Museum-archived and recent acquisition nitrates from the Atacama Desert, Chile, South America: refinement of the dual isotopic compositions (δ15N vs. δ18O).

Sodium nitrate ores from the Atacama Desert in South America were economically important as they represented huge natural resources for the fertilizer and explosives industries during the early nineteenth to early twentieth centuries. Nitrogen and oxygen isotope ratios (δ15N and δ18O) of these desert nitrates generally show unique compositions (from close to 0 and up to ca. +50 ‰, respectively). The nitrates indicate the provenance as atmospheric in origin due to the mass-independent photochemical reaction of nitric oxide (NO) with ozone (O3) in the atmosphere to produce nitrate (NO3-). This paper examines the previously existing isotope data for specimens acquired from the Atacama Desert. It then reports new data from dual isotope analysis of historic nitrate specimens archived in museums in the UK. In the stable isotope signatures for nitrates from two areas of the Atacama Desert, Tarapacá in the north and Antofagasta in the south, were examined, and this analysis enabled a more detailed definition of their isotopic compositional ranges. This improved database is useful for tracing the provenance of the historic nitrates used in gunpowder and saltpetre, and also the cause of nitrate pollution in natural environments for which routine chemistry alone cannot provide the definite evidence for the origin.

Dual isotopic (δ15N-δ18O) characterization of saltpetre currently prevailing in Lao PDR and its global compilation: new insight into isotope fractionation during production processes.

Saltpetre (KNO3; potassium nitrate) is one of the major ingredients of gunpowder. Simplex saltpetre (total 126 samples) together with gunpowder (total 93 samples) commodities which are currently prevailing in local markets as used for wildlife hunting and rocket festivals (local name in Lao: Boun Ban Fai) were collected from throughout Lao PDR. Dual isotopic composition of nitrates (δ15N, δ18O) was analyzed by the microbial denitrification method. Binary plotting of the data was conducted to characterize the mode of formation. In Lao PDR, almost all the commodities were imported from neighbouring Thailand, and to a lesser extent from Israel. Binary plotting of δ15N vs. δ18O of nitrates shows their intrinsic origin manufactured by Haber-Bosch and subsequently Ostwald processes. We observed an inverse correlation (δ15Nnitrate: up to + 12 ‰; δ18Onitrate: down to + 15 ‰), deviating from the reservoir values (free air) of δ15N (dinitrogen; up to 0 ‰) and δ18O (oxygen; +23.5 ‰), interpreted this as an indication of isotope fractionation during manufacture. The most plausible interpretation for this is the fractionation associated with formation of NO following NO2 and finally NO3 products. A nearly comparable inverse relationship is also observed for nitrates in pyrotechnics manufactured in China.

Dual (oxygen and nitrogen) isotopic characterization of the museum archived nitrates from the United States of America, South Africa and Australia.

Dual (oxygen and nitrogen) isotopic composition of the museum archived nitrates from the United States of America, South Africa and Australia was studied. The analyzed specimens were collected in middle 19th to early 20th centuries, and represent world-wide acquisition of the Smithsonian Institution Natural Museum of Natural History (Washington, D. C., USA) and the Natural History Museum (London, UK). The samples consist of transparent to semi-transparent aggregates of minute nitrate, euhedral crystallites which imply precipitation from percolating fluids under ample space and dry regimes. The major nitrate chemistry is saltpetre (KNO3) with minor nitratine (NaNO3). A binary plot of δ15N vs. δ18O of almost all nitrates indicates a trend, reflecting microbial origin through nitrification of ammonium. The diagram excludes the contribution of meteoric origin formed by mass-independent, photochemical reaction of NO with ozone in stratosphere. Calculated paleo-ambient fluid compositions responsible for microbial nitrification imply extreme evaporative concentration of relevant fluids under dry climatic regimes in the Northern Cape Province (South Africa) and in the Northern Territory (central Australia), and even throughout the United States of America. The dual isotopic characterization provides direct evidence to the origin of the museum archived nitrates.

Diet-consumer nitrogen isotope fractionation for prolonged fasting arthropods.

Nitrogen acquisition for cellular metabolism during diapause is a primary concern for herbivorous arthropods. Analyses of naturally occurring stable isotopes of nitrogen help elucidate the mechanism. Relevant articles have cited (58 times up to mid-June 2011) anomalously elevated δ(15)N (per mil deviation of (15)N/(14)N, relative to atmospheric nitrogen=0 ‰) values (diet-consumer nitrogen isotope fractionation; up to 12 ‰) for a prolonged fasting raspberry beetle (Byturus tomentosus Degeer (Coleoptera: Byturidae)), which feeds on red raspberries (Rubus idaeus: δ(15)N= ~ +2 ‰). Biologists have hypothesised that extensive recycling of amino acid nitrogen is responsible for the prolonged fasting. Since this hypothesis was proposed in 1995, scientists have integrated biochemical and molecular knowledge to support the mechanism of prolonged diapausing of animals. To test the validity of the recycling hypothesis, we analysed tissue nitrogen isotope ratios for four Japanese arthropods: the shield bug Parastrachia japonensis Scott (Hemiptera: Cydnidae), the burrower bug Canthophorus niveimarginatus Scott (Hemiptera: Cydnidae), leaf beetle Gastrophysa atrocyanea Motschulsky (Coleoptera: Chrysomelidae) and the Japanese oak silkworm Antheraea yamamai (Lepidoptera: Saturniidae), all of which fast for more than 6 months as part of their life-history strategy. Resulting diet-consumer nitrogen isotope discrimination during fasting ranged from 0 to 7‰, as in many commonly known terrestrial arthropods. We conclude that prolonged fasting of arthropods does not always result in anomalous diet-consumer nitrogen isotope fractionation, since the recycling process is closed or nearly closed with respect to nitrogen isotopes.

Effects of pre-treatment on the nitrogen isotope composition of Japanese black pine (Pinus thunbergii) tree-rings as affected by high N input.

Temporal changes in the acquisition of nitrogen (N) are recorded in tree-rings together with unique N isotopic values. Some debate continues regarding the importance of wood pre-treatment in isotope analysis and, thus, this study focuses on the removal of labile components to determine the intrinsic nature of N in tree-rings. The total concentration and stable isotopic value of N in annual tree-rings were determined for two cores from Japanese black pine (Pinus thunbergii) from areas colonized by black cormorant (Phalacrocorax carbo). One core sample was also collected from a control site, without cormorants. Sharp increases in tree-ring δ(15)N values associated with migration of the cormorant population indicate positive incorporation of N from soils, whereas a less pronounced trend was observed for ring samples for periods without or substantially less migration, and for those obtained from the control site. All labile N components were removed by repeated extraction with toluene/ethanol (1:1) solution. Radial translocation of labile N is limited in tree-rings from Japanese black pine, providing intrinsic records on N acquisition. The difference in N isotopic values (up to 7.0‰) following pre-treatment was statistically significant for trees affected by the avian colony, whereas the pre-treatment of the control samples did not influence N values. The implication is that in agreement with previous studies pre-treatment is not necessary when trees are exposed to natural N concentrations in the soil but the removal of enriched δ(15)N labile components is necessary when woody plants are exposed to unusually high inputs of N into soils. However, the temporal trend in tree-ring δ(15)N series of the avian N affected trees did not change. Thus, if the priority is not the value but the trend then pre-treatment is not necessary.

Differential response of two Pinus spp. to avian nitrogen input as revealed by nitrogen isotope analysis for tree rings.

Temporal variations in N concentration and δ(15)N value of annual tree rings (1 year of time resolution) of two Japanese Black Pine (Pinus thunbergii) and three Japanese Red Pine (Pinus densiflora) trees under current breeding activity of the Great Cormorant (Pharacrocorax carbo) and the Black-tailed Gull (Larus crassirostris), respectively, in central and northeastern Japan were studied. Both species from control sites where no avian input occurs show negative values (δ(15)N = around -4 ‰ to -2 ‰) which are common among higher plants growing under high rainfall regimes. The δ(15)N values of P. densiflora show uniformly positive values several years before and after the breeding event, indicating N translocation that moved the absorbed N of a given growth year to tree rings of the previous year while a clear historical value of soil N dynamics was kept intact in the annual rings of P. thunbergii. Long-term N trends inferred from tree rings must take into account tree species with limited translocation rates that can retain actual N annual acquisition.