Separation of total nitrogen from sediments into organic and inorganic forms for isotopic analysis

Abstract

Nitrogen isotopic (δ 15N) analysis is widely applied in palaeoceanography, palaeolimnology and soil science. Most measurements are performed on untreated bulk samples containing both organic and inorganic nitrogen (ON and IN), which could sometimes confound isotopic signals. Here we propose a sample pretreatment method to physically and quantitatively separate the total nitrogen into ON and IN for subsequent concentration and isotopic measurements. In the method, the sediment is first demineralized with HCl and HCl–HF, adsorbed and bound IN being liberated into the acid solutions during the demineralization. Then, organic matter (OM) dissolved in the acid solutions is recovered by a sorbent of styrene divinyl benzene polymer (Bond Elut PPL, Varian) and is then combined with the acid-resistant OM to obtain the total OM. Finally, IN in the acid solutions passing through the PPL sorbent is recovered by way of steam distillation. Total nitrogen recovery with the method is 92.4% and isotopic mass balance calculations show that the δ 15N value of total nitrogen can be quantitatively partitioned into the organic and inorganic forms. The δ 13C values of the separated OM show a small positive excursion of 0.2‰ relative to those of bulk OM, ruling out significant loss of ON during the pretreatment. By comparison, the KOBr method, widely used to remove ON from bulk samples for isotope measurements, gives lower IN concentration and higher δ 15N IN values, attributed to the partial loss of IN and escape of some oxidation-resistant ON.