Isotopic evidence for the occurrence of biological nitrification and nitrogen deposition processing in forest canopies.

This study examines the role of tree canopies in processing atmospheric nitrogen (Ndep ) for four forests in the United Kingdom subjected to different Ndep : Scots pine and beech stands under high Ndep (HN, 13-19 kg N ha(-1)  yr(-1) ), compared to Scots pine and beech stands under low Ndep (LN, 9 kg N ha(-1)  yr(-1) ). Changes of NO3 -N and NH4 -N concentrations in rainfall (RF) and throughfall (TF) together with a quadruple isotope approach, which combines δ(18) O, Δ(17) O and δ(15) N in NO3 (-) and δ(15) N in NH4 (+) , were used to assess N transformations by the canopies. Generally, HN sites showed higher NH4 -N and NO3 -N concentrations in RF compared to the LN sites. Similar values of δ(15) N-NO3 (-) and δ(18) O in RF suggested similar source of atmospheric NO3 (-) (i.e. local traffic), while more positive values for δ(15) N-NH4 (+) at HN compared to LN likely reflected the contribution of dry NHx deposition from intensive local farming. The isotopic signatures of the N-forms changed after interacting with tree canopies. Indeed, (15) N-enriched NH4 (+) in TF compared to RF at all sites suggested that canopies played an important role in buffering dry Ndep also at the low Ndep site. Using two independent methods, based on δ(18) O and Δ(17) O, we quantified for the first time the proportion of NO3 (-) in TF, which derived from nitrification occurring in tree canopies at the HN site. Specifically, for Scots pine, all the considered isotope approaches detected biological nitrification. By contrast for the beech, only using the mixing model with Δ(17) O, we were able to depict the occurrence of nitrification within canopies. Our study suggests that tree canopies play an active role in the N cycling within forest ecosystems. Processing of Ndep within canopies should not be neglected and needs further exploration, with the combination of multiple isotope tracers, with particular reference to Δ(17) O.

Isotopic Fingerprint for Phosphorus in Drinking Water Supplies.

Phosphate dosing of drinking water supplies, coupled with leakage from distribution networks, represents a significant input of phosphorus to the environment. The oxygen isotope composition of phosphate (δ(18)OPO4), a novel stable isotope tracer for phosphorus, offers new opportunities to understand the importance of phosphorus derived from sources such as drinking water. We report the first assessment of δ(18)OPO4 within drinking water supplies. A total of 40 samples from phosphate-dosed distribution networks were analyzed from across England and Wales. In addition, samples of the source orthophosphoric acid used for dosing were also analyzed. Two distinct isotopic signatures for drinking water were identified (average = +13.2 or +19.7‰), primarily determined by δ(18)OPO4 of the source acid (average = +12.4 or +19.7‰). Dependent upon the source acid used, drinking water δ(18)OPO4 appears isotopically distinct from a number of other phosphorus sources. Isotopic offsets from the source acid ranging from -0.9 to +2.8‰ were observed. There was little evidence that equilibrium isotope fractionation dominated within the networks, with offsets from temperature-dependent equilibrium ranging from -4.8 to +4.2‰. While partial equilibrium fractionation may have occurred, kinetic effects associated with microbial uptake of phosphorus or abiotic sorption and dissolution reactions may also contribute to δ(18)OPO4 within drinking water supplies.

High-temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry: simultaneous measurement of the stable isotopes of oxygen and carbon in cellulose.

Stable isotope analysis of cellulose is an increasingly important aspect of ecological and palaeoenvironmental research. Since these techniques are very costly, any methodological development which can provide simultaneous measurement of stable carbon and oxygen isotope ratios in cellulose deserves further exploration. A large number (3074) of tree-ring α-cellulose samples are used to compare the stable carbon isotope ratios (δ(13)C) produced by high-temperature (1400°C) pyrolysis/gas chromatography (GC)/isotope ratio mass spectrometry (IRMS) with those produced by combustion GC/IRMS. Although the two data sets are very strongly correlated, the pyrolysis results display reduced variance and are strongly biased towards the mean. The low carbon isotope ratios of tree-ring cellulose during the last century, reflecting anthropogenic disturbance of atmospheric carbon dioxide, are thus overestimated. The likely explanation is that a proportion of the oxygen atoms are bonding with residual carbon in the reaction chamber to form carbon monoxide. The 'pyrolysis adjustment', proposed here, is based on combusting a stratified sub-sample of the pyrolysis results, across the full range of carbon isotope ratios, and using the paired results to define a regression equation that can be used to adjust all the pyrolysis measurements. In this study, subsamples of 30 combustion measurements produced adjusted chronologies statistically indistinguishable from those produced by combusting every sample. This methodology allows simultaneous measurement of the stable isotopes of carbon and oxygen using high-temperature pyrolysis, reducing the amount of sample required and the analytical costs of measuring them separately.