Restoring Halite Fluid Inclusions as an Accurate Palaeothermometer: Brillouin Thermometry Versus Microthermometry

Halite traps inclusions of the mother fluid when precipitating. When unchanged, the density of these fluid inclusions (FIs) records the water temperature T_f at the time of crystal formation. As halite is ubiquitous on Earth and geological time, its FIs possess a high potential as temperature archives. However, the use of FIs in halite as an accurate palaeothermometer has been hampered due to limitations of microthermometry, the most commonly used analytical method. Here, we show how Brillouin spectroscopy in halite FIs bypasses these limitations and allows recovering T_f to within 1 °C or less. To demonstrate this, we measured samples synthesised at 24.6 ± 0.5 °C and 33 ± 1 °C, and obtained 24.8 ± 0.4 °C and 31.9 ± 0.4 °C, respectively. This novel approach thus provides an accurate palaeothermometer for lacustrine and marine environments. Moreover, Brillouin spectroscopy solves the long‐standing debate on damage of halite fluid inclusions through quantifying the acceptable temperature excursion for preserving elastic behaviour: [l/(1 µm)]^?0.64 × (90 °C), where l is the FI size. This threshold is lower for FIs close to the surface of the host crystal or to another FI. We also list ‘best practices’ for applying both microthermometry and Brillouin thermometry.     

利用薄膜扩散平衡技术分析沉积物间隙水溶解态反应性磷

沉积物间隙水溶解态反应性磷(SRP)是反映沉积物磷地球化学特征的敏感指标,对其高分辨率获取一直是难点.基于薄膜扩散平衡(DET)原理,以琼脂糖为原料制备薄膜,通过平衡、切片、提取、测定等步骤,获得溶解态反应性磷的含量信息.实验确定薄膜在磷溶液中的平衡时间为24h,通过0.25mol/L硝酸提取16h可将薄膜萃取的磷提取完全.利用DET技术对不同沉积物间隙水SRP进行了分析,与实际浓度的差异在±5%以内;对沉积物剖面的分析结果与Rhizon、微型Peeper等采样技术基本一致,垂直分辨率可达到3mm左右.利用DET技术对太湖草型和藻型湖区沉积物间隙水SRP进行丁分析,发现草型湖区间隙水剖面SRP呈峰形分布,且横向空间分异明显;藻型湖区间隙水SRP随沉积深度的增加呈升高趋势,扩散梯度随水温升高而增强.     

温带森林土壤溶液溶解性N2O和CO2含量特征及其影响机制

利用陶瓷头土壤溶液收集器采集2006年7月～2007年8月问长白山阔叶红松天然林不同深度(15cm和60 cm)土壤溶液,探讨应用气液萃取平衡-气相色谱法测定森林土壤溶液中溶解性气体N_2O和CO_2浓度的可行性,并利用此方法研究林地不同深度土壤溶液中两种气体含量特征及其影响机理.研究结果显示观测期内林地15 cm和60 cm深度土壤溶液中溶解性CO_2浓度的变化范围分别为5.26～10.71μg·mL~(-1)(C)和3.13～6.16 μg·mL~(-1)(C),溶解性N_2O浓度的变化范围分别为2.44～13.40 ng·mL~(-1)(N)和3.23～27.98 ng·mL~(-1)(N).阔叶红松天然林土壤溶液中溶解性CO_2和N_2O浓度均呈现出明显的季节性变化.春融后的降水促进了土壤溶液中溶解性N_2O产生,尤其在60 cm深度.与60 cm深度相比,林地15 cm深度溶液中溶解性CO_2浓度的季节性变化更明显,尤其在植物生长旺季.逐步回归分析显示,水溶性有机碳含量可以解释林地不同深度溶液中溶解性CO_2浓度变化的29%;水溶性有机氮含量可以解释林地60 cm深度溶解性N_2O浓度变化的34%.因此,水溶性有机碳和有机氮分别是长白山阔叶红松林土壤溶液溶解性CO_2和N_2O形成的重要因子.同时研究结果表明本文实验方法对于测定林地不同深度土壤溶液中溶解性N_2O和CO_2含量均有较好的适用性,连续三次萃取后所获得的气体浓度可有效反映溶液中的实际气体浓度.     

尖晶石在地幔橄榄岩部分熔融和亚固相平衡过程中的化学指示——实验研究及在自然岩石中的应用

以三组不同的重组的尖晶石橄榄岩为起始成分.在压力为0.10—0.15GPa和温度为1000—1380℃条件下,进行了系统的部分熔融和亚固相平衡实验。实验结果显示,在部分熔融过程中,尖晶石的Mg＃,即Mg/(Mg+Fe),和Cr＃,即Cr/(Cr+Al),随熔融度的增大而增大;在亚固相平衡过程中,尖晶石的Mg＃随温度的升高而增大,但Cr＃在纯橄榄岩中保持不变,而在二辉和方辉橄榄岩中稍有增大。尖晶石的Mg＃—Cr＃间反相近线性代表了一种非整体平衡的等热关系。计算模拟得到同样的结果。这同时被自然橄榄岩中尖晶石的Mg＃—Cr＃间的关系所证明。由于亚固相条件下平衡的结果,尖晶石的化学成分中只有Cr＃变化不大,故能用来衡量其所在岩体曾经受的相对熔融度。即尖晶石的Cr＃越大,所在岩体经受的熔融度越大。相反,尖晶石的Mg＃和Cr＃在岩浆结晶过程中应随温度的降低而减小;因此,可用玄武岩中尖晶石的Cr＃来指示其岩浆的原始Cr_2O_3/Al_2O_3特征,及用尖晶石的环带特征来探讨岩浆的演化(冷却速度,混染情况)。     

Henry’s law constant for phosphine in seawater: determination and assessment of influencing factors

The Henry’s Law constant (k) for phosphine in seawater was determined by multiple phase equilibration combined with headspace gas chromatography. The effects of pH, temperature, and salinity on k were studied. The k value for phosphine in natural seawater was 6.415 at room temperature (approximately 23°C). This value increases with increases in temperature and salinity, but no obvious change was observed at different pH levels. At the same temperature, there was no significant difference between the k for phosphine in natural seawater and that in artificial seawater. This implies that temperature and salinity are major determining factors for k in marine environment. Double linear regression with Henry’s Law constants for phosphine as a function of temperature and salinity confirmed our observations. These results provide a basis for the measurement of trace phosphine concentrations in seawater, and will be helpful for future research on the status of phosphine in the oceanic biogeochemical cycle of phosphorus.     

Intercomparison of soil pore water extraction methods for stable isotope analysis

Measurements of δ²H and δ¹⁸O composition of pore waters in saturated and unsaturated soil samples are routinely performed in hydrological studies. A variety of in‐situ and lab‐based pore water extraction methods for the analysis of the stable isotopes of water now exist. While some have been used for decades (e.g. cryogenic vacuum extraction) others are relatively new, such as direct vapour equilibration or the microwave extraction technique. Despite their broad range of application, a formal and comprehensive intercomparison of soil water extraction methods for stable isotope analysis is lacking and long overdue. Here we present an intercomparison among five commonly used lab‐based pore water extraction techniques (high pressure mechanical squeezing, centrifugation, direct vapour equilibration, microwave extraction, and cryogenic extraction). We applied these extraction methods to two physicochemically different soil types that were dried and rewetted with water of known isotopic composition at three different water contents. Our results showed that the extraction approach can have a significant effect on pore water isotopic composition as all methods exhibited significant deviations from the spiked reference water, depending secondarily on the soil type and soil water content. Most pronounced, cryogenic water extraction showed large deviations from the spiked reference water, whereas mechanical squeezing and centrifugation provided results closest to the spiked water for both soil types. We also compared results for each extraction method – where liquid water was obtained – on both an OA‐ICOS and IRMS. Differences between these two analytical instruments were negligible for these organic compound‐free waters. We suggest that users of soil water extraction approaches carefully choose an extraction technique that is suitable for the specific research question, adapted to the dominant soil type and water content of the study. Copyright © 2016 John Wiley & Sons, Ltd.