土壤磷酸盐氧同位素前处理方法的优化研究

<正>近年来,土壤磷素流失造成的环境问题和潜在环境问题严重,查明环境中磷的来源及迁移转化对于改变目前现状意义重大。稳定同位素是元素循环的有效示踪剂,但自然界中磷只有一种稳定同位素,不能通过磷的稳定同位素对磷循环进行研究。由于P-O键在自然环境中具有高稳定性,因此磷酸盐氧同位素技术成为环境中磷迁移转化以及生物地球化学循环的一种有效示踪手段。为避免极端pH调节可能造成有机质水解以及磷酸盐损失等问题,本研究在综合了已有研究方法的基础上进行了优化。该方法主要通过不同土     

苏州城市河道底泥对磷酸盐的吸附与释放特征

为了探讨苏州古城区河道底泥对磷酸盐的吸附-释放特征,文中分别从改变上覆水的pH值、底泥吸附-释放动力学和等温吸附实验三个方面进行了研究。结果表明:(1)随着上覆水pH值的增大,苏州河道底泥对磷的吸附量逐渐减小;(2)底泥对磷的吸附过程是一个复合动力学过程,通常包括快吸附和慢吸附两个过程。底泥对磷的快速吸附在2h内快速进行,之后为慢吸附过程,到6h左右,基本达到一种动态吸附平衡;底泥对磷释放的动力学过程也包括快释放和慢释放过程。底泥释放磷在1·5h内快速进行,之后进入慢释放过程,磷酸盐含量基本稳定,达到释放平衡;(3)底泥具有较大的吸附磷的能力。随着上覆水的磷酸盐浓度增高,底泥吸附磷酸盐的量也增加。上覆水与底泥的比值越大,底泥对磷的吸附率越小。     

水和水蒸气辅助粗晶三水铝石转化为勃姆石的机制研究

在165℃、175℃、185℃和195℃的温度条件下,对水热处理前和处理后的粗晶三水铝石样品分别进行了XRD分析和SEM表征,研究了粗晶三水铝石在水蒸气和热水中转变成勃姆石的相变过程。结果表明,水热条件下粗晶三水铝石转化成勃姆石的过程受控于溶解-再沉淀机制,而并非是通常认为的固体状态下的转变;相对于在热水中,水蒸气环境可以加速三水铝石向勃姆石的转化;所形成的勃姆石的粒径（4~7 μm）明显比前驱体三水铝石的粒径（120~200 μm）要小得多,表明可以利用粗晶三水铝石生产微晶勃姆石。在转化过程中,勃姆石微晶首先生长在三水铝石的晶体表面上,通过控制反应温度和反应时间,可形成壳层为勃姆石、壳下为三水铝石的具有双层结构的铝的氢氧化物颗粒,也有可能形成具有中空结构的勃姆石集合体颗粒。     

黄河泥沙对硝基氯苯的吸附机理研究

通过静态吸附实验,研究了黄河底泥对硝基氯苯的吸附机理,并在此基础上研究了影响吸附的不同条件。实验结果表明,最佳平衡吸附时间为2h;吸附量随着平衡浓度的增加而增加,随着含沙量的增加而降低;温度对吸附的影响随含沙量不同而不同,含沙量较高时,温度对吸附影响不大,含沙量较低时,吸附量随温度的升高呈先下降后增加的趋势;在本实验条件下,吸附量随着pH值的增加而下降,随离子强度增加而增加。     

工业膨胀蛭石对水体中磷的去除研究

研究了工业膨胀蛭石对模拟养殖废水中磷酸盐的吸附性能,考察了pH值、吸附时间、固液比对吸附效果的影响,并通过原子吸收光谱法测定了蛭石在对磷酸盐吸附过程中主要金属元素的浸出含量,探究膨胀蛭石吸附水中磷的吸附平衡,对吸附机理进行了探讨。结果表明,工业膨胀蛭石对磷酸盐的吸附量可达2.76 mg/g,pH值在3~9的范围内有较高的吸附量;K、Ca、Mg这3种元素的浸出含量随着溶液中磷酸盐浓度升高而增加,Fe、Al元素则相应减少;工业膨胀蛭石对磷的吸附机理主要是先通过离子交换作用交换出层间阳离子,然后与H2PO-4、HPO2-4反应形成沉淀被吸附;吸附等温曲线均符合Freundlich公式与Langmuir公式,相关系数分别为0.978 1和0.985 1。     

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。     

鄂尔多斯盆地东北缘准格尔煤田煤中超常富集勃姆石的发现

运用X射线衍射分析(XRD)、带能谱仪的扫描电镜(SEM-EDX)和光学显微镜等技术,首次在鄂尔多斯盆地东北缘准格尔矿区6号巨厚煤层中发现了超常富集的勃姆石及其特殊的矿物组合,勃姆石含量可高达13.1%,与勃姆石伴生的矿物有磷锶铝石、锆石、金红石、菱铁矿、方铅矿、硒铅矿和硒方铅矿。重矿物的组合特征与华北地区本溪组铝土矿中的重矿物组合特征相似,高含量的勃姆石主要来源于聚煤盆地北偏东方向本溪组风化壳铝土矿,三水铝石以胶体溶液的形式从铝土矿中被短距离带入泥炭沼泽中,在泥炭聚积阶段和成岩作用早期经压实作用脱水凝聚而形成勃姆石。     

内蒙古阿刀亥矿晚古生代煤中矿物的赋存状态及成因

运用偏光显微镜、低温灰化+X射线衍射仪、带能谱的扫描电镜对内蒙古大青山煤田阿刀亥矿晚古生代CP2煤层中矿物的赋存状态及其成因进行了研究.研究表明阿刀亥矿CP2煤层中矿物包括硬水铝石、勃姆石、磷钡铝石、高岭石、铵伊利石、方解石、白云石、菱铁矿、锐钛矿、氟磷灰石、石英和黄铁矿.硬水铝石、勃姆石、磷钡铝石、高岭石和铵伊利石一般充填在丝质体、半丝质体、结构镜质体胞腔中或者分布在基质镜质体中.方解石和白云石主要充填在裂隙中.硬水铝石、勃姆石和磷钡铝石是由来源于本溪组铝土矿风化壳的物质在泥炭聚集时沉积形成的.铵伊利石是由于花岗岩侵入体的影响形成的.方解石和白云石可能来源于岩浆热液.     

铁锰氧化物在碱性条件下对镉的吸附特征研究

实验研究了不同的pH值、初始离子浓度、矿物用量、温度以及时间等因素对针铁矿和软锰矿吸附镉的影响。结果表明:在pH值从酸性到近中性的范围内,两种氧化矿物对镉的吸附量增加较快,然后在碱性条件下吸附量保持着最大值;反应前后两种氧化矿物溶液的pH值均有不同程度的变化,其中针铁矿和软锰矿的临界pH值分别为8和6.5;两种矿物对镉的吸附在6 h左右达到了吸附平衡,吸附等温线都较好地符合Freundlich等温方程式;随着两种氧化物用量的增加,其吸附量也有增加;室温下,针铁矿和软锰矿对镉的吸附效果较好。     

密云水库中总磷迁移转化机制的分析

通过对2001、2002年进行的四次大规模取样测试结果进行分析,认为密云水库目前为中营养型水库,富营养化趋势明显,水中磷的主要来源为以工业、生活污水及水土流失携带进入水体的外源磷和以水库底泥释放为主的内源磷。磷在表层水中浓度小于底层水中的浓度,东西库区的浓度小于内湖的浓度;垂向上由上至下逐渐增高。磷的迁移转化途径为:一部分在水体悬浮物表层吸附或沉积,另一部分被水中的藻类吸收,进入生物作用。对水中磷的迁移转化影响较大的因素为:水中的pH值、溶解氧含量、温度、水动力条件及生物作用。     

31P and 27Al solid-state nuclear magnetic resonance study of taranakite

High-resolution ²⁷Al solid-state nuclear magnetic resonance (NMR) spectroscopy indicates that aluminum in taranakite is probably restricted to six-coordinate sites. High-resolution ³¹P solid-state NMR spectroscopy reveals that phosphate groups exist in two environments in taranakite. The rate of ¹H-induced dipolar dephasing of the ³¹P signals in cross-polarization, magic-angle-spinning NMR spectra of taranakite suggests that one or more oxygens of one of two phosphates are directly protonated. The same experiments suggests that the oxygens of the second form of phosphate are not directly protonated but may be hydrogen-bond receptors. The ratio of protonated phosphate to non-protonated phosphate, as measured from ³¹P single-pulse excitation, magic-angle-spinning spectra, is approximately one to three. Current address: Department of Soil Science, 1525 Observatory Drive, University of Wisconsin-Madison, Madison, WI 53706, USA     

Overestimation of the importance of phytate in NaOH-EDTA soil extracts as assessed by P NMR analyses

Solution ³¹P NMR analysis of NaOH-EDTA extracts is the most widely used method for determining the speciation of organic P in soils. In this paper, we bring together results from a number of our recent studies that highlight some of the difficulties in obtaining accurate quantitative results and propose that these difficulties may have resulted in the systematic overestimation of soil phytate concentrations. The first problem is peak identification, which is complicated by variations in chemical shift with pH and ionic strength, and the impracticality of the primary ³¹P chemical shift reference (85% H₃PO₄). Unambiguous peak assignment can be achieved by spiking suspected compounds directly into soil extracts prepared for NMR analysis; this ensures native and added compounds experience exactly the same chemical environment. The second problem is quantifying NMR signal for individual species in the crowded and overlapping phosphate monoester region. Spectral deconvolution has been employed for this purpose, but very different results are obtained depending on whether or not the fitting procedure includes a broad signal that probably comes from P in large, “humic” compounds. In particular, failing to consider this broad peak in the deconvolution procedure results in overestimation of small organic P compounds, including phytate. The ready decomposition of phytate is demonstrated with an incubation experiment in which phytate added at various concentrations to a calcareous soil is shown to be decomposed to produce orthophosphate. The decomposition follows a first order exponential decay with a half-life of 4-8 weeks.     

The Chemical Nature of Phosphorus in Subtropical Lake Sediments

The phosphorus (P) composition of sediment profiles in three subtropical lakes of contrasting trophic state in Florida, USA, was determined by sequential fractionation and solution ³¹P NMR spectroscopy. Sediment from Lake Annie, an oligo-mesotrophic sinkhole with moderately acidic sediment (pH 5.4; loss on ignition 58 %), contained higher total P concentrations than sediment from eutrophic Lake Okeechobee (pH 7.7, loss on ignition 36 %) and hyper-eutrophic Lake Apopka (pH 7.5, loss on ignition 69 %). The chemical nature of sediment P varied markedly among the three lakes, suggesting the predominance of different diagenetic processes. Lake Okeechobee sediment was dominated by inorganic P, indicating the dominance of abiotic reactions; Lake Annie sediment contained abundant organic P throughout the sediment profile, indicating the importance of organic P stabilization at acidic pH; Lake Apopka contained almost half of its sediment P in microbial biomass, indicating the importance of biotic processes in regulating P dynamics. Solution ³¹P NMR spectroscopy of NaOH–EDTA extracts revealed that organic P occurred mainly as phosphomonoesters in all lakes. However, sediment from Lake Apopka also contained abundant phosphodiesters and was the only lake to contain detectable concentrations of polyphosphate, perhaps due to a combination of alternating redox conditions and high concentrations of inorganic phosphate and organic carbon. Organic P concentrations determined by sequential fractionation and solution ³¹P NMR spectroscopy were similar for all lakes when microbial P was included in values for sequential fractionation. We conclude that the chemical nature of sediment P varies markedly depending on trophic state and can provide important information on the dominant processes controlling P cycling in subtropical lakes.     

Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative ¹⁹F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due to differences in the reactive species present on the surfaces of these glasses, variations in the rate of acid-mediated dissolution (pH 4) for samples in this suite cannot be explained by variations in geometric or BET-measured surface area. In contrast, the rates scale directly with the surface density of TFS-reactive sites as measured by solid-state NMR. These data are consistent with the inference that the TFS-reactive M-OH species on the glass surface, which are known to be non-hydrogen-bonded Q³ groups, represent loci accessible to and affected by proton-mediated dissolution. The second suite of samples, originating from a chronosequence in Kozushima, Japan, is comprised of four rhyolites that have been weathered for 1.1, 1.8, 26, and 52 ka. The number of TFS-reactive sites per gram increases with duration of weathering in the laboratory for the “Icelandic” samples and with duration of field weathering for both “Icelandic” and Japanese samples. One hypothesis is consistent with these and published modeling, laboratory, and field observations: over short timescales, dissolution is controlled by fast-dissolving sites, but over long timescales, dissolution is controlled by slower-dissolving sites, the surface density of which is proportional to the number of TFS-reactive Q³ sites. These latter sites are not part of a hydrogen-bonded network on the surface of the glasses, and measurement of their surface site density allows predictions of trends in reactive surface area. The TFS treatment method, which is easily monitored by quantitative ¹⁹F solid-state NMR, therefore provides a chemically specific and quantifiable proxy to understand the nature of how sites on dissolving silicates control dissolution. Furthermore, ²⁷Al NMR techniques are shown here to be useful in identifying clays on the glass surfaces, and these methods are therefore effective for quantifying concentrations of weathering impurities. Our interpretations offer a testable hypothesis for the mechanism of proton-promoted dissolution for low-iron aluminosilicate minerals and glasses and suggest that future investigations of reactive surfaces with high-sensitivity NMR techniques are warranted.     

Evaluation of silica-water surface chemistry using NMR spectroscopy

We have combined traditional batch and flow-through dissolution experiments, multinuclear nuclear magnetic resonance (NMR) spectroscopy, and surface complexation modeling to re-evaluate amorphous silica reactivity as a function of solution pH and reaction affinity in NaCl and CsCl solutions. The NMR data suggest that changes in surface speciation are driven by solution pH and to a lesser extent alkali concentrations, and not by reaction time or saturation state. The ²⁹Si cross-polarization NMR results show that the concentration of silanol surface complexes decreases with increasing pH, suggesting that silanol sites polymerize to form siloxane bonds with increasing pH. Increases in silica surface charge are offset by sorption of alkali cations to ionized sites with increasing pH. It is the increase in these ionized sites that appears to control silica polymorph dissolution rates as a function of pH. The ²³Na and ¹³³Cs NMR results show that the alkali cations form outersphere surface complexes and that the concentration of these complexes increases with increasing pH. Changes in surface chemistry cannot explain decreases in dissolution rates as amorphous silica saturation is approached. We find no evidence for repolymerization of the silanol surface complexes to siloxane complexes at longer reaction times and constant pH.     

Deposition and mobilization of functionalized multiwall carbon nanotubes in saturated porous media: effect of grain size,flow velocity and solution chemistry

Carbon nanotubes (CNTs) are widely manufactured nanoparticles which are utilized in a number of consumer products, such as sporting goods, electronics and biomedical applications. Due to their accelerating production and use, CNTs constitute a potential environmental risk if they are released to soil and groundwater systems. It is, therefore, essential to improve the current understanding of environmental fate and transport of CNTs. The current study systematically investigated the effect of solution chemistry (pH and ionic strength) and physical conditions (collector grain size and flow rate) on the deposition and mobilization of functionalized multiwall carbon nanotubes (MWCNTs) using a series of column experiments under fully saturated conditions. A one-dimensional convection–dispersion model including collector efficiency for cylindrical nanoparticles was used to simulate the transport of MWCNTs in porous media. It was observed that an increase in pH resulted in increased mobility of MWCNTs. However, the transport of MWCNTs was strongly dependent on ionic strength of the background solution and a critical deposition concentration was observed between 3 and 4 mM NaCl concentration, with more than 99 % filtration of MWCNTs at 4 mM. The finer sand grains were able to filter a significant amount of MWCNTs (15 % more than coarse sand) from the inflow solution; this was likely caused by grain-to-grain straining mechanisms in the finer sand. A decrease in pore water velocity also led to more deposition of MWCNTs due to lowering of the kinetic energy of the particles. The results from this study indicated that a weak secondary minimum existed under unfavorable conditions for deposition, but the particles were trapped at both primary and secondary minimum.     

Fluid-rock interaction modeling to constrain Au enrichment: Implication for the giant Jiaodong Au mineralization,eastern North China Craton

The devolatilization model of the metasomatized lithospheric mantle without pre-enriched gold has been proposed to account for the giant gold mineralization. An excellent example is the world-class Jiaodong gold province with >5000 tonnes Au resources in the eastern North China Craton. The auriferous fluid transport and gold enrichment during wallrock alterations are two vital processes to determine the giant gold mineralization formation in this province. However, the effects of the fluid-rock interaction with alterations on the auriferous fluid transport and gold enrichment still keep poor understanding, which leads the above model to be imperfect. The giant Jiaojia goldfield in this province recorded a wallrock alteration evolution from K-feldspar alteration to pyrite-sericite-quartz alteration, and some parts of the latter can become gold orebodies when the gold grade is >1 ppm. This study conducts thermodynamic fluid-rock interaction modeling to reveal auriferous fluid transport and coupled relationship between gold enrichment and alteration mineral assemblage based on the alteration-mineralization and ore fluid characteristics of the goldfield. The modeling of fluid-rock interaction with cooling indicates the transformation of Au-Cl complexes to Au-S complexes combined with the total sulfur concentration decrease by pyrite precipitation when cooling from ∼460 °C can trigger the dispersive gold precipitation, which should hinder the gold long-range transport to lower ambient temperature. The high oxygen fugacity at >400 °C can enhance Au-Cl complexes stability, and the low pH can maintain high total sulfur concentration in the auriferous fluid, both of which facilitate the long-range gold transport to a lower-temperature environment. The auriferous fluid would acquire higher pH by the buffering of feldspars or sericite, which was beneficial for the high-efficiency precipitations of pyrite and gold. The ankerite-siderite assemblage without pyrophyllite in the pyrite-sericite-quartz alteration zone indicates that a cumulative fluid to rock mass ratio (f/r) of 3.8–4.8 should be needed for the transformation from K-feldspar alteration to pyrite-sericite-quartz alteration according to the fluid-rock interaction modeling at 300 °C and 2000 bar. In the case of auriferous fluids with ≤200 ppb Au concentration, the single fluid-rock interaction can only elevate the gold grade to ≤0.69–0.87 ppm in the pyrite-sericite-quartz alteration zone at f/r 3.8–4.8. Therefore, the fracture-induced fluid flow coupled with fluid-rock interaction is proposed to the prerequisite to elevate the gold grade to >1 ppm in the pyrite-sericite-quartz alteration zone. The metasomatized lithospheric mantle volume for the required ore fluid and Au in the Jiaodong province is estimated according to the modeling results and alteration-mineralization characteristics, which provides a link between the mantle without abnormal Au enrichment and the alteration-mineralization processes.     

Pesticide transport and transformation modeling in soil column and groundwater contamination prediction

Pesticide transport and transformation were modeled in soil column from the soil surface to groundwater zone. A one dimensional dynamic mathematical and computer model is formulated to simulate two types of pesticides namely 2,4-dichlorophenoxy acetic acid and 1,2-dibromo 3-chloro propane in soil column. This model predicts the behavior and persistence of these pesticides in soil column and groundwater. The model is based on mass balance equation, including convective transport, dispersive transport and chemical adsorption in the phases such as solid, liquid and gas. The mathematical solution is obtained by finite difference implicit method. The model was verified with experimental measurements and also with analytical solution. The simulation results are in good agreement with measured values. The major findings of this research are the development of the model which can calculate and predict the concentration of pesticides in soil profiles, as well as groundwater after 4, 12, 31 days of pesticide application under steady state and unsteady water flow condition. With the results of this study, the distribution of various types of pesticides in soil column to groundwater table can be predicted.     

干湿交替条件下包气带土柱中氮素迁移转化规律实验

干湿交替的回灌方法常被用于解决地面回灌补给地下水的堵塞问题。研究干湿交替条件下地面回灌对地下水的影响对于指导再生水回灌地下水具有重要实际意义。通过室内土柱模拟实验,在入渗强度为10.5 mm/h的条件下,日均进水量3 888 mL;用干湿交替的地面回灌模式持续运行136 d,累计灌入氨氮含量为5 mg/L的模拟再生水23 894 L,研究包气带土柱对氨氮的去除效果及氮素在包气带中的迁移转化规律。研究表明,充分利用包气带的好氧、兼氧和厌氧环境,生物脱氮是地下水回灌过程中脱氮的主要途径。包气带对氨氮的去除机理主要为土壤对氨氮的吸附作用和微生物的降解作用。回灌过程中累积在土颗粒表面的氨氮在干期发生硝化作用,干湿交替会加强氮素在包气带的迁移转化,导致干期后的回灌初期大量硝态氮迁移到饱和带地下水中。