水合铝离子单体和二聚体的DFT研究

用DFT方法在B3LYP/6-31G·水平下,对水合铝离子的单体和二聚体形态进行计算.在单体[Al(H2O)6]3 ,[Al(OH)(H2O)5]2 ,[Al(OH)2(H2O)4] 和二聚体[Al2(OH)2(H2O)8]4 ,[Al2(OH)3(H2O)7]3 ,[Al2(OH)4(H2O)6]2 ,[Al2(OH)5(H2O)5] 及其异构体中, Al和羟基O之间的键长明显小于Al和H2O中O之间的键长.将H2O代以羟基后,六配位的Al-O八面体骨架发生了较大的畸变.在[Al2(OH)4(H2O)6]2 形态的不同几何异构体中,当2个羟基相互邻近时稳定性较低.羟铝比(OH/Al)增大将有更多的电子流向Al(Ⅲ),同时,单体和二聚体中H2O的氢原子所带正电荷均有所减小.二聚体的羟桥氢原子所带正电荷随OH/Al比的增大而减小.各形态的键强度呈现:Al-O(H2O)＜Al-O(OH)-Al＜Al-O(OH),即Al-Ow＜Al-Ob-h＜Al-Oh.对单体形态,随OH/Al比增大, Al-Ow和Al-Oh键强度均逐渐减小.二聚体形态OH/Al比增大, Al-Ow键强度减小,但Al-Ob-h键强度基本不变, Al-Oh则呈不规则变化.无论是单体还是二聚体,OH/Al比较大形态的HOMO能级与OH/Al比较小形态的LUMO能级相近或前者稍高,前者很容易向后者提供电子.聚合过程主要是在不同形态组分之间进行.     

水中稀释对聚合氯化铝形态分布的影响

本文用~(27)Al NMR、超离心沉降平衡及计时比色分析等方法,研究了水中稀释对水处理混凝剂聚合氯化铝(PAC)中铝的形态分布的影响。结果表明,若PAC的羟铝比(r)≤2.0时,水中稀释(Al_T<0.5 mol/l)会导致PAC羟铝聚合大分子(聚合度>13)的分解,产生聚合度较小的组分;羟铝比越小,这种倾向越大。PAC与硫酸铝在使用中的一个区别是,前者在水中分解,形态“由大到小”,后者在水中聚合,形态“由小到大”。     

聚硅氯化铝(PASC)的形态分布及转化规律Ⅱ.27Al-NMR法研究PASC溶液中铝的形态分布

采用27Al-NMR法比较研究了PASC与PAC中铝的形态分布.实验结果表明,在PASC中,由于聚硅酸与铝水解聚合产物间的相互作用,使得铝的水解聚合形态分布及转化情况发生了变化.在相同B值条件下,PASC中Al单和Al13的含量低于 PAC中相应Al单和Al13的含量,而PASC中Al其它的含量却大于PAC中Al其它的含量,其差值随着碱化度(B)和Al/Si摩尔比的减小而增大.共聚法制备的PASC(共 )与复合法制备的PASC(复)相比较,PASC(复)具有较高的Al单和Al13含量,较低的A l其它含量.这说明制备工艺对PASC中铝的形态分布具有一定的影响.     

土壤环境中具有Keggin结构的Al13草酸盐胶体合成及其表征

采用XRD,FTIR和MAS27 Al NMR方法表征从Al13溶液中合成的草酸盐胶体.结果表明:胶体具有明显的XRD衍射峰,有别于常见的Al系及其草酸盐沉淀;位于810cm-1处络合物中Al-O伸缩振动证明胶体是由Al13和草酸根直接络合形成;红外光谱中位于725cm-1处的(Al-O)Td键和固体核磁共振波谱中位于约61ppm处的Al(O)4特征峰共同证明胶体具有特殊的Keggin结构,高pH(=7.8)环境下Al13草酸盐胶体仍能保持Keggin结构;经过化学分析,该草酸盐胶体化学式为AlO4Al12(OH)24(H2O)12(C2O4)7/2.     

聚硅氯化铝(PASC)的形态分布及转化规律Ⅲ.Al-Ferron逐时络合比色法与27Al-NMR法的比较

本文对Al-Ferron逐时络合比色法和27Al-NMR法对PASC和PAC 中铝的形态分布的测定结果进行了对比分析和讨论.结果表明,在PAC中,Al13和Al b之间具有良好的对应关系,Al13/Alb比值为1.0左右.但对PASC而言,情况有所不同,在低碱化度(B)和低Al/Si摩尔比情况下,Al13和Alb之间不存在对应关系,Al13和Alb比值远远小于1.0,随着B值和Al/Si摩尔比的升高,Al13 /Alb比值逐渐趋近于1.0.这意味着在低B值和低Al/Si摩尔比情况下,由于聚硅酸与铝水解聚合产物间的相互作用,形成了铝硅复合新产物,该新产物对PASC中铝的形态分布产生了影响.     

聚硅氯化铝(PASC)的形态分布及转化规律——Ⅲ.Al-Ferron逐时络合比色法与(27)~AI-NMR法的比较

本文对Al-Ferron逐时络合比色法和~(27)AI-NMR法对PASC和PAC中铝的形态分布的测定结果进行了对比分析和讨论.结果表明,在PAC中,Al_(13)和AI_b之间具有良好的对应关系,Al_(13)/Al_b比值为1.0左右 但对PASC而言,情况有所不同,在低碱化度(B)和低Al/Si摩尔比情况下,Al_(13)和Al_b之间不存在对应关系,Al_(13)和Al_b比值远远小于1.0,随着B值和Al/Si摩尔比的升高,Al_(13)/Al_b比值逐渐趋近于1.0.这意味着在低B值和低Al/Si摩尔比情况下,由于聚硅酸与铝水解聚合产物间的相互作用,形成了铝硅复合新产物,该新产物对PASC中铝的形态分布产生了影响.     

聚硅氯化铝(PASC)的形态分布及转化规律Ⅰ.Al-Ferron逐时络合比色法研究PASC溶液中铝的形态分布及转化规律

采用Al-Ferron逐时络合比色法比较研究了PASC与PAC中铝的形态分布及转化规律.实际结果表明,在PASC中,由于聚硅酸与铝水解聚合产物间的相互作用,使得铝的水解聚合形态分布及转化情况发生了变化.在相同B值条件下,PASC中Ala和Al b的含量低于PAC中相应Als和Alb的含量,而PASC中Alc的含量却大于PAC中Alc的含量.共聚法制备的PASC(共)与复合法制备的PASC(复)相比较,PASC(复)具有较高的Ala和 Alb含量,较低的Alc含量.这说明制备工艺对PASC中铝的形态分布具有一定的影响.     

Al(Ⅲ)与Fe(Ⅲ)溶液共聚合研究

以AlCl_3·6H_2O和FeCl_3·6H_2O混合溶液通过滴加NaOH溶液的方法制备了不同Al/Fe(摩尔比,下同)和不同[OH]_b/[Al+Fe]值的共聚物.测定了聚合过程和熟化过程中的pH值变化,并对不同碱化度和熟化时间下的聚合物进行了混凝效能实验.结果表明,在共聚过程中,Fe(Ⅲ)与 OH~-的络合速度比Ai(Ⅲ)快,即 Fe(Ⅲ)具有较强的共聚合活性.Al/Fe,[OH」_b/[Al+Fe]值对铝铁共聚物形态分布有明显影响.不同条件下共聚物混凝对比实验表明,在Al/Fe为5:5,[OH]_b/[Al+Fe]为 1.6,熟化时间为24h时,显示出了较优异的混凝效能.     

聚合铁的红外光谱和电导特征

Fe(Ⅲ)在加碱中和时生成红色凝胶,凝朕经干燥制成固体样品.本文用IR光谱鉴定其结构,证实为羟桥连接的铁聚合物.其IR光谱图不同于类似化学组成的α-Fe_2O_3,α-FeOOH和Fe(OH)_3(am)等.880cm~(-1)的Fe-OH-Fe弯曲振动证实有聚合态存在,1000cm~(-1),670cm~(-1)和420cm~(-1)的Fe-O-H弯曲振动初步归属为铁与羟基结构的特征吸收峰. 0.01mol/L Fe(Ⅲ)水解溶液的电导随OH/Fe及熟化时间的变化,揭示了胶体颗粒的尺度及所带电荷等固有性质的改变,变化规律与可见光谱、pH驰豫等一致.     

聚合氯化铝中纳米Al13的层析法分离及其水解过程研究

采用聚丙烯酰胺凝胶层析法分离纯化聚合氯化铝(PAC)中的Al13形态,并采用Al-Ferron逐时络合比色法和27Al-NMR对Al13形态进行分析和表征;结果表明,在层析法分离中,随着洗脱时间的延长各种铝形态按分子的大小依次被洗脱下来,因此,截取中间组分即可得到最高含量为99%以上的纳米Al13形态;通过对水解过程的研究可以推断,各种铝形态最终水解产物的粒径多集中在20μm和100μm附近,不同的铝形态到达最终水解产物的速度各不相同,具有最高Alb含量的纳米Al13形态具有较高的水解稳定性.     

Importance of greater interdisciplinarity and geographic scope when tackling the driving forces behind biological invasions

Invasive non-native species are important drivers of ecosystem change, yet the driving forces of biological invasions themselves are poorly understood. Such information is essential to ensure policies focus on the most relevant drivers, and that future scenarios capture the full range of potential outcomes for invasive non-native species. I carried out a bibliometric analysis of articles published from 2000 to 2020 that address either invasive non-native species or biodiversity and ecosystem services and that also mention 1 or more drivers of ecosystem change. I examined 5 indirect drivers (demographic, economic, governance, sociocultural, and technological) and 6 direct drivers (climate change, invasive non-native species, land-use or sea-use change, natural hazards, pollution, and resource extraction). Using the Web of Science core collection of citation indexes, I undertook searches of article titles and keywords and retrieved 27,462 articles addressing invasive non-native species and 110,087 articles dealing with biodiversity or ecosystem services. Most research to date on biological invasions as well as on biodiversity and ecosystem services has focused on anthropogenic direct drivers of ecosystem change rather than indirect drivers. Yet currently, less than 18% of articles addressing biological invasions examined drivers of ecosystem change, a similar level to that found over 20 years ago for biodiversity or ecosystem services. Knowledge of the drivers of biological invasions is limited, emphasizes tractable drivers over those that require an interdisciplinary approach, and is biased toward developed economies. Drivers generally deemed important for biological invasions, such as governance and resource extraction, accounted for less than 2% of research effort. The absence of a systematic understanding of the forces that drive invasive non-native species and how they interact means that attempts to mitigate or forecast biological invasions are likely to fail. To address biological invasions requires a much better orientation of national and international research on drivers in relation to both their actual importance as well as their policy relevance.     

Mitigating the effects of climate change on the nests of sea turtles with artificial irrigation

For sea turtles, like many oviparous species, increasing temperatures during development threaten to increase embryonic mortality, alter offspring quality, and potentially create suboptimal primary sex ratios. Various methods are being implemented to mitigate the effects of climate change on reproductive success, but these methods, such as breeding programs, translocations, and shading, are often invasive and expensive. Irrigation is an alternative strategy for cooling nests that, depending on location, can be implemented relatively quickly and cheaply. However, multiple factors, including ambient conditions, nest substrate, and species characteristics, can influence irrigation success. Additionally, irrigation can vary in duration, frequency, and the volume of water applied to nests, which influences the cooling achieved and embryonic survival. Thus, it is critical to understand how to maximize cooling and manage risks before implementing irrigation as a nest-cooling strategy. We reviewed the literature on nest irrigation to examine whether artificial irrigation is feasible as a population management tool. Key factors that affected cooling were the volume of water applied and the frequency of applications. Embryonic responses varied with species, ambient conditions, and the timing of irrigation during development. Nest inundation was the key risk to a successful irrigation regime. Future irrigation regimes must identify clear targets, either primary or adult sex ratios, that maximize population viability. Monitoring population responses and adjusting the irrigation regime in response to population characteristics will be critical. Most studies reported on the manipulation of only one or two variables, further research is required to understand how altering multiple factors in an irrigation regime influences the cooling achieved and embryonic responses.     

Positive and Negative Effects of a Threatened Parrotfish on Reef Ecosystems

Species that are strong interactors play disproportionately important roles in the dynamics of natural ecosystems. It has been proposed that their presence is necessary for positively shaping the structure and functioning of ecosystems. We evaluated this hypothesis using the case of the world's largest parrotfish (Bolbometopon muricatum), a globally imperiled species. We used direct observation, animal tracking, and computer simulations to examine the diverse routes through which B. muricatum affects the diversity, dispersal, relative abundance, and survival of the corals that comprise the foundation of reef ecosystems. Our results suggest that this species can influence reef building corals in both positive and negative ways. Field observation and simulation outputs indicated that B. muricatum reduced the abundance of macroalgae that can outcompete corals, but they also feed directly on corals, decreasing coral abundance, diversity, and colony size. B. muricatum appeared to facilitate coral advancement by mechanically dispersing coral fragments and opening up bare space for coral settlement, but they also damaged adult corals and remobilized a large volume of potentially stressful carbonate sediment. The impacts this species has on reefs appears to be regulated in part by its abundance—the effects of B. muricatum were more intense in simulation scenarios populated with high densities of these fish. Observations conducted in regions with high and low predator (e.g., sharks) abundance generated results that are consistent with the hypothesis that these predators of B. muricatum may play a role in governing their abundance; thus, predation may modulate the intensity of the effects they have on reef dynamics. Overall our results illustrate that functionally unique and threatened species may not have universally positive impacts on ecosystems and that it may be necessary for environmental managers to consider the diverse effects of such species and the forces that mediate the strength of their influence. Efectos Positivos y Negativos de un Pez Loro Amenazado Sobre Ecosistemas Arrecifales     

Form-specific fragances fromOphrys insectifera L. (Orchidaceae) attract species of different pollinator genera. Evidence of sympatric speciation?

Two closely related forms ofOphrys insectifera were observed in the field to attract different pollinator species selectively.O. i. ssp.insectifera attracted males of two species ofArgogorytes (Sphecidae, Hymenoptera Aculeata) andO. i. ssp.aymoninii attractedAndrena combinata males (Andrenidae, Apoidea, Hymenoptera Aculeata). A third form,O. aff.i. ssp.insectifera, attracted none of these three species. Volatile compounds from flowers and inflorescences of the three forms (originating from Öland, Sweden, and Aveyron, France) were collected, using entrainment, enfleurage, and solvent extraction techniques, and identified by gas chromatography — mass spectrometry. Scent differences between the three forms were confirmed in the amounts of aliphatic hydrocarbons (C₁₁–C₁₉), methyl esters (C₁₄–C₁₈), short chain aliphatic 1-alcohols (C₆–C₁₂), and monoterpene alcohols (C₁₀).     

Estimation of the surface stress from the streamwise pressure gradient: The Kármán Integral Momentum Equation revisited

A method is developed to estimate the stress at the surface in a portable wind tunnel for wind erosion studies. The boundary layer height and the pressure gradient are used in a simple expression from the Kármán Integral Momentum Equation. Values of friction velocity u _* are within 10% of experimental values obtained through correlation techniques, including measurements of differential pressures with the Murdoch Turbulence Probe MTP and the X-wire, hot-wire anemometer XWA. Wind velocity and stress profiles reveal logarithmic trends and a constant stress layer near the surface in the DAWA portable wind tunnel. Realignment of the statistics with the mean wind is essential.     

Using decision science to evaluate global biodiversity indices

Global biodiversity indices are used to measure environmental change and progress toward conservation goals, yet few indices have been evaluated comprehensively for their capacity to detect trends of interest, such as declines in threatened species or ecosystem function. Using a structured approach based on decision science, we qualitatively evaluated 9 indices commonly used to track biodiversity at global and regional scales against 5 criteria relating to objectives, design, behavior, incorporation of uncertainty, and constraints (e.g., costs and data availability). Evaluation was based on reference literature for indices available at the time of assessment. We identified 4 key gaps in indices assessed: pathways to achieving goals (means objectives) were not always clear or relevant to desired outcomes (fundamental objectives); index testing and understanding of expected behavior was often lacking; uncertainty was seldom acknowledged or accounted for; and costs of implementation were seldom considered. These gaps may render indices inadequate in certain decision-making contexts and are problematic for indices linked with biodiversity targets and sustainability goals. Ensuring that index objectives are clear and their design is underpinned by a model of relevant processes are crucial in addressing the gaps identified by our assessment. Uptake and productive use of indices will be improved if index performance is tested rigorously and assumptions and uncertainties are clearly communicated to end users. This will increase index accuracy and value in tracking biodiversity change and supporting national and global policy decisions, such as the post-2020 global biodiversity framework of the Convention on Biological Diversity.     

Assessing the extent and nature of wildlife trade on the dark web

Use of the internet as a trade platform has resulted in a shift in the illegal wildlife trade. Increased scrutiny of illegal wildlife trade has led to concerns that online trade of wildlife will move onto the dark web. To provide a baseline of illegal wildlife trade on the dark web, we downloaded and archived 9852 items (individual posts) from the dark web, then searched these based on a list of 121 keywords associated with illegal online wildlife trade, including 30 keywords associated with illegally traded elephant ivory on the surface web. Results were compared with items known to be illegally traded on the dark web, specifically cannabis, cocaine, and heroin, to compare the extent of the trade. Of these 121 keywords, 4 resulted in hits, of which only one was potentially linked to illegal wildlife trade. This sole case was the sale and discussion of Echinopsis pachanoi (San Pedro cactus), which has hallucinogenic properties. This negligible level of activity related to the illegal trade of wildlife on the dark web relative to the open and increasing trade on the surface web may indicate a lack of successful enforcement against illegal wildlife trade on the surface web.     

Estimating freshwater turtle mortality rates and population declines following hook ingestion

Freshwater turtle populations are susceptible to declines following small increases in the mortality of adults, making it essential to identify and understand potential threats. Freshwater turtles ingest fish hooks associated with recreational angling, and this is likely a problem because hook ingestion is a source of additive mortality for sea turtles. We used a Bayesian‐modeling framework, observed rates of hook ingestion by freshwater turtles, and mortality of sea turtles from hook ingestion to examine the probability that a freshwater turtle in a given population ingests a hook and subsequently dies from it. We used the results of these analyses and previously published life‐history data to simulate the effects of hook ingestion on population growth for 3 species of freshwater turtle. In our simulation, the probability that an individual turtle ingests a hook and dies as a result was 1.2–11%. Our simulation results suggest that this rate of mortality from hook ingestion is sufficient to cause population declines. We believe we have identified fish‐hook ingestion as a serious yet generally overlooked threat to the viability of freshwater turtle populations.     

Content analysis of newspaper coverage of the Florida panther

Populations of large carnivores are declining globally, and analysis of public discourse about carnivores is useful for understanding public opinion and influences on management and policy. Portrayal of carnivores in the media affects public perceptions and support for their conservation. We conducted a content analysis of 513 articles about Florida panthers (Puma concolor coryi) published from 2003 to 2006 in newspapers with local circulation in core panther habitat in southwest Florida and papers with statewide circulation to compare the differences in the amount of coverage and portrayals of panther risks to people and property on the basis of proximity of human communities to panthers. Local papers published significantly more news articles and significantly longer news articles primarily about panthers. Articles in local and statewide papers used both episodic frames, which focus on specific occurrences (e.g., a panther sighting or predation) and thematic frames, which focus on general trends (e.g., abundance of panthers over time). Local articles more often emphasized risks that panthers might harm people, pets, or livestock than statewide papers. Our results are consistent with theory that proximity to human-carnivore conflict influences perceptions and salience of risks posed by large carnivores. Most articles mentioned panthers as a secondary topic, which we believe was a result of the relevance an endangered carnivore has in discussions of public land management, development, and regulations in Florida. Claims made by sources quoted in each article had a neutral to positive depiction of panthers, and most quotations were from federal and state agency scientists. We suggest continued use by the media of agency sources provides the opportunity for clear, concordant messages about panther management. Content analysis provides a way to monitor media portrayal of carnivores for consistency with agency outreach goals.