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.

     

Determination of PCDDs,PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland

Background The aim of the project was to measure the actual emissions of PCDD/F, PCBs and HCB from 20 selected metallurgical installations in Poland, in order to update the national inventory of dioxin emission from metallurgical industry for developing a strategy for dioxins and furans emission abatement from the subject facilities (UNEP 2005). Methods Sampling methodology used in this work was developed at the Cracow University of Technology because of the complexity of simultaneous sampling and determining PCDFs, PCDDs, PCB and HCB. For the determination a GC-MS/MS system was used. Results and Discussion Results from the work indicate that the highest dioxins and PCB concentrations were recorded for iron ore sintering plants at 1.10–1.32 ng total¹ TEQ/Nm³ followed by aluminium scrap melting at 0.03–0.66 ng total TEQ/Nm³. The highest HCB concentrations at 613–1491 ng/Nm³ were also recorded for iron ore sintering plants, whereas at aluminium plants the HCB concentrations were in the range of only 10.1–22.7 ng/Nm³. Conclusions The above investigations indicate that secondary aluminium production is the most significant dioxins source, if calculated as emission factor values. However, iron ore sintering plants are operating at much higher production capacity, causing this process to become the major source of dioxins, PCB and HCB pollution to the atmosphere in Poland. Recommendations and Perspectives Based on the performed tests and the environmental reviews of selected plants several recommendations were formulated for the reduction of generation or of emission of these pollutants from iron ore sintering plants, electric arc furnace steel production processes, hot-blast furnace operations, secondary aluminium smelting and primary zinc production from zinc cathodes.     

酒精行业循环经济模式研究

分析了发酵类酒精行业各工段的特点,根据循环经济"3R"原则,提出了一种新型的循环经济模式,包括酒糟废液厌氧发酵产生的沼气的回收利用、利用发酵沼渣制取生态复合肥、收集利用酒精发酵产生的二氧化碳和杂醇油副产物、工艺产出热能的热泵回收利用等.该循环经济模式提高了酒精行业的资源和能源的利用率,降低了各种副产物的排放量,在一定范围内实现了资源的循环利用,为社会和企业带来了巨大的生态和经济效益.     

化工园区污水特征分析及生物毒性研究

对天津市某化工园区9个主要污染企业及总排放口的废水进行监测分析,测定了12项水质常规指标和8项重金属指标,采用主成分分析法和生物毒性测试对化工区废水的水质进行了综合评价。结果表明,水质指标中大部分常规项目(如COD、氨氮和重金属含量)在多数企业污水中都符合排放标准,总氮、总磷污染较重,其中磷的污染最严重,最高超标23.83倍;影响污水性质的第一主成分为氯化物、电导率、全盐量和Cr,第二主成分为溶解氧、悬浮物、氨氮、总氮、总磷和As;废水具有一定的生物毒性,且不同化工企业之间毒性差异较大。水质化学测定的结果和生物毒性程度有一定相关性,但也存在差异,应该结合两者综合评价水质污染特征。     

珠江三角洲制鞋行业挥发性有机化合物排放系数研究

采用工艺调查与现场监测相结合的方法,以物料衡算法为依据,通过现场监测结果进行验证,研究了制鞋行业挥发性有机化合物(VOCs)排放系数。结果表明,水性胶粘剂使用企业的VOCs排放系数为(5.25±2.67)g/双,油性胶粘剂使用企业的VOCs排放系数为(30.11±10.60)g/双,根据不同类型胶水在制鞋行业中所占的权重,可得到反映地方特色的制鞋行业VOCs排放系数。     

能源结构变化对兰州市大气质量的影响

将2001—2010年的主要能源材料消耗、主要污染物变化及主要行业分布进行了相关性分析,结果表明:兰州市大气4种主要污染物中除烟尘呈下降趋势外,废气总量、SO2、NOx仍呈上升趋势;主要污染源为燃煤,主要污染行业为电力、蒸汽热水产供业;废气和SO2排放总量与燃煤和燃气呈强正相关,而NOx排放只与燃气呈强正相关。建议发挥兰州地域优势,加大以水电供应为主的能源结构调整,对改善当地空气质量有重要价值。     

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.     

萧山市羽绒行业污染源调查与排污系数的确定

通过对萧山市羽绒行业中典型企业－－浙江三弘国际羽绒有限公司排放废水的监测分析,计算其羽绒废水中各污染物的排放量,由此确定羽绒行业污染物排放系数和排污总量,为污染物排放总量的控制管理提供了有效依据。     

江苏省水泥制造业经济发展与大气环境变化相关性分析

选取了2001—2014年的相关数据,分析了江苏省水泥制造业的经济发展、资源能源消耗和污染物排放特征,同时对行业经济发展与大气环境污染变化进行了相关性分析。结果表明,2001—2014年,江苏省水泥制造业工业总产值呈现波动增加趋势,工业煤炭消费量呈现波动增加趋势,投入产出比呈现逐年波动上升态势;SO2的排放强度呈现波动下降的趋势,低于全省平均水平;烟粉尘的排放强度波动下降,高于全省平均水平;NOX的排放强度呈现波动上升的趋势,高于全省平均水平;SO2与烟粉尘排放量与GDP均高度呈负相关,回归曲线模拟基本类似U型的左半段,随着GDP的增加,SO2和烟粉尘的排放量呈现下降趋势。