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.     

Perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish blood collected near the outfall of wastewater treatment plant (WWTP) in Beijing

Perfluorinated compounds (PFCs) were measured in zooplankton and five fish species collected from Gaobeidian Lake, which receives discharge from wastewater treatment plant (WWTP) in Beijing, China. The mean total PFCs in five fish were in the order: crucian carp > common carp > leather catfish > white semiknife carp > tilapia. Perfluorooctane sulfonate (PFOS) occurred at the greatest concentrations, with mean concentrations ranging from 5.74 to 64.2 ng/ml serum. Perfluorodecanoic acid (PFDA) was the second dominant PFC in fish samples except for common carp in which perfluorooctane sulfonamide (PFOSA) was dominant. A positive linear relationship (r² = 0.85, p < 0.05) was observed between ln PFOS concentrations (ln ng/ml) and trophic level (based on δ¹⁵N) if tilapia was excluded. The risk assessment showed that PFOS might not pose an immediate risk to fish in Gaobeidian Lake.     

The influence of gill and liver metabolism on the predicted bioconcentration of three pharmaceuticals in fish

The potential for xenobiotic compounds to bioconcentrate is typically expressed through the bioconcentration factor (BCF), which has gained increased regulatory significance over the past decade. Due to the expense of in vivo bioconcentration studies and the growing regulatory need to assess bioconcentration potential, BCF is often calculated via single-compartment models, using K(OW) as the primary input. Recent efforts to refine BCF models have focused on physiological factors, including the ability of the organism to eliminate the compound through metabolic transformation. This study looks at the ability of in vitro biotransformation assays using S9 fractions to provide an indication of metabolic potential. Given the importance of the fish gill and liver in metabolic transformation, the metabolic loss of ibuprofen, norethindrone and propranolol was measured using rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) gill and liver S9 fractions. Metabolic transformation rates (k(M)) were calculated and integrated into a refined BCF model. A significant difference was noted between BCF solely based on K(OW) and BCF including k(M). These studies indicate that the inclusion of k(M) in BCF models can bring predicted bioconcentration estimates closer to in vivo values.     

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.     

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.     

Determination of selected fate and aquatic toxicity characteristics of acrylic acid and a series of acrylic esters

Acrylic acid, methyl acrylate, ethyl acrylate, and butyl acrylate are commercially important and widely used materials. This paper reports the results of a series of fate and aquatic toxicity studies. The mobility in soil of acrylic acid and its esters ranged from 'medium' to 'very high'. Calculated bioconcentration factors ranged from 1 to 37, suggesting a low bioconcentration potential. Acrylic acid and methyl acrylate showed limited biodegradability in the five day biochemical oxygen demand (BOD5) test, while ethyl acrylate and butyl acrylate were degraded easily (77% and 56%, respectively). Using the OECD method 301D 28-d closed bottle test, degradability for acrylic acid was 81% at 28 days, while the acrylic esters ranged from 57% to 60%. Acrylic acid degraded rapidly to carbon dioxide in soil (t1/2 < 1 day). Toxicity tests were conducted using freshwater and marine fish, invertebrates, and algae. Acrylic acid effect concentrations for fish and invertebrates ranged from 27 to 236 mg/l. Effect concentrations (LC50 or EC50) for fish and invertebrates using methyl acrylate, ethyl acrylate, and butyl acrylate ranged from 1.1 to 8.2 mg/l. The chronic MATC for acrylic acid with Daphnia magna was 27 mg/l based on length and young produced per adult reproduction day and for ethyl acrylate was 0.29 mg/l based on both the reproductive and growth endpoints. Overall these studies show that acrylic acid and the acrylic esters studied can rapidly biodegrade, have a low potential for persistence or bioaccumulation in the environment, and have low to moderate toxicity.     

The solid-phase controls on the mobility of heavy metals at the Copper Cliff tailings area, Sudbury, Ontario, Canada

The Copper Cliff Tailings Disposal Area, located near Sudbury, Ontario, covers an area of approximately 2200 ha and constitutes more than 10% of the total area of all mine tailings in Canada. The area has been utilized since 1936, receiving sulphide-containing tailings from the Inco Sudbury operations. Field measurements of pore-gas oxygen and carbon dioxide in the vadose zone indicate that sulphide oxidation has progressed to depths of 1.6 m to 1.7 m within the tailings. The oxidation of sulphide minerals within the vadose zone, and the accompanying dissolution of carbonate and aluminosilicate minerals within these tailings releases SO₄, Fe(II) and other metals to the pore water. In the vadose and saturated zones, concentrations of Fe and Ni exceed 10100 mg/l and 2210 mg/l, respectively. These high concentrations of dissolved metals are attenuated by a series of precipitation, coprecipitation and adsorption reactions. The precipitation of secondary sulphate and hydroxide phases also create hardpan layers at or near the oxidation front. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary-phase precipitation is occurring at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of jarosite, gypsum and goethite within the shallow tailings, suggesting that these phases are controlling the dissolved concentrations of Fe, SO₄ and Ca. Extraction experiments conducted on the tailings solids indicate that the constituents contained in the water-soluble fraction of the shallow, weathered tailings are derived from the original pore water and the dissolution of highly soluble phases such as gypsum. The acid-leachable fraction of the weathered tailings accounts for up to 25% of the heavy metals, and the reducible fraction may contain up to 100% of the heavy metals within the shallow, weathered tailings. Based on the pore water profiles and the geochemistry of the tailings solids, a relative mobility scale of Fe=Mn=Ni=Co>Cd Zn>Cr=Pb>Cu can be determined.