Anoxic nitrification: Evidence from Humber Estuary sediments (UK)

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.     

The mass accommodation coefficient of ammonia on water

The mass accommodation coefficient of ammonia gas on water has been determined by measuring the absorption rate of 50–200 ppm NH₃ in one atm of air or helium into a liquid jet of 97 µm diameter as function of the exposed jet length, and comparing the results with numerical simulations which treat as the only free parameter. The model considers in detail transport of NH₃ by molecular diffusion, penetration of the gas/water interface, hydrolysis in the acidified water, and transport of the solutes from the surface into the jet. A correction is applied for the time evolution of the jet surface speed, using literature data on the fluid mechanics of liquid jets. The result of nine sets of independent measurements is

Os水吸收液ICP-MS测量信号强度衰减原因研究

蒸馏法能从样品中有效分离出OsO_4,吸收液直接用于ICP-MS测定,是辉钼矿Re-Os定年的关键技术环节。但实验发现,长时间放置的吸收液中Os信号强度显著降低。根据OsO_4化学性质推测原因在于一是挥发使吸收液Os含量减少,二是还原使+8价Os变成低价态,气态比例降低,若雾化效率不变,进入质谱仪的Os减少,两者都会导致信号降低,但具体影响情况不明,需深入研究。本文利用辉钼矿标准物质制备不同放置时间、酸度和温度的吸收液,对比上述条件对ICP-MS信号强度的影响。实验时将残余吸收液与稀释剂、氧化剂封入Carius管加热蒸馏,测定Os含量。结果表明:吸收液放置时间越长,酸度越低,温度越高,信号降幅越大,幅度达到3.2%~68.6%。室温下放置相同时间,低酸度吸收液的Os保存率高于高酸度吸收液,但Os信号强度低于后者,证明了挥发和还原共同导致信号衰减,且还原是主导原因。本文提出,冷冻(-18℃)可抑制OsO_4挥发,提高酸度(约3.5 mol/L)可减弱OsO_4还原,两者结合抑制信号衰减,提高了蒸馏法的灵活性和适用性。     

Emission of aliphatic amines from animal husbandry and their reactions: Potential source of N2O and HCN

We measured the emissions of volatile aliphatic amines and ammonia produced by the manure of beef cattle, dairy cows, swine, laying hens and horses in livestock buildings. The amine emissions consisted almost exclusively of the three methylamines and correlated with those of ammonia. The molar emission ratios of the methylamines to ammonia, and data on NH₃ emissions from animal husbandry in Europe, together with global statistics on domestic animals, were used to estimate the global emissions of amines. Annual global methylamine-N input to the atmosphere from animal husbandry in 1988 was 0.15±0.06 TgN (Tg=10¹² g). Almost 3/4 of these emissions consisted of trimethylamine-N. This represents about half of all methylamine emissions to the atmosphere. Other sources are marine coastal waters and biomass burning.Possible reaction pathways for atmospheric methylamines are shown. Among various speculative but possible products N₂O and HCN are of interest because the emission of methylamines could contribute to the global budgets of these compounds. Maximum atmospheric N₂O production from methylamines are below 0.4 Tg N/year, which is less than 10% of the annual N₂O growth rate. Although we do not expect the methylamine emissions to contribute in a major way to the atmospheric N₂O budget, more studies are needed to establish this conclusion beyond doubt. Similar conclusions hold for HCN.     

Characterisation of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

Tobelite (NH₄) Al₂ [AlSi₃O₁₀] (OH)₂, the ammonium analogue of muscovite, and its deuterated form ND₄-tobelite (ND₄) Al₂ [AlSi₃O₁₀] (OD)₂ have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO₂-Al₂O₃ oxide mix with Al₂O₃ in excess of 5 mol% and a 25% NH₃ solution whose relative abundance was such that the amount of NH₄ ⁺ stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND₄-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K⁺ in muscovite, the NH₄ ⁺ or ND₄ ⁺ molecule occupies the interlayer site. IR absorption bands caused by NH₄ ⁺ and ND₄ ⁺ can be explained, to a very good approximation, on the basis of T_d symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal T_d symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K⁺ by NH₄ ⁺ has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND₄-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M ₁ (C2/c) and 2M ₂ (C2/c). Tobelite and ND₄-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND₄-tobelite synthesised at 200 Mpa, is 2M ₂. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH₄ ⁺ or ND₄ ⁺ compared to K⁺ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND₄-tobelite.     

The ocean as source or sink of reactive trace-gases

Summary After a brief review on recent experimental work on the uptake resp release of SO₂ and NH₃ by the ocean, new results on the distribution of these reactive trace-gases in the marine atmosphere are presented. In the case of SO₂ there is no doubt that the ocean acts as a sink. In the case of NH₃ new observations and calculations show that under certain conditions the ocean may be a NH₃ source.     

稳定同位素分馏蒸汽压效应的计算方法

稳定同位素分馏的蒸汽压效应（vaporpressureisotopeeffects,简称VPIE）,在地球化学和天体化学上有着非常重要的研究意义。大部分情况下,由于轻重同位素体具有不同的蒸汽压,在经历挥发和蒸发过程时,含有重同位素的物种挥发得慢,轻同位素物种挥发得快,最终结果导致凝聚相富集重同位素,气相含有较多的轻同位素。在地球化学上,VPIE直接同非常重要的地学参数——同位素平衡分馏系数仅联系在一起。本文应用Bigeleisen提出的方法,直接将VPIE和约化配分函数比（RPFR）相联系,只需要通过理论计算获得两种物质的简谐振动频率,就能够得到非高压情况下该物质的VPIE。本文以水和硫镉矿（CdS）为例,详细介绍了如何计算蒸发和气化过程VPIE的方法,并指出了其在天体化学和矿床学中的一些潜在应用。     

Hypervelocity impact craters in ammonia rich ice

Research on the impact cratering process on icy bodies has been largely based on the most abundant ice, water. However little is known about the influence of other relatively abundant ices such as ammonia. Accordingly, data are presented studying the influence on cratering in ammonia rich ice using spherical 1 mm diameter stainless steel projectiles at velocities of 4.8±0.5 km s⁻¹. The ice target composition ranged from pure water ice, to solutions containing 50% ammonia and 50% water by weight. Results for crater depth, diameter, volume and depth/diameter ratio are given. The results showed that the presence of ammonia in the ice had a very strong influence on crater diameter and morphology. It was found that with only a 10% concentration of ammonia, crater diameter significantly decreased, and then at greater concentrations became independent of ammonia content. Crater depth was independent of the presence of ammonia in the ice, and the crater volume appeared to decrease as ammonia concentration increased. Between ammonia concentrations of 10 and 20% crater morphology visibly changed from wide shallow craters with a deeper central pit to craters with a smoothly increasing depth from the crater rim to centre. Thus, a small amount of ammonia within a water ice surface may have a major effect on crater morphology.     

Chemical dynamics of N-containing ionic species in a boreal forest snowcover during the spring melt period

A study of the changes in the ionic loads of NO, NH, SO and H⁺ in a boreal forest snowpack at Lake Laflamme, Québec was carried out using hydrological and chemical data from field lysimeters. The results showed that depletion of the N-containing species occurs periodically in the snowpack during meltwater discharge. Rain-on-snow events led to in-pack losses of NO and NH at a rate of 130 μeq m^?2 day^?1 and 101·3 μeq m^?2day^?1 respectively. On dry days, however, dry deposition and deposition of organic debris from the canopy resulted in increases of 183·3 μeq m^?2day^?1 for NO and 4·5 μeq m^?2day^?1 for NH in the pack. In contrast, SO₄^2? showed continual in-pack increases due to deposition of 5·0 μeq m^?2day^?1 for wet days and 92·6 μeq m^?2day^?1 for dry days. The depletion of NO and NH is due to microbiological uptake of these nutrients during periods when the free water content of the pack is high. Controlled melts in a laboratory snowmelt simulator containing snow and organic matter from the forest canopy at Lake Laflamme showed losses of NO and NH similar to those observed in the field. As the microbiological uptake proceeds at a rate comparable to that of ionic load increases in the pack by dry deposition, models of the chemical dynamics of snowmelt should take the former into account in any system where organic content of the snowpack is appreciable.