亚洲主要河流的沉积地球化学示踪研究进展

发源于喜马拉雅—青藏高原的亚洲几条大河的河流地球化学研究揭示了高原隆升、流域风化剥蚀、大气CO2消耗和亚洲季风气候变化之间的耦合关系。研究认为南亚主要河流流域的化学风化对全球大气CO2消耗和海洋化学通量变化贡献较大,河流沉积地球化学研究反映的高原阶段性隆升过程、流域剥蚀速率以及亚洲季风演化信息也明显比东亚主要河流的记录清晰;尤其是最近几年运用河流碎屑单矿物化学和年代学方法来示踪流域构造演化、沉积物从源到汇过程以及河流演化历史等,取得了许多重要的研究成果。比较而言,我国的河流在元素地球化学和水化学组成方面虽然开展了大量基础研究工作,但目前急需进一步提炼科学目标,与国际性的研究计划结合,综合多学科的研究力量,在研究思路和关键方法上需要突破和深入,加强研究的广度和深度。长江更可以作为一个突破口和研究平台,来开展深入的沉积地球化学示踪研究。     

Agpaicity revisited: pattern recognition in the chemistry of nepheline syenite rocks

An attempt is made to describe global variations in the geochemistry of major and minor elements within a population of nepheline syenite samples defined by mineralogical criteria.Using correspondence analysis, a new pattern recognition procedure, it is possible to define a few trends of common behaviour which reflect most of the initial dispersion.As Al and Na participate in the scattering along the two main trends, agpaicity is recorded by them. However, the traditional form of the coefficient which measures it is proved to be unsatisfactory as variations of K are not significant.     

Major ion chemistry of groundwater in a river basin: a study from India

Groundwater is the prime source in the area of Varaha River Basin, Andhra Pradesh, India. Groundwater samples collected during pre- and post-monsoon were analyzed for major ion chemistry to understand the operating mechanism of geochemical processes for variation of groundwater quality. Low ionic concentration is observed in the groundwater occurring at topographic-highs and towards the river compared to the rest of the area. This is caused by the influence of recharge water. Geochemistry of groundwater is observed to be mainly controlled by the rock-weathering, mineral dissolution, leaching, ion exchange and evaporation, and is subsequently modified by the anthropogenic and marine activities. Contribution of residual soluble salts below the depth of 5 m from the ground surface is high, while it is low beyond the depth of 5 m. Anthropogenic activities cause an accumulation of excess residual soluble salts in the former depth and the content of this soluble matter is reduced by the clay products beyond the latter depth. Seasonal ionic concentration of groundwater is greatly influenced by the recharge process with reference to topographical features, lithological characteristics and anthropogenic activities. Groundwater quality is classified as mixed and non-carbonate alkali groups due to a combined action of geogenic/anthropogenic and marine sources, respectively. The groundwater quality is above the adequacy level for both drinking and irrigation, and appropriate management measures are recommended for sustainable development.     

天星河、文峰河流域岩溶水化学及影响因素

重庆东北部地区巫溪天星河、文峰河的岩溶流域水化学特征研究结果表明:研究区泉水样品的p H值为6.47~8.28,平均值为7.79;流域河水饱和指数(SIc)的平均值为0.14,表明其变化受到流域碳酸盐岩分布的控制。水化学类型以HCO3-Ca型水为主,Ca2+和HCO-3平均分别占阳、阴离子的75%和82%。通过分析Gibbs图,发现泉水的主要组分属于"岩石风化类型",主要反映了岩石的溶解作用对泉水水化学的影响。流域内部分水样NO-3和SO2-4较高,可能是受工农业生产等人类活动的影响引起,此外硫酸也参与了碳酸盐矿物的溶解。     

芙蓉锡矿田骑田岭花岗岩黑云母矿物化学组成及其对锡成矿的指示意义

芙蓉锡矿田骑田岭复式岩体主要由早阶段角闪石黑云母花岗岩和晚阶段黑云母花岗岩组成.电子探针分析结果表明角闪石黑云母花岗岩中的黑云母属于铁黑云母,黑云母花岗岩中的黑云母属于铁叶云母.相对于黑云母花岗岩,角闪石黑云母花岗岩中黑云母的MgO、TiO2含量偏高,Al2O3含量偏低.矿物化学研究结果显示,角闪石黑云母花岗岩中黑云母的结晶温度、氧逸度(logfO2)分别为680℃～740℃、-16.00～-15.31,黑云母花岗岩中黑云母的结晶温度、氧逸度分别为530℃～650℃、-19.20～-17.50.从角闪石黑云母花岗岩到黑云母花岗岩,岩浆结晶温度和氧逸度逐渐降低.与花岗岩有关的共存流体性质的研究发现,与角闪石黑云母花岗岩共存的热液流体log(fH2O/fHF)fluid,log(fH2O/fHCl)fluid,log(fHF/fHCl)fiuid值分别为4.22～4.39,2.78～3.24,-1.82～-1.73,而与黑云母花岗岩共存的热液流体log(fH2O/fHF)fluid,log(fH2OfHCl)fluid,log(fHF/fHCl)fluid值分别为3.27～3.53,2.85～3.22,-0.75～-0.22,可见与两种岩石类型共存热液流体的性质存在明显差异,且热液中Cl、Sn含量变化与岩浆结晶分异指数呈正相关关系.骑田岭岩体从角闪石黑云母花岗岩到黑云母花岗岩,随着岩浆的演化.岩浆结晶期后分异出的热液流体向富Cl和Sn方向演化.芙蓉锡矿田的成矿流体应主要来源于黑云母花岗岩岩浆结晶期后分异出的岩浆热液.     

Water chemistry and heavy metal distribution in an AMD highly contaminated river

Environmental impacts of acid mine drainage (AMD) from Dexing Copper Mine, the largest open pit copper mine in Asia, on Le An River were well documented 10 years ago. However, ore production of the mine has increased fourfold and the contamination situation of the river now is unknown. Our studies indicated that heavy metal concentrations in riverwaters (dissolved), suspended solids (SS) and sediments all showed highly localized distribution patterns closely associated with two AMD-contaminated tributaries (Dawu River and Ji River) and are significantly different from the previous findings. Compared with the previous reports, most of the sampling sites in Le An River displayed lower contents of sediments of 2005 because several historical upstream and downstream heavy metal sources disappeared or became unimportant. The surprised decrease of copper contents in sediments at the mixing location with Dawu River was mainly due to dilution from the sufficient input of poor copper ore (<0.3%).     

Superplastic flow and changes in crystal chemistry of feldspars

Comparison of observed microstructures and deduced physical parameters of natural deformations with those encountered in superplastic metals permits identification of superplastic behaviour in rocks. From microstructural evidence, superplastic flow of feldspar is inferred to have occurred in the deformation of a granite from Miéville, Aiguilles-Rouges massif, Switzerland. The original igneous orthoclase and oligoclase phenocrysts have both recrystallised to fine-grained albite which has deformed by superplastic flow. This change in crystal chemistry was associated with a large negative change in free energy, enabling recrystallised grains of a very small size to be stable under the prevailing conditions, thereby producing the pre-requisite conditions for superplastic behaviour.     

Influence of ignimbrite on the chemistry of river water in Shirasu plateau,Japan

River, rain and spring water samples from a region covered in “Shirasu” ignimbrite were collected on Kyushu Island, Japan. The analytical results were subjected to multivariate statistical analysis and stoichiometric calculation to understand the geographical distribution of chemical components in water and to extract geochemical underlying factors. The multivariate statistical analysis showed that the river-water chemistry is only slightly influenced by hot springs or polluted waters, but is highly controlled by weathering of ignimbrite. On the basis of the stoichiometric calculation based on water–rock interaction, the water chemistry was successfully estimated by a simple equation:\({\left[ {{\text{Si}}} \right]}{\text{ = 2}}{\left[ {{\text{Na}}^{{\text{ + }}} } \right]}{\text{ + }}{\left[ {{\text{Mg}}^{{{\text{2 + }}}} } \right]}\) in the upstream area, complemented by \({\left[ {{\text{Si}}} \right]}{\text{ = }}{\left[ {{\text{Na}}^{{\text{ + }}} } \right]}{\text{ - 3}}{\left[ {{\text{K}}^{{\text{ + }}} } \right]}{\text{ + }}{\left[ {{\text{Mg}}^{{{\text{2 + }}}} } \right]}{\text{ - 2}}{\left[ {{\text{Ca}}^{{{\text{2 + }}}} } \right]}\) in the downstream area.     

Tracing the sources of nitrate in karstic groundwater in Zunyi,Southwest China: a combined nitrogen isotope and water chemistry approach

Nitrate (NO₃ ⁻) is major pollutant in groundwater worldwide. Karst aquifers are particularly vulnerable to nitrate contamination from anthropogenic sources due to the rapid movement of water in their conduit networks. In this study, the isotopic compositions (δ¹⁵N–NO₃ ⁻, δ¹⁵N–NH₄ ⁺) and chemical compositions(e.g., NO₃ ⁻, NH₄ ⁺, NO₂ ⁻, K⁺) were measured in groundwater in the Zunyi area of Southwest China during summer and winter to identify the primary sources of contamination and characterize the processes affecting nitrate in the groundwater. It was found that nitrate was the dominant species of nitrogen in most of the water samples. In addition, the δ¹⁵N–NO₃ ⁻ values of water samples collected in summer were lower than those collected in winter, suggesting that the groundwater received a significant contribution of NO₃ ⁻ from agricultural fertilizer during the summer. Furthermore, the spatial variation in the concentration of nitrate and the δ¹⁵N–NO₃ ⁻ value indicated that some of the urban groundwater was contaminated with pollution from point sources. In addition, the distribution of δ¹⁵N–NO₃ ⁻ values and the relationship between ions in the groundwater indicated that synthetic and organic fertilizers (cattle manure) were the two primary sources of nitrate in the study area, except in a few cases where the water had been contaminated by urban anthropogenic inputs. Finally, the temporal and spatial variation of the water chemistry and isotopic data indicated that denitrification has no significant effect on the nitrogen isotopic values in Zunyi groundwater.     

The short term climatic sensitivity of carbonate and silicate weathering fluxes: Insight from seasonal variations in river chemistry

Large seasonal variations in the dissolved load of the headwater tributaries of the Marsyandi river (Nepal Himalaya) for major cations and ⁸⁷Sr/⁸⁶Sr ratios are interpreted to result from a greater dissolution of carbonate relative to silicate at high runoff. There is up to a 0.003 decrease in strontium isotope ratios and a factor of 3 reduction in the Si(OH)₄/Ca ratio during the monsoon. These variations, in small rivers sampling uniform lithologies, result from a different response of carbonate and silicate mineral dissolution to climatic forcing. Similar trends are observed in compiled literature data, from both Indian and Nepalese Himalayan rivers. Carbonate weathering is more sensitive to monsoonal runoff because of its faster dissolution kinetics. Silicate weathering increases relative to carbonate during the dry season, and may be more predominant in groundwater with longer water-rock interaction times. Despite this kinetic effect, silicate weathering fluxes are dominated by the monsoon flux, when between 50% and 70% of total annual silicate weathering flux occurs.     

河西内陆河流域冰川融水近期变化

基于第一次中国冰川编目数据库,以国家气象台站的月降水与月气温资料为驱动数据,利用度日模型重建了河西内陆河流域各水系1961～2006年冰川物质平衡和融水径流序列,并与短期观测资料的对比验证表明,模型具有较高的可信度.河西内陆河流域1961～2006年平均冰川物质平衡为-49.5 mm/a,从东段石羊河流域到西段疏勒河、...     

Controls on water chemistry of the Pilcomayo river (Bolivia,South-America)

In order to reveal the intra-annual variability of the major ion composition of the Pilcomayo river, a dryland river, and its relationship to discharge, water samples were taken at regular time intervals from May 1998 until February 1999 at the town of Villa Montes (Bolivia). Water chemistry of the Pilcomayo river was highly variable during the year and strongly influenced by differences in discharge between the wet and the dry season. Halite dissolution appeared to play an important role and both Cl and Na concentrations became very high (±10 mmol L⁻¹) during the dry season. Pyrite weathering and dissolution of gypsum, dolomite and calcite determined Ca, Mg, CO₃ and SO₄ chemistry. At the onset of the rainy season `rinse out' effects occurred, resulting in marked concentration peaks especially for the least soluble ions. Possible effects on biota, such as consequences for trace metal toxicity, are discussed briefly.     

Solution of rare earth elements in silicate solid phases; henry's law revisited in light of defect chemistry

It is shown that experimentally observed departures from Henry's law at high dilution conditions for rare earth elements (REE) in garnet, clinopyroxene and plagioclase can be referred to stabilization in the lattice point defects. The solution process involves negative interaction parameters (?500/?3,000 cal for garnet). On the basis of the experimental data, the activity coefficients of the trace REE can be approximated by a model based on trace cation/cationic vacancy binary solid solution, taking into account association phenomena between them as well.     

Hydrologic controls on water chemistry and mercury biotransformation in a closed river system: The Carson River,Nevada

The Carson River flows in a closed basin system and the total flow of the river water decreases downstream due to both evaporation and consumptive uses. This river system is fed primarily by snow pack in the Sierra Nevada during the winter, which flows down gradient following melting in spring and summer. Water loss through evaporation in the Carson River results in a downstream buildup of conservative elements such as Cl⁻ and certain oxyanion forming elements including Se, Mo and W, which are known to interfere with the transformation of Hg within the S cycle. In addition to these naturally occurring hydrologic processes and the resulting affects on water chemistry, the Carson River Basin has been historically impacted by Au and Ag mining that used Hg amalgamation techniques. Contamination of Hg in the Carson River system is now well documented and published Hg concentrations in different environmental compartments are extremely high. In this study, hydrologically driven changes in water chemistry of the river system and the resulting effects on Hg cycling were examined. Results show that periods of low water flow correspond to high water pH (up to 8.3), relatively high concentrations of oxyanion forming elements (e.g., As, Se, Mo and W), and low Hg methylation potential in sediment. In contrast, periods of high flow bring about dilution, which results in lower pH (∼7), lower concentrations of oxyanion forming elements, but higher Hg methylation potential. Overall, changes in flow regimes likely affect rates of methyl-Hg (MeHg) production through a combination of factors such as high pH, which favors MeHg demethylation, and the occurrence of relatively high concentrations of Group VI oxyanions that could interfere with microbial SO₄ reduction and MeHg production.     

Innovative monitoring tools for the complex spatial dynamics of river chemistry: case study for the Alpine region

Chemical reactions in aqueous geochemical systems are driven by nonequilibrium conditions, and their dynamics can be deduced through the distributional analysis (identification of probability laws) of complex compositional indices. In this perspective, compositional data analysis offers the possibility to investigate the behavior of the composition as a whole instead of isolated chemical species, with the awareness that multispecies systems are characterized by the simultaneous interactions among all their parts. We addressed this problem using D???1 isometric log-ratio coordinates describing the D compositional dataset of the river chemistry of the Alpine region (D number of variables), thus working in the \({{\mathbb{R}}^{D - 1}}\) statistical sample space. The D???1 coordinates were chosen using the decreasing variance criterion so that each one could provide information about different space–time properties for the investigated geochemical system. Coordinates dominated by heterogeneity appear to be able to capture regime shifts only on a long-time period and monitor processes on a very wide scale. On the other hand, coordinates characterized by lower variability present multimodality, thus capturing the presence of alternative states in the analyzed spatial domain also for the current time. Further developments are needed to determine the ranges of conditions for which variability and other statistics can be useful indicators of regime shifts on different time–space scales in geochemical systems.     

A comment on ‘Agpaicity revisited: pattern recognition in the chemistry of nepheline syenite rocks’ by Dagbert et al.

The conclusions of Dagbertet al. (1975) on agpaicity are based on chemical and mineralogical data which may be characteristic of peralkalinity but not necessarily of agpaicity. Lack of significant variations in K in correspondence analysis can be explained on petrogenetic grounds and do not imply insignificance in agpaitic processes. The agpaitic coefficient merely indicates peralkalinity.     

Quantifying changes in groundwater level and chemistry in Shahrood,northeastern Iran

Temporal changes in the quantity and chemical status of groundwater resources must be accurately quantified to aid sustainable management of aquifers. Monitoring data show that the groundwater level in Shahrood alluvial aquifer, northeastern Iran, continuously declined from 1993 to 2009, falling 11.4 m in 16 years. This constitutes a loss of 216 million m³ from the aquifer’s stored groundwater reserve. Overexploitation and reduction in rainfall intensified the declining trend. In contrast, the reduced abstraction rate, the result of reduced borehole productivity (related to the reduction in saturated-zone thickness over time), slowed down the declining trend. Groundwater salinity varied substantially showing a minor rising trend. For the same 16-year period, increases were recorded in the order of 24% for electrical conductivity, 12.4% for major ions, and 9.9% for pH. This research shows that the groundwater-level declining trend was not interrupted by fluctuation in rainfall and it does not necessarily lead to water-quality deterioration. Water-level drop is greater near the aquifer’s recharging boundary, while greater rates of salinity rise occur around the end of groundwater flow lines. Also, fresher groundwater experiences a greater rate of salinity increase. These findings are of significance for predicting the groundwater level and salinity of exhausted aquifers.     

城市重污染河道环境因子对底质氮释放影响

以苏州市古城区劣Ⅴ类水体为研究对象,利用模拟试验方法,研究和探讨了水体环境条件(DO、Eh、pH值、温度)变化和疏浚深度对河道底泥氮释放的影响.底泥供试样中NH₄+-N与NO₃--N含量一般为0.277 g/kg与0.0012g/kg,上覆水体NH₄+-N与NO₃--N含量一般为6.743 mg/L与1.500 mg/L.试验结果表明:厌氧环境(DO<0.5 mg/L)、强还原环境(Eh<-108 mV)、酸性环境(pH<6.0)及温度升高均有利于底泥中NH₄+-N的释放,NO₃--N的迁移转化规律则相反;供试样控制疏浚深度5 cm、10 cm、15 cm、20 cm,当疏浚深度15 cm时,泥-水界面向上覆水体中扩散的氮通量最小;疏浚深度、DO和Eh对底泥NH₄+-N释放程度的影响大于pH和温度,通过曝气等方式保持水体中适当的溶解氧或使底泥保持较强的氧化电位环境可以有效抑制底泥中NH₄+-N的释放.     

广州流溪河河水主要化学组成时空分布特征及控制因素

本次研究报道了位于广州市典型热带-亚热带河流流溪河上游、中游和下游3个站点(东星、乌石和江高)河水的主要化学成分在近1年的持续变化时间序列。结果显示,3个站点河水的阳离子均主要来自硅酸盐的化学风化输出,但贡献率略有差异,其中在上游的东星站贡献率最大,下游的江高站次之,中游的乌石站相对较少。相较之下,阴离子的来源更为多样,其中F-主要来自于岩石风化, Cl^-、SO₄^2-和NO₃^-更多地受到海洋源降雨或咸潮作用的影响。流域内主要化学风化反应以钾长石、钠长石和钙长石的溶解为主。从上游到下游, Si/TZ+*比值和Si/(Na^*+K)比值逐渐降低,说明上游硅酸盐岩风化较下游更为强烈。从上游到下游,随工农业生产活动的增加,人类活动对河流水化学组成的贡献逐渐增大,岩石风化输出的相对贡献逐渐减小。     

Paricutin revisited: A review of man's attempts to adapt to ecological changes resulting from volcanic catastrophe

During nine years of activity, the Paricutin volcano devastated forest and crop lands. Lava flow and ashfall forced thousands of Itzicuaro Valley inhabitants to migrate. To restore an ecologically valuable landscape, four zones representing the effects of volcanism on vegetation are recognized. Land use data on each of these zones were mapped and tabulated from pre-eruption photos. The success or failure of individual species is correlated to ash depth, site characteristics, and other factors. Post-eruption crop cultivation is dependent upon (1) removal of ash mantle, or (2) enrichment of infertile ash. The Upper Itzicuaro Valley is not yet recovered from the Paricutin eruption.