Explore the vast range of titles available.

18O isotope exchange measurements of photosystem II (PSII) in thylakoids from wild-type and mutant Synechocystis have been performed to investigate binding of substrate water to the high-affinity Mn4 site in the oxygen-evolving complex (OEC). The mutants investigated were D1-D170H, a mutation of a direct ligand to the Mn4 ion, and D1-D61N, a mutation in the second coordination sphere. The substrate water 18O exchange rates for D61N were found to be 0.16±0.02 s−1 and 3.03±0.32 s−1 for the slow and fast phases of exchange, respectively, compared with 0.47±0.04 s−1 and 19.7±1.3 s−1 for the wild-type. The D1-D170H rates were found to be 0.70±0.16 s−1 and 24.4±4.6 s−1 and thus are almost within the error limits for the wild-type rates. The results from the D1-D170H mutant indicate that the high-affinity Mn4 site does not directly bind to the substrate water molecule in slow exchange, but the binding of non-substrate water to this Mn ion cannot be excluded. The results from the D61N mutation show an interaction with both substrate water molecules, which could be an indication that D61 is involved in a hydrogen bonding network with the substrate water. Our results provide limitations as to where the two substrate water molecules bind in the OEC of PSII.

We investigated the fusion of high-speed liquid droplets as a way to record the kinetics of liquid-phase chemical reactions on the order of microseconds. Two streams of micrometer-size droplets collide with one another. The droplets that fused (13 μm in diameter) at the intersection of the two streams entered the heated capillary inlet of a mass spectrometer. The mass spectrum was recorded as a function of the distancexbetween the mass spectrometer inlet and the droplet fusion center. Fused droplet trajectories were imaged with a high-speed camera, revealing that the droplet fusion occurred approximately within a 500-μm radius from the droplet fusion center and both the size and the speed of the fused droplets remained relatively constant as they traveled from the droplet fusion center to the mass spectrometer inlet. Evidence is presented that the reaction effectively stops upon entering the heated inlet of the mass spectrometer. Thus, the reaction time was proportional toxand could be measured and manipulated by controlling the distancex. Kinetic studies were carried out in fused water droplets for acid-induced unfolding of cytochromecand hydrogen–deuterium exchange in bradykinin. The kinetics of the former revealed the slowing of the unfolding rates at the early stage of the reaction within 50 μs. The hydrogen–deuterium exchange revealed the existence of two distinct populations with fast and slow exchange rates. These studies demonstrated the power of this technique to detect reaction intermediates in fused liquid droplets with microsecond temporal resolution.

• Understanding P uptake in soil–plant systems requires suitable P tracers. The stable oxygen isotope ratio in phosphate (expressed as δ18OP) is an alternative to radioactive labelling, but the degree to which plants preserve the δ18OP value of the P source is unclear. We hypothesised that the source signal will be preserved in roots rather than shoots. • In soil and hydroponic experiments with spring wheat (Triticum aestivum), we replaced irrigation water by 18O-labelled water for up to 10 d. We extracted plant inorganic phosphates with trichloroacetic acid (TCA), assessed temporal dynamics of δ18OTCA-P values after changing to 18O-labelled water and combined the results with a mathematical model. • Within 1 wk, full equilibration of δ18OTCA-P values with the isotope value of the water in the growth medium occurred in shoots but not in roots. Model results further indicated that root δ18OTCA-P values were affected by back transport of phosphate from shoots to roots, with a greater contribution of source P at higher temperatures when back transport was reduced. • Root δ18OTCA-P partially preserved the source signal, providing an indicator of P uptake sources. This now needs to be tested extensively for different species, soil and climate conditions to enable application in future ecosystem studies.

Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.

In batch experiments, we studied the isotope fractionation of nitrogen and oxygen during denitrification of two bacterial strains (Azoarcus sp. strain DSM 9056 and Pseudomonas pseudoalcaligenes strain F10). Denitrification experiments were conducted with succinate and toluene as electron donor in three waters with a distinct oxygen isotope composition. Nitrate consumption was observed in all batch experiments. Reaction rates for succinate experiments were more than six times higher than those for toluene experiments. Nitrogen and oxygen isotopes became progressively enriched in the remaining nitrate pool in the course of the experiments; the nitrogen and oxygen isotope fractionation varied between 8.6-16.2 and 4.0-7.3‰, respectively. Within this range, neither electron donors nor the oxygen isotope composition of the medium affected the isotope fractionation process. The experimental results provide evidence that the oxygen isotope fractionation during nitrate reduction is controlled by a kinetic isotope effect which can be quantified using the Rayleigh model. The isotopic examination of nitrite released upon denitrification revealed that nitrogen isotope fractionation largely follows the fractionation of the nitrate pool. However, the oxygen isotope values of nitrite are clearly influenced by a rapid isotope equilibration with the oxygen of the ambient water. Even though this equilibration may in part be due to storage, it shows that under certain natural conditions (re-oxidation of nitrite) the nitrate pool may also be indirectly affected by an isotope equilibration.

The authors continue their set of studies on the separation of boron isotopes by means of chemical exchange in liquid–liquid systems using tri- n -octylamine as the main component of the organic phase. Degree of separation K = 1.0961 ± 0.0016 was obtained using experimental modeling of the operation of a rectangular cascade for separating boron isotopes in a 30-h long period of separation in the mode of product extraction. The obtained data are used to determine period τ = 19–21 h of concentration needed to reach a steady state when operating with product extraction at maximum degree of separation K m = 1.109. The time needed to reach a steady state is τ = 130–160 h when operating in the mode without product extraction, which corresponds to maximum degree of separation K m = 1.131.

We report a simple approach for enumeration of non-labile oxygen atoms in individual molecules of dissolved organic matter (DOM), using acid-catalyzed [.sup.16]O/[.sup.18]O exchange and ultrahigh-resolution Fourier-transform ion-cyclotron-resonance mass spectrometry (FTICR-MS). We found that by dissolving DOM in [H.sub.2][.sup.18]O at 95 °C for 20 days it is possible to replace all oxygen atoms of DOM molecules (excluding oxygen from ether groups) with [.sup.18]O. The number of exchanges in each molecule can be determined using highresolution FTICR. Using the proposed method we identified the number of non-labile oxygen atoms in 231 molecules composing DOM. Also, using a previously developed hydrogen-deuterium (H/D)-exchange approach we identified the number of labile hydrogen atoms in 450 individual molecular formulas. In addition, we observed that several backbone hydrogen atoms can be exchanged for deuterium under acidic conditions. The method can be used for structural and chemical characterization of individual DOM molecules, comparing different DOM samples, and investigation of biological pathways of DOM in the environment. Keywords Isotope exchange * Dissolved organic matter * FTICR * ESI

Amide (NH) proton exchange rates were measured in 0.0 to 0.7 M guanidinium chloride (GdmCl) for 23 slowly exchanging peptide NH protons of ribonuclease A (RNase A) at pH* 5.5 (uncorrected pH measured in D$_2$O), 34°C. The purpose was to find out whether GdmCl induces exchange through binding to exchange intermediates that are partly or wholly unfolded. It was predicted that, when the logarithm of the exchange rate is plotted as a function of the molarity of GdmCl, the slope should be a measure of the amount of buried surface area exposed to GdmCl in the exchange intermediate. The results indicate that these concentrations of GdmCl do induce exchange by means of a partial unfolding mechanism for all 23 protons; this implies that exchange reactions can be used to study the unfolding and stability of local regions. Of the 23 protons, nine also show a second mechanism of exchange at lower concentrations of GdmCl, a mechanism that is nearly independent of GdmCl concentration and is termed \"limited structural fluctuation.\"

Variants of combined technologies for separating isotopes of light chemical elements, using both thermodynamically reversible and irreversible separation methods, are considered from a historical point of view. The main criteria for assessing the efficiency of combining different isotope separation processes are indicated. Based on the specified criteria, a number of problems of obtaining highly enriched carbon-13 and boron-10 isotopes are analyzed.

Diffusion of hydrogen in natural alkali feldspars (Eifel sanidine and adularia from unknown locality) containing strongly bonded OH defects was investigated by D/H isotope exchange in the T range 600–1050 °C at ambient pressure and at elevated pressures up to 8 kbar. Runs at 1 atm were performed in a fused silica tube connected to a liquid D 2 O reservoir at room temperature. In the high- pressure experiments samples were sealed with D 2 O in gold capsules and processed up to 4 kbar in externally heated pressure vessels using Ar/D 2 O as the pressure medium. Experiments at 6–8 kbar were performed in an internally heated gas pressure vessel using the double capsule technique to minimize isotopic contamination by the pressure medium. Diffusion coefficients were determined either by measuring concentration-distance profiles of OH and OD with an IR microscope or by measuring the total exchange of oriented plates after various run durations using a macroscopic IR technique. Both methods gave consistent data. D/H interdiffusion, D D/H , is almost identical in the adularia and in the sanidine implying that the chemical composition and the degree of Al/Si disorder have minor influence on the hydrogen isotope exchange in alkali feldspars. Furthermore, no effect of crystallographic orientation was found for D D/H in both feldspars. D D/H in sanidine, however, depends on the thermal pre-treatment. Heating for several days at 900 °C leads to a lowering of D by a factor of 2.3, indicating a corresponding decrease in mobile hydrogen species. Data for sanidine pre-annealed at 900 °C are well described in the T range 600–1050 °C by D D/H m 2 /s = 6.9 · 10 - 6 exp - 162 kJ / mol R · T The diffusivity is strongly enhanced by water pressures ( P H2O ), i.e., in the range of 0–2 kbar. At P H2O  = 2 kbar the following equation applies in the T -range of 645–800 °C: D D / H m 2 / s = 1.2 · 10 - 6 exp - 131 kJ / mol R · T Experiments with D 2 O/CO 2 mixture of ratio 1:1 gave smaller exchange rates compared to pure D 2 O fluids, confirming that that not the pressure but the water fugacity leads to the increase in the mobility of hydrogen species. At 720 °C and pressures of 4–8 kbar, chemical diffusivities of H 2 O, D ~ H 2 O , were determined by fitting the weighted sum of the absorbances of the OH and the OD band vs. distance. The D ~ H 2 O values are similar to those reported by Kronenberg et al. (Geochim Cosmochim Acta 60:4075–4094, 1996) for dehydration of Kristallina adularia at ambient pressure. It is concluded that in both cases high concentrations of H 2 O molecules on interstitial sites govern the transport of hydrogen. Comparison of D/H interdiffusion to O diffusion in sanidine (Freer et al. in Phil Mag A75:485–503, 1997) implies that not only interstitial H 2 O but also protons contribute to the transport of hydrogen under hydrothermal conditions. On the other hand, the high D D/H at ambient pressure is attributed to an interdiffusion of protons and Na + , which is supported by Na tracerdiffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363:79–84, 2015). A basic conclusion of this research is that hydrogen storage capacity and hydrogen diffusion in feldspars are largely determined by extrinsic defects, such as substitutional defects (i.e., Al 3+ +  H + for Si 4+ ) and associates of water molecules with vacancies. The bonding of hydrogen species to the defects can vary greatly, depending on the genesis of the feldspars, so that quantitative predictions are difficult.