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.     

The effect of EDTA and citric acid on phytoremediation of Cd, Cr, and Ni from soil using Helianthus annuus

The possibility to clean heavy metal contaminated soils with hyperaccumulator plants has shown great potential. One of the most recently studied species used in phytoremediation applications are sunflowers. In this study, two cultivars of Helianthus annuus were used in conjunction with ethylene diamine tetracetic acid (EDTA) and citric acid (CA) as chelators. Two different concentrations of the chelators were studied for enhancing the uptake and translocation of Cd, Cr, and Ni from a silty-clay loam soil. When 1.0 g/kg CA was used, the highest total metal uptake was only 0.65 mg. Increasing the CA concentration posed a severe phytotoxicity to both cultivars as evidenced by stunted growth and diminished uptake rates. Decreasing the CA concentration to 0.1 and 0.3 g/kg yielded results that were not statistically different from the control. EDTA at a concentration of 0.1 g/kg yielded the best results for both cultivars achieving a total metal uptake of approximately 0.73 mg compared to approximately 0.40 mg when EDTA was present at 0.3 g/kg.     

Isomer-specific analysis of chlorinated biphenyls,naphthalenes and dibenzofurans in Delor: polychlorinated biphenyl preparations from the former Czechoslovakia

Technical polychlorinated byphenyl (PCB) preparations--Delors 103, 104, 105, and 106--produced in the former Czechoslovakia were analyzed for their chlorobiphenyl (CB), chloronaphthalene (PCN) and chlorinated dibenzofuran (PCDF) composition and content using high resolution gas chromatography-mass spectrometry techniques. The congener patterns of Delors 103, 104, 105, and 106 resembled Aroclors 1242, 1248, 1254, and 1260. Delors contained PCNs and PCDFs, as impurities, at microgram per gram concentrations. Concentrations of PCNs and PCDFs in Delors were greater than those found in the corresponding Aroclors. The potential for the emissions of PCNs and PCDFs from Delor was estimated to be 3680 and 860 kg, respectively. Non- and mono-ortho PCBs were the major contributors to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents in Delor mixtures.     

Effects of bis(tributyltin)oxide on antipredator behavior in threespine stickleback Gasterosteus aculeatus L.

Antipredator behavior was used as a parameter to detect effects caused by exposure to the organotin compound bis(tributyltin)oxide (TBTO). Three groups of threespine sticklebacks (Gasterosteus aculeatus L.) were exposed to 3, 9 and 27 ppb TBTO, respectively. A fourth control group was given the same treatment as the other three groups, but no TBTO. Antipredator behavior of the fish was evoked using a dummy heron (Ardea cinerea) bill. TBTO exposure caused significant changes in the spatial position of the fish in the aquarium (P(Loc)), their response to predator attack (P(Res)), recovery time (P(Rec)) and latency time (P(Lat)). Some of the effects were, however, reversible after the exposure was terminated. We suggest that behavior as an indicator of pollution may be used as an ecologically relevant integrative biomarker.     

Effect of applying chemical fertilizers on forms of lead and cadmium in red soil

A three-month incubation study was undertaken to examine the influence of N, P and K on the various forms (soluble plus exchangeable (SE), weakly specifically adsorbed (WSA), Fe-Mn oxides bound (OX), organic matter complexed (OM) and residual fractions (RES)) of lead (Pb) and cadmium (Cd) in a red soil. Application of urea at the rate of 200 mg N/kg significantly lowered the SE fraction, but raised the WSA or OX fraction of both metals. Supply of 80 mg P/kg caused a decrease in the SE fraction of the two metals. The WSA fraction of Pb was reduced, whereas that of Cd increased by adding P. However, addition of 100 mg K/kg led to an increase in the SE fraction, but a decrease in the WSA fraction of Pb and Cd. Applying chemical fertilizers had no significant consistent influences on the other fractions of metals. These findings suggest that in heavy metal contaminated red soil, applying fertilizers does not only provide plant nutrients, but may also change the speciations and thus biovailability of heavy metals.     

The sensitivity of surface waters of Great Britain to acidification predicted from catchment characteristics

Using a combination of soil, land use and geological information, a map of Great Britain has been derived which indicates the sensitivity of surface waters to acidification. For the geological information, a slightly modified version of an available map was used which indicated the sensitivity of groundwaters to acidification. For soils, 1-km databases of soil information for England and Wales and for Scotland were employed to map the soil sensitivity as determined by buffering capacity. The derived soils map was modified to take account of agricultural liming in arable and managed grassland areas using the ITE Land Classification. The final map of surface water sensitivity was obtained by using a geographic information system overlay procedure which enabled each combination of soil and geology sensitivity to be uniquely defined. The final sensitivity classification was based upon expert knowledge and the experience of a similar sensitivity mapping exercise for Wales.     

Persistent organochlorine compounds in soils and sediments of European high altitude mountain lakes

The composition of persistent organochlorine compounds (OC) in soils and sediments from two high altitude European mountain lakes, Redon in the Pyrenees and Ladove in the Tatra mountains, has been studied. Sediment cores from two additional lakes in the Tatra mountains, Starolesnianske Pleso and Dlugi Staw, have also been examined. DDTs (1.7-13 ng g(-1)) were the most abundant OC in soils followed by total polychlorobiphenyls (PCBs; 0.41-1.5 ng g(-1)) and hexachlorobenzene (HCB; 0.15-0.91 ng g(-1)). In sediments, the dominant OC were also DDTs (3.3-28 ng g(-1)) and PCBs (2.3-15 ng g(-1)). These concentrations are low, involving absence of major pollution sources in these high mountain regions. The downcore OC profiles in soils and sediments were similar but higher concentrations and steeper vertical gradients were observed in the latter. Radiometric determinations showed absence of significant OC transport from catchment to lake. The sediment-soil difference points therefore to a better retention of the OC load in sediments than soils which may be related to the low temperatures that are currently encountered at the bottom of the lake water column and the depletion of sediment bioturbation in these cold environments. Significant qualitative changes in the soil PCB distributions are observed downcore. These involve a dominance of the high molecular weight congeners in the top core sections and those of lower weight (i.e. less chlorinated) in the bottom. Anaerobic dechlorination of higher molecular weight congeners occurring in microsites, e.g. as observed in flooded or poorly drained soils, could be responsible for these changes. This process could be concurrent to bioturbation.     

Remediation of contaminated agricultural soils near a former Pb/Zn smelter in Austria: batch, pot and field experiments

Metal contaminated crops from contaminated soils are possible hazards for the food chain. The aim of this study was to find practical and cost-effective measures to reduce metal uptake in crops grown on metal contaminated soils near a former metal smelter in Austria. Metal-inefficient cultivars of crop plants commonly grown in the area were investigated in combination with in-situ soil amendments. A laboratory batch experiment using 15 potential amendments was used to select 5 amendments to treat contaminated soil in a pot study using two Barley (Hordeum vulgare L.) cultivars that differed in their ability to accumulate cadmium. Results from this experiment identified 3 of these amendments for use in a field trial. In the pot experiment a reduction in ammonium nitrate extractable Cd (<41%) and Pb (<49%) compared to the controls was measured, with a concurrent reduction of uptake into barley grain (Cd<62%, Pb<68%). In the field extractable fractions of Cd, Pb, and Zn were reduced by up to 96%, 99%, and 99%, respectively in amended soils.     

An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands

An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17 alpha-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects.     

Combustion aerosols: factors governing their size and composition and implications to human health

Particulate matter (PM) emissions from stationary combustion sources burning coal, fuel oil, biomass, and waste, and PM from internal combustion (IC) engines burning gasoline and diesel, are a significant source of primary particles smaller than 2.5 microns (PM2.5) in urban areas. Combustion-generated particles are generally smaller than geologically produced dust and have unique chemical composition and morphology. The fundamental processes affecting formation of combustion PM and the emission characteristics of important applications are reviewed. Particles containing transition metals, ultrafine particles, and soot are emphasized because these types of particles have been studied extensively, and their emissions are controlled by the fuel composition and the oxidant-temperature-mixing history from the flame to the stack. There is a need for better integration of the combustion, air pollution control, atmospheric chemistry, and inhalation health research communities. Epidemiology has demonstrated that susceptible individuals are being harmed by ambient PM. Particle surface area, number of ultrafine particles, bioavailable transition metals, polycyclic aromatic hydrocarbons (PAH), and other particle-bound organic compounds are suspected to be more important than particle mass in determining the effects of air pollution. Time- and size-resolved PM measurements are needed for testing mechanistic toxicological hypotheses, for characterizing the relationship between combustion operating conditions and transient emissions, and for source apportionment studies to develop air quality plans. Citations are provided to more specialized reviews, and the concluding comments make suggestions for further research.