The formation and fate of chlorinated organic substances in temperate and boreal forest soils

Background, aim and scope  Chlorine is an abundant element, commonly occurring in nature either as chloride ions or as chlorinated organic compounds (OCls). Chlorinated organic substances were long considered purely anthropogenic products; however, they are, in addition, a commonly occurring and important part of natural ecosystems. Formation of OCls may affect the degradation of soil organic matter (SOM) and thus the carbon cycle with implications for the ability of forest soils to sequester carbon, whilst the occurrence of potentially toxic OCls in groundwater aquifers is of concern with regard to water quality. It is thus important to understand the biogeochemical cycle of chlorine, both inorganic and organic, to get information about the relevant processes in the forest ecosystem and the effects on these from human activities, including forestry practices. A survey is given of processes in the soil of temperate and boreal forests, predominantly in Europe, including the participation of chlorine, and gaps in knowledge and the need for further work are discussed. Results  Chlorine is present as chloride ion and/or OCls in all compartments of temperate and boreal forest ecosystems. It contributes to the degradation of SOM, thus also affecting carbon sequestration in the forest soil. The most important source of chloride to coastal forest ecosystems is sea salt deposition, and volcanoes and coal burning can also be important sources. Locally, de-icing salt can be an important chloride input near major roads. In addition, anthropogenic sources of OCls are manifold. However, results also indicate the formation of chlorinated organics by microorganisms as an important source, together with natural abiotic formation. In fact, the soil pool of OCls seems to be a result of the balance between chlorination and degradation processes. Ecologically, organochlorines may function as antibiotics, signal substances and energy equivalents, in descending order of significance. Forest management practices can affect the chlorine cycle, although little is at present known about how. Discussion  The present data on the apparently considerable size of the pool of OCls indicate its importance for the functioning of the forest soil system and its stability, but factors controlling their formation, degradation and transport are not clearly understood. It would be useful to estimate the significance and rates of key processes to be able to judge the importance of OCls in SOM and litter degradation. Effects of forest management processes affecting SOM and chloride deposition are likely to affect OCls as well. Further standardisation and harmonisation of sampling and analytical procedures is necessary. Conclusions and perspectives  More work is necessary in order to understand and, if necessary, develop strategies for mitigating the environmental impact of OCls in temperate and boreal forest soils. This includes both intensified research, especially to understand the key processes of formation and degradation of chlorinated compounds, and monitoring of the substances in question in forest ecosystems. It is also important to understand the effect of various forest management techniques on OCls, as management can be used to produce desired effects.     

Butanol extraction to predict bioavailability of PAHs in soil

The feasibility of a mild-solvent extraction procedure to predict the bioavailability of individual polycyclic aromatic hydrocarbons (PAHs) in soil was assessed. The quantities that were degraded during the course of biodegradation of phenanthrene and pyrene in soil with or without plants correlated with the amounts extracted by n-butanol, with R2 values of 0.971 and 0.994, respectively. Six consecutive groups of earthworms removed ca. 70% of the pyrene remaining after extensive biodegradation, a value similar to the quantity extracted by n-butanol. The amount of chrysene aged in sterilized soil that was extracted by n-butanol was not statistically different from the quantities assimilated by earth-worms (Eisenia fetida) introduced into the soil. Such a mild extraction procedure may be useful as a means of predicting PAH bioavailability.     

Chemical assays of availability to earthworms of polycyclic aromatic hydrocarbons in soil

The bioavailable concentration of an organic pollutant is less than the concentration determined by vigorous extraction of soil. Because bioavailability varies with the particular compound, soil, and aging time, an assay for bioavailability is needed. Three methods were tested: extraction with a 25% aqueous solution of tetrahydrofuran (THF), 95% ethanol, and C18 membranes. Evaluations were conducted with a mixture of four polycyclic aromatic hydrocarbons (PAHs) added to five dissimilar soils and with pyrene as sole PAH added to six soils, and the availability of aged and freshly added compounds was determined. Assimilation by earthworms (Eisenia fetida) was used to assess bioavailability. For extraction with THF and earthworm uptake, the correlation coefficients of determination (R2) for anthracene, chrysene, pyrene, and benzo(a)pyrene added as a mixture exceeded 0.85. The R2 values for assays with the C18 membrane were 0.77 or higher. The values for pyrene added alone were 0.710 and 0.823, respectively. R2 values for assays with ethanol often exceeded 0.87, but lower values were sometimes obtained. We suggest that such solvent or solid-phase extractions may be useful in assessing PAH bioavailability.     

Energy Resources and Conversion Technologies for the 21st Century

A variety of energy sources will compete to provide the energy services that humans will require over the next 100 years. The balance of these sources will depend upon the availability of fossil fuels and the development of new technologies including renewable energy technologies, and will be one of the keys in projecting greenhouse gas emissions. There is uncertainty about each of the energy sources. With oil, for example, there are two alternate views of future reserves, one that reserves are geologically limited and that supplies will decline within a decade or two, the other that there are enormous quantities of hydrocarbon in the earth’s crust and that reserves are a function of developing technology and price. With solar voltaics, as a second example, there is optimism that the technology will become increasingly competitive, but there is uncertainty about the rate at which costs can come down and about ultimate cost levels. This paper reviews the reserves of fossil fuels and the prospects for nuclear power and the renewables. It also reviews the main energy conversion technologies that are available now or are expected to become increasingly available through time. However, it should be noted that, over a time horizon of 100 years, there may be quite radical changes in both production and conversion technologies that cannot be predicted and it is quite possible for some as yet unheard of technology to be developed and to transform the markets. The paper has been written to aid the development of new scenarios for the emission of greenhouse gases for the Intergovernmental Panel on Climate Change.     

Plant performance, dioxygenase-expressing rhizosphere bacteria, and biodegradation of weathered hydrocarbons in contaminated soil

Two greenhouse pot experiments were conducted to investigate the potential of 13 plant species (grasses, cruciferes, legumes, herbs) to thrive in a long-term contaminated soil from a former manufactured gas plant (MGP) site, to promote the proliferation of total and aromatic ring dioxygenase-expressing bacteria (ARDB) in the root zone, and to foster the biodegradation of petrol hydrocarbons (PHCs) and polycyclic aromatic hydrocarbons (PAHs). PHCs at 23200 mg kg(-1) and PAHs at 2194 mg kg(-1) reduced seed germination, plant survival, and shoot yields for most plants. Total bacteria and ARDB were generally more abundant in contaminated soil and were most numerous in the rhizosphere of mustard. During 68 d, the loss of total petrol hydrocarbons (TPHs) and total US EPA priority PAHs (TPAHs) was greatest in soil planted with hemp and mustard. Pea, cress, and pansy increased the amounts of PAHs extracted from soil, including an almost 60% increase for dibenzo(ah)anthracene. Plants may enhance the chemical extractability and perhaps biological availability of initially unextractable molecules.