地下水化学类型对硫系还原剂去除Cr (VI)的影响

为研究铬污染地下水化学类型对硫系还原剂除铬的影响,采用批实验的方式,分别比较了3种还原剂焦亚硫酸钠（Na2S2O5）、连二亚硫酸钠（Na2S2O4）、多硫化钙（CaSx）对SO4-Na型、SO4-Ca型、Cl-Na型和HCO3-Ca型4种地下水中去除Cr（VI）的效果。结果表明,在20℃有氧条件下,4种地下水环境中还原剂的除铬能力受到了不同程度的抑制,其中HCO3-Ca型地下水中的抑制作用最大。但当Na2S2O5、Na2S2O4、CaSx投加量分别为理论投加量的30.8、21.7和2.4倍时,4种地下水中Cr（VI）的去除率均大于90%。Na2S2O5投加量与水中HCO3-含量的摩尔比大于0.5时,Cr（VI）才可能被还原去除;Na2S2O4对Cr（VI）的去除率由高到低排序是：SO4-Na型 > Cl-Na型 > SO4-Ca型 > HCO3-Ca型;CaSx的除铬效果在不同地下水化学类型中的差异最小。地下水的HCO3-含量越高,缓冲能力越强,抑制作用越明显,所需还原剂投加量越多。     

Part IV: Fitness for Aquatic Systems Long-term Forecast: Key to groundwater protection

Groundwater resources are at risk from pollution, climate change and land-management practices. Long-term forecast is a tool to demonstrate future development and to support decisions on measures which can be implemented, controlled and eventually corrected. As the basis for preventive action, a forecast can be viewed as a key to groundwater protection. The soil zone plays a vital role in groundwater protection. Research on soil and groundwater trends, as affected by change of climate and/or land-management practices, is on the agenda. Integrated research is necessary to develop numerical soil-water system models reflecting all relevant transport processes at various scales. Even relatively simple problems like forecasting pollutant release from contaminated materials are difficult to resolve. Batch tests may be sufficient in low-risk cases. At higher risk when contaminated substrates are chosen for deposition on a large scale, a thorough characterization of the materials is necessary covering all aspects of stability and possible changes of the environment.     

略论我国的环境化学研究进展

本文概略论述了２０多年来我国环境化学的研究状况,就环境污染分析化学、环境污染化学、环境污染控制化学今后的研究趋势和重点研究方向提出了自己的看法。     

Is tree growth reduction related to direct foliar injuries or soil chemistry modifications?

In the context of intense emissions causing atmospheric pollution, tree growth reductions could be related to soil chemistry modifications or direct foliar injuries. To verify these hypotheses, mineral soils were sampled in an area (Murdochville, Canada) where previous studies had demonstrated that tree growth was impacted by smelter emissions and that forest floor lead concentrations could be used as a proxy for atmospheric pollutant depositions. Samples were analysed for Al, Pb (concentrations and isotope ratios), basic cations (Ca, K, P, and Mg) and Zr. Mass balance calculations were performed on soil profiles to assess vertical migration of elements. Pb concentrations in litter diminished gradually with distance from the smelter. The Pb isotope ratios in these organic soil layers were close to those measured in the Murdochville ores. These patterns were not encountered in mineral soil layers. Pb isotope ratios in these layers were close to those measured in uncontaminated geological materials, and Pb concentrations and basic cation depletions were not related to the proximity of the smelter. Growth reduction was closely associated with litter Pb concentrations, which were used as a proxy for atmospheric deposition, but was not correlated with any elemental concentration or cation depletion measured in mineral soil layers. Our overall results suggest that trees responded mainly to direct atmospheric emissions, which caused foliar damage, rather than to soil chemistry modifications.     

The Precision of Precipitation Chemistry Measurements in the Canadian Air and Precipitation Monitoring Network (CAPMoN)

Precision estimates are presented for precipitation chemistry and depth measurements made by the Canadian Air and Precipitation Monitoring Network (CAPMoN). The estimates were made for daily measurements of ion concentration and precipitation depth as well as for weekly, 28-day, seasonal and annual precipitation-weighted mean concentrations and depths. The data on which the estimates are based were collected from collocated samplers at five CAPMoN sites during the period 1985 to 1993. The data pairs from the collocated samplers were used to calculate the between-instrument error defined as 1/2 times the difference between the paired sample concentrations (or depths). For all of the ion concentrations and depths, the between-sampler errors were found not to be normally distributed, but the normality of the distributions improved with the length of the (volume-weighting) time period considered. A set of quantitative measures of overall network precision were derived in absolute (mg L^-1) and relative (%) units. These included the Modified Median Absolute Deviation (M.MAD), the P90% probability values and the Coefficient of Variation (CoV). The latter, defined as the percent ratio of the M.MAD to the median concentration (or depth), represents the relative precision at the center of the error and concentration (and depth) distributions. Based on the CoV values, the relative precision of the CAPMoN measurements was very high (better than 4%) for SO ₄ ^2- , NO ₃ ^- , pH, H⁺, NH ₄ ⁺ , sample depth and standard gauge depth, and not as high (between 10 and <35%) for Cl^-, Na⁺, Ca²⁺, Mg²⁺, and K⁺. The ions with the lowest median concentrations had the poorest relative precision since so many of the concentrations were at or near the analytical detection limit. Except for the sample and standard gauge depths, both the absolute and relative precision improved with the length of the precipitation-weighting period. Detailed statistical testing established that the precision of the daily measurements is dependent on a number of factors, the most dominant being sample depth and concentration, i.e., the absolute precision improves with increasing sample depth and decreasing concentration. The strength of these relationships diminished with the length of the precipitation-weighting period being considered. Laboratory-related sources of imprecision were found to account for less than 4% of the overall daily measurement imprecision for most species, while field-related sources of imprecision accounted for the balance. Specialized plots are shown which allow data users to estimate the absolute and relative precision at any concentration and depth value.     

Synchronous variation in water chemistry for 80 lakes in Southern Sweden

Variation in water chemistry was studied in 80 lakes in southern Sweden. The lakes had forest dominated catchments. The length of the time series was 14 years. Synchrony was calculated as Pearsons product moment correlation coefficients for all combinations of lakes, i.e. 3160 lake-pairs. The chemical variables studied were non-marine sulphate (SO₄ ^*), non-marine calcium (Ca^*), absorbance and acid neutralising capacity (ANC). Statistically significant synchrony occurred in 93% of all lake-pairs for SO₄ ^*, and between 58 and 67% for absorbance, Ca^* and ANC. In 70% of all lake-pairs, the synchrony was \s>0.71 for SO₄ ^*, which means that more than half of the variation in one lake could be explained by the variation in the other lake. For absorbance, Ca^* and ANC, about 25% of the lake-pairs had a synchrony \s>0.71. The relatively high synchrony for SO₄ ^* occurred during an overall downward trend in SO₄ ^* concentration.The degree of synchrony in our study was at a level comparable to other studies in northern America and England. However, our study included lakes in a much larger area, with distances of up to 500 km between the lakes, while earlier studies were made on small lake districts with lakes located within approximately 50 km. In contrast to these earlier studies, there was no correlation between synchrony and distance, lake characteristics or catchment characteristics. However, when a small subset of 15 lakes in the southeast of Sweden was selected, such relations were found.     

Combined use of rapid bioassessment protocols and sediment quality triad to assess stream quality

Physical, chemical and biological conditions at five stations on a small southeastern stream were evaluated using the Rapid Bioassessment Protocols (RBP) and the Sediment Quality Triad (SQT) to assess potential biological impacts of a municipal wastewater treatment facility (WWTF) on downstream resources. Physical habitat, benthic macroinvertebrates and fish assemblages were impaired at Stations 1 and 2 (upstream of the WWTF), suggesting that the degraded physical habitat was adversely impacting the fish and benthic populations. The SQT also demonstrated that Stations 1 and 2 were degraded, but the factors responsible for the impaired conditions were attributed to the elevated concentrations of polycylclic aromatic hydrocarbons (PAHs) and metals (Mn, Pb) in the sediments. The source of contaminants to the upper reaches of the stream appears to be storm-water runoff from the city center. Increased discharge and stabilized base flow contributed by the WWTF appeared to benefit the physically-altered stream system. Although the two assessment procedures demonstrated biological impairment at the upstream stations, the environmental factors identified as being responsible for the impairment were different: the RBP provided insight into contributions associated with the physical habitat and the SQT contributed information on contaminants and sediment quality. Both procedures are important in the identification of physical and chemical factors responsible for environmental impairment and together they provide information critical to the development of appropriate management options for mitigation.     

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.     

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.