Low energy electron attachment to cyanamide (NH2CN)

Cyanamide (NH2CN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. In the present investigation, dissociative electron attachment to NH2CN has been studied in a crossed electronmolecular beams experiment in the electron energy range from about 0 eV to 14 eV. The following anionic species were detected: NHCN-, NCN-, CN-, NH2-, NH-, and CH2-. The anion formation proceeds within two broad electron energy regions, one between about 0.5 and 4.5 eV and a second between 4.5 and 12 eV. A discussion of possible reaction channels for all measured negative ions is provided. The experimental results are compared with calculations of the thermochemical thresholds of the anions observed. For the dehydrogenated parent anion, we explain the deviation between the experimental appearance energy of the anion with the calculated corresponding reaction threshold by electron attachment to the isomeric form of NH2CN-carbodiimide(VLID)1020340Accepted versio

Challenges in measuring nitrogen isotope signatures in inorganic nitrogen forms: An interlaboratory comparison of three common measurement approaches

Rationale Stable isotope approaches are increasingly applied to better understand the cycling of inorganic nitrogen (Ni) forms, key limiting nutrients in terrestrial and aquatic ecosystems. A systematic comparison of the accuracy and precision of the most commonly used methods to analyze δ15N in NO3− and NH4+ and interlaboratory comparison tests to evaluate the comparability of isotope results between laboratories are, however, still lacking. Methods Here, we conducted an interlaboratory comparison involving 10 European laboratories to compare different methods and laboratory performance to measure δ15N in NO3− and NH4+. The approaches tested were (a) microdiffusion (MD), (b) chemical conversion (CM), which transforms Ni to either N2O (CM-N2O) or N2 (CM-N2), and (c) the denitrifier (DN) methods. Results The study showed that standards in their single forms were reasonably replicated by the different methods and laboratories, with laboratories applying CM-N2O performing superior for both NO3− and NH4+, followed by DN. Laboratories using MD significantly underestimated the “true” values due to incomplete recovery and also those using CM-N2 showed issues with isotope fractionation. Most methods and laboratories underestimated the at%15N of Ni of labeled standards in their single forms, but relative errors were within maximal 6% deviation from the real value and therefore acceptable. The results showed further that MD is strongly biased by nonspecificity. The results of the environmental samples were generally highly variable, with standard deviations (SD) of up to ± 8.4‰ for NO3− and ± 32.9‰ for NH4+; SDs within laboratories were found to be considerably lower (on average 3.1‰). The variability could not be connected to any single factor but next to errors due to blank contamination, isotope normalization, and fractionation, and also matrix effects and analytical errors have to be considered

Reconstructing seasonality using δ18O in incremental layers of human enamel : a test of the analytical protocol developed for SHRIMP IIe/MC ion microprobe

A number of recent studies dealing with palaeoclimate and environmental reconstruction include the measurement of oxygen isotope composition of mammalian teeth. Some of them analyse a temporal sequence of the changes recorded in bioapatite from enamel layers representing the whole period of tooth development. Enamel samples display large intra-tooth δ18O variations that may reflect a seasonal fluctuation in the δ18O of local palaeoclimate parameters. The present paper provides an effective analytical protocol for sequential δ18O analysis of human teeth using SHRIMP IIe/MC ion microprobe. It is possible to follow the inner enamel layer along enamel-dentine junction on a high spatial scale in a range about 0.02 mm of spot diameter and 0.12–0.14 mm of the distance between spots. Using the methodology described herein, we can achieve an external precision for δ18O analysis <0.2‰ (1σ). The number of 60 to 90 single analyses covering the enamel layer between the incisal and apical ends is enough to obtain temporal resolution of less than one month and to document precisely seasonal fluctuation caused by local environmental and climate factors. The methodology of δ18O in situ measurements has been tested on human teeth from Tell Majnuna, a 4th millennium BCE cemetery in Northern Mesopotamia, which is a relatively arid area with high seasonal differences in precipitation and temperature. Observed pattern of δ18O variations is consistent with expected seasonal fluctuations, although the overall effect is blurred by some inertia in the enamel maturation

Sulphur isotope measurements of sulphide minerals from the polymetallic ore deposits in the Sudetes, using the SHRIMP IIe/MC ion microprobe

W artykule opisano wyniki analiz izotopowych siarki siarczkowej przeprowadzonych po raz pierwszy w PIG-PIB za pomocą nowoczesnej mikrosondy jonowej SHRIMP IIe/MC. Rezultaty wskazują na dużą precyzję i szybkość analiz metodą SIMS oraz na wysoką powtarzalność wyników. W porównaniu z analizą stosunków izotopowych siarki konwencjonalną metodą spektrometrii gazowej IRMS stwierdzono zdecydowaną przewagę na korzyść techniki SIMS. W metodzie tej możliwa jest obserwacja analizowanej powierzchni w skali mikronów i precyzyjne wybranie miejsca analizy (ok. 20 μm), w tym uniknięcie inkluzji lub stref spękań w badanych kryształach siarczków. W przypadku analiz izotopowych siarki metodą konwencjonalną IRMS efekt homogenizacji próbek znacznie wpływa na końcowy wynik. Technika mikrosondy jonowej SIMS, dzięki wysokiej rozdzielczości przestrzennej, dostarcza bardziej szczegółowych wyników. Skład izotopowy siarki wyznaczony w wyniku badań próbek pirytów z rejonu zarzuconego złoża Au–Cu–As w Radzimowicach w nieznacznym stopniu odbiega od δ[sup]34[/sup]S = 0‰ (średnia ważona δ34S dla próbki 10B = +0,84 ±0,24‰ , n = 60, dla próbki M20 = +0,37 ±0,13‰, n = 35, a dla próbki M21 = –0,03 ±0,32‰, n = 26), co wskazuje na źródło siarki związane z magmą odpowiadającą stopom płaszczowym lub dolnoskorupowym. Z kolei w przypadku pirytu z wyrobiska w rejonie Leszczyńca uzyskano ujemne wartości δ34S poniżej –1‰ (zakres od –3,24 ±0,08‰ do –1,19 ±0,09‰), co świadczy o udziale procesu kontaminacji i o niewielkim wpływie osadowego protolitu podczas generacji stopu.Results of sulphur isotope analyses in sulphides by use of modern ion microprobe equipment – SHRIMP IIe/MC – are described in the paper. Measurements with an application of the SIMS method indicate high precision, fast procedure as well as high repeatability of results. Considering the sulphur isotopic ratio measured by the IRMS (the conventional method of gas spectrometry), advantage of the SIMS method is clearly visible. It allows for observation of the analysed surface at the micron-scale and for very precise selection of the area of analysis (about 20 μm in diameter), including the avoiding of other mineral microinclusions or microfractures in sulphide crystals, which are common features. In the case of the IRMS sulphur isotope analyses sample homogenization strongly influenced obtained results. The SIMS ion microprobe technique provides high spatial resolution which enables more reliable results. In the case of pyrites analysed from the abandoned Au–Cu–As Radzimowice deposit results of isotopic sulphur are close to δ34S = 0‰ (weighted average of δ34S for sample 10B is +0.84 ±0.24‰, n = 60, for sample M20 +0.37 ±0.13‰, n = 35, and for sample M21 –0.03 ±0.32‰, n = 26), which indicates the source of sulphur from processes related to magmas probably of mantle or lower crust origins. On the other hand pyrites from the old mining prospect in Leszczyniec have negative δ[sup]34[/sup]S values below –1‰ (ranging from –3.24 ±0.08‰ to –1.19 ±0.09‰), which suggest a contaminationprocess and possible minor input of sedimentary protolith during the magma generation

Formation of Negative Ions upon Dissociative Electron Attachment to the Astrochemically Relevant Molecule Aminoacetonitrile

Aminoacetonitrile (NH2CH2CN, AAN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. It is a very important molecule in the Strecker diagram explaining the formation of amino acids. In the present investigation, dissociative electron attachment to NH2CN was studied in a crossed electron-molecular beams experiment in the electron energy range from about 0 to 17 eV. In this electron energy range, the following six anionic species were detected: C2H3N2-, C2H2N2-, C2H2N-, C2HN-, CN, and NH2-. Possible reaction channels for all the measured negative ions are discussed, and the experimental results are compared with calculated thermochemical thresholds of the observed anions. Similar to other nitrile and aminonitrile compounds, the main anions detected were the negatively charged nitrile group, the dehydrogenated parent molecule, and the amino group. No parent anion was observed. Low anion yields were observed indicating that AAN is less prone to electron capture. Therefore, AAN can be considered to exhibit a relatively long lifetime under typical conditions in outer space.(VLID)2519684Submitted versio