Strong Isotope-dependent Photodissociation Branching Ratios of N2 and Their Potential Implications for the 14N/15N Isotope Fractionation in Titan's Atmosphere

The origin and evolution of the 14N/15N ratio of Titan’s atmosphere has long been a subject of debate. Clearly a better understanding of the N isotopic fractionation mechanism would greatly help resolve this. Photodissociation of N2 by solar radiation has been suggested to either play a negligible role in fractionating the N isotopes in Titan, due to its rather low escape velocity, or to preferentially remove 15N through self-shielding controlled photochemical reactions. Here, we systematically measure the branching ratios of 14N15N between N(4S)+N(2P) and N(4S)+N(2D) channels. We find that many of its absorption states predominantly dissociate into N(4S)+N(2P) with a strong isotope effect between 14N2 and 14N15N. Since N atoms produced from N(4S)+N(2P) acquire velocities close to Titan’s escape velocity, these findings provide a new N isotope fractionation mechanism for Titan that has not been considered before, potentially providing important constraints on the origin and evolution of Titan’s N2-dominated atmosphere.

Behavior of the 238U, 235U, and 234U isotopes at weathering of volcanic rocks with u mineralization: a case study at the Tulukuevskoe deposit, Eastern Transbaikalia

The trend fractionation of the 238U and 235U isotopes and the extent of this process at the oxidative weathering of uranium minerals were evaluated by studying the variations in the U isotope composition of rocks, minerals, and fracture waters sampled in the quarry of the broadly known Tulukuevskoe uranium deposit in the Streltsovskoe ore field, eastern Transbaikalia. In the rock block in question, fine uranium minerals disseminated in the rocks were weathered under the effect of oxidizing fracture waters. Uranium isotope composition was measured in 22 water samples, eleven samples of the mineralized rocks, and eight uranium minerals. High-precision (±0.07‰, 2SD) measurements of the 238U/235U were carried out by MC-ICP-MS, using a 233U–236U double spike. The results involve the 238U/235U and 234U/238U ratios and the overall range of the δ238U variations determined in the rocks and waters (from –0.13 to –1.0‰ and from –0.22 to –0.59‰, respectively). Interaction between the waters and rocks induces U(IV) → U(VI) oxidation, U(VI) transfer into the aqueous phase, and 0.15–0.28‰ enrichment of U dissolved in the water in the 235U isotope. When the pitchblende is replaced by U(VI) minerals, the 238U and 235U isotopes also fractionate with ~0.3‰ enrichment of the younger U(VI) mineral phases in the light 235U isotope. The 238U/235U and 234U/238U ratios are proved to correlate, and hence, the fractionation of the 238U and 235U isotopes and the enrichment of the aqueous phase in the light 235U isotope proceed simultaneously with the well known shift in equilibrium the 238U–234U system with the accumulation of excess amounts of the 234U in the aqueous phase. Uranium leaching from uranium minerals, which is associated with the enrichment of the aqueous phase in excess amounts of the 234U isotope, can be viewed as a process that controls isotope fractionation in the 238U–235U system. This should be taken into account in describing the fractionation mechanism of the 238U and 235U isotopes at U(IV) → U(VI) oxidation. The fractionation of the 238U and 235U isotopes, which results in the isotopic "lightening" of U in the aqueous phase, largely controlled the complicated distribution pattern of the 238U/235U ratio in the quarry. In addition to isotope fractionation, this distribution was likely also affected by isotope exchange between uranium dissolved in the water and uranium in the finely dispersed minerals. The isotopically light uranium of the water could participate in forming U(VI) minerals at lower levels of the quarry.

The fractionation of nitrogen and oxygen isotopes in macroalgae during the assimilation of nitrate

In order to determine and understand the stable isotope fractionation of 18O and 15N manifested during assimilation of NO3− in marine macro-benthic algae, two species (Ulva sp. and Agardhiella sp.) have been grown in a wide range of NO3− concentrations (2–500 μM). Two types of experiments were performed. The first was one in which the concentration of the NO3− was allowed to drift downward as it was assimilated by the algae, between 24 hour replacements of media. These experiments proceeded for periods of between 7 and 10 days. A second set of experiments maintained the NO3− concentration at a low steady-state value by means of a syringe pump. The effective fractionation during the assimilation of the NO3− was determined by measuring the δ15N of both the (i) new algal growth and (ii) residual NO3− in the free-drift experiments after 0, 12, 24 and 48 h. Modelling these data show that the fractionation during assimilation is dependent upon the concentration of NO3− and is effectively 0 at concentrations of less than ~2 μM. The change in the fractionation with respect to concentration is the greatest at lower concentrations (2–10 μM). The fractionation stablizes between 4 and 6‰ at concentrations of between 50 and 500 μM. Although the δ18O and δ15N values of NO3− in the residual solution were correlated, the slope of relationship also varied with respect to NO3− concentration, with slopes of greater than unity at low concentration. These results suggest shifts in the dominant fractionation mechanism of 15N and 18O between concentrations of 1 and 10 μM NO3−. At higher NO3− concentrations (>10–50 μM), fractionation during assimilation will lead to δ15N values in algal biomass lower than the ambient NO3− and 15N enrichments in the residual NO3−.

The fractionation of nitrogen and oxygen isotopes in macroalgae during the assimilation of nitrate

In order to determine and understand the stable isotope fractionation of 18O and 15N manifested during assimilation of NO3− in marine macro-benthic algae, two species (Ulva sp. and Agardhiella sp.) have been grown in a wide range of NO3- concentrations (2–500 μM). Two types of experiments were performed. The first was one in which the concentration of the NO3− was allowed to drift downward as it was assimilated by the algae, between 24 h replacements of media. These experiments proceeded for periods of between seven and ten days. A second set of experiments maintained the NO3− concentration at a low steady state value by means of a syringe pump. The effective fractionation during the assimilation of the NO3− was determined by measuring the δ15N of both the (i) new algal growth, and (ii) residual NO3− in the free drift experiments after 0, 12, 24, and 48 h. Fitting models to these data show that the fractionation during assimilation is dependent upon the concentration of NO3− and is effectively zero at concentrations of less than 1 μM. The change in the fractionation with respect to concentration is the greatest at lower concentrations (1–10 μM). The fractionation determined using the δ15N of the NO3− or the solid algal material provided statistically the same result. Therefore, at typical marine concentrations of NO3−, fractionation during assimilation can probably be considered to be negligible. Although the δ18O and δ15N of NO3− in the residual solution were correlated, the slope of the relationship varied with NO3− concentration, with slopes of greater than unity at low concentration. These results suggest shifts in the dominant fractionation mechanism between 1 and 10 μM NO3−. At typical marine concentrations of NO3−, fractionation during assimilation can be considered to be negligible. However, at higher concentrations, fractionation during assimilation will lead to both δ15N values for algal biomass lower than the NO3− source, but also 15N enrichments in the residual NO3−.