开发研制预防污染的绿色化学产品

文章叙述绿色化学在环境保护中的应用,绿色化学是一门从源头上彻底阻止污染的化学,简介了几种开发研制的对人类健康和环境安全的绿色化学产品及研究开发进展。     

Metals in biomass

Background, Aim and Scope

Metal ions generally share the ability/tendency of interacting with biological material by forming complexes, except possibly for the heavy alkali metals K, Rb and Cs. This is unrelated to the metals being either essential for sustaining life and its reproduction, apparently insignificant for biology, although perhaps undergoing bioconcentration or even being outright toxic, even at low admission levels. Yet, those different kinds of metal-biomass interactions should in some way depend on properties describing coordination chemistries of these very metals. Nevertheless, both ubiquitously essential metals and others sometimes used in biology should share these properties in numeric terms, since it can be anticipated that they will be distinguished from nonessential and/or toxic ones. These features noted above include bioconcentration, the involvement of metal ions such as Zn, Mg, Cu, Fe, etc. in biocatalysis as crucial components of metalloenzymes and the introduction of a certain set of essential metals common to (almost) all living beings (K, Mg, Mo, Mn, Fe, Cu and Zn), which occurred probably very early in biological evolution by ‘natural selection of the chemical elements’ (more exactly speaking, of the metallomes).

Materials and Methods

The approach is semiempirical and consists of three consecutive steps: 1) derivation of a regression equation which links complex stability data of different complexes containing the same metal ion to electrochemical data pertinent to the (replaced) ligands, thus describing properties of metal ions in complexes, 2) a graphical representation of the properties-two typical numbers c and x for each metal ion-in some map across the c/x-space, which additionally contains information about biological functions of these metal ions, i.e. whether they are essential in general (e.g. Mg, Mn, Zn) or, for a few organisms of various kinds (e.g. Cd, V), not essential (e.g. rare earth element ions) or even generally highly toxic (Hg, U). It is hypothesized that, if coordination properties of metals control their biological ‘feasibility’ in some way, this should show up in the mappings (one each for mono and bidentate-bonding ligands). 3) eventually, the regression equation produced in step 1) is inverted to calculate complex stabilities pertinent to biological systems: 3a) complex stabilities are mapped for ligands delivered to soil (-water) by green plants (e.g. citrate, malate) and fungi and, compared to their unlike selectivities and demands of metal use (photosynthesis taking place or not), 3b) the evolution of the metallome during late chemical evolution is reconstructed.

Results

These maps show some ‘window of essentiality’, a small, contrived range/area of c and x parameters in which essential metal ions gather almost exclusively. c and x thus control the possibility of a metal ion becoming essential by their influencing details of metal-substrate or (in cases of catalytic activities) metal-product interactions. Exceptions are not known to be involved in biocatalysis anyhow.

Discussion

Effects of ligands secreted, e.g. from tree roots or agaric mycelia to the soil on the respective modes (selectivities) of metal bioconcentration can be calculated by the equation giving complex stability constants, with obvious ramifications for a thorough, systematic interpretation of biomonitoring data. Eventually, alterations of C, N and P-compounds during chemical evolution are investigated — which converted CH₄ or CO₂, N₂ and other non-ligands to amino acids, etc., for example, with the latter behaving as efficient chelating ligands: Did they cause metal ions to accumulate in what was going to become biological matter and was there a selectivity, a positive bias in favour of nowessential metals (see above) in this process? Though there was no complete selectivity of this kind, neither a RNA world in which early ribozymes effected most of biocatalysis, nor a paleoatmosphere containing substantial amounts of CO could have paved the way to the present biochemistry and metallomes.

Conclusions

This way of reasoning provides a causal account for abundance distributions described earlier in the Biological System of Elements (BSE; Markert 1994, Fränzle &; Markert 2000, 2002). There is a pronounced change from chemical evolution, where but few transformations depended on metal ion catalysis to biology.

Recommendations and Perspectives

The application of this numerical approach can be used for modified, weighted evaluation of biomonitoring analytical data, likewise for the prediction of bioconcentration hazards due to a manifold of metal ions, including organometallic ones. This is relevant in ecotoxicology and biomonitoring. In combining apoproteins or peptides synthesized from scratch for purposes of catalysing certain transformations, the map and numerical approaches might prove useful for the selection of central ions which are even more efficient than the ‘natural’ ones, like for Co²⁺ in many Zn enzymes.

     

Relations of Habitat-Specific Algal Assemblages to Land Use and Water Chemistry in the Willamette Basin, Oregon

Benthic algal assemblages, water chemistry, and habitat were characterized at 25 stream sites in the Willamette Basin, Oregon, during low flow in 1994. Seventy-three algal samples yielded 420 taxa — mostly diatoms, blue-green algae, and green algae. Algal assemblages from depositional samples were strongly dominated by diatoms (76% mean relative abundance), whereas erosional samples were dominated by blue-green algae (68% mean relative abundance).Canonical correspondence analysis (CCA) of semiquantitative and qualitative (presence/absence) data sets identified four environmental variables (maximum specific conductance, % open canopy, pH, and drainage area) that were significant in describing patterns of algal taxa among sites. Based on CCA, four groups of sites were identified: streams in forested basins that supported oligotrophic taxa, such as Diatoma mesodon;small streams in agricultural and urban basins that contained a variety of eutrophic and nitrogen-heterotrophic algal taxa; larger rivers draining areas of mixed land use that supported planktonic, eutrophic, and nitrogen-heterotrophic algal taxa; and streams with severely degraded or absent riparian vegetation (> 75% open canopy) that were dominated by other planktonic, eutrophic, and nitrogen-heterotrophic algal taxa. Patterns in water chemistry were consistent with the algal autecological interpretations and clearly demonstrated relationships between land use, water quality, and algal distribution patterns.     

梯度淋洗离子色谱法同时测定雨水中12种有机酸和无机阴离子的研究

研究了用离子色谱梯度洗脱-抑制电导检测器同时分离12种有机酸和无机阴离子的规律和色谱务件,建立了最佳梯度程序.在所选实验务件下,方法对所测有机酸和无机阴离子的线性相关系数为0.9929～0.9998,相对标准偏差为4.2%～9.3%,加标回收率为91.4%～107.0%,最低检测限为0.0069～0.34mg/L.方法用于雨水样品的测定,结果令人满意.     

晴隆锑矿和煤矿矿集区岩溶地下水环境质量评估

锑是环境中广泛分布、具有慢性毒性和潜在致癌性的典型毒害重金属,是一种新兴的全球性环境污染物。过去对锑的地球化学行为研究较多,但对岩溶地下水的环境质量影响的研究较少。选择锑矿和煤矿分布广泛的贵州晴隆县境内龙摆尾地下河为研究对象,对研究区的地表水和地下水的水化学特征和污染特征进行研究,以《生活饮用水卫生标准》(GB 5749—2006)和《地表水环境质量标准》(GB 3838—2002)中的Ⅲ类标准值为评价标准对该地区水质予以评价。结果表明:在锑矿未开采情况下,第四系碧痕营组地下水中锑的浓度较高,平均值为1.55μg/L,最高为6.32μg/L;锑、砷的迁移受氧化还原条件的控制;岩溶地下水整体来说水质符合生活饮用水标准,但碧痕营组水中锑、锰超标,龙潭组中节理裂隙水存在pH、锰超标情况;而煤矿开采污染的地表水中锰、铁的污染具有普遍性,含量均超过地表水环境质量标准的限值,且超标倍数较大。因此,该研究区岩溶地下水可直接作为饮用水源,而碧痕营组和龙潭组中地下水须做处理后才可饮用。     

Temporal variability in 20 chemical elements content of Parasol Mushroom (Macrolepiota procera) collected from two sites over a few years

Mature specimens of Parasol Mushroom were collected annually in the outskirts of the Siemiany (2000–2003) and Rafa (2001–2003) sites in the northern part of Poland to examine temporal variations and similarities in the composition of 20 chemical elements. Analysis was done under the same condition and using well-validated analytical methods. Elements were determined by inductively coupled plasma–atomic emission spectroscopy and cold vapour–atomic absorption spectroscopy (Hg). The ranges of Ag, Al, Ba, Ca, Cd, Co, Cu, Cr, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn concentrations in the caps of fruiting bodies were similar (p > 0.05; Mann-Whitney U test) for both geographically distant sites, and these specimens from Rafa were more contaminated with Pb (p < 0.05; Mann-Whitney U test). The annual collections of caps in the Siemiany site varied in Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, Hg, Na, Rb and Sr and contents (0.05 < p < 0.001), while they were similar in Cr, K, Mg, Mn, Ni, P, Pb and Zn (p > 0.05; Mann-Whitney U test). The annual collections of specimens from the Rafa site varied in contents of Ag, Al, Ba, Ca, Fe, Hg, K, Mg, Mn, P, Rb and Zn (p > 0.05), while they were similar in Cd, Co, Cr, Cu, Na, Ni, Pb and Sr (p < 0.05). The results of this study imply that metallic elements content of Parasol Mushroom collected at the same undisrupted sites, and hence keeping the same geochemical condition for mushroom development and fructification (the same stands and probably the same mycelia), can fluctuate over the years or the life-span of mycelium. Hence, when assessing the nutritional value of essential metallic elements and status of non-essential or toxic metallic elements in Parasol's Mushroom caps (and probably also of other mushrooms species) to man, the possible fluctuation in contents over time have to be taken into account.     

Leaching of Cu and Zn from discarded boat paint particles into tap water and rain water

We studied the leaching of copper and zinc from particles of discarded boat paint added to tap water (pH 7.3) and rain water (pH = 4.7), simulating conditions encountered during the hosing or runoff of antifouling waste. Leaching rates appeared to be diffusion-controlled and were greater in rain water than in tap water and were greater for Zn than for Cu. After a period of 120 h, between about 0.5% and 3% of total Cu and 5-30% of total Zn had been released to the aqueous phase. These observations suggest that Cu and Zn mobilised from fine antifouling particulates during washdown or rainfall events may be important contaminants of runoff and soils in the vicinity of boat repair facilities.     

污水处理中的恶臭对周边环境的污染及其治理

就污水处理厂运行过程中产生的臭气对周边环境产生的污染情况,针对臭气的治理方法,重点介绍了物理脱臭法、化学脱臭法、生物脱臭法的作用原理、工艺流程及设计参数。     

Development of a nonlocal convective mixing scheme with varying upward mixing rates for use in air quality and chemical transport models

BACKGROUND, AIM, AND SCOPE: Asymmetrical convective non-local scheme (CON) with varying upward mixing rates is developed for simulation of vertical turbulent mixing in the convective boundary layer in air quality and chemical transport models. MATERIALS AND METHODS: The upward mixing rate form the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. RESULTS: This scheme provides a less rapid mass transport out of surface layer into other layers than other asymmetrical convective mixing schemes. DISCUSSION: In this paper, we studied the performance of a nonlocal convective mixing scheme with varying upward mixing in the atmospheric boundary layer and its impact on the concentration of pollutants calculated with chemical and air-quality models. This scheme was additionally compared versus a local eddy-diffusivity scheme (KSC). Simulated concentrations of NO(2) and the nitrate wet deposition by the CON scheme are closer to the observations when compared to those obtained from using the KSC scheme. CONCLUSIONS: Concentrations calculated with the CON scheme are in general higher and closer to the observations than those obtained by the KSC scheme (of the order of 15-20%). Nitrate wet deposition calculated with the CON scheme are in general higher and closer to the observations than those obtained by the KSC scheme. RECOMMENDATIONS AND PERSPECTIVES: To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO(2)) and nitrate wet deposition was compared for the year 2002. The comparison was made for the whole domain used in simulations performed by the chemical European Monitoring and Evaluation Programme Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.     

化学品污染的成因及预防

世界化学工业迅速发展,各种化学品的产量大幅度增加,新化学品不断涌现。人们在充分利用化学品的同时,也产生了大量的化学废物,其中不乏有毒有害物质。由于毫无控制地随意排放及化学品其他途径的泄放,使环境状况日益恶化,如何认识化学品污染的成因及危害,最大限度地降低化学品污染,加强环境保护力度,已是人们亟待解决的重大问题。