Linear Free Energy Relationships for Metal-Ligand Complexation: Bidentate Binding to Negatively-Charged Oxygen Donor Atoms

Stability constants for metal complexation to bidentate ligands containing negatively-charged oxygen donor atoms can be estimated from the following linear free energy relationship (LFER): log K_ML = χ_OO(α_O log K_HL,1 + α_O log K_HL,2) where K_ML is the metal-ligand stability constant for a 1:1 complex, K_HL,1 and K_HL,2 are the proton-ligand stability constants (the ligand pK_a values), and α_O is the Irving-Rossotti slope. The parameter χ_OO is metal specific and has slightly different values for five and six membered chelate rings. LFERs are presented for 21 different metal ions and are accurate to within approximately 0.30 log units in predictions of log K_ML values. Ligands selected for use in LFER development include dicarboxylic acids, carboxyphenols, and ortho-diphenols. For ortho-hydroxybenzaldehydes, α-hydroxycarboxylic acids, and α-ketocarboxylic acids, a modification of the LFER where log K_HL,2 is set equal to zero is required. The chemical interpretation of χ_OO is that it accounts for the extra stability afforded to metal complexes by the chelate effect. Cu-NOM binding constants calculated from the bidentate LFERs are similar in magnitude to those used in WHAM 6. This LFER can be used to make log K_ML predictions for small organic molecules. Since natural organic matter (NOM) contains many of the same functional groups (i.e. carboxylic acids, phenols, alcohols), the LFER log K_ML predictions shed light on the range of appropriate values for use in modeling metal partitioning in natural systems.     

Towards sustainable groundwater use: setting long-term goals, backcasting, and managing adaptively

The sustainability of crucial earth resources, such as groundwater, is a critical issue. We consider groundwater sustainability a value-driven process of intra- and intergenerational equity that balances the environment, society, and economy. Synthesizing hydrogeological science and current sustainability concepts, we emphasize three sustainability approaches: setting multigenerational sustainability goals, backcasting, and managing adaptively. As most aquifer problems are long-term problems, we propose that multigenerational goals (50 to 100 years) for water quantity and quality that acknowledge the connections between groundwater, surface water, and ecosystems be set for many aquifers. The goals should be set by a watershed- or aquifer-based community in an inclusive and participatory manner. Policies for shorter time horizons should be developed by backcasting, and measures implemented through adaptive management to achieve the long-term goals. Two case histories illustrate the importance and complexity of a multigenerational perspective and adaptive management. These approaches could transform aquifer depletion and contamination to more sustainable groundwater use, providing groundwater for current and future generations while protecting ecological integrity and resilience.     

墨脱公路地质灾害发育分布特征

墨脱县地处喜马拉雅山南麓,南迦巴瓦峰东侧,是目前我国唯一不通公路的县。在墨脱地质灾害调查过程中,笔者通过对波（密）—墨（脱）线;派（区）—墨（脱）线和沿江线的实地考察,结合遥感技术,基本了解了墨脱地区地质灾害的基本类型和发育分布规律,并对地质灾害的成因和影响因素进行了分析。     

Temporal and spatial variations in nutrient stoichiometry and regulation of phytoplankton biomass in Hong Kong waters: influence of the Pearl River outflow and sewage inputs

In 2001, the Hong Kong government implemented the Harbor Area Treatment Scheme (HATS) under which 70% of the sewage that had been formerly discharged into Victoria Harbor is now collected and sent to Stonecutters Island Sewage Works where it receives chemically enhanced primary treatment (CEPT), and is then discharged into waters west of the Harbor. The relocation of the sewage discharge will possibly change the nutrient dynamics and phytoplankton biomass in this area. Therefore, there is a need to examine the factors that regulate phytoplankton growth in Hong Kong waters in order to understand future impacts. Based on a historic nutrient data set (1986-2001), a comparison of ambient nutrient ratios with the Redfield ratio (N:P:Si=16:1:16) showed clear spatial variations in the factors that regulate phytoplankton biomass along a west (estuary) to east (coastal/oceanic) transect through Hong Kong waters. Algal biomass was constrained by a combination of low light conditions, a rapid change in salinity, and strong turbulent mixing in western waters throughout the year. Potential stoichiometric Si limitation (up to 94% of the cases in winter) occurred in Victoria Harbor due to the contribution of sewage effluent with high N and P enrichment all year, except for summer when the frequency of stoichiometric Si limitation (48%) was the same as P, owing to the influence of the high Si in the Pearl River discharge. In the eastern waters, potential N limitation and N and P co-limitation occurred in autumn and winter respectively, because of the dominance of coastal/oceanic water with low nutrients and low N:P ratios. In contrast, potential Si limitation occurred in spring and a switch to potential N, P and Si limitation occurred in eastern waters in summer. In southern waters, there was a shift from P limitation (80%) in summer due to the influence of the N-rich Pearl River discharge, to N limitation (68%) in autumn, and to N and P co-limitation in winter due to the dominance of N-poor oceanic water from the oligotrophic South China Sea. Our results show clear temporal and spatial variations in the nutrient stoichiometry which indicates potential regulation of phytoplankton biomass in HK waters due to the combination of the seasonal exchange of the Pearl River discharge and oceanic water, sewage effluent inputs, and strong hydrodynamic mixing from SW monsoon winds in summer and the NE monsoon winds in winter.     

利用Kaiser效应测试地应力的实验研究

介绍了利用岩石声发射Kaiser效应测试地应力的原理、方法以及测试技术,根据弹性力学理论推导出岩体测点处地应力方程.通过对三个不同里程段的岩样进行六个特殊方向的制取,对岩样进行声发射测试,并由此结果计算出单向正应力值和三个主应力的大小及方向,为工程应用中的具体问题处理提供了参考.     

Multilevel samplers as microcosms to assess microbial response to biostimulation

Passive multilevel samplers (MLS) containing a solid matrix for microbial colonization were used as in situ microcosms in conjunction with a push-pull biostimulation experiment designed to promote biological U(VI) and Tc(VII) reduction. MLS were deployed at 24 elevations in the injection well and two downgradient wells to investigate the spatial variability in microbial community composition and growth prior to and following biostimulation. The microbial community was characterized by real-time quantitative polymerase chain reaction (Q-PCR) quantification of bacteria, NO(3)(-)-reducing bacteria (nirS and nirK), delta-proteobacteria, Geobacter sp., and methanogens (mcrA). Pretest cell densities were low overall but varied substantially with significantly greater bacterial populations detected at circumneutral pH (t-test, alpha= 0.05), suggesting carbon substrate and low pH limitations of microbial activity. Although pretest cell densities were low, denitrifying bacteria were dominant members of the microbial community. Biostimulation with an ethanol-amended ground water resulted in concurrent NO(3)(-) and Tc(VII) reduction, followed by U(VI) reduction. Q-PCR analysis of MLS revealed significant (1 to 2 orders of magnitude, Mann-Whitney U-test, alpha= 0.05) increases in cell densities of bacteria, denitrifiers, delta-proteobacteria, Geobacter sp., and methanogens in response to biostimulation. Traditionally, characterization of sediment samples has been used to investigate the microbial community response to biostimulation; however, collection of sediment samples is expensive and not conducive to deep aquifers or temporal studies. The results presented demonstrate that push-pull tests with passive MLS provide an inexpensive approach to determine the effect of biostimulation on contaminant concentrations, geochemical conditions, and the microbial community composition and function.     

岩石扩容与超声波横波速率

通过超声波对单轴压缩试验中岩石扩容现象的测试,分析了超声横波在不同岩石压缩过程中的传播情况。利用超声横波的特性测出岩石在压缩的不同阶段的微裂纹发展情况和体积变化情况,进一步证明了不同岩石在单轴压缩过程中扩容的时间和程度是有所差异的。     

Eradication success down under: heat treatment of a sunken trawler to kill the invasive seaweed Undaria pinnatifida

Eradication of invasive species is difficult in the marine environment, and there have only been a few successes. We report the successful eradication of the invasive seaweed Undaria pinnatifida from a sunken trawler in the Chatham Islands, New Zealand. New heat-treatment methods were developed as the most cost effective and environmentally acceptable option to kill Undaria. Monitoring of the trawler for three years after it sank found no Undaria after the vessel was treated. Key factors in the success of the eradication programme included: early detection, a rapid response, pre-existing knowledge of Undaria, an adaptive management approach, targeting of multiple life history stages, and the cooperation of the vessel's insurer.     

Seasonal and spatial dynamics of nutrients and phytoplankton biomass in Victoria Harbour and its vicinity before and after sewage abatement

This study investigated the seasonal and spatial dynamics of nutrients and phytoplankton biomass at 12 stations in Hong Kong (HK) waters during a three year period from 2004 to 2006 after upgraded sewage treatment and compared these results to observations before sewage treatment. Pearl River estuary (PRE) discharge significantly increased NO(3) and SiO(4) concentrations, particularly in western and southern waters when rainfall and river discharge was maximal in summer. Continuous year round discharge of sewage effluent resulted in high NH(4) and PO(4) in Victoria Harbour (VH) and its vicinity. In winter, spring and fall, the water column at all stations was moderately mixed by winds and tidal currents, and phytoplankton biomass was relatively low compared to summer. In summer, the mean surface phytoplankton chl biomass was generally > 9 microL(-1) in most areas as a result of thermohaline stratification, and high nutrients, light, and water temperature. In summer, the potential limiting nutrient is PO(4) in the most productive southern waters and it seldom decreased to limiting levels ( approximately 0.1 microM), suggesting that phytoplankton growth may be only episodically limiting. The mean bottom dissolved oxygen (DO) remained > 3.5 mg L(-1) at most stations, indicating that the eutrophication impact in HK waters was not as severe as expected for such a eutrophic area. After the implementation of chemically enhanced primary sewage treatment in 2001, water quality in VH improved as indicated by a significant decrease in NH(4) and PO(4) and an increase in bottom DO. In contrast, there were an increase in chl a and NO(3), and a significant decrease in bottom DO in southern waters in summer, suggesting that hypoxic events are most likely to occur in this region if phytoplankton biomass and oxygen consumption keep increasing and exceed the buffering capacity of HK waters maintained by monsoon winds, tidal mixing and zooplankton grazing. Therefore, future studies on the long-term changes in nutrient loading from PRE and HK sewage discharge will be crucial for developing future strategies of sewage management in HK waters.