腐殖酸三维荧光光谱特性研究

腐殖质的荧光特性被广泛用来解析其在各种天然环境中的来源及分布.由于荧光光谱分析具有灵敏度高,选择性好,且不破坏样品结构的优点,非常适合用来研究腐殖质的结构和官能团等特征.利用三维荧光激发-发射光谱研究了 Fluka腐殖酸的荧光光谱特性,结果显示,离子强度(0～0.05 mol/L KClO4)对 Fluka腐殖酸的三维荧光光谱特性影响非常小,而腐殖酸的浓度(5～100 mg/L)和溶液 pH(2～12)对其三维荧光光谱特性影响显著.当腐殖酸浓度增大时,荧光峰出现明显红移现象.荧光强度一般随着 pH的升高而增大,当 pH大于 10后呈下降趋势,我们从垃圾渗滤液溶解有机质的实验结果中也得到相同结论;在浓度为 50 mg/L和 100 mg/L的 Fluka腐殖酸中,荧光峰 B(fulvic-like)的荧光强度却在 pH=5.0左右时达到最大值,与前人报道的土壤富里酸的行为一致,质子化常数 lgK′ HL分别为 3.57和 3.13,与二羧基化合物接近,说明荧光峰 B可能与 Fluka腐殖酸结构中的羧基有关;荧光峰 A与荧光峰 B的荧光强度比值 r(A/B)在 0.61～2.59之间,并且在 pH=2～11范围内, r(A/B)与 pH具有较好的线性相关关系,表明荧光峰 A和荧光峰 B随着 pH值的改变有着相同的变化趋势.     

埋藏有机酸性流体对四川盆地东北部飞仙关组储层的溶蚀改造作用：溶解动力学实验研究

通过白云岩化鲕粒灰岩与0.1 mol/L乙酸的旋转盘溶解动力学实验,研究了深埋藏中有机质热演化过程中伴生的有机酸对鲕粒灰岩储层的改造作用机理.结果显示,白云岩化鲕粒灰岩溶解反应的速率在3.26×10-7～6.66×10-7 mol/(cm2·s)之间,并且溶蚀速率随温度和转速的增加而增大.反应前后样品表面的扫描电子显微...     

酸雨对桂林枯水期岩溶地下水δ13CDIC及碳汇效应的影响

定量评价硫酸对岩溶碳汇效应的影响有助于提高岩石风化碳汇通量估算精度, 对当前全球气候变化研究意义重大.选取受酸雨影响的桂林岩溶区为研究对象, 在枯水期对研究区14个岩溶大泉和15条地下河水化学成分和碳同位素进行了测试分析, 结果表明: 岩溶大泉和地下河中阳离子以Mg2+和Ca2+为主, 阴离子以HCO₃-为主, 分别占阳离子和阴离子组成的90%以上, SO₄2-含量较低, 其含量范围为0.004~0.213mmol/L; 所占阴离子组成比例为0.12%~6.11%;δ13C_DIC、[Ca2++Mg2+]/[HCO₃-]更偏向于碳酸溶解端元, 离硫酸溶解端元距离远, 证实硫酸参与碳酸盐岩的溶解对地下水无机碳(dissolved inorganic carbon, 简称DIC)及δ13C_DIC的影响有限; 与Sr2+/Ca2+值一样, δ13C_DIC主要受径流条件控制, 其大小可以反映地下水径流条件的强弱.利用化学计量关系计算出由硫酸溶蚀碳酸盐岩的平均比例为22.64%, 产生的DIC(HCO₃-_H2SO4)占总DIC的平均比例为13.04%, 碳酸产生的DIC(HCO₃-_H2CO3)占地下水总DIC的比例为86.96%, 其中来源于土壤大气中的HCO₃-比例为43.48%.因此, 扣除硫酸对地下水中DIC的贡献后, 岩溶碳汇效应将减少13.04%.      

江南造山带新元古代中期(830～750Ma)岩浆活动及对构造演化的制约

连接扬子地块和华夏地块的江南造山带是华南前寒武纪最重要的构造单元,其形成和演化长期以来备受关注。在江南造山带的范围内广泛发育了新元古代岩浆岩,它们是探讨江南造山带构造演化的重要对象,但其成因和形成的构造背景却备受争论。本文系统收集和分析了江南造山带830~820 Ma花岗岩、800~780 Ma酸性岩和800~750 Ma基性岩的地球化学数据。研究表明,不同时间段的岩石成因类型存在系统差异,830~820 Ma的花岗岩主要为S型花岗岩,800~780 Ma的酸性岩主要为A型酸性岩,而800~750 Ma的基性岩以拉斑系列和碱性系列为主,并在构造判别图中显示了板内玄武岩(WPB)和洋中脊玄武岩(MORB)的特征。综合同位素年代学、岩石地球化学和沉积学等学科领域的研究成果我们认为:扬子北缘和西缘应先于东南缘在1000~900 Ma期间发生碰撞,而此时的东南缘仍为活动大陆边缘;直到~830 Ma,扬子地块与华夏地块沿江南造山带发生拼贴,但只是陆-弧-(微)陆之间的"软碰撞",而无山脉隆升和高级变质作用,各个块体之间处于"联而不合"的状态,大洋岩石圈拆沉之后的软流圈上涌和由拆沉所引起的拉张作用导致了上覆岩石圈和陆壳发生部分熔融,产生了江南造山带830~820 Ma的S型花岗岩;随着全球Rodinia超大陆的裂解,~820 Ma,华南裂谷盆地开启,并在随后的裂解过程中发育了大量与伸展有关的800~780 Ma A型酸性岩和基性岩脉/墙,而其明显高于同时代MORB源区的地幔潜能温度显示,导致Rodina超大陆裂解的地幔柱可能对该时期岩浆岩的地幔源区有一定影响;随着拉张作用的不断加强,出现了760~750 Ma碱性系列和具MORB特征的基性岩,此时的软流圈地幔既提供热量又有物质供应。     

黄土醋酸淋溶实验及其碳酸盐组分的地球化学特征

选择性的化学淋溶实验 ,广泛用于沉积物的地球化学研究中。通过对比 1mol/L的盐酸和醋酸两种溶剂对黄土和古土壤的淋溶效果 ,发现 1mol/L的醋酸能选择性淋溶黄土和古土壤中碳酸盐组分 ,对硅酸盐、铁的氧化物等影响很小。在确定溶剂后 ,以 1mol/L醋酸溶液选择性淋溶了洛川剖面 4 3个黄土和古土壤样品 ,通过分析淋溶液的组成 ,得出黄土和古土壤中碳酸盐组分的平均成分 (wB)为 :MgO 1.71% ,MnO 670× 10 - 6 ,Sr 4 90× 10 - 6 。淋溶结果较好地反映了黄土-古土壤剖面的风化成壤程度 ,其中醋酸淋溶液中MnO含量能更好地反映当时的古气候信息。     

在高氯酸—酒石酸—硫脲介质中原子吸收法测定多种矿石中的银

介绍了在ＨＣｌＯ４－酒石酸－硫脲混合介质中原子吸收测定Ａｇ的方法,避免了Ｃｕ、Ｓｂ、Ｗ等常见元素对Ａｇ的干扰,方法经ＭＧＩ系统金银地质标准参考样分析检验,结果与标准值相符,应用于含Ａｇ在１０＾－３～１０＾－６级的不同矿石中Ａｇ的测定,结果与王水介质中测Ａｇ的结果相符,对含Ａｇ１０＾－６水平的试样９次测定的ＲＳＤ〈５％。     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

模拟酸雨及施磷对水稻土中铅的淋溶特性影响

采用pH=3.0、pH=4.5与对照pH=5.6的3种模拟酸雨淋溶土柱的方法,研究酸雨及含磷酸雨淋溶下合肥市郊水稻土中铅的释放特征与规律。结果表明:经过相当于1 980 mm降水量的淋溶后,铅释放量总体上表现为随着酸雨强度增加累积淋溶量也增加的现象。酸雨作用下,施磷量越多土壤中铅的淋失总量越大。在酸雨及施磷条件下,大兴地区黄褐土中Pb较义城地区水稻土中易于淋失。     

Impact of Montmorillonite and Calcite on Release and Adsorption of Cyanobacterial Fatty Acids at Ambient Temperature

Minerals might act as important sorbents of sedimentary organic matter and reduce biodegradation, which favors the formation of hydrocarbon source rocks in the earth's history. Since most organic matter is degraded during the sinking process, at ambient temperature, it is important to investigate the adsorption capacity of different minerals during this process, to assess the organic loss from primary productivity to sedimentary organic matter. In this study, montmorillonite and calcite have been selected to study the impact of different minerals on the release, adsorption, and deposition of cyanobacterial (Synechococcus elonpata) fatty acids (FAs) at ambient temperature. Gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS) have been utilized to detect the variation in fatty acids. Primary results suggest that minerals have a different impact on dissolved organic matter. Montmorillonite can specifically enhance the release of fatty acids from cyanobacterial cells by lowering the pH values of the solution. The adsorption of the dissolved organic matter by montmorillonite will also be enhanced under a lower pH value. Conjunction of fatty acids with montmorillonite to form a complex will favor the sinking and preservation of these organics. Selective adsorption is observed among fatty acids with different carbon numbers. In contrast, calcite does not show any impact on the release and adsorption of organic matter even though it is reportedly capable of acting as a catalyst during the transformation of organic matter at high temperature. The primary data bridge a link between primary productivity and sedimentary organic matter, suggesting the relative importance of claystones in the formation of hydrocarbon source rocks in the earth's history.     

钽钼杂多酸—碱性染料多元缔合物体系的研究

在PVA、OP或Tween-60存在下,采用平衡移动法确定了碱性染料亚甲基蓝、耐尔蓝(NB)、罗丹明B(RB)、丁基罗丹明B(BRB)、结晶紫(CV)、乙基紫(EV)与Ta的摩尔比是1:1至7:1;考察了NB(或BRB)-钽钼杂多酸缔合物的红外光谱,初步探讨了反应机理:比较了几个碱性染料-钽钼杂多酸缔合物体系的光度特性,筛选出两个摩尔吸光系数>2×10~6的分析体系,并用于合金钢和地质标样中痕量Ta的测定,方法可行。