同步辐射X射线吸收近边结构光谱技术在磷素固相形态研究中的应用

固相形态磷是控制环境中磷素生物可利用性、迁移流失能力的重要形态.基于同步辐射光源的X射线吸收近边结构(XANES)光谱技术可在分子水平上识别目标元素周围的局部化学信息,在非破坏性、原位直接表征等方面体现出其独特的优越性,成为表征化学物质存在形态和阐明化学反应微观机制的前沿技术之一,在环境化学领域中得到了广泛关注.本文简述了磷的XANES的基本理论,综述了XANES技术在矿物、土壤及有机肥中磷素固相形态研究中的应用进展,并分析了该技术应用在环境介质中磷形态表征中所面临的挑战及发展趋势,指出XANES技术应与其他微观光谱技术及宏观试验方法有机结合,多种表征技术取长补短,以期为环境介质中磷素形态表征及转化机制研究提供全面有效的技术支撑.     

土壤胶体磷活化迁移的影响因素及分析技术

胶体在土壤磷素迁移中起重要作用.土壤胶体磷活化迁移对土壤磷库的变化和周围水环境质量产生影响.本文介绍了土壤胶体磷研究的相关进展,探讨了土壤理化性质、施肥、降雨、土壤改良剂等因素对胶体磷在土壤赋存迁移中的影响,分析了流场分离、电镜能谱、同步辐射X光近边吸收结构光谱和核磁共振等技术在胶体磷研究中的应用,以及降低胶体磷流失的方法,以期为胶体磷在土壤中赋存变化和迁移机制的研究提供重要信息.
     

连续提取和液体磷核磁共振表征太湖梅梁湾沉积物中磷的剖面分布

应用连续提取法(SMT)和液体磷核磁共振(³¹PNMR)技术研究了太湖北部梅梁湾沉积物中磷形态和组成的剖面变化。结果表明,铁/铝磷是沉积物中磷的主要形态,约占总磷含量的44.0-54.6%。总磷、无机磷、有机磷和铁/铝磷含量均随沉积深度增加呈降低趋势,至18cm以下略有增加,而钙磷却在柱样下部随沉积深度增加呈累积趋势。³¹PNMR显示,沉积物磷主要由正磷酸盐(72.0-99.2%)和磷酸单酯(0.8-25.9%)构成,磷酸二酯、膦酸盐和焦磷酸盐的相对含量非常低,分别为1.0%、0.4-1.0%和 0.1%。正磷酸盐含量在沉积物表层9cm内减少了65%,9cm以下波动变化,但总体呈降低趋势。这些特征表明沉积物中磷对梅梁湾上覆水体具有强烈的释放潜力,是太湖富营养化发生的重要因素。     

土壤磷素形态及其分级方法研究进展

磷作为植物必需的大量营养元素,在维持农业的可持续发展和生态系统的平衡中起着重要作用.采用适宜的土壤磷素分级方法研究土壤中磷素形态、转化及其有效性,对揭示土壤磷素供应和流失状况都具有重要意义.本文结合国内外已有研究,从土壤无机磷和有机磷的形态划分、分级方法和传统土壤磷素分级方法的局限性等方面进行了总结.Hedley磷素分级方法在分级过程中兼顾了无机磷和有机磷两种磷素形态,有利于了解土壤磷素的生物有效性和动态变化,是目前应用较广的磷素分级方法.本文介绍了Hedley磷素方法的分级流程和应用范围,并对其改进方法Tiessen磷素分级法进行了详细论述.     

有机物料对白浆土金属氧化物形态转化和迁移的影响及其肥力效应

通过土柱淋溶试验研究了牧草粉腐解物对白浆土Ｆｅ、Ｍｎ、Ａｌ氧化物形态转化及剖面迁移的影响及其对土壤Ｐ素形态转化和有效性的影响．结果表明,加有机物料淋溶使土壤ＤＴＰＡ提取态或有机络合Ｆｅ、Ｍｎ、Ａｌ氧化物含量显著上升;有效磷含量也极显著上升,主要在于铝磷和铁磷含量的增加;白浆层土壤中有效态磷及无机磷各形态均随着腐熟牧草粉用量的加大而极显著地升高,表层土壤中有效态磷、铝磷、铁磷的变化也与加入的腐熟牧草粉极显著正相关．土壤有效态磷、铝磷、铁磷与ＤＴＰＡ提取态和有机络合态Ｆｅ、Ｍｎ显著或极显著相关,但在表层土壤磷素各形态与ＤＴＰＡ及焦磷酸钠提取的Ａｌ呈极显著负相关,而白浆层却是极显著正相关．     

陆地生态系统磷素循环及其影响因素

 磷是生命系统的重要组成成分,其在生态系统内的迁移转化是生态系统结构和功能的决定性因素之一。近20年来,磷在陆地生态系统内的重要性受到越来越多的关注。该文总结了国内外磷循环研究的成果,从磷的来源、在土壤中的存在形态和固定特性、影响因素的复杂性等方面分析了磷素循环的特点;系统阐述了磷在陆地生态系统各库之间及其内部,主要是植被-土壤亚系统内的迁移转化规律及影响因素。陆地生态系统磷素循环主要是系统内部的生物化学循环,由植物自身的遗传特性和土壤的生物、理化性质共同控制,不同控制因素的相对重要性因生态系统类型、时间和空间尺度而异。文章简述了磷循环研究方法的发展及存在的局限性;另外,分析了干旱、半干旱地区磷循环研究的重要性和意义;干旱区生态系统的脆弱性及其植被、土壤特性决定了其磷素循环有其自身的特点及研究的必要性。最后指出了当前陆地生态系统磷循环研究的发展趋势。     

泉州湾洛阳江河口沉积物中磷的形态分布

分析了泉州湾洛阳江河口沉积物中总磷及5种形态磷(可交换态磷(DP)、铁铝结合态磷(Fe/Al-P)、钙结合态磷(Ca-P)、有机磷(OP)和闭蓄态磷(Re-P))的含量,探讨了它们的垂向分布特征、相互关系及环境指示意义。结果表明:沉积物中的总磷(TP)以无机磷为主,占TP比例76%~89%;除可交换态磷外,沉积物中形态磷的垂向分布规律具有相似性,大体随深度增加而减小,且在表层有富集现象,反映了沉积物中总磷和各形态磷的分布受人类活动影响较明显;通过相关性分析,钙结合态磷是总磷和无机磷的主要控制因素,而总磷和其他形态磷(除了可交换态磷外)相互间均具有显著相关性,且有机质对各形态磷的分布均有一定影响;TP和各形态磷含量,以及(Fe/Al-P)/TP、Ca-P/TP、OP/TP都在同一层出现了显著变化,反映了水利设施和围垦工程对沉积环境和各形态磷迁移转化有较大影响。     

低分子量有机酸对土壤磷活化及其机制研究进展

近30年来,过量施用磷肥导致土壤磷素累积继而引起水体富营养化等问题备受关注。植物根系分泌的低分子量有机酸能活化土壤积累态磷,提高土壤磷素有效性,已成为研究热点问题之一。本文结合国内外已有研究,从低分子量有机酸的类型、添加浓度、土壤类型和土壤磷素水平等方面总结了低分子量有机酸活化土壤无机磷与有机磷的效果,并通过对比土壤磷活化试验前后各形态磷的变化探讨了低分子量有机酸对土壤磷的活化机制。低分子量有机酸对土壤无机磷的活化主要是促进了土壤中有效性低的无机磷形态向有效性较高的形态转化,而低分子量有机酸对土壤有机磷的活化结论尚不一致,活化机制也不明确,仍需进一步研究。未来研究应关注低分子量有机酸与磷肥之间的协同增效机制,并进一步探索低分子量有机酸对土壤磷素(特别是有机磷)的活化机制。     

生物炭对土壤中氮磷有效性影响的研究进展

利用生物炭在贫瘠的土壤上培育出肥沃的"黑土"正成为土壤学家研究的热点.氮、磷等大量养分是衡量土壤肥力高低的重要指标,生物炭对其有效性影响表现出极大的复杂性.不同研究得出的结论不尽相同,关键是缺乏对其机制的深入研究.由于氮和磷的不合理利用还可能造成非点源污染而带来环境风险,再加之生物炭施用的不可逆性,必须确保生物炭在任何情况下都不会对土壤和环境带来不利的影响.为此,本文综述了生物炭添加对氮肥和磷肥在土壤-植物系统迁移转化过程中的作用,重点讨论了不同生物炭处理方式对土壤磷素吸附解吸和形态转化的影响,生物炭对土壤氮素转化的关键过程(矿化作用、硝化作用和固持作用)的影响,以及生物炭C/N比值对土壤氮素转化的影响,同时指出了目前研究存在的不足和需要加强的方面,从而为生物炭的应用和推广提供思路.     

蒙东地区水肥耦合对紫花苜蓿土壤磷组分的影响

磷素在土壤中可分为有机磷和无机磷两大组分,不同形态的磷供给植物营养的难易程度不同,应用液体³¹P核磁共振技术(³¹P-NMR)探明土壤磷组分可为进一步调控土壤磷营养提供重要的理论依据。本研究采用盆栽试验,以紫花苜蓿和栗钙土为对象,设置常规和干旱水分处理,并设置不同的施磷水平(P₀～P₄:0、0.025、0.05、0.1、0.2 g P₂O₅·kg^-1土),应用液体³¹P-NMR技术测定土壤磷组分,研究水肥耦合条件下紫花苜蓿土壤磷组分特征。结果表明: 不同水肥条件下,土壤无机磷主要包括无机正磷酸盐、无机焦磷酸盐和无机多磷酸盐。无机正磷酸盐在土壤无机磷组分中占主导地位,干旱会降低无机正磷酸盐含量;无机焦磷酸盐和无机多磷酸盐可存在于高施磷水平(P₄)的土壤中。有机磷组分中,正磷酸单酯占主导地位,干旱影响紫花苜蓿对土壤中正磷酸单酯的转化和利用。综上,合理的水肥管理可对蒙东地区紫花苜蓿土壤磷营养的转化和利用进行有效的调控。     

Degradation and conversion of somatostatin in normal and diabetic rats in vivo and in vitro

Plasma somatostatin-like immunoreactivity in the portal and jugular veins of streptozotocin diabetic rats was compared with that in normal control rats. In the diabetic group, somatostatin levels in the portal (p less than 0.05) and jugular (p less than 0.01) veins were both elevated compared with those in the control group. Moreover, the degree of elevation was greater in the jugular vein than in the portal vein. To further investigate the role of the liver in the clearance of somatostatin-28 in vivo, 2 micrograms of somatostatin-28 was administered as a bolus into the external jugular vein of intact and functionally hepatectomized rats. The mean half-time of somatostatin-28 was significantly longer in intact diabetic rats than in controls (p less than 0.05). The functional hepatectomy did not cause a significant difference in the half-time in diabetic rats but made it longer in control rats. These results suggest that the longer half-time of somatostatin-28 in diabetic rats in vivo is due to its slower hepatic clearance. The hepatic clearance of somatostatin-28 and somatostatin-14 was further studied in vitro using a recirculating liver perfusion method. The hepatic clearance of 1.2 nM of either somatostatin-28 or somatostatin-14 was significantly lower in diabetic rats than in controls (p less than 0.01). This indicates that elevated plasma somatostatin levels in diabetic rats are caused at least in part by decreased hepatic clearance of somatostatin.(ABSTRACT TRUNCATED AT 250 WORDS)     

Production of arsine and methylarsines in soil and in culture

Arsenate, arsenite, monomethylarsonate, and dimethylarsinate were added to different soils, and evolution of gaseous arsenical products was determined over 3 weeks. Arsine was produced in all three soils from all substrates, whereas methylarsine and dimethylarsine were produced only from methylarsonate and dimethylarsinate, respectively. At least three times more arsine than dimethylarsine was produced in soil incubated with dimethylarsinate. Resting cell suspensions of Pseudomonas and Alcaligenes produced arsine as the sole product when incubated anaerobically in the presence of arsenate or arsenite. In all instances, no trimethylarsine was observed, nor could any evidence be shown for the methylation of any arsenical substrate in soil or in culture. It was concluded that reduction to arsine, not methylation to trimethylarsine, was the primary mechanism for gaseous loss of arsenicals from soil.     

Activity of native and dextran-modified hyaluronidase in in vitro and in vivo systems

Modified hyaluronidase derivatives have been obtained. Covalent coupling of the enzyme with aldehyde dextran results in 65-85% protein binding to the carrier, residual catalytic activity accounting for 90-100% of the baseline. Modified hyaluronidase is more thermostable than the native enzyme. The data on intravenous drug distribution in the mouse organs are promising and ensure effective use of modified hyaluronidase for the treatment of pulmonary diseases.     

Development and comparison of in vivo and in vitro models for endometritis in cows and mares

In order to investigate pathogenic mechanisms of acute endometritis in cows and mares, we established an in vivo model in both species. Based on the results of an in vitro transmigration system, human recombinant interleukin-8 (rhIL-8; 1.25 microg per mare and 5 microg per cow in 50 ml phosphate-buffered saline) was used to attract polymorphonuclear neutrophil granulocytes (PMNs) into the uteri. Peak numbers of uterine neutrophils were attracted after 6h, in both cows and mares. On average, mares responded more sensitively than cows, with 15 times higher numbers of rhIL-8-attracted uterine neutrophils (72+/-8 x 10(7)cells). In contrast to in vitro studies, in vivo migrated neutrophils (uterine neutrophils) of both species displayed a significantly reduced MHC class I expression. Expression of the CD11a molecule was significantly enhanced on equine uterine neutrophils but downregulated on bovine cells. Compared with untreated autologous peripheral neutrophils, both uterine and in vitro migrated neutrophils showed no alteration of phagocytic capacity. The ability to generate reactive oxygen species (ROS) was significantly upregulated in bovine and equine uterine neutrophils. This was also observed after in vitro migration of equine neutrophils, whereas ROS generation by bovine neutrophils was significantly depressed. In summary, the concept of inducing endometritis directly by local application of human interleukin-8 has been reliably successful in cows and mares. The model permits the analysis of PMN migration into the uterus under defined and controlled conditions. The observed differences between cows and mares with respect to phenotypical and functional characteristics of in vivo attracted uterine cells point to species-related features of neutrophil migration. In vitro transmigrated bovine and equine cells partially differ in phenotype and function from uterine neutrophils. Therefore, the in vitro transmigration assay cannot completely represent the in vivo endometritis model described here.     

Importance of guanine nitration and hydroxylation in DNA in vitro and in vivo

Guanine (Gua) modification by nitrating and hydroxylating systems was investigated in DNA. In isolated calf thymus DNA, 8-NO(2)-Gua and 8-oxo-Gua were dose-dependently formed with peroxynitrite, and 8-NO(2)-Gua was released in substantial amounts. Myeloperoxidase (MPO) with H(2)O(2) and NO(2)(-) reacted with calf thymus DNA to form 8-NO(2)-Gua dose dependently without release of 8-NO(2)-Gua. The frequency of strand breaks was higher than the sum of 8-NO(2)-Gua and 8-oxo-Gua, particularly in the MPO-treated DNA, indicating the importance of other types of damage. The activation of human neutrophils and lymphocytes with phorbol ester did not induce 8-NO(2)-Gua and 8-oxo-Gua in their nuclear DNA. However, 8-NO(2)-Gua was found in calf thymus DNA co-incubated with activated neutrophils in the presence of NO(2)(-). No significant formation of 8-NO(2)-Gua was found in liver DNA from mice treated with Escherichia coli lipopolysaccharide. The incubation of peroxynitrite or MPO-H(2)O(2)-NO(2)(-)-treated DNA with formamidopyrimidine glycosylase (Fpg) released 8-oxo-Gua, but not 8-NO(2)-Gua, indicating that 8-NO(2)-Gua is not a substrate for Fpg. Although 8-NO(2)-Gua was generated in isolated DNA by different nitrating systems, other types of damage were formed in abundance, and the lesion could not be found reliably in nuclear DNA, suggesting that the biological importance is limited.     

Interactions of cadmium and selenium in rat plasma in vivo and in vitro

⁷⁵Se and ¹⁰⁹Cd tracers were used to study the binding of Se and Cd to plasma proteins at various SeO₃^2? doses and times up to 24 h after the simultaneous subcutaneous administration of SeO₃^2? and CdCl₂ to adult male rats. The simultaneous injection of CdCl₂ and SeO₃^2? markedly increased both Se and Cd plasma levels over that in control animals. Gel permeation chromatography of plasma indicated that at all times up to 24 h Cd and Se were bound in an atomic ratio of approx. 1 : 1 in 330 000 and 130 000 dalton fractions. From 4 to 24 h, Cd and Se appeared in the 420 000 dalton fraction, also with an atomic ratio of approx. 1 : 1. The 330 000 dalton molecules appeared to have a maximal binding capacity for the Cd-Se complex at a concentration of approx. 30 μmol/ml of plasma, while the 130 000 and 420 000 dalton molecules show a higher binding capacity. Studies in vitro revealed that SeO₃^2? does not interact directly with Cd and plasma proteins. It is metabolized by erythrocytes to a form that interacts in an atomic ratio of 1 : 1 with Cd to form a protein-bound complex of 130 000 daltons.     

Biosynthesis of beta-glucuronides of retinol and of retinoic acid in vivo and in vitro

After the intraportal injection of retinol-6,7-(14)C to rats, the O-ether derivative of retinol, retinyl -glucosiduronate, appears in the bile. Both retinoyl -glucuronide and retinyl -glucosiduronate are also synthesized in vitro when washed rat liver microsomes are incubated with uridine diphosphoglucuronic acid (UDPGA) and either retinoic acid or retinol, respectively. The synthesis of retinoyl -glucuronide was also demonstrated in microsomes of the kidney and in particulate fractions of the intestinal mucosa. The glucuronides were characterized by their UV absorption spectra, by their quenching of UV light or fluorescence under it, by their thin-layer chromatographic behavior in two solvent systems, and by the identification of products released during their hydrolysis by -glucuronidase. With retinoic acid as the substrate, the UDP glucuronyl transferase of rat liver microsomes had a pH optimum of 7.0, a temperature optimum of 38 degrees C, and a marked dependence on the concentrations of both retinoic acid and UDPGA, but was unaffected by a number of possible inhibitors, protective agents, and competitive substrates. The conversion of retinal to retinoic acid and the synthesis of retinoyl -glucuronide from retinoic acid could not be detected in whole homogenates, cell fractions, or outer segments of the bovine retina.