NMR relaxation study of disorder in condensed matter: solid solutions of betaine phosphate and phosphite

Proton NMR relaxation measurements have been carried out in anti-ferroelectric Betaine phosphate (BP), ferroelectric Betaine phosphite (BPI) and the mixed system BPI(1-x)BPx, at 11.4MHz and 23.3MHz from 300K to 80K for x=0.0, 0.25, 0.45, 0.85, and 1.0. The temperature dependence of spin lattice relaxation time T, exhibits two minima as expected from the BPP model in BP and BPI. The Larmor frequency dependence of T, in the mixed system is rather unusual and exhibits different slopes for the low temperature wings at the two frequencies, which is a clear experimental evidence of the presence of different methyl groups with different activation energies (E-a) indicating disorder.

红枫湖、百花湖水中溶解有机物分子量分布特征及环境地球化学意义

溶解有机物（dissolved organio matter， DOM）通常是指能够通过0.45μm滤膜的有机物质。0.45μm的定义是根据传统的过滤滤膜直径来划分的，不是一个绝对的定义。DOM在水环境中起着重要的作用，它是水环境中重要的配位体和吸附载体。DOM在水化学和生态环境中的重要作用，主要表现在它不仅可以和基本的金属离子和有机化合物结合，还可以与毒性金属离子和除草剂、杀虫剂结合（wershow ond Goldberg，1972）。湖泊水中DoM的浓度及物理化学性质能够影响水生态环境的结构及初级生产力。溶解有机物按元素组成来分，主要含有C、O、H、N、P、S以及灰分。按重量计算，其中C占总有机物的50％，其次是O（科O％）、H（一5％）、N（0.5～6.5％）、P（＜1.0％）、S（＜1.0％）和灰分（1.2-5.0％）（Thurman，1985）。DOM一般由多种有机化合物组成，其中腐殖物质是溶解有机质的主要组成部分，一般占有机质总量的50-80％。目前通常可人为地将腐殖物质划分为胡敏素、胡敏酸和富里酸（Aiken et oL，1 985）。其余的非腐殖类物质主要包括碳水化合物、氨基酸、叶绿素、藻类分泌物、酚酮类化合物、脂肪酸和亲水性有机酸等（Thurman，1985）a在水环境中一些金属离子和微量元素通常和DOM相结合，而这些元素的作用和在水中的迁移都受DoM的分子量分布的影响（chiou etal．，1986）。 DOM的分子量及其分布是指示水质量的一个重要参数，同时在水处理过程中对于研究DOM的去处效率有重要作用（vuorio et oL，1998）。具有不同分子量分布的DOM与金属的络合能力也不同，则它们对金属的生物有效性的作用就不同（wuetal．，2002）。分子量变化的程度可以进一步理解DOM的自然形成过程，也可以在弓！用水处理过程中优化腐殖质的去除过程。红枫湖和百花湖是贵州地区两个人工水库，通过对两湖水文条件的测量，探讨了影响DOM分子量及分布变化的环境因素，包括溶解氧的含量、水体温度、pH值、叶绿素。的含量、光照强度、藻类生长情况、生物活动等，以及溶解有机物的来源，人为污染情况等。本文采样高效体积排阻色谱法（High PerformanceSizeExclusion cbromatograP场，HPsEC）测量了红枫湖、百花湖水中的DOM的含量及分子量分布，得出了以下几点认识：1、选择HPsEC实验的最佳条件：0.03M NaCl和0.002的磷酸盐缓冲液作为流动相，pH为6.8，离子强度为0．034mol几，紫外检测波长为254nm。2、红枫湖、百花湖水中DOM主要以分子量小于3500Da的组分为主，占总溶解有机物的90％以上。根据洗脱曲线的峰面积，可以把DOM分为3个不同 分子量的组分，其中大分子量组分（MW＞2000Da）的含量占总DOM的35％一68％；中等分子量组分（Z000Da＞MW>1000Da）的含量为27％-57％；小分子量组分（MW＜1000Da）占总DOM的3％一31％。 3、红枫湖、百花湖水中Doc含量受气候条件的影响。丰水期，水体上部DOC含量较大，下部较小‘平水期和枯水期，上下水体中DOC含量一致。各组分DOc含量变化与总DOC含量变化相似。DOC含量也表现出明显的季节性变化特征。丰水期DOC含量较高，而在平水期和枯水期含量较低。红枫湖和百花湖二者之间DOC含量没有明显的差别。4、红枫湖、百花湖水中DOM平均分子量也受气候条件的影响。丰水期，随深度的增大，DoM平均分子量增大；平水期和枯水期，上下水体DOM平均分子量一致。DO入左的季节性变化与DOC相反，丰水期，DOM平均分子量偏低；而在平水期和枯水期，DOM平均分子量偏高。5、重均分子量和数均分子量虽然变化趋势相似，但是它们的变化幅度不同，所以多分散系数也会发生变化。总的来说，在水体上部多分散系数偏大，水体下部偏小。丰水期多分散系数较大，平水期和枯水期多分散系数较小。6、随着气候条件的变化，各分子量组分的DOM含量及DOC浓度也在发生变化。大分子量组分随深度而增大，而中等和小分子量组分随深度而减小。丰水期，中等和小分子量组分含量较多，而大分子量组分较少；平水期和枯水期，大分子量组分含量较多，中等和小分子量组分含量较少。

Origin, seasonality and chemical characteristics of rainwater in Aveiro

Este trabalho teve como objectivo caracterizar quimicamente a água da chuva recolhida na cidade de Aveiro, localizada a sudoeste da Europa, no período de Setembro de 2008 a Setembro de 2009. Para matrizes diluídas como a da água da chuva, as metodologias analíticas a utilizar para se conseguir uma rigorosa caracterização química são de grande importância e ainda não estão uniformizadas. Assim, para caracterizar a fracção orgânica, primeiramente foram comparadas duas metodologias de filtração (0.22 e 0.45 μm) e foram estudados dois procedimentos de preservação da água da chuva (refrigeração e congelação), utilizando a espectroscopia de fluorescência molecular. Além disso, foram comparados dois procedimentos de isolamento e extracção da matéria orgânica dissolvida (DOM) da água da chuva, baseados na sorção nos sorbentes DAX-8 e C-18, utilizando as espectroscopias de ultravioleta-visível e fluorescência molecular. Relativamente aos resultados das metodologias de filtração e preservação, é recomendada a filtração por 0.45 μm, assim como, as amostras de água da chuva deverão ser mantidas no escuro a 4ºC, no máximo até 4 dias, até às análises espectroscópicas. Relativamente à metodologia de isolamento e extracção da DOM, os resultados mostraram que o procedimento de isolamento baseado na C-18 extraiu a DOM que é representativa da matriz global, enquanto que o procedimento da DAX-8 extraiu preferencialmente a fracção do tipo húmico. Como no presente trabalho pretendíamos caracterizar a fracção do tipo húmico da DOM da água da chuva, foi escolhida a metodologia de isolamento e extracção baseada na sorção no sorvente DAX-8. Previamente ao isolamento e extracção da DOM da água da chuva, toda a fracção orgânica das amostras de água da chuva foi caracterizada pelas técnicas de ultravioleta-visível e de fluorescência molecular. As amostras mostraram características semelhantes às de outras águas naturais, e a água da chuva do Verão e Outono apresentou maior conteúdo da matéria orgânica dissolvida cromofórica que a do Inverno e Primavera. Posteriormente, a fracção do tipo húmico de algumas amostras de água da chuva, isolada e extraída pelo procedimento baseado na DAX-8, foi caracterizada utilizando as técnicas espectroscópicas de ultravioleta-visível, fluorescência molecular e ressonância magnética nuclear de protão. Todos os extractos continham uma mistura complexa de compostos hidroxilados e ácidos carboxílicos, com uma predominância da componente alifática e um baixo conteúdo da componente aromática. A fracção inorgânica da água da chuva foi caracterizada determinando a concentração das seguintes espécies iónicas: H+, NH4 +, Cl-, NO3 -, SO4 2-. Os resultados foram comparados com os obtidos na chuva colectada no mesmo local entre 1986-1989 e mostraram que de todos os iões determinados a concentração de NO3 - foi a única que aumentou (cerca do dobro) em 20 anos, tendo sido atribuído ao aumento de veículos e emissões industriais na área de amostragem. Durante o período de amostragem cerca de 80% da precipitação esteve associada a massas de ar oceânicas, enquanto a restante esteve relacionada com massas que tiveram uma influência antropogénica e terrestre. De um modo geral, para as fracções orgânica e inorgânica da água da chuva analisadas, o conteúdo químico foi menor para as amostras que estiveram associadas a massas de ar marítimas do que para as amostras que tiveram contribuições terrestres e antropogénicas.

Effets des nanoparticules d'argent sur les processus enzymatiques des sols

Les nanomatériaux sont de plus en plus présents dans les produits consommables du quotidien. L’argent est le métal le plus utilisé en nanotechnologie pour ses propriétés antimicrobiennes. Par différentes voies d’entrée, les nanoparticules d’argent (nAg) se retrouvent dans l’environnement en quantité significative, notamment dans les sols suite à la valorisation agricole des biosolides municipaux. Il est prévu qu’une interaction négative sur la communauté microbienne terrestre ait des répercussions sur la fertilité du sol et les processus biogéochimiques. Les mesures de l’activité enzymatique ont déjà montré leur efficacité et leur sensibilité dans la détection d’une perturbation physique et chimique du sol. Les effets potentiels des nAg sur l’écosystème terrestre ont été évalués en mesurant l’activité des enzymes β-D-glucosidase (EC 3.2.1.21), leucine-aminopeptidase (EC 3.4.11.1), phosphomonoesterase (EC 3.1.3) et arylsulfatase (EC 3.1.6.1) intervenant dans les cycles des éléments essentiels C, N, P et S, respectivement. L’activité enzymatique est mesurée à l’aide d’une technique basée sur la fluorescence qui requière des substrats synthétiques liés à un fluorophore. Un sol de type sableux a été échantillonné au Campus Macdonald de l’Université McGill (Sainte-Anne-de-Bellevue, Qc) puis exposé aux nAg (taille ~20 nm) ou à la forme ionique Ag+ (Ag-acetate) à des concentrations nominales de 1,25 × 10-3, 1,25 × 10-2, 0,125, 1,25, 6,25 et 31,25 mg Ag kg-1 sol. De plus, le rôle de la matière organique (MO) a été évalué en effectuant un amendement du sol avec un compost de feuilles. Pour mieux comprendre les effets observés, des analyses de spéciation de l’Ag ont été réalisées. Les concentrations en Ag dissous ont été déterminées après filtration à travers des membranes de 0,45 µm ou de 3 kDa (~1 nm, ultrafiltration) pour séparer la phase particulaire des ions dissous. De façon générale, une inhibition de l’activité enzymatique a été observée pour les 4 enzymes en fonction de l’augmentation de la concentration en Ag (totale et dissoute) mais elle est significativement moins importante avec l’ajout de la MO. Les résultats suggèrent que l’inhibition de l’activité des enzymes aux faibles expositions aux nAg est due aux nanoparticules puisqu’une très faible fraction des nAg est réellement dissoute et aucun effet significatif n’a été observé pour les sols traités à des concentrations similaires en Ag+. Par contre, les effets mesurés aux concentrations plus élevées en nAg sont semblables aux expositions à l’Ag+ et suggèrent un rôle de l’Ag colloïdale dans l’inhibition du processus enzymatique des sols.

Dissolved and particulate organic carbon in the Sea of Okhotsk

Data on distribution of dissolved and particulate organic matter obtained during Cruises 21 and 24 of R/V Akademik A. Nesmeyanov in June-August 1992 and 1993 are presented. In general a remarkable heterogeneity in distributions of both dissolved and particulate organic carbon is revealed. Concentrations of dissolved organic carbon vary from 98 to 700 µmol/l and those of particulate organic carbon vary from 3 to 50 µmol/l. Maximum concentrations are commonly observed in the shelf region while minimum concentrations - in the central basin. Run-off of the Amur River raises dissolved matter concentration in the Sakhalin Bay, while oil exploitation at the Sakhalin shelf maximizes particulate organic carbon concentration and minimizes dissolved one. Concentrations of dissolved and particulate organic carbon in the surface microlayer were estimated for the first time and are shown to be 1.5-2.0 times higher than in surface waters.

Lipids in ocean particulate matter and bottom sediments

Lipid contents both in particulate matter and bottom sediments decreases with passage from the shelf toward the open ocean. Lipid concentration in particulate matter collected by a separator (Ls) decreases by a factor of 7 (from 7.05 to 0.95 % of dry matter), while in particulate matter collected on filters (Lf) it decreases by a factor of 13 (from 78 to 6 µg/l) in the vicinity of the Limpopo River and by a factor of 6 (from 74 to 13 µg/l) in the vicinity of the Zambezi River. Concentration of Lf also decreased with depth. In the upper sediment layers lipid concentration was 0.0028-0.039% of dry matter; all mud samples were richer in lipids, than sand samples. During sedimentogenesis there is an increase in proportion of lipids relative to other classes of organic matter, proportion of low-polarity compounds increases among the lipids, and proportion of hydrocarbons rises among these compounds. Sediments inherit composition of particulate matter to the greatest degree in the vicinity of river mouths.

Facies and diagenesis of organic matter in sediments at DSDP Leg 87

A series of upper Pliocene to Pleistocene sediment samples from DSDP Sites 582 and 583 (Nankai Trough, active margin off Japan) were investigated by organic geochemical methods including organic carbon determination, Rock- Eval pyrolysis, gas chromatography of extractable hydrocarbons, and kerogen microscopy. The organic carbon content is fairly uniform and moderately low (0.35 to 0.77%) at both sites, although accompanied by high sedimentation rates. The low organic matter concentrations are the result of the combined effect of several factors: low bioproductivity, oxic depositional environment, and dilution with lithogenic material. Organic petrography revealed a mixture of three maceral types: (1) fresh, green fluorescent alginites of aquatic origin probably transported by turbidites from the shelf edge, (2) gelified huminites and paniculate liptinites derived from the erosion of unconsolidated peat, and (3) highly reflecting inertinites derived from continental erosion. By a combination of organic petrography and Rock-Eval pyrolysis results, the organic matter is characterized as mainly type III kerogen with a slight tendency to a mixed type II-III. During Rock-Eval pyrolysis, a mineral matrix effect on the generated hydrocarbons was observed. The organic matter in all sediments has a low level of maturity (below 0.45% Rm) and has not yet reached the onset of thermal hydrocarbon generation according to several geochemical maturation parameters. This low maturity is in contrast to anomalously high extract yields at both sites and large hydrocarbon proportions in the extracts at Site 583. This contrast may be due to early generation of polar compounds and perhaps redistribution of hydrocarbons caused by subduction tectonics. Carbon isotope data of the interstitial hydrocarbon gases indicate their origin from bacterial degradation of organic matter, although only very few bacterially degraded maceral components were detected.