Phytoremediation of polyaromatic hydrocarbons, anilines and phenols

Phytoremediation technologies based on the combined action of plants and the microbial communities that they support within the rhizosphere hold promise in the remediation of land and waterways contaminated with hydrocarbons but they have not yet been adopted in large-scale remediation strategies. In this review plant and microbial degradative capacities, viewed as a continuum, have been dissected in order to identify where bottle-necks and limitations exist. Phenols, anilines and polyaromatic hydrocarbons (PAHs) were selected as the target classes of molecule for consideration, in part because of their common patterns of distribution, but also because of the urgent need to develop techniques to overcome their toxicity to human health. Depending on the chemical and physical properties of the pollutant, the emerging picture suggests that plants will draw pollutants including PAHs into the plant rhizosphere to varying extents via the transpiration stream. Mycorrhizosphere-bacteria and -fungi may play a crucial role in establishing plants in degraded ecosystems. Within the rhizosphere, microbial degradative activities prevail in order to extract energy and carbon skeletons from the pollutants for microbial cell growth. There has been little systematic analysis of the changing dynamics of pollutant degradation within the rhizosphere; however, the importance of plants in supplying oxygen and nutrients to the rhizosphere via fine roots, and of the beneficial effect of microorganisms on plant root growth is stressed. In addition to their role in supporting rhizospheric degradative activities, plants may possess a limited capacity to transport some of the more mobile pollutants into roots and shoots via fine roots. In those situations where uptake does occur (i.e. only limited microbial activity in the rhizosphere) there is good evidence that the pollutant may be metabolised. However, plant uptake is frequently associated with the inhibition of plant growth and an increasing tendency to oxidant stress. Pollutant tolerance seems to correlate with the ability to deposit large quantities of pollutant metabolites in the 'bound' residue fraction of plant cell walls compared to the vacuole. In this regard, particular attention is paid to the activities of peroxidases, laccases, cytochromes P450, glucosyltransferases and ABC transporters. However, despite the seemingly large diversity of these proteins, direct proof of their participation in the metabolism of industrial aromatic pollutants is surprisingly scarce and little is known about their control in the overall metabolic scheme. Little is known about the bioavailability of bound metabolites; however, there may be a need to prevent their movement into wildlife food chains. In this regard, the application to harvested plants of composting techniques based on the degradative capacity of white-rot fungi merits attention.     

Means to improve the effect of in situ bioremediation of contaminated soil: an overview of novel approaches

Different aspects of bacterial degradation of organic contaminants in soil, and how to improve the efficiency and reproducibility is discussed in this review. Although bioremediation in principle includes the use of any type of organism in improving the condition of a contaminated site, most commonly bacteria are the degraders and other organisms, such as soil animals or plant roots, play a role in dissemination of bacteria and, indirectly, plasmids between bacteria, and in providing nutrients and co-substrates for the bacteria active in the degradation process. There are a number of different procedures that have been tested more-or-less successfully in attempts to improve reliability, cost efficiency and speed of bioremediation. The methods range from minimal intervention, such as mere monitoring of intrinsic bioremediation, through in situ introduction of nutrients and/or bacterial inocula or improvement of physico-chemical conditions, all the way to excavation followed by on site or ex situ composting in its different varieties. In the past the rule has been that more intervention (leading to higher costs) has been more reliable, but novel ideas are continuously tried out, both as a means to come up with new truly functional applications and also as a line of studies in basic soil microbial ecology. Both approaches generate valuable information needed when predicting outcome of remediation activities, evaluating environmental risks, deciding on cleaning-up approaches, etc. The emphasis of this review is to discuss some of the novel methods for which the value has not been clearly shown, but that in our view merit continued studies and efforts to make them work, separately or in combination.     

A correlation between the fate and non-extractable residue formation of 14C-metalaxyl and enzymatic activities in soil

Extracellular, oxidative soil enzymes like monophenol oxidases and peroxidases play an important role in transformation of xenobiotics and the formation of organic matter in soil. Additionally, these enzymes may be involved in the formation of non-extractable residues (NERs) of xenobiotics during humification processes. To examine this correlation, the fate of the fungicide ¹⁴C metalaxyl in soil samples from Ultuna (Sweden) was studied. Using different soil sterilization techniques, it was possible to differentiate between free, immobilized, and abiotic (“pseudoenzyme”-like) oxidative activities. A correlation between the formation of metalaxyl NER and soil organic matter content, biotic activities, as well as extracellular phenoloxidase and peroxidase activities in the bulk soil and its particle size fractions was determined. Extracellular soil-bound enzymes were involved in NER formation (up to 8% of applied radioactivity after 92 days) of the fungicide independently from the presence of living microbes and different distributions of the NER in the soil humic subfractions.     

Determination of 10 particle-associated multiclass polar and semi-polar pesticides from small streams using accelerated solvent extraction

A new analytical method using accelerated solvent extraction was developed for the determination of 10 particle-associated polar and semipolar pesticides. In addition, six deuterated analogues of the target compounds were evaluated as internal standards. The method yielded acceptable accuracy (73–103% recovery) and precision (<25% relative standard deviation) for eight compounds. Using size exclusion chromatography (SEC) as cleanup step resulted in higher recoveries compared to solid phase extraction (SPE) cleanup.

Deuterated standards with 10 or more deuterium atoms performed well as internal standards concerning similar recovery and correlation with the target analytes.

The method was employed to extract particle-associated pesticides from 16 streams located in an area with intense agriculture in France. Acetochlor, pirimicarb, tebuconazole, fenpropidin, -endosulfan and chlorfenvinphos were detected at concentrations up to 1 mg kg⁻¹ dry weight. A comparison with aquatic toxicity data indicated potential risk to the benthic fauna exposed to these concentrations of pirimicarb, -endosulfan and chlorfenvinphos.

We suggest that the method presented here be used for the extraction and quantitation of particle-associated polar pesticides.     

Differences in the growth response of three bryophyte species to nitrogen

The effect of nitrogen on biomass production, shoot elongation and relative density of the mosses Pleurozium schreberi, Hylocomium splendens and Dicranum polysetum was studied in a chamber experiment. Monocultures were exposed to 10 N levels ranging from 0.02 to 7.35 g N m⁻² during a 90-day period. All the growth responses were unimodal, but the species showed differences in the shape parameters of the curves. Hylocomium and Pleurozium achieved optimum biomass production at a lower N level than Dicranum. Pleurozium had the highest biomass production per tissue N concentration. Tolerance to N was the widest in Dicranum, whereas Hylocomium had the narrowest tolerance. Dicranum retained N less efficiently from precipitation than the other two species, which explained its deviating response. All species translocated some N from parent to new shoots. The results emphasize that the individual responses of bryophytes to N should be known when species are used as bioindicators.     

Nitrogen and metals in two regions in Central Europe: Significant differences in accumulation in mosses due to land use?

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 landuse. To this end, two regions of Central Europe were selected for investigation: the Weser-Ems Region (WER) and the Euro Region Nissa (ERN). They were assumed to have land use-specific accumulation profiles. Thus, the metal and N accumulations in both regions were examined by means of geostatistically based comparative moss analysis. The sampling and chemical analysis of mosses were conducted in accordance with the convenient guidelines and methods, respectively. The spatial representativity of the sampling sites was computed by means of a land classification which was calculated for Europe by means of classification trees and GIS-techniques. The differences of deposition loads were tested for statistical significance with regard to time and space. The measurement values corroborated the decline of metal accumulation observed since the beginning of the European Metals in Mosses Surveys in 1990. The metal loads of the mosses in the ERN exceeded those in the WER significantly. The opposite holds true for the N concentrations: those in the WER were significantly higher than those in the ERN. The reduction of emissions from power plants, factories and houses was strongly correlated with the decline of deposition and bioaccumulation of metals. As proved by the European Metals in Mosses Surveys, this tendency is due to successful environmental policies. But no such success could be verified by monitoring the accumulation of N in mosses.     

Organic pollutants in compost and digestate. Part 1. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and molecular markers

In Europe, 9.3 x 10(6) t(dry weight (dw)) of compost and digestate are produced per year. Most of this is applied to agricultural land, which can lead to considerable inputs of organic pollutants, such as polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) to soil. This paper presents an inventory of the pollutant situation in source-separated composts, digestates and presswater in Switzerland by a detailed analysis of over 70 samples. PCB concentrations ( summation PCB 28, 52, 101, 118, 138, 153, 180) were significantly higher in urban (median: 30 microg kg(-1)dw, n = 52) than in rural samples (median: 14 microg kg(-1)dw, n = 16). Together with low concentrations in general, this points to aerial deposition on compost input material as the major contamination pathway. Enantiomeric fractions of atropisometric PCB were close to racemic. Median PAH concentration was 3010 microg kg(-1)dw( summation 15PAH, n = 69), and one quarter of the samples exhibited concentrations above the relevant Swiss guide value for compost (4000 microg kg(-1)dw). The levels were influenced by the treatment process (digestate > compost), the season of input material collection (spring-summer > winter > autumn), the particle size (coarse-grained > fine-grained), and maturity (mature > less mature). The main source of PAH in compost was pyrogenic, probably influenced mainly by liquid fossil fuel combustion and some asphalt abrasion, as suggested by multiple linear regression. This study, together with a companion paper reporting on other organic contaminates including emerging compound classes, provides a starting point for a better risk-benefit estimation of the application of compost and digestate to agricultural soil in Switzerland.     

Chemical composition of the slippery epicuticular wax blooms on Macaranga (Euphorbiaceae) ant-plants

Summary. The stems of many Macaranga ant-plants (Euphorbiaceae) are covered by epicuticular wax crystals rendering the surface very slippery for most insects. These wax blooms act as selective barriers protecting the symbiotic ant partners, which are specialized “wax-runners”, against the competition of other ants. Glaucous stems occur almost exclusively among the ant-plants of the genus Macaranga (). We analyzed the cuticular lipids of 16 Macaranga species by GC-MS and investigated the wax crystal morphology using SEM. Presence of crystalline wax blooms was strongly correlated with high concentrations (52%–88%) of triterpenoids. In contrast epicuticular waxes of glossy Macaranga surfaces contained only 0% to 36% of these dominant components. Therefore we conclude that triterpenoids are responsible for the formation of the thread-like Macaranga wax crystals. In all Macaranga ant-plants investigated, the principal components were epitaraxerol and taraxerone accompanied by smaller portions of taraxerol, β-amyrin and friedelin. Only in the case of the non-myrmecophytic M. tanarius did β-amyrin predominate. Moreover, we found that only in M. tanarius, the dense wax crystal lacework is torn into large mosaic-like pieces in the course of secondary stem diameter growth. Both chemical and macroscopic differences may contribute to a reduced slipperiness of M. tanarius stems and appear to be functionally important. The distribution of wax crystals and their composition amongst different sections of the genus suggests that glaucousness is a polyphyletic character within Macaranga. Received 7 October 1999; accepted 3 December 1999     

Das Biologische System der Elemente (BSE): Eine modelltheoretische Betrachtung zur Essentialität von chemischen Elementen

The correlation of data on the elements obtained by instrumental chemical analysis of highly representative plant samples led to the establishment of a first Biological System of Elements (BSE) in 1994. Including other physiological parameters like availability of chemical elements, transport, storage, etc. it is clear, that aside from the bioinorganic aspects of coordination chemistries of given elements, features of essentiality or toxicity depend on their interference with enzymatic processes. Notably, the latter are not to be considered as purely catalytic transformations, but are instead related to the reproduction of organisms in a direct or indirect manner — as autocatalytic: a process whereby a protein containing some metal or burdened in function by its presence is indirectly involved in its own reproduction. Stoichiometric Network Analysis (SNA) explicitly deals with the general dynamics of such autocatalytic systems. Given there is a relationship between the kinds of metal or metalloid species and the key biological/biochemical transformations to be promoted using them — a relationship which is the topic of bioinorgnaic chemistry-, and that biochemistry is in effect about systems which can reproduce and thus behave autocatalytically, one can expect SNA to yield statements on the basic features of biology and biochemistry as well.     

On the potential use of magnesium and strontium concentrations as ecological indicators in the calcite skeleton of the red coral (Corallium rubrum)

 The variability of magnesium, strontium and calcium concentrations in the two skeleton types (sclerites and axis) of the red coral (Corallium rubrum) was assessed by using X-ray fluorescence spectroscopy and microprobe analysis as a prerequisite for their use as ecological indicators. Axis cross sections showed light and dark circular growth bands corresponding to fast and slow growth, respectively. Using microprobe analyses the Mg and Sr concentrations ranged from 2.8 to 3.0% and from 0.21 to 0.29%, respectively, in the sclerites and from 2.4 to 3.0% and from 0.1 to 0.28%, respectively, in the axis. Mg/Ca and Sr/Ca ratios varied within sclerites (average, 12% for both ratios) and within the axis of single colonies (average, 20% for Mg/Ca and 48% for Sr/Ca). Sr/Ca ratios in the axis were lower in fast-growing branch tips than in older, more basal parts of the colonies, whereas the Mg/Ca ratio did not differ significantly between colony regions. Mg/Ca and Sr/Ca ratios in the axis decreased significantly with depth, and we estimated an increase of the Mg/Ca ratio of 0.004–0.006 per degree Celsius. In all depth layers, Sr/Ca ratios showed a significant direct relationship with skeleton density in axis cross sections, whereas there was no significant relationship for Mg/Ca. Overall, our data indicate that temperature promotes the incorporation of Mg in C. rubrum as in other calcite skeletons, whereas Sr concentrations are inversely related to growth rate. This preliminary study suggests that Mg and Sr concentrations in the axis of the red coral have a strong potential as ecological indicator for temperature and growth rate. Received: 3 March 2000 / Accepted: 30 August 2000