Ab initio infra-red spectra of iron-polycyclic aromatic hydrocarbon compounds: a model case

C₁₀H₆-Fe⁺ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C₁₀H₆-Fe⁺ systems are models for larger PAHs-Fe⁺ complexes, which are believed to play a key rôle in space chemistry.     

Effet de l'agrégation sur le transport de la kaolinite recouverte d'acide humique à travers un sable de quartz d'origine naturelleAggregation effect on the transport of humic-coated kaolinite colloids through a natural quartz sand

To evaluate the risk of contaminant transport by mobile colloids, it is necessary to understand how colloids and associated pollutants behave during their migration through uncontaminated soil or groundwater. In this study, we investigated the influence of aggregation induced by Ca²⁺ and trace metals (Pb²⁺, Cu²⁺) concentrations on the transport of humic-coated kaolinite colloids through a natural quartz sand at pH=4. Adsorbed divalent cations reduce the colloids surface charge and thereby induce aggregation and deposition in porous media. To cite this article: R. Ait Akbour et al., C. R. Geoscience 334 (2002) 981–985.     

Base cation concentrations in forest litter and topsoil have different responses to climate and tree species along elevational gradients

The forest litter is an essential reservoir of nutrients in forests, supplying a large part of absorbable base cations(BC) to topsoil, and facilitating plant growth within litter-soil system. To characterize elevational patterns of base cation concentrations in the forest litter and topsoil, and explore the effects of climate and tree species, we measured microclimate and collected the forest litter and topsoil(0-10 cm) samples across an elevational range of more than 2000 m(1243 ～ 3316 m a.s.l.),and analyzed the concentrations of BC in laboratory. Results showed that: 1) litter Ca concentration displayed a hump-shaped pattern along the elevational gradients, but litter K and Mg showed saddle-shaped patterns. Soil Ca concentration increased with elevation, while soil K and Mg had no significant changes. 2) Ca concentration in the forest litter under aspen(Populus davidiana) was significantly higher than that in all other species, but in topsoil, Ca concentration was higher under coniferous larch and fir(Larix chinensis and Abies fargesii). Litter K and Mg concentrations was higher under coniferous larch and fir, whereas there were nosignificant differences among tree species in the concentrations of K and Mg in topsoil. 3) Climatic factors including mean annual temperature(MAT), growing season precipitation(GSP) and non-growing season precipitation(NGSP) determined BC concentrations in the forest litter and topsoil. Soil C/N and C/P also influenced BC cycling between litter and soil. Observation along elevations within different tree species implies that above-ground tree species can redistribute below-ground cations, and this process is profoundly impacted by climate. Litter and soil Ca, K and Mg with different responses to environmental variables depend on their soluble capacity and mobile ability.     

Controls on surface water chemistry in two lake‐watersheds in the Adirondack region of New York: differences in nitrogen solute sources and sinks

The southwestern Adirondack region of New York receives among the highest rates of atmospheric nitrogen (N) deposition in the USA. Atmospheric N deposition to sensitive ecosystems, like the Adirondacks, may increase the acidification of soils through losses of exchangeable nutrient cations, and the acidification of surface waters associated with enhanced mobility of nitrate (NO₃^?). However, watershed attributes, including surficial terrestrial characteristics, in‐lake processing, and geological settings, have been found to complicate the relationships between atmospheric N deposition and N drainage losses. We studied two lake‐watersheds in the southwestern Adirondacks, Grass Pond and Constable Pond, which are located in close proximity (～26 km) and receive similarly high N deposition, but have contrasting watershed attributes (e.g. wetland area, geological settings). Since the difference in the influence of N deposition was minimal, we were able to examine both within‐ and between‐watershed influences of land cover, the contribution of glacial till groundwater inputs, and in‐lake processes on surface water chemistry with particular emphasis on N solutes and dissolved organic carbon (DOC). Monthly samples at seven inlets and one outlet of each lake were collected from May to October in 1999 and 2000. The concentrations of NO₃^? were high at the Grass Pond inlets, especially at two inlets, and NO₃^? was the major N solute at the Grass Pond inlets. The concentrations of likely weathering products (i.e. dissolved Si, Ca²⁺, Mg²⁺, Na⁺) as well as acid neutralizing capacity and pH values, were also particularly high at those two Grass Pond inlets, suggesting a large contribution of groundwater inputs. Dissolved organic N (DON) was the major N solute at the Constable Pond inlets. The higher concentrations of DON and DOC at the Constable Pond inlets were attributed to a large wetland area in the watershed. The DOC/DON ratios were also higher at the Constable Pond inlets, possibly due to a larger proportion of coniferous forest area. Although DON and DOC were strongly related, the stronger relationship of the proportion of wetland area with DOC suggests that additional factors regulate DON. The aggregated representation of watershed physical features (i.e. elevation, watershed area, mean topographic index, hypsometric‐analysis index) was not clearly related to the lake N and DOC chemistry. Despite distinctive differences in inlet N chemistry, NO₃^? and DON concentrations at the outlets of the two lakes were similar. The lower DOC/DON ratios at the lake outlets and at the inlets having upstream ponds suggest the importance of N processing and organic N sources within the lakes. Although an inverse relationship between NO₃^? and DOC/DON has been suggested to be indicative of a N deposition gradient, the existence of this relationship for sites that receive similar atmospheric N deposition suggest that the relationship between NO₃^? and the DOC/DON ratio is derived from environmental and physical factors. Our results suggest that, despite similar wet N deposition at the two watershed sites, N solutes entering lakes were strongly affected by hydrology associated with groundwater contribution and the presence of wetlands, whereas N solutes leaving lakes were strongly influenced by in‐lake processing. Copyright © 2006 John Wiley & Sons, Ltd.     

Temporal variability of selected dissolved elements in the lower Orinoco River,Venezuela

Monthly analyses of pH, conductance, alkalinity, total suspended solids, dissolved major cations (Na, K, Ca and Mg), and selected dissolved trace elements (Fe, Al, Mn, Cu, Zn and Cr) were conducted on waters of the lower Orinoco River from February 2004 to May 2006. The data show strong seasonal variability. Major cations had maximum concentrations at low water, and were correlated with pH, conductance and alkalinity because of the tributaries coming from the Andean zones, where the weathering of evaporites and carbonate shales controls water chemistry. K concentrations did not show any relation with evaporite weathering, probably because large amounts of K come from the Guayana Shield rivers as a consequence of feldspar weathering. The concentrations of dissolved Fe, Mn and Cu were highest during the high water stage. Concentrations of the elements K, Cr, Zn and Cu are correlated with each other but not with dissolved Fe and Al, which probably are complexed with humic and fulvic substances. Mn concentrations did not show relationships with other variables. Inter‐annual variability of dissolved elements is explained by temporal changes in precipitation. Copyright © 2008 John Wiley & Sons, Ltd.     

Ca-H-Al exchanges and aluminium mobility in two Chinese acidic forest soils: a batch experiment

Exchange reactions between Ca²⁺, H⁺ and Al species and their effects on the aluminium mobility in two Chinese acidic forest soils were studied. The study was based on a batch experiment using extractant solutions with different base cation (calcium) concentrations and pH. The experimental data showed that increased Ca²⁺ concentrations increased the release of soil hydrogen—and aluminium ions, especially from the more acid soil. In agreement with a cation exchange process, the treatment with Ca²⁺ extracts gave significantly decreased soil aluminium saturation (AlS) and increased calcium saturation (CaS) on the ion exchanger. Geochemical calculation using AlCHEMI program showed that activities of Al³⁺ in the extracts were all strongly under-saturated with respect to any gibbsite mineral in the studied pH region (i.e. below 4.1). There were instead apparently two different mechanisms controlling the activities of Al³⁺ in extracts. At pH between about 4.1 and 3.7, the Al³⁺ activity did not change significantly with pH. This is especially the case in the more acid soil. Apparently there are no sizeable pools available to release Al in this pH region. At pH below 3.7 (induced by higher Ca²⁺concentration) the activity of Al³⁺ increased with H⁺ though not in a pattern that complies with a gibbsite solubility control. An increase of base cation deposition would therefore mainly enhance the release of hydrogen ions between pH 4.1 and 3.7 and aluminium ions below pH 3.7 from Chinese mature acidic soils. This will cause an increased acidity of soil water in the short term and a decrease in the soil acidity in the long term. More attention should be paid to this fact in Chinese acid rain studies and control options.     

Chemistry of throughfall,stemfall and litterfall in fertilized and irrigated Pinus radiata

The chemical inputs by rainfall, throughfall and stemflow were studied in a pine plantation located in Pierces Creek Forest, Canberra, Australia. Three treatments were included in the study: a control (C) and two fertilizer treatments. The first fertilizer treatment (F) involved two applications of mixed fertilizers at high rates, the second (IL) involved application of a complete liquid fertilizer with irrigation, so as to remove nutrient and water restrictions to growth. The application rates of nutrients were higher for IL than F. Net inputs of elements in throughfall and stemflow, obtained by subtracting the amounts in the rainfall, were compared for different treatments. For cations (the sum of Ca, Mg, Na and K), the treatment effect on leaching by throughfall and stemflow was IL > F > C; but the F to C differences were greater for throughfall than stemflow. The effects were almost entirely due to increases in concentration, rather than the amount of rainfall becoming throughfall or stemflow. The concentration of nitrogen (as NH₄ or NO₃) in throughfall or stemflow could be lower or higher than in rainfall, indicating net removal or leaching, respectively. Net removal occurred for most rainfall events for the control treatment, for a substantial number of events for treatment F, but for few events for treatment IL. The ammonium ion was preferentially removed from throughfall, and nitrate from stemflow. Transfers of potassium and total nitrogen by litterfall, throughfall and stemflow were also studied. The proportions of potassium and nitrogen being transferred by these processes showed little difference between treatments; the overall values for potassium being 60% by throughfall, 4% by stemflow and 36% by litterfall. In contrast the transfer of nitrogen was dominated by litterfall (81%), with 18% by throughfall and 1% by stemflow. © 1997 John Wiley & Sons, Ltd.     

Analysis of seawater and different highly saline natural waters by capillary zone electrophoresis

Innovative applications of capillary zone electrophoresis (CZE) to the determination of inorganic ions in environmental aquatic samples of high salinity and, particularly, in seawater are reviewed. Emphasis is placed on advanced approaches utilized for securing separation performance from being degraded by the presence of matrix salts and for simultaneous separation of ions different in natural abundance. Also covered are methodologies of present or possible use to evolve the method's practical utility to trace-level ions. Surveyed procedures are tabulated for the purpose of facilitating the method selection or further development. In addition, brief background information on basic methodological principles of CZE in inorganic ion analysis is given for a better orientation of those intending or just beginning to put CZE to work. Finally, possible future research trends and developments of CZE in the area are briefly discussed.     

袁复礼石的矿物学新资料及晶体结构

袁复礼石是一种Ｍｇ、Ｆｅ３＋、Ａｌ３＋和Ｔｉ的硼酸盐新矿物。除了与遂安石、硬石膏和磷灰石共生外，还与硼铝镁石、镁橄榄石和方解石等共生，形成两个矿物共生组合。单矿物化学分析表明，后一组合中的袁复礼石更富铁，特别是Ｆｅ３＋，相对贫镁。袁复礼石的晶体结构分析证明，袁复礼石与硼钛镁石的结构类型一致，阳离子的占位为Ｍ（１）＝Ｍｅ３＋，Ｍ（２）＝Ｍｅ２＋。袁复礼石是Ｍ（１）位置上为Ｆｅ端员组分，Ｍ（２）位置上为Ｍｇ端员组分的新矿物。     

膨润土作为药用赋形剂对Pb~(+2),Cd~(+2),Cr~(+6)离子的吸附研究

本文选用吉林省九台、小梨河、净月产地的膨润土为原料,测试了不同粒级的膨润土对Pb 2、Cd 2、Cr 6离子的吸附时间、吸附温度、吸附量,同时,又在模拟人胃条件下进行了试验,结果证实膨润土可以作为药用赋形剂。