芳香型偶氮污染物紫外光谱量子力学指认及不同共轭态偶氮键电子激发研究

偶氮化合物是重要的工业化学品,也是常见的环境污染物,其紫外激发特征及"分子结构-紫外吸收"的构效关系暂未完全明确.本研究借助量子化学计算,通过对波函数与激发态"电子-空穴"的分析,描述偶氮化合物紫外吸收光谱和激发态特征.结果表明:反式偶氮苯实验紫外光谱的第一主要吸收峰应指认为π→π^*跃迁,对应其S₀→S₂激发,电子从最高占据轨道(HOMO)跃迁到最低未占据轨道(LUMO);它的第一激发过程(S₀→S₁)振子强度很小(f=0.031),对光谱贡献可以忽略.反式偶氮苯吸收峰位置与顺式相比普遍红移,表明反式结构中偶氮键通过"桥接效应"形成全局共轭,降低了激发能,对偶氮化合物的紫外吸收产生显著影响;在水溶液中,钠离子对偶氮键的电荷分布存在显著扰动,因此,孤立阴离子模型计算得到的甲基橙光谱与实验存在较大误差."推拉"电子官能团促使甲基橙分子高度极化,与钠离子和水分子作用较强,正确处理偶氮键附近的阳离子扰动是建立预测模型的关键.通过量子化学计算指认偶氮污染物紫外可见吸收光谱能为污染修复、环境工程技术开发、光学材料合成提供理论依据,具有重要意义.     

Evaluating Flow Diversion Impacts to Groundwater‐Dependent Riparian Vegetation with Flow Alteration and Groundwater Model Analysis

An approach for assessing the potential ecologic response of groundwater‐dependent riparian vegetation to flow alteration is developed, focusing on change to groundwater. Groundwater requirements for riparian vegetation are reviewed in conjunction with flow alteration statistics. Where flow alteration coincides with groundwater‐related vegetation sensitivities, scenarios are developed for groundwater simulation. Groundwater depths and recession rates in the riparian zone are simulated for baseline and altered stream hydrographs, with changes to river stage and width represented with a transient, flow‐dependent boundary condition. Potential flow diversion from the Upper Gila River in New Mexico is examined. Statistical flow alteration analysis, applying prospective diversions to a 76‐year record of daily flow, shows that flows in the winter‐spring months and within the high‐pulse to small flood range are subject to greatest potential change. Groundwater simulation scenarios are developed for these flow conditions in representative dry, near‐average, and wet years. Differences in groundwater elevations, generally less than 0.25 m during the flow alteration period, dissipate rapidly following cessation of diversion. Relating groundwater depth, recession rates and range of fluctuations to riparian vegetation needs, we find adverse ecological response is not expected from groundwater impacts for the flow alteration examined.     

Tax evasion and optimal environmental taxes

This paper introduces a new argument to the debate about the role of environmental taxes in modern tax systems. Some environmental taxes, particularly taxes on gasoline or electricity, are more difficult to evade than taxes on labor or income. When the tax base is shifted in a revenue-neutral manner toward these environmental taxes, the result is a net reduction in the amount of tax evasion. Using a carbon tax as a motivating example, the “tax evasion effect” is shown to sharply reduce the welfare cost of controlling emissions. A simple computable general equilibrium model suggests that the impact of considering tax evasion can be large: costs are lowered by 28% in the United States, by 89% in China, and by 97% in India. In countries with high levels of pre-existing tax evasion, a carbon tax will pay for itself through improvements in the efficiency of the tax system.     

Effects of Climate Change,Invasive Species,and Disease on the Distribution of Native European Crayfishes

Climate change will require species to adapt to new conditions or follow preferred climates to higher latitudes or elevations, but many dispersal‐limited freshwater species may be unable to move due to barriers imposed by watershed boundaries. In addition, invasive nonnative species may expand into new regions under future climate conditions and contribute to the decline of native species. We evaluated future distributions for the threatened European crayfish fauna in response to climate change, watershed boundaries, and the spread of invasive crayfishes, which transmit the crayfish plague, a lethal disease for native European crayfishes. We used climate projections from general circulation models and statistical models based on Mahalanobis distance to predict climate‐suitable regions for native and invasive crayfishes in the middle and at the end of the 21st century. We identified these suitable regions as accessible or inaccessible on the basis of major watershed boundaries and present occurrences and evaluated potential future overlap with 3 invasive North American crayfishes. Climate‐suitable areas decreased for native crayfishes by 19% to 72%, and the majority of future suitable areas for most of these species were inaccessible relative to native and current distributions. Overlap with invasive crayfish plague‐transmitting species was predicted to increase. Some native crayfish species (e.g., noble crayfish [Astacus astacus]) had no future refugia that were unsuitable for the modeled nonnative species. Our results emphasize the importance of preventing additional introductions and spread of invasive crayfishes in Europe to minimize interactions between the multiple stressors of climate change and invasive species, while suggesting candidate regions for the debatable management option of assisted colonization. Efectos del Cambio Climático, Especies Invasoras y Enfermedades sobre la Distribución de Cangrejos de Río Europeos Nativos     

Characterizing species co-occurrence patterns of imperfectly detected stream fishes to inform species reintroduction efforts

Species reintroduction efforts can improve the recovery of imperiled species, but successful implementation of this conservation strategy requires a thorough understanding of the abiotic and biotic factors influencing species viability. Species interactions are especially understudied, in particular by omitting the effect of imperfect detection on negative, neutral, or positive associations within a community. Using repeat surveys from 5 southern Ontario, Canada, Great Lakes tributaries, we quantified species co-occurrence patterns with the eastern sand darter (ESD) (Ammocrypta pellucida), listed as federally threatened, and characterized how imperfect detection during sampling can influence inference regarding these relationships. We used a probabilistic framework that included 3 approaches of increasing complexity: probabilistic co-occurrence analysis ignoring imperfect detection; single-species occupancy models with subsequent co-occurrence analysis; and 2-species occupancy models. We then used our occupancy models to predict suitable sites for potential future reintroduction efforts while considering the influence of negative species interactions. Based on the observed data, ESD showed several positive associations with co-occurring species; however, species associations differed when imperfect detection was considered. Specifically, a negative association between ESD and rosyface shiner (Notropis rubellus) was observed only after accounting for imperfect detection in the Grand River. Alternatively, positive associations in the Grand River between ESD and northern hogsucker (Hypentelium nigricans) and silver shiner (Notropis photogenis) were observed regardless of whether imperfect detection was accounted for. Our models predicted several potential reintroduction sites for ESD in formerly occupied watersheds with high levels of certainty. Overall, our results demonstrate the importance of investigating imperfect detection and species co-occurrence when planning reintroduction efforts.     

Preventing behavioural interactions with a male facilitates sex change in female bluebanded gobies, Lythrypnus dalli

Sex change in marine teleost fishes is commonly regulated by social factors. In species that exhibit protogynous sex change, such as the bluebanded goby Lythrypnus dalli, the most dominant female typically initiates sex change when a male is removed from the social group. Females can use visual, chemical or tactile cues to assess the presence or absence of a male. The primary goal of our study was to determine whether the olfactory and visual presence of a male versus its behavioural interactions with females were important for mediating sex change. We exposed females to three different treatments: absence of a male, presence of a male that could physically interact with her and presence of a male behind a barrier that allowed visual and olfactory interactions but prohibited physical interactions. Sex change occurred in the absence of a male but not in the presence of a male that could physically interact with the female. The presence of a male behind the barrier did not prevent sex change but affected the timing of sex change. Season appeared to affect the latency to initiate male typical courtship, with a delay at the end of the reproductive season only when the male was present behind the barrier. We discuss the seasonal results in terms of L. dalli life history and the potential benefits and costs of changing sex late in the season in the presence or absence of aggressive reinforcement by the male. Our results identify direct behavioural interactions as an important proximate mechanism in the social regulation of sex change in L. dalli.     

Streamflow Response to Climate as Influenced by Geology and Elevation1

Mayer, Timothy D. and Seth W. Naman, 2011. Streamflow Response to Climate as Influenced by Geology and Elevation. Journal of the American Water Resources Association (JAWRA) 47(4):724‐738. DOI: 10.1111/j.1752‐1688.2011.00537.x Abstract: This study examines the regional streamflow response in 25 predominately unregulated basins to warmer winter temperatures and snowpack reductions over the last half century in the Klamath Basin of California and Oregon. Geologic controls of streamflow in the region result in two general stream types: surface‐dominated and groundwater‐dominated basins. Surface‐dominated basins were further differentiated into rain basins and snowmelt basins on the basis of elevation and timing of winter runoff. Streamflow characteristics and response to climate vary with stream type, as discussed in the study. Warmer winter temperatures and snowpack reductions have caused significantly earlier runoff peaks in both snowmelt and groundwater basins in the region. In the groundwater basins, the streamflow response to changes in snowpack is smoothed and delayed and the effects are extended longer in the summer. Our results indicate that absolute decreases in July‐September base flows are significantly greater, by an order of magnitude, in groundwater basins compared to surface‐dominated basins. The declines are important because groundwater basins sustain Upper Klamath Lake inflows and mainstem river flows during the typically dry summers of the area. Upper Klamath Lake April‐September net inflows have decreased an estimated 16% or 84 thousand acre‐feet (103.6 Mm³) since 1961, with the summer months showing proportionately more decline. These changes will exacerbate water supply problems for agriculture and natural resources in the region.     

Identifying and Managing Threatened Invertebrates through Assessment of Coextinction Risk

Abstract: Invertebrates with specific host species may have a high probability of extinction when their hosts have a high probability of extinction. Some of these invertebrates are more likely to go extinct than their hosts, and under some circumstances, specific actions to conserve the host may be detrimental to the invertebrate. A critical constraint to identifying such invertebrates is uncertainty about their level of host specificity. We used two host‐breadth models that explicitly incorporated uncertainty in the host specificity of an invertebrate species. We devised a decision protocol to identify actions that may increase the probability of persistence of a given dependent species. The protocol included estimates from the host‐breadth models and decision nodes to identify cothreatened species. We applied the models and protocol to data on 1055 insects (186 species) associated with 2 threatened (as designated by the Australian Government) plant species and 19 plant species that are not threatened to determine whether any insect herbivores have the potential to become extinct if the plant becomes extinct. According to the host‐breadth models, 18 species of insect had high host specificity to the threatened plant species. From these 18 insects, the decision protocol highlighted 6 species that had a high probability of extinction if their hosts were to become extinct (3% of all insects examined). The models and decision protocol have added objectivity and rigor to the process of deciding which dependent invertebrates require conservation action, particularly when dealing with largely unknown and speciose faunas.     

Vocal interactions in common nightingales (<Emphasis Type="Italic">Luscinia megarhynchos</Emphasis>): males take it easy after pairing

Seasonal patterns of bird song have been studied intensively with a focus on individual males. However, little is known about seasonal patterns of singing during vocal interactions between males. Vocal interactions have been shown to be important in sexual selection as males may signal aspects of motivation or quality. Here, we investigated in nightingales (Luscinia megarhynchos) whether a male’s behaviour in vocal interactions at different stages of the breeding season is influenced by its mating status. We examined how males that differ in their subsequent mating success respond to a non-interactive, nocturnal playback presented during the period of mate attraction and subsequently during the egg-laying period. We found that mated males overlapped fewer songs and had a lower song rate during the egg-laying period compared to their responses during the mate-attraction period, whereas unpaired males did not vary in their responses between the two periods. Our results suggest that mating status is a key factor affecting singing behaviour in vocal interactions and that a time-specific singing pattern like song overlapping is used flexibly during vocal interactions. Because song overlapping is thought to be a signal of aggression in male–male vocal interactions, it seems that males vary the level of aggression in vocal interactions according to their mating status and to the stage in the breeding season.