withdrawn (Suzuki, 1993). Essentially, all other HTC methods used since the early 1990s report DON values within the same range as the wet chemical methods. However, most comparisons have been indirect.

A direct comparison performed several years ago in one laboratory showed comparable results with both the UV and HTC methods and apparently comparable results with PO for oceanic samples (Walsh, 1989). Also, good comparability between HTC and PO methods was demonstrated for river and domestic wastewater samples (Ammann et al., 2000).

The DON subgroup report from the Seattle DOC/DON workshop evaluated published reports of various DON methods and unpublished results from the participants; they concluded that there was no strong indication of wet chemical methods giving lower yields than HTC methods (Hopkinson et al., 1993). A direct comparison was also made at that workshop by 13 analysts using a variety of HTC instruments and two wet chemical methods (Hedges et al., 1993). While agreement among the analyses was not great, there was no indication of wet chemical methods measuring less DON than HTC (Hedges et al., 1993). With data from the 13 analyses, the reproducibilities of analyses gave coefficients of variation values (see Section 2.2 below) of 9–49% for the four samples.

A direct comparison between a commercial HTC analyzer and PO and UV methods was done in Bronk's laboratory recently (Bronk et al., 2000). In that comparison, differences between methods were found for standard chemicals and for natural samples with differing distinctions. For example, the PO method gave best recovery of most standard chemicals, but not all, and the HTC method gave higher values for oceanic samples than wet chemical methods but did not for nearshore samples. The UV method, in its standard format, appeared not to give complete recovery for standard compounds and gave lower values for natural samples. When modified using persulfate as an added oxygen source instead of peroxide, the UV method gave better results. Most of the natural samples in this comparison had relatively high DON content. One oceanic sample appeared to give comparable results by HTC and PO but lower values by UV even with the modified chemistry. It was concluded that different methods have advantages for different types of samples (Bronk et al., 2000).

At this time, large differences in DON concentrations are not expected by different methods, and there is an inherent assumption that all methods are acceptable. However, recent publications give indirect comparison of large scatter for subsurface oceanic DON concentrations. Examining some of the recent literature, DON concentrations for oceanic samples below 200 m ranged from less than 2 to over 8 μM N Hansell and Waterhouse, 1997, Kahler et al., 1997, Wheeler et al., 1997, Ogawa et al., 1999. These reports represent use of UV, PO, and two hybrid HTC methods. Thus, it appears that a broad community evaluation of DON methodology is timely.

Several of us involved in this paper (Sharp, Hansell, Burdige, Cauwet, and Ogawa) started a small-scale methods comparison recently; results of which have been reported in national meetings. Samples from an oceanic depth profile and from an estuarine gradient were analyzed by UV, PO, and HTC methods. For the depth profile, there was relatively good agreement for total dissolved nitrogen (TDN) analysis but after subtracting the large dissolved inorganic nitrogen (DIN) concentration, the variability for the small remaining DON pool was large in relative terms. In the estuarine gradient with TDN concentrations in the range of 10–50 and DON in the range of 7–9, good agreement was found (unpublished data). A larger community effort was thought to be the best next step.

This study involves a comparison of a small number of samples by a large number of analysts, i.e., a broad community comparison with replicate samples sent to all interested participants. The comparison represented here is different from recent DOC comparisons (Sharp et al., 2002) in that it included only five samples, all seawater, and no blank or pure water references were included. Also, the majority of analysts participating in the DOC comparison used HTC methods; the majority for this DON comparison used wet chemical methods.

Section snippets

Samples, sample preparation, and analysts

Five samples were used, from estuarine, coastal, and open ocean surface and deep environments. Most samples were aged for several months to allow oxidation of more reduced inorganic ions (NH4+ and NO2) to the highest oxidation state (NO3) and decomposition of labile dissolved organic matter. The purpose of the aging, in 5-gal glass carboys closed with silicone rubber stoppers, was to render the samples stable for the period of time necessary to include a large number of analysts (about 6

Results

A number of laboratories also performed analysis of N&N prior to treatment for the TDN analysis and reported those data along with the TDN data. Some of them also analyzed for NO2 and NH4+. Results of all of these DIN data are listed in Table 4. For the 12 N&N analyses, the agreement is not very good (%cv values ranging from 13% to 73%). In addition, some samples by a few analysts had higher initial N&N than the final TDN for that same sample, potentially indicating error in initial DIN

Discussion

The three families of methods (HTC, PO, and UV) differ in chemistry of conversion of TDN and in complexity of analysis. The wet chemical methods entail oxidation of all nitrogen to the highest oxidation state in aqueous medium while the HTC methods use pyrolysis to yield an intermediate gaseous form that is not in the highest oxidation state. The HTC methods are more automatic with less handling while the other two methods involve more manual manipulation and, hence, have more potential for

Acknowledgements

This research was partially supported by NSF grants OCE 96-33296 and OCE 00-82238 to JHS, who also thanks Douglas Miller for assistance with statistical analysis of the data and John Hedges for data from the 1991 Seattle workshop. The results reported here were contributed by many individuals; in addition to the authors, all others listed in Table 2 made valuable contributions to the success of the research.

Associate editor: Dr. Edward T. Peltzer.

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