壳聚糖的磺化产物对大鼠血栓和凝血时间的影响

甲壳质及壳聚糖的硫酸酯化反应是其化学修饰中最吸引人的研究内容之一。由于它们与肝素有相似骨架， 经硫酸酯化，引入-NHSO3H， - CH2OSO3H - OSO3H， COOH，-CH2COOH基团后得到甲壳质(壳聚糖)类肝素药物，显示出抗栓、抗凝血性能(李鹏程等，1998；曾宪放等，1992；Proeyanat et al.，2002)；如Muzzarelli(1985)早已预见并证实其抗凝血活性；莫斯科血液研究中心病理药理系止血组的研究人员也证明了壳聚糖硫酸酯具有抗凝血活性，他们将肝素与壳聚糖硫酸酯以1∶1的比例给家兔静脉注射各0.5mg/kg，与单纯用肝素1mg/kg对照组比较，其抗凝血效应基本接近，但对照组有出血副作用，而试验组无副作用，可以证明壳聚糖硫酸酯具有既抗凝血又止血的双重调节作用；Tokura等(1994)证实分子质量大小和脱乙酰度不同对磺化产物的抗凝血活力有影响，样品分子质量26000 Da的活性最高，脱乙酰度70%比45%的抗凝血活性更强，脱乙酰度为95%的壳聚糖磺化后抗凝血活性最弱。在中国这方面的研究相对较少，特别是分子中含硫的多寡对生物活性的影响还未见报道。本文作者就壳聚糖的磺化产物对大鼠抗栓、抗凝血进行了研究，表明壳聚糖硫酸酯具有一定的抗栓、抗凝血效果，且具有一定的量效关系，这对今后该方面的进一步研究提供了科学理论依据。     

~(35)SO_4~(2-)示踪法测定九龙江河口沉积中硫酸盐还原速率

在2011年7月利用35SO2-4培养示踪法测定九龙江河口两个站位(A站位位于咸淡混合区,盐度3~5;B站位位于海相区,盐度20~25)沉积柱中硫酸盐还原速率的垂直分布。结果显示A站位沉积柱中硫酸盐还原速率变化范围为54~2 345nmol/(cm3·d),从表层到底部先增大后减小,最大值出现在20cm深度附近;B站位硫酸盐还原速率在24~987nmol/(cm3·d)之间,分别在10cm和78cm深度附近出现两个峰值,分别为876nmol/(cm3·d)和987nmol/(cm3·d)。综合分析两个站位孔隙水中SO2-4、甲烷浓度和沉积物中总有机碳、温度和氧化还原电位的垂直变化趋势与其硫酸盐还原速率的分布规律,表明A站位沉积物中硫酸盐还原以有机矿化为主;B站位受到有机质矿化和甲烷厌氧氧化的共同作用;两个站位硫酸盐还原速率及垂直分布趋势受孔隙水中SO2-4浓度、有机质活性和温度的共同影响;根据各个层位硫酸盐还原速率估算两个站位硫酸盐还原通量(以硫计)分别为527.9mmol/(m2·d)和357.1mmol/(m2·d),表明硫酸盐还原是九龙江河口有机质厌氧矿化的重要路径。     

Acid drainage generation and associated Ca-Fe-SO4 minerals in a periglacial environment, Eagle Plains, Northern Yukon, Canada: A potential analogue for low-temperature sulfate formation on Mars

Near Eagle Plains, northern Yukon, Canada, acidic Ca-Fe-Mg sulfate waters are discharging year-long from disturbed permafrosted sandstone bedrock overlying pyritiferous black shales. These acidic waters are precipitating gypsum with minor amounts of jarosite-K (Na), schwertmannite and hematite. This mineral assemblage is similar to that observed at Meridiani Planum (and other location on Mars), making this site a valuable analogue for low-temperature sulfate geochemistry and mineral formation on Mars. Stable O-S isotope analysis of the acidic waters near Eagle Plains revealed that the oxygen in the dissolved sulfate is mostly derived from water (ca. 70%), suggesting that the sulfide oxidation process could be in part biomediated (i.e., accelerated by acidophilic Fe-oxidizing bacteria). However, unlike the dissolved sulfate in the waters, the formation of the Ca-Fe-SO₄ minerals appears to be purely abiotic. The stable O-S isotope composition of the sulfate minerals is well within the predicted equilibrium range at low temperature, suggesting that they formed through physico-chemical processes (i.e., evaporation or freezing). Low-temperature geochemical modeling with FREZCHEM and PHREEQC suggests that the mineral assemblage at Eagle Plains precipitated mainly through the freezing of Ca-Fe-Mg-SO₄ acidic waters, rather than through evaporation during the dry summer season, although the latter is still possible. This suggests that the sulfate mineral assemblage observed on Mars could have also formed under a periglacial-type climate. Considering that the active layer in the zone affected by acid drainage does not freeze-over during winter, the residual talik offers a localized niche environment to support acidophilic microorganisms. Overall, the fact that acid drainage is presently active near Eagle Plains allows the direct observation of the low-temperature geochemical processes responsible for generating acid drainage conditions and precipitation of gypsum, schwertmannite, jarosite-K, jarosite-Na, goethite and hematite.     

地质流体自然类型与成矿流体类型

水是地球上特征的地质流体 ,大部分矿床是在水热流体参与下形成的 ,但并不是所有流体都参与成矿。根据水的主要存在环境把水分为地质流体和成矿流体类型。各种环境广泛存在的水所构成的地质流体 ,又可细分为大气降水、盆地建造水、海水、岩浆水和变质水各种类型。研究认为成矿流体的形成主要与地质作用有关 ,是地质流体在特定环境特定演化阶段形成的特征产物。成矿流体则可划分为高温硅钾卤水、中温碳酸盐卤水及低温硫酸盐卤水。高温硅钾卤水中硅钾组分含量与温度、盐度成正相关关系 ,并且其中富含F-、B2 O3组分。这些特征与成矿作用中的高温钾化、硅化、萤石化及电气石化蚀变及热水沉积特征是一致的 ,高温成矿流体在演化过程中依次可以演变为中温或低温成矿流体。中温成矿流体以碳酸盐型流体为主 ,以富含Mn2 +,Fe2 +,Mg2 +的碳酸盐化合物为特征。低温成矿流体一般为硫酸盐型卤水 ,主要是Ba2 +,Sr2 +,Ca2 +的硫酸盐化合物 ,在海陆相各环境中广泛存在。大洋底部成矿流体是特殊环境下的地质流体类型 ,具有更广泛的温度区间 ,可以是从高温到中低温的系列流体类型 ,并且具有特殊地球化学组成。一般形成高温硅钾卤水与岩浆作用或变质作用有关 ,由于充分的水岩交代作用 ,可以获得较高的温度及足够的溶质组分 ;     

Porewater geochemistry and solute flux from bottom sediments,Devils Lake,North Dakota

Sediment cores were collected for pore-water analysis from the eastern end of Devils Lake, located in northeastern North Dakota, to determine diagenetic reactions occurring in surficial bottom sediments and to evaluate the impact of these reactions on chemical concentrations in the overlying lake water. Sediment pore waters are enriched in major ions and nutrients relative to lake water. The principal sources of major ions to pore water are saline sediments located in the upper 1 m of bottom sediment. The principal source of titration alkalinity and nutrients to pore water is microbial decomposition of sedimentary organic matter by sulfate reduction. Sediment pore waters in the eastern part of Devils Lake have higher major-ion concentrations and solute-flux rates than the sediment pore waters in the central part of the lake. In contrast, sediment pore waters in the central part of Devils Lake have significantly higher nutrient concentrations and solute-flux rates. Major-ion concentrations and solute-flux rates in sediment pore water increase from west to east. These trends indicate that bottom-sediment diagenetic processes are, in part, responsible for the observed concentration gradient in the lake. The higher nutrient concentrations and the higher nutrient diffusional-flux rates in Main Bay are the result of more labile sedimentary organic matter and the occurrence of sulfate reduction. Environmentally-reactive trace-metal concentrations (Cu, Pb, Zn, and Fe) in bottom sediments decrease from west to east with distance from the surface-water sources and with increasing surface-water salinity.     

Zur Systematik der Kohlenstoff-Schwefel-Eisen-Verhältnisse in Auftriebssedimenten

Abundances of organic carbon, sulfur, and reactive iron in sediments of three upwelling environments (Peru, Oman and Benguela) suggest that organic carbon/reduced sulfur ratios (C/S-ratios) in this category of marine sediments deviate considerably from previously established empirical ratios in normal marine sediments. To clarify the discrepancies, we investigated those components of the diagenetic system that limit the formation of pyrite: sulfate concentrations and reduction rates in pore waters, availability of reactive iron, and the quantity and quality of organic matter. All three limitations are evident in our sample pools. The results suggest that C/S-ratios in recent and fossil marine sediments rich in organic matter may be unsuitable as paleoenvironmental indicators.

     

Hydrogeochemical Anomalies in the Springs of the Chiayi Area in West-central Taiwan as Possible Precursors to Earthquakes

Water samples from both hot and artesian springs in Kuantzeling in west-central Taiwan have been collected on a regular basis from July 15, 1999 to the end of August 2001 to measure cation and anion concentrations as a tool to detect major earthquake precursors. The data identify chloride and sulfate ion anomalies few days prior to major quakes and lasting a few days afterward. These anomalies are characterized by increases in Cl^- concentrations from 34.9% to 41.2% and 71.5% to 138.1% as well as increases in SO₄^2- concentrations from 232.7% to 276.8% and 100.0% to 155.1% above the means in both hot and artesian springs. The occurrence of these anomalies is probably explained first as stress/strain-induced pressure changes in the subsurface water systems which then generate precursory limited geochemical discharges at the levels of subsurface reservoirs. Therefore, finally leading to the mixing of previously separated subsurface water bodies occurs. This suggests that the hot and artesian springs in the Kuantzeling area are possible ideal sites for recording strain changes serving well as earthquake precursors.     

Sulfuric acid as a weathering agent of carbonate weathering constrained by δ^13C： Examples from Southwest China

Rock weathering by carbonic acid is one of the important atmosphere CO2 sequestration. Actually, it depends on whether carbonic acid or other acids as weathering agents, which is important to understand the model of global carbon cycle. For example, sulfuric acid derived from oxidation of pyrite takes part in the rock weathering, which might counteract one part of CO2 drawdown by silicate weathering. In this study, chemicals and carbon isotopic composition of waters were determined in the Beipan River, Guizhou. The δ^13C values of dissolved inorganic carbon in the province, Southwest China. The values of the samples range from -13.1‰ to -2.4‰, which show a good negative correlation with the equivalent ratio of [HCO3]/（[Ca^2＋＋Mg^2＋]） and a good positive correlation with the equivalent ratio of [SO4^2-]/（[Ca^2＋＋Mg^2＋]） and [SO4^2-]/[HCO3^-]. The relationships suggest that sulfuric acid took part in carbonate weathering. Acid rain is thus a significant source of sulfuric acid to the karstic rivers of Guizhou Province.     

Pretreatment of diosgenin wastewaters using polyferric sulfate as a main coagulant

Diosgenin is produced from Dioscrea L, mainly using D.zingiberensis as the raw material. During the process, particularly in the process of acidic hydrolysis, large quantities of high-strength wastewaters are discharged. The waste liquids are characteristic of strong acidity, usually with pH value less than 1, and high concentrations of organic matter with average CODcr （chemical organic demand） in the range of 20000-3000 mg/L. Without proper treatment, their free disposal would pose serious threat to natural ecosystem and cause considerable environmental problems. Since diosgenin wastewaters contain high load organics and acidity, appropriate pretreatment is needed before they are biologically degraded. Coagulation is a common method for eliminating colloid particles and/or high molecule organic chemicals from wastewaters. Poly-ferric sulfate is found to be most effective in removing organic matter. The objective of this study is to investigate the effectiveness and feasibility of poly-ferric sulfate to reduce CODcr and turbidity from diosgenin wastewaters. Due to its high acidic nature, the pH value of diosgenin wastewater was neutralized with Ca（OH）2 solution before being coagulated. Various factors that influence the coagulation process, such as pH value, the dosage of poly-ferric sulfate, polyelectrolyte aids and mixing conditions were examined in the experiments.     

Chemical Assessment of Oceanic and Terrestrial Sulfur in the Marine Boundary Layer over the Northern North Pacific during Summer

Dimethylsulfide (DMS) in surface seawater and the air, methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ²–) in aerosol, and radon-222 (Rn-222) were measured in the northern North Pacific, including the Bering Sea, during summer (13 July – 6 September 1997). The mean atmospheric DMS concentrations in the eastern region (21.0 ± 5.8 nmole/m³ (mean ± S.D.), n=30) and Bering Sea (19.9 ± 9.8 nmole/m³, n=10) were higher than that in the western region (11.1 ± 6.4 nmole/m³, n=31) (p<0.05), although these regions did not significantly differ in the mean DMS concentration in surface seawater. Mean sea-to-air DMS flux in the eastern region (21.0 ± 10.4 mole/m²/day, n=19) was larger than those in the western region (11.3 ± 16.9 mole /m²/day, n=22) and Bering Sea (11.2 ± 7.8 mole/m²/day, n=7) (p<0.05). This suggests that the longitudinal difference in atmospheric DMS was produced by that in DMS flux owing to wind speed, while the possible causes of the higher DMS concentrations in the Bering Sea include (1) later DMS oxidation rates, (2) lower heights of the marine boundary layer, and (3) more inactive convection. The mean MSA concentrations in the eastern region (1.18 ± 0.84 nmole/m³, n=35) and Bering Sea (1.17 ± 0.87 nmole/m³, n=13) were higher than that in the western region (0.49 ± 0.25 nmole/m³, n=28) (p < 0.05). Thus the distribution of MSA was similar to that of DMS, while the nss-SO₄ ²– concentrations were higher near the continent. This suggests that nss-SO₄ ²– concentrations were regionally influenced by anthropogenic sulfur input, because the distribution of nss-SO₄ ²– was similar to that of Rn-222 used as a tracer of continental air masses.