Dendroremediation of trinitrotoluene (TNT) part 1: Literature overview and research concept

BACKGROUND, AIM AND SCOPE: For decades, very large areas of former military sites have been contaminated diffusely with the persistent nitroaromatic explosive 2,4,6-trinitrotoluene (TNT). The recalcitrance of the environmental hazard TNT is to a great extent due to its particulate soil existence, which leads to slow but continuous leaching processes. Although improper handling during the manufacture of TNT seems to be a problem of the past in developed countries, environmental deposition of TNT and other explosives is still going on unfortunately, resulting from thousands of unexploded ordnance or low order explosions at munitions test areas and at current battlefields. OBJECTIVE: Sustainable phytoremediation strategies for explosives in Germany, which intend to use trees to decontaminate soil and groundwater ('dendroremediation'), have to consider that most of the former German military sites are already covered with woodlands, mainly with conifer stands. Therefore, parallel investigation of the remediation potential is necessary for both of the selected hybrids of fast growing broadleaf trees, which are waiting for planting and forest conifers, which have already proven for decades that they are able to grow on explosive contaminated sites. MAIN FEATURES: A short literature review is given regarding phytoremediation of TNT with herbaceous plants and some general aspects of dendroremediation are discussed. Furthermore, an overview of our TNT-dendroremediation research network is introduced, which has the strategic goal to make dendroremediation more calculable for a series of potent trees for site-adapted in situ application and for the assessment of tree remediation potentials in natural attenuation processes. RESULTS AND DISCUSSION: Some of our methods, results and conclusions yet unpublished are presented. For a preliminary calculation of area-related annual TNT dendroremediation potential of five-year-old trees, the following values were assessed: Salix EW-13 6.0, Salix EW-20 8.5, Populus ZP-007 4.2, Betula pendula 5.2, Picea abies 1.9 and Pinus sylvestris 0.8 g m(-2) a(-1). For a 45-year-old spruce forest, an annual natural attenuation potential of 4.2 g TNT m(-2) a(-1) was found. CONCLUSION, RECOMMENDATIONS AND PERSPECTIVE: Our main results deliver quantitative proposals for dendroremediation strategies in situ and provide decision aids. Also aspects of growth of raw materials for energy production are considered. Our dendroremediation research concept for TNT and its congeners can be easily completed for other trees of interest and it can also be applied to herbaceous plants. Knowing the current bottlenecks of phytoremediation and considering the known environmental behaviour of other contaminants, elements of our methodological approach may be easily adapted to those pollutant groups, e.g. for pesticides, pharmaceuticals, PAHs, chlorinated recalcitrants and, with some restrictions, to inorganics and to multiple contaminations. Our dynamical dendrotolerance test systems will help to predict tree growth on polluted areas. To provide some light into the black box of TNT dendroremediation, experimental data regarding the uptake, distribution and degradation of [14C]-TNT in mature tree tissues will be reported in the second part of this publication.     

Past changes in Arctic terrestrial ecosystems, climate and UV radiation

At the last glacial maximum, vast ice sheets covered many continental areas. The beds of some shallow seas were exposed thereby connecting previously separated landmasses. Although some areas were ice-free and supported a flora and fauna, mean annual temperatures were 10-13 degrees C colder than during the Holocene. Within a few millennia of the glacial maximum, deglaciation started, characterized by a series of climatic fluctuations between about 18,000 and 11,400 years ago. Following the general thermal maximum in the Holocene, there has been a modest overall cooling trend, superimposed upon which have been a series of millennial and centennial fluctuations in climate such as the "Little Ice Age spanning approximately the late 13th to early 19th centuries. Throughout the climatic fluctuations of the last 150,000 years, Arctic ecosystems and biota have been close to their minimum extent within the most recent 10,000 years. They suffered loss of diversity as a result of extinctions during the most recent large-magnitude rapid global warming at the end of the last glacial stage. Consequently, Arctic ecosystems and biota such as large vertebrates are already under pressure and are particularly vulnerable to current and projected future global warming. Evidence from the past indicates that the treeline will very probably advance, perhaps rapidly, into tundra areas, as it did during the early Holocene, reducing the extent of tundra and increasing the risk of species extinction. Species will very probably extend their ranges northwards, displacing Arctic species as in the past. However, unlike the early Holocene, when lower relative sea level allowed a belt of tundra to persist around at least some parts of the Arctic basin when treelines advanced to the present coast, sea level is very likely to rise in future, further restricting the area of tundra and other treeless Arctic ecosystems. The negative response of current Arctic ecosystems to global climatic conditions that are apparently without precedent during the Pleistocene is likely to be considerable, particularly as their exposure to co-occurring environmental changes (such as enhanced levels of UV-B, deposition of nitrogen compounds from the atmosphere, heavy metal and acidic pollution, radioactive contamination, increased habitat fragmentation) is also without precedent.     

Reconstructed mass-spectrometric pattern for characterization of carbon compounds in smoker's lung in situ

BACKGROUND: Cigarette smoke is a major anthropogenic pollutant and contributes to the permanent load of ambient particulate matter in the air, particularly indoors. It is the leading risk factor for premature loss of life due to chronic bronchitis, emphysema and lung cancer. Smoker's lung and graphite pneumoconiosis are pathological states characterized by the deposition of carbonaceous particles. METHODS: Mass spectrometry was used to evaluate unstained lung sections obtained in vivo from a heavy smoker and a patient with occupationally acquired graphite pneumoconiosis. RESULTS AND DISCUSSION: The composition of carbon compounds deposited in lung tissue samples is demonstrated here for the first time. Thirty carbonaceous-containing microareas from ten biopsies (three areas per biopsy) of lung tissues were analyzed mass-spectrometrically. In each case, the samples were taken from a smoker's lung or those demonstrating a graphite pneumoconiosis. The lung-tissue samples were selected by light microscopy before they were evaporated for mass spectrometry. First-order criteria were anionic and cationic mass peaks which occur within the mass patterns in lung tissues of smoker's lung, although not in graphite pneumoconiosis. Second-order criteria were mass peaks from smoker's lung with standard deviations SD < or = 14% of the mean value. First and second-order mass peaks matched the mass peaks of experimental cigarette-smoke condensate in 9 out of 11 peaks. A software program was developed that enabled fast, automated recognition of the typical mass peaks, and thereby confirmed the histological diagnosis of smoker's lung. CONCLUSIONS: The analysis of carbonaceous particles within lung biopsies from a heavy smoker corresponded to the spectra of tobacco condensate and not to the investigated biopsies of graphite peneumoconiosis. RECOMMENDATION AND OUTLOOK: The analyses were performed in order to find out whether mass-spectrometric criteria exist for the differentiation of carbonaceous lung-tissue deposits. Mass spectrometry may be a valuable tool in determining the composition of carbon compounds deposited in human lung tissue. So far, qualitative assessment of the composition of deposits in lung tissue is only possible after the patient is deceased (autopsy).     

Developing conceptual frameworks for the recovery of aquatic biota from acidification

Surface water acidity is decreasing in large areas of Europe and North America in response to reductions in atmospheric S deposition, but the ecological responses to these water-quality improvements are uncertain. Biota are recovering in some lakes and rivers, as water quality improves, but they are not yet recovering in others. To make sense of these different responses, and to foster effective management of the acid rain problem, we need to understand 2 things: i) the sequence of ecological steps needed for biotic communities to recover; and ii) where and how to intervene in this process should recovery stall. Here our purpose is to develop conceptual frameworks to serve these 2 needs. In the first framework, the primarily ecological one, a decision tree highlights the sequence of processes necessary for ecological recovery, linking them with management tools and responses to bottlenecks in the process. These bottlenecks are inadequate water quality, an inadequate supply of colonists to permit establishment, and community-level impediments to recovery dynamics. A second, more management-oriented framework identifies where we can intervene to overcome these bottlenecks, and what research is needed to build the models to operationalize the framework. Our ability to assess the benefits of S emission reduction would be simplified if we had models to predict the rate and extent of ecological recovery from acidification. To build such models we must identify the ecological steps in the recovery process. The frameworks we present will advance us towards this goal.     

Sorption behavior of metolachlor, isoproturon, and terbuthylazine in soils

The sorption-desorption of metolachlor [2-chloro-N-(ethyl-6-methyl phenyl)-N-(2-methoxy-1-methyl ethyl) acetamide], isoproturon [3-(4-isopropyl phenyl)-1,1-dimethyl urea] and terbuthylazine [N6-tert butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine] herbicides was studied in two German soils at 1:10 soil to water ratio by batch method. Equilibrium of herbicides between soil and water (0.01 M CaCl2) was attained in 2 h. Sorption data fitted very well to Freundlich equation, represented by very high correlation coefficient (r2 > 0.934). Comparison of Freundlich K values indicated that sorption of all the three herbicides was most pronounced in soil having higher organic carbon content. Koc values were as expected nearly identical for each herbicide in the two soils. The Freundlich constant (1/n) was about 1 for metolachlor and less than 1 for terbuthylazine and isoproturon indicating a L-type of sorption isotherms. Desorption of all the three herbicides showed hysteresis. Nearly equal amounts of metolachlor, isoproturon and terbuthylazine were desorbed from both soils. There was a good correlation between Koc and solubility.     

A comparative characterization of dissolved organic matter by means of original aqueous samples and isolated humic substances

The aim of our study is to test the use of less time-consuming spectroscopic methods applied on original water samples in order to obtain information about DOM composition without any sample preparation. These results were directly compared with results from a conventional isolation and characterization procedure of dissolved humic substances (fulvic acids – FA) isolated from the same water sample. FAs were characterized by UV-, fluorescence-, FTIR spectroscopy and elemental composition. UV absorbance and fluorescence behavior of FAs and original water samples follow the same pattern. A lower UV absorbance and a lower humification index (derived from the synchronous fluorescence spectra) of about 15% is typical for water samples compared to the FAs. We computed linear relationships between properties of the original water sample (UV-, synchronous fluorescence spectra) and the isolated FA (IR absorption, C/N ratio). The application of synchronous fluorescence and UV spectroscopy of aqueous samples has been proved to result in similar information about DOM composition as the characterization of isolated humic substances concerning the content of aromatic structures and the degree of humification.     

The toxicity of copper,cadmium and zinc to four different Hydra (Cnidaria: Hydrozoa)

An acute toxicity study of three metals to Hydra species carried out using two different assessment methods, (i) determination of the LC50 and (ii) measurement of progressive morphological changes, demonstrated that relative toxicity decreased from copper to cadmium with zinc the least toxic for all species. The latter method revealed more details of the effect on Hydra in terms of physical damage to the polyp but both methods indicated that H. viridissima was more sensitive to copper and cadmium than H. vulgaris¹ (Zurich strain, male clone), H. vulgaris² (a dioecious strain reproducing sexually and asexually) and H. oligactis (dioecious, reproducing sexually and asexually). The responses to zinc were similar for all Hydra. The possible role of metabolic interactions between H. viridissima and its symbiotic green algae in contributing to the greater sensitivity of this polyp is discussed.     

Biological solubilization and mineralization as novel approach for the pretreatment of food waste

The performance of a garbage disposal system to solubilize and mineralize food wastes through biological solubilization was evaluated through the examination of the effects of operational conditions like water supply volume, water supply frequency and aeration on the amount of waste solubilized, mineralized and accumulated in the reactor. The biological solubilization process consisted of a solubilization reactor and a circulation tank. Food waste and fresh water were supplied into the solubilization reactor with support media. Wastewater from the solubilization reactor was discharged to the circulation tank and water in the circulation tank was periodically pumped back to the solubilization reactor. In case of the total food waste loading of 16 kg m(3-1) d(-1), little carbon (0-5.7%) accumulated in the reactor as long as the system was kept under aerobic condition through large volume of water supply (higher than 3.5 lh(-1)) or applying aeration in the circulation tank. However, 42% of the loaded carbon accumulated under anaerobic condition in low water supply (less than 1.8 lh(-1)). The rest of the waste was either solubilized or mineralized. The aeration in the circulation tank, therefore, was effective to provide similar solubilization and mineralization as the large volume of water supply. However, frequency of feeding at the large volume of water supply had no significant effect on the amount of waste solubilization and mineralization.     

Ethoxyresorufin-O-deethylase (EROD) Activity in Dab (Limanda limanda) as Biomarker for Marine Monitoring (6 pp)

Goal, Scope and Background Ethoxyresorufin-O-deethylase (EROD) is a well-accepted marker for biological effects in fish and is, therefore, part of numerous monitoring programmes. EROD activity was measured in livers of dab (Limanda limanda) from the German Bight (North Sea) from 1995 to 2003. The aim of the present long-term study was (a) time trend monitoring of EROD activity of dab from the German Bight and (b) to elucidate the needs for a successful application of EROD activity as an early warning system. Methods. EROD activities were determined fluorimetrically in dab liver microsomes, using resorufin as an external standard. The limit of detection (LD) and the limit of quantification (LQ) were calculated. Results were referred to protein concentrations. Results and Discussion. EROD activities of 610 female dab caught in different seasons between January 1995 and August 2003 were analyzed individually. Activities varied from 〈 LD to 1768 pmol/(min mg protein) and showed an annual cycle as well as significant differences between the years. Highest EROD activities were observed in early summer and lowest activities during the winter period. In autumn 2002, significantly elevated EROD activities were detected, possibly related to effects of the River Elbe flood event. Two scenarios with different EROD baseline data are presented to discuss the prerequisites for the use of EROD as a monitoring tool. The comparison of these scenarios underlines the importance of appropriate season-specific baseline data. Conclusion. The use of EROD as an early warning tool for contaminant effects in dab in the German Bight has different prospects during the year, because, due to the high background variability, elevated EROD activities are less easy to detect in spring/summer than during the remaining times of the year. Recommendation and Outlook. The availability of site-specific data on the EROD baseline level, its random variation and its annual cycle is a necessary prerequisite for monitoring. If monitoring is to be carried out only for a limited time period of the year, a season with low background variability in EROD activity (autumn) should be chosen to avoid the need for a compensation of the temperature-triggered shift in sexual cycles and the resulting changes in EROD activity.