Comparison of percolation to batch and sequential leaching tests: Theory and data

Leaching tests are becoming more relevant in assessing solid waste material, particularly with respect to groundwater risks. In the field, water infiltration is the dominant leaching mechanism, which is simulated in the lab with batch and column tests. In this study, we compared percolation, through analytical solutions of the advection–dispersion equation, to laboratory batch and sequential leaching tests. The analytical solutions are supported with comprehensive data from various field and laboratory leaching of different solutes from waste materials and soils collected in long-term joint research projects funded by the German Federal Ministry for Education and Research and the Federal Environment Agency. The comparison of theory and data is facilitated if concentrations and cumulative release are plotted versus the liquid–solid ratios (LS). Both theory and data indicate that leaching behaviour is independent of duration and physical dimensions of the leaching tests. This holds even if field lysimeters are compared to laboratory columns of different size, different flow velocities as well as different contact times. In general, laboratory batch tests over predict effluent concentrations (for LS < K_d). Leaching of solutes from solid samples of certain materials (e.g. chloride from incineration ashes or sulphate from demolition waste) in column and lysimeter tests compares very well and agrees with the analytical solutions. Overall, reproducibility and agreement with theory of column tests are better than batch tests, presumably because the latter are prone to artefacts (e.g. in liquid–solid separation steps). Theory and data fit surprisingly well, despite the fact that the theory is based on the local equilibrium assumption; non-linear sorption and chemical reactions in the solid waste materials are not considered.     

Growth of Lygeum spartum in acid mine tailings: response of plants developed from seedlings, rhizomes and at field conditions

Lygeum spartum is a native species in semiarid Mediterranean areas that grows spontaneously on acid mine tailings. We aimed to study the suitability of this plant for phytostabilization. L. spartum was grown from both seeds and rhizomes in acid mine tailings with various fertilizer and lime treatments. Untreated soils had a solution pH of 2.9 with high concentrations of dissolved salts (Electrical Conductivity 25 dS m(-1)) and Zn (3100 mg L(-1)). Plants grown on untreated soil had high shoot metal concentrations (>4000 mg kg(-1)Zn). Liming increased the solution pH to 5.5 and reduced the dissolved salts by more than 75%, resulting in lower shoot metal accumulation. Plants grown from rhizomes accumulated less metal than those grown from seeds. Plants collected in the field had metal concentrations an order of magnitude less than plants raised in the growth chamber. These differences may be due to the higher moisture content and homogeneous nature of the soils used in the pot experiment.     

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.

     

Humanarzneimittel im aquatischen Ökosystem

Goal

In the Brandenburg State Office for the Environment an approach to assess the potential risk of drug residues in aquatic ecosystems has been developed based on an investigation of the consumption amounts in 1999 to identify or to exclude a potential environmental risk of important human drugs and further to define priority substances for monitoring programs in Brandenburg in the future.

Method

This assessment approach tested with 60 drug agents is based on an exposure estimation considering the main path for the entry human—waste water—sewage plant—surface water, on a substance specific analysis of effects and on an analysis of the environmental fate as compartment distribution, bioaccumulation and persistence.

Results

In Brandenburg surface waters the drug agent concentration for eight of the considered substances is supposed to be greater than 1 μg/l and for at least 13 of the considered substanoes the PNEC in aquatic ecosystems is assumed to be lower than 1 μg/l. A potential risk for the environment can be seen for the antibiotics Ciprofloxacin-HCl and Clarithromycin, the disinfectants Benzalkonium Chloride, Cocospropylendiaminguaniacetat, Glucoprotamine, Laurylpropylenediamine and Polyvidone-iodine, the sexual hormon Ethinylestradiol, the antidiabetic Metformin-HCl, the antiepileptic Carbamazepine and the lipid regulator Clofibrinic acid on the basis of effects because their PEC:PNEC-relation is about 1 or higher. For further 19 drug agents an environmental risk is to be assumed because of their environmental behaviour without support by ecotoxicological data at present.

Conclusion

Although there is only a small base of valid ecotoxicological data, this risk assessment shows that adverse effects in the aquatic environment by some drug agents cannot be excluded. However, it should be noted that this first assessment gives only a crude orientation. Appropriate test data are necessary to refine the assessment in future.     

Moosmonitoring als Spiegel der Landnutzung?

Goal, Scope and Background

The study was conducted to test the hypothesis that the regional variability of nitrogen (N) and metal accumulations in terrestrial ecosystems are due to historical and recent ways of land use. To this end, in two regions of Central Europe the metal and N accumulations in both regions should be examined by comparative moss analysis. The regions should be of quantitatively specified representativity for selected ecological characteristics of Europe. Within both regions these characteristics should be covered by the sites where the moss samples were collected. The number of samples should allow for geostatistical estimation of the measured nitrogen and metal loads.

Methods

The two regions of investigation were selected according to an ecological land classification of Europe which was computed by classification trees. Within each of both research areas the sampling points were localized according to the areas occupied by the ecologically defined land classes. The sampling and chemical analysis of mosses was conducted in accordance with an appropriate UNECE guideline by means of ICP-MS (metals) and combustion analysis (N). The quality of measurements was assured using certified reference materials. The differences of deposition loads were tested for statistical significance with regard to time and space. Variogram analysis was used to examine and model the spatial autocorrelation function of the measurements. Ordinary kriging was then applied for surface estimations.

Results

By use of the ecological regionalisation of Europe the Weser-Ems Region (WER) and the Euro Region Nissa (ERN) were selected for investigation. The sampling sites represent quite well the natural landscapes and the land use categories of both regions. The measurement values corroborate the decline of metal accumulation observed since the beginning of the European Mosses Monitoring Survey in 1990. The metal loads of the mosses in the ERN exceed those in the WER significantly. The opposite holds true for the N concentrations: those in the WER are significantly higher than those in the ERN.

Discussion

The decrease of heavy metal emissions is correlated with lowered deposition and accumulation rates in terrestrial ecosystems. The accumulation of nitrogen in the biosphere is not following this trend.

Conclusions

The technique of moss analysis is adequate for spatially valid biomonitoring of spatial and temporal trends of metals and nitrogen in terrestrial ecosystems. By this, it enables to prove the efficiency of environmental policies.

Recommendations and Perspectives

The accumulation of N in ecosystems is still a serious environmental problem. Related ecological impacts are the eutrophication of aquatic ecosystems like ground waters, lakes, rivers and oceans as well as the biocoenotic changes in terrestrial ecosystems. Thus, a statistically valid exposure analysis must encompass both, accumulation of metals and N bioaccumulation. Further, the bioaccumulation of persistent organic pollutants should be monitored. Finally, environmental biomonitoring should be conducted in much closer contact with human health aspects.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

Energy at work: A measurement validation and linkage to unit effectiveness

We introduce the notion that the energy of individuals can manifest as a higher‐level, collective construct. To this end, we conducted four independent studies to investigate the viability and importance of the collective energy construct as assessed by a new survey instrument—the productive energy measure (PEM). Study 1 (n = 2208) included exploratory and confirmatory factor analyses to explore the underlying factor structure of PEM. Study 2 (n = 660) cross‐validated the same factor structure in an independent sample. In study 3, we administered the PEM to more than 5000 employees from 145 departments located in five countries. Results from measurement invariance, statistical aggregation, convergent, and discriminant‐validity assessments offered additional support for the construct validity of PEM. In terms of predictive and incremental validity, the PEM was positively associated with three collective attitudes—units' commitment to goals, the organization, and overall satisfaction. In study 4, we explored the relationship between the productive energy of firms and their overall performance. Using data from 92 firms (n = 5939_employees), we found a positive relationship between the PEM (aggregated to the firm level) and the performance of those firms. Copyright © 2011 John Wiley & Sons, Ltd.