Trichloroacetic acid in Norway spruce/soil-system. I. Biodegradation in soil.

Trichloroacetic acid (TCA) as a phytotoxic substance affects health status of coniferous trees. It is known as a secondary air pollutant (formed by photooxidation of tetrachloroethene and 1,1,1-trichloroethane) and as a product of chlorination of humic substances in soil. Its break-down in soil, however, influences considerably the TCA level, i.e. the extent of TCA uptake by spruce roots. In connection with our investigations of TCA effects on Norway spruce, microbial processes in soil were studied using 14C-labeling. It was shown that TCA degradation in soil is a fast process depending on TCA concentration, soil properties, humidity and temperature. As a result, the TCA level in soil is determined by a steady state between uptake from the atmosphere, formation in soil, leaching and degradation. The process of TCA degradation in soil thus participates significantly in the chlorine cycle in forest ecosystems.

Uptake, translocation and fate of trichloroacetic acid in a Norway spruce/soil system.

Trichloroacetic acid (TCA) is a secondary atmospheric pollutant formed by photooxidation of chlorinated solvents in the troposphere--it has, however, recently been ranked among natural organohalogens. Its herbicidal properties might be one of the factors adversely affecting forest health. TCA accumulates rapidly in conifer needles and influences the detoxification capacity in the trees. The aim of the investigations--a survey of which is briefly given here--was to elucidate the uptake, distribution and fate of TCA in Norway spruce. For this purpose young nursery-grown plants of Norway spruce (Picea abies (L.) Karst.) were exposed to [1,2-14C]TCA and the fate of the compound was followed in needles, wood, roots, soil and air with appropriate radio-indicator methods. As shown by radioactivity monitoring, the uptake of TCA from soil by roots proceeded most rapidly into current needles at the beginning of the TCA treatment and was redistributed at later dates so that TCA content in older needles increased. The only product of TCA metabolism/biodegradation found in the plant/soil-system was CO(2) (and corresponding assimilates). TCA biodegradation in soil depends on TCA concentration, soil humidity and other factors.

Trichloroacetic acid in Norway spruce/soil-system. II. Distribution and degradation in the plant.

Independently from its origin, trichloroacetic acid (TCA) as a phytotoxic substance affects coniferous trees. Its uptake, distribution and degradation were thus investigated in the Norway spruce/soil-system using 14C labeling. TCA is distributed in the tree mainly by the transpiration stream. As in soil, TCA seems to be degraded microbially, presumably by phyllosphere microorganisms in spruce needles. Indication of TCA biodegradation in trees is shown using both antibiotics and axenic plants.

Microbiological aspects of determination of trichloroacetic acid in soil.

Soils have been shown to possess a strong microbial trichloroacetic acid (TCA)-degrading activity. High TCA-degradation rate was also observed during soil extraction with water. For correct measurements of TCA levels in soil all TCA-degrading activities have to be inhibited immediately after sampling before analysis. We used rapid freezing of soil samples (optimally in liquid nitrogen) with subsequent storage and slow thawing before analysis as an efficient technique for suppressing the degradation. Frozen soil samples stored overnight at -20 degrees C and then thawed slowly exhibited very low residual TCA-degrading activity for several hours. Omitting the above procedure could lead to the confusing differences between the TCA levels previously reported in the literature.

Microbial chlorination of organic matter in forest soil: investigation using 36Cl-chloride and its methodology.

Chloride, which comes into the forest ecosystem largely from the sea as aerosol (and has been in the past assumed to be inert), causes chlorination of soil organic matter. Studies of the chlorination showed that the content of organically bound chlorine in temperate forest soils is higher than that of chloride, and various chlorinated compounds are produced. Our study of chlorination of organic matter in the fermentation horizon of forest soil using radioisotope 36Cl and tracer techniques shows that microbial chlorination clearly prevails over abiotic, chlorination of soil organic matter being enzymatically mediated and proportional to chloride content and time. Long-term (>100 days) chlorination leads to more stable chlorinated substances contained in the organic layer of forest soil (overtime; chlorine is bound progressively more firmly in humic acids) and volatile organochlorines are formed. Penetration of chloride into microorganisms can be documented by the freezing/thawing technique. Chloride absorption in microorganisms in soil and in litter residues in the fermentation horizon complicates the analysis of 36Cl-chlorinated soil. The results show that the analytical procedure used should be tested for every soil type under study.