五硼酸钾溶液中含硼物种分布研究

采用物种分布图和核磁共振实验研究了五硼酸钾溶液中含硼物种的类型、含量和溶液浓度间关系。研究表明五硼酸钾在稀溶液中几乎全部水解为B(OH)3和B(OH)4-;在较浓溶液中主要物种为B3O3(OH)4-和B(OH)3,而B5O6(OH)4-和[B4O5(OH)42-]的含量较小。核磁共振实验研究给出了B(OH)4-, B3O3(OH)4-和B5O6(OH)4-的生成常数K1, K3, K5,研究得出B5O6(OH)4-含量很少的原因是其解聚为其它类型硼酸根离子。外加离子促进五硼酸根离子的生成,而高温条件促进B5O6(OH)4-发生解聚反应。     

Phosphorus retention in constructed wetlands enhanced by zeolite- and clinopyroxene-dominated lava sand

Constructed wetlands (CWs) are engineered systems for treating wastewater by sequestering nutrients and contaminants. Our aim was to assess the main phosphorus (P) binding states in operating CWs to assess P saturation and indications on P recycling potential of filter materials, which might be necessary under future peak P scenarios. The investigated vertical flow CWs (operation time up to 16 years) are based on either fluviatile (Fluv) sand or zeolite- (Ze-LS) and clinopyroxene (Cl-LS)-dominated lava sand. Organic and inorganic P accumulated in all CWs independent of filter materials and showed a considerable increase with operation time. Concentrations of P decreased sharply with depth in the Fluv-CWs compared to only a slight decrease in the lava sand CWs, with P concentrations of deeper horizons approximating the relatively P enriched original lava sand substrates. Orthophosphate was the dominant pool in all CWs, while the sum of organic fractions ranged between 11% and 33%. Sequential extraction indicated that P was mainly associated with Fe and Al (hydr)oxides for Fluv-CWs and Ze-LS-CWs, while Ca and Mg bound mineral phosphates dominated in Cl-LS-CWs. Oxalate extractions pointed to a clear dominance of P fractions associated with poorly crystalline Fe- and Al-(oxy)hydroxides. Solution ³¹P NMR analyses revealed that inositol hexakisphosphates were a major pool of organic P in surface layers of CWs, which increased with operation time. With a maximum of 0.5% P content, filter sands do not appear to be a suitable fertilizer for direct application to agricultural fields. The dominance of inorganic, poorly crystalline P species point to potentially high desorption capacity which might be investigated further, to assess recycling potential of P or usage of filter materials as soil amendments with relatively high plant available P. The latter might become feasible and economically attractive under future P scarcity. Simultaneously, P saturation indexes (DPS) did not indicate an imminent P saturation of filters, since P accumulation was not restricted by binding to Al and Fe minerals.     

核磁共振测井的正则化-启发式阈值降噪研究

核磁共振(NMR)测井是在高温、高压的极端条件下进行,样品体积小,回波幅度微弱.受到来源复杂的噪声影响,NMR信号通常被淹没在噪声中,测量数据的信噪比较低.提出正则化-启发式阈值算法(Regularization Heursure, R-Heursure)对小波分解后的细节系数阈值降噪,正则化因子的选取与地层孔隙结构和测量数据的原始信噪比相关.通过最大相关系数能量准则选取最优化的母小波函数、消失矩和分解层次,采用正则化因子约束估计的阈值,使选取的阈值恰好能大于噪声水平而不损失小孔(或微孔)的响应信息.数值模拟和实际测井资料处理验证了R-Heursure算法的降噪性能,NMR测井数据的信噪比得以有效改善,为储层评价提供更准确的信息.     

Monitoring water transport in sandstone using flow propagators: A quantitative comparison of nuclear magnetic resonance measurement with lattice Boltzmann and pore network simulations

A comparison of advective displacement probability distributions (flow propagators) obtained by nuclear magnetic resonance (NMR) experiment with both lattice Boltzmann (LB) and pore network (PN) simulations is presented. Here, we apply all three methods to the exact same sample for the first time: we consider water transport in a Bentheimer sandstone. The LB and PN simulations are based on X-ray micro-tomography (XMT) images of a small rock sample; the NMR experiments are conducted on a much larger rock core-plug from which the small rock sample originated. Despite the limited size of the simulation domains, good agreement is achieved between all three sets of results, verified quantitatively by comparison of the low order moments of the flow propagators. We are concerned primarily with validating the simulations at high liquid flow rates (>10 ml min⁻¹) in high permeability sandstone, ultimately for future application to geological carbon sequestration studies. Under these conditions the LB simulation is found, as expected, to be more robust than the PN model due primarily to the reduced requirement to manually tune the simulation lattice to match the petro-physical properties of the rock.     

利用测井资料计算阳离子交换量Qv的方法对比

为了准确计算泥质砂岩储层的Q_v,提出了利用核磁共振测井计算Q_v的方法,通过对56块同时具有阳离子交换量和孔隙度、渗透率数据的岩心样品的分析,建立了阳离子交换量与综合物性指数的关系模型。为了解决准确而连续地计算综合物性指数的问题,提出了利用核磁共振测井横向驰豫时间几何平均值求取Swanson参数、进而利用Swanson参数获取综合物性指数的方法。同时利用核磁共振测井法、自然伽马测井相对值法、自然电位测井图版法3种计算Q_v的方法对准噶尔盆地南缘4口井资料进行了处理,并对处理结果作了对比分析。结果表明：在泥质砂岩厚层段,3种方法都可以简单而有效地计算Q_v。与岩心资料相比,核磁共振测井法计算的相对误差为13%,自然伽马测井法计算的相对误差为19%,自然电位测井法计算的相对误差为22%;在砂泥岩薄互层,用核磁共振测井法计算的Q_v比其它两种方法计算的结果更为可靠,更能反映地层的真实情况。     

羟基磷灰石除氟的实验地球化学研究

中国和世界上许多国家（地区） 都面临着饮用水氟含量超标的问题,因此研究氟的环境地球化学行为以及探索除氟 技术和原理至关重要。本实验采用廉价的非金属矿物羟基磷灰石作为吸附材料,研究羟基磷灰石吸附溶解态F-的地球化学 行为和机制,考察反应时间、pH、初始F-浓度等环境参数对吸附反应的影响。实验结果发现羟基磷灰石对F-的吸附反应需 进行到48 h以上时才接近反应平衡。在实验条件下（pH≥4）,F-的吸附量随pH升高而降低,羟基磷灰石对F-的吸附受pH 调控。同时还发现羟基磷灰石在pH=6条件下对F-的吸附等温线既满足Langmuir等温模式（R2=0.89） 同时也满足Freundlich 等温模式（R2=0.99）,并推导出该条件的理论最大吸附量为21.6×10-3。本研究还进一步采用了先进的XRD、SEM、 HR-TEM、19F NMR手段,系统地表征了反应前后吸附产物的形态和成分变化,发现在高F-浓度条件下,F-在羟基磷灰石表 面的吸附机制不再是单层的表面配位。核磁共振的结果表明F-可部分取代羟基磷灰石结构中的隧道羟基而形成含氟羟基磷 灰石。研究结果表明羟基磷灰石是一种相当具有潜力的除氟材料,值得进一步开发。     

核磁共振测井在火成岩地层应用的适应性分析

火成岩岩石具有高磁化率特征,与沉积岩差别明显,岩石的高磁化率会对核磁共振信号产生显著影响,开展核磁共振测井在火成岩地层应用的适应性分析研究,为广泛使用核磁共振测井用于火成岩储层评价提供参考.采用理论模拟、实验分析及实际测井资料相结合的方法,分析了高磁化率岩石的核磁共振响应特征.分析结果表明,火成岩岩石具有很高的磁化率,从酸性火成岩到基性火城岩,岩石的磁化率一般是逐渐增大的.高磁化率岩石孔隙内部会产生强梯度磁场,孔隙内部的磁场梯度越强,核磁共振的T2谱前移越明显,核磁信号衰减幅度也越大,核磁分析孔隙度与常规分析的孔隙度误差也越大;相同岩石磁化率情况下,岩石孔径越小,岩石孔隙内部磁场梯度越强,核磁信号衰减越大,核磁共振测井计算的孔隙度也越低.因此,核磁共振测井与岩性有关系,核磁共振测井会受到高磁化率岩石的显著影响.核磁共振测井在部分火成岩,尤其在中基性火成岩和小孔径火成岩储层中应用具有很大的局限性.     

The influence of salinity on toxicological effects of arsenic in digestive gland of clam Ruditapes philippinarum using metabolomics

Ruditapes philippinarum,a clam that thrives in intertidal zones of various salinities,is a useful biomonitor to marine contaminants.We investigated the influence of dilution to 75% and 50% of normal seawater salinity(31.1) on the responses of the digestive gland of R.philippinarum to arsenic exposure(20 μg/L),using nuclear magnetic resonance(NMR)-based metabolomics.After acute arsenic exposure for 48 h,salinity-dependent differential metabolic responses were detected.In normal seawater,arsenic exposure increased the concentrations of branched-chain amino acids,and of threonine,proline,phosphocholine and adenosine,and it decreased the levels of alanine,hypotaurine,glucose,glycogen and ATP in the digestive glands.Differential changes in metabolic biomarkers observed at lower salinity(～23.3) included elevation of succinate,taurine and ATP,and depletion of branched-chain amino acids,threonine and glutamine.Unique effects of arsenic at the lowest salinity(～15.6) included down-regulation of glutamate,succinate and ADP,and up-regulation of phosphocholine.We conclude that salinity influences the metabolic responses of this clam to arsenic.     

致密砂岩储层CO2驱油特征的核磁共振实验研究

利用核磁共振技术对致密砂岩储层不同渗透率级别基质岩心和裂缝基质岩心不同驱替压力下CO2驱油特征进行了研究,简述核磁共振原理及实验方法。表明:致密砂岩储层特低、超低渗透基质岩心在初始CO2驱替压力下,岩心毛细孔隙和微毛细孔隙区间的油不同程度被采出,随着CO2驱替压力增大,特低、超低渗透基质岩心毛细孔隙区间油的采出程度不断增加且累积采出程度不同。裂缝致密砂岩储层岩心,裂缝和毛细孔隙区间的油在初始CO2驱替压力下,岩心裂缝中的油及毛细孔隙中的部分油被驱替出来,CO2驱替压力提高毛细孔隙、微毛细区间油的采出程度和累积采收程度较小。致密砂岩储层特低、超低渗透基质岩心和裂缝致密砂岩储层岩心,随着CO2驱替压力增大毛细孔隙区间的部分剩余油成正比增加进入到微毛细孔隙区间改变储层剩余油分布。核磁共振技术能够深入研究致密砂岩储层CO2不同驱替压力阶段,岩心裂缝、毛细孔隙区间、微毛细孔隙区间油的采出程度和剩余油分布情况,对于研究致密砂岩储层微观驱油机理具有较重要的价值。