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1.
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.  相似文献   

2.
Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of 14C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-14C]TCA combined with extraction of the resultant 14C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g−1) of carrier-less [1,2-14C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [36Cl]TCA determination in chlorination studies with 36Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO2 in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl3 extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO2.  相似文献   

3.
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.  相似文献   

4.
[Carbonyl-14C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0-2.5 cm soil layer was removed from the lysimeter. This soil contained about 40% of the applied radioactivity. Using 0,01 M CaCl2 solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non-extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3.6; 2.2; and 0.9% of the radioactivity from soils containing aged MBT residues, MBT residues non-extractable with 0.01 M CaCl2 or MBT residues non-extractable with organic solvents, respectively. About 20% of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0.01 M CaCl2 and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.  相似文献   

5.
BACKGROUND, AIM AND SCOPE: Problems of long-term existence of the environmental contaminant 2,4,6-trinitrotoluene (TNT) and necessities for the use of trees ('dendroremediation') in sustainable phytoremediation strategies for TNT are described in the first part of this paper. Aims of the second part are estimation of [14C]-TNT uptake, localisation of TNT-derived radioactivity in mature tree tissues, and the determination of the degree of TNT-degradation during dendroremediation processes. METHODS: Four-year-old trees of hybrid willow (Salix spec., clone EW-20) and of Norway spruce (Picea abies) were cultivated in sand or ammunition plant soil (AP-soil) in wick supplied growth vessels. Trees were exposed to a single pulse application with water solved [U-14C]-TNT reaching a calculated initial concentration of 5.2 mg TNT per kg dry soil. Two months after application overall radioactivity and extractability of 14C were determined in sand/soil, roots, stem-wood, stem-bark, branches, leaves, needles, and Picea May sprouts. Root extracts were analysed by radio TLC. RESULTS: 60 days after [14C]-TNT application, recovered 14C is accumulated in roots (70% for sand variants, 34% for AP-soil variant). 15-28% of 14C remained in sand and 61% in AP-soil. 3.3 to 14.4% of 14C were located in aboveground tree portions. Above-ground distribution of 14C differed considerably between the angiosperm Salix and the gymnosperm Picea. In Salix, nearly half of above-ground-14C was detected in bark-free wood, whereas in Picea older needles contained most of the above-ground-14C (54-69%). TNT was readily transformed in tree tissue. Approximately 80% of 14C was non-extractably bound in roots, stems, wood, and leaves or needles. Only quantitatively less important stem-bark of Salix and Picea and May shoots of Picea showed higher extraction yields (up to 56%). DISCUSSION: Pulse application of [14C]-TNT provided evidence for the first time that after TNT-exposure, in tree root extracts, no TNT and none of the known metabolites, mono-amino-dinitrotoluenes (ADNT), diaminonitrotoluenes (DANT), trinitrobenzene (TNB) and no dinitrotoluenes (DNTs) were present. Extractable portions of 14C were small and contained at least three unknown metabolites (or groups) for Salix. In Picea, four extractable metabolites (or groups) were detected, where only one metabolite (or group) seemed to be identical for Salix and Picea. All unknown extractables were of a very polar nature. CONCLUSIONS: Results of complete TNT-transformation in trees explain some of our previous findings with 'cold analytics', where no TNT and no ADNT-metabolites could be found in tissues of TNT-exposed Salix and Populus clones. It is concluded that 'cold' tissue analysis of tree organs is not suited for quantitative success control of phytoremediation in situ. RECOMMENDATIONS AND OUTLOOK: Both short rotation Salicaceae trees and conifer forests possess a dendroremediation potential for TNT polluted soils. The degradation capacity and the large biomass of adult forest trees with their woody compartments of roots and stems may be utilized for detoxification of soil xenobiotics.  相似文献   

6.
Trichloroacetic acid (TCA, CCl(3)COOH) has been associated with forest damage but the source of TCA to trees is poorly characterised. To investigate the routes and effects of TCA uptake in conifers, 120 Sitka spruce (Picea sitchensis (Bong.) Carr) saplings were exposed to control, 10 or 100 microg l(-1) solutions of TCA applied twice weekly to foliage only or soil only over two consecutive 5-month growing seasons. At the end of each growing season similar elevated TCA concentrations (approximate range 200-300 ng g(-1) dwt) were detected in both foliage and soil-dosed saplings exposed to 100 microg l(-1) TCA solutions showing that TCA uptake can occur from both exposure routes. Higher TCA concentrations in branchwood of foliage-dosed saplings suggest that atmospheric TCA in solution is taken up indirectly into conifer needles via branch and stemwood. TCA concentrations in needles declined slowly by only 25-30% over 6 months of winter without dosing. No effect of TCA exposure on sapling growth was measured during the experiment. However at the end of the first growing season needles of saplings exposed to 10 or 100 microg l(-1) foliage-applied TCA showed significantly more visible damage, higher activities of some detoxifying enzymes, lower protein contents and poorer water control than needles of saplings dosed with the same TCA concentrations to the soil. At the end of each growing season the combined TCA storage in needles, stemwood, branchwood and soil of each sapling was <6% of TCA applied. Even with an estimated half-life of tens of days for within-sapling elimination of TCA during the growing season, this indicates that TCA is eliminated rapidly before uptake or accumulates in another compartment. Although TCA stored in sapling needles accounted for only a small proportion of TCA stored in the sapling/soil system it appears to significantly affect some measures of sapling health.  相似文献   

7.
Impacts of UV-B radiation on the glutathione level were studied in mature Scots pine needles (Pinus sylvestris L.) during the third season of a UV-B field experiment. Studies were made on 4-week-old (July) to 14-week-old (September) current-year needles and 3-year-old needles which had their third UV-B-exposure season in progress. Depending on the season and the year (1996-98), the supplemental UV-B dose varied from 0.92 to 5.09 kJ m-2 day-1 UV-BBE compared to 0.47-2.44 kJ m-2 day-1 UV-BBE under the ambient treatment. Fully grown UV-B-treated current-year needles showed lower total glutathione concentrations after the vegetation period in September, whereas in UV-B-treated 3-year-old needles the total glutathione content was significantly lower and the proportion of oxidized glutathione (GSSG%) 56% higher in July. The significant differences in total glutathione in current-year needles in September and in active 3-year-old needles in July seem to indicate that the effect of enhanced UV-B radiation on glutathione status could be cumulative.  相似文献   

8.
Abstract

The relative biological availability of [benzene ring‐U‐14C] and Ctriazine‐U‐14C] anilazine for maize plants was studied in a degraded loess soil in a standardized microecosystem. The total uptake of radiocarbon in the course of the 4‐week experiment was 3.1 and 4 % respectively of the radioactivity applied if anilazine was uniformly mixed into the soil immediately before beginning the experiment. However, if anilazine was subjected to a degradation at 65 % of the maximum water holding capacity of the soil and temperatures varying daily between 16 and 27°C for 100 days before the plant experiment then the uptake was reduced to 0.4 or 0.7 % respectively. The uptake from soil with non‐extractable (bound) anilazine residues was similarly low. The mineralization rate of aged and bound anilazine residues was below 0.1 % of the radioactivity applied. Up to 2/3 of the radioactivity present in the soil after the plant experiment remained in the humic fraction.  相似文献   

9.
Abstract

[Carbonyl‐ C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0–2,5 cm soil layer was removed from the lysimeter. This soil contained about 40 % of the applied radioactivity. Using 0,01 M CaCl2 solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non‐extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3,6; 2,2; and 0,9 % of the radioactivity from soils containing aged MBT residues, MBT residues non‐extractable‐with 0,01 MCaCl2 or MBT residues non‐extractable with organic solvents, respectively. About 20 % of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0,01 M CaCl2 and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.  相似文献   

10.
This paper reports the results of total sulphur content, photosynthetic pigments, ascorbic acid (vitamin C) and alpha-tocopherol (vitamin E) analysed in current-year needles of Norway spruce (Picea abies (L.) Karst.) in the area influenced by sulphur emissions from the Sostanj Thermal Power Plant (STPP), Slovenia, in the period 1991-2004. Ten differently polluted sampling sites in the emission area of STPP were selected. After desulphurization of emission gases from STPP total sulphur content in needles decreased and vitality parameters of needles increased. Moreover, a strong correlation between the average annual emissions of SO(2) from STPP and average annual sulphur content (increase) or average annual chlorophyll content (decrease) in current-year needles was found. The results showed that spruce needles may be an useful bioindicator for detecting changes in the emission rates of SO(2).  相似文献   

11.
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.  相似文献   

12.
Trichloroacetic acid (TCA) can be found in various environmental compartments like air, rain and plants all over the world. It is assumed that TCA is an atmospheric degradation product of volatile chloroorganic hydrocarbons. The herbicide effect of TCA in higher concentrations is well known, but not much is known about the phytotoxic effects in environmentally relevant concentrations. It can be shown in this study by using the 13C/15N stable isotope tracer technique that [13C]TCA is taken up by roots of two-year-old seedlings of Pinus sylvestris L. and transported into the needles. At the same time the effect of the substance on nitrogen metabolism can be analyzed by measuring the incorporation of 15NO3- into different nitrogen fractions of the plant. The more [13C]TCA incorporation, the higher the synthesis of 15N labelled amino acids and proteins is. These effects on the nitrogen metabolism are probably based on the activation of stress- and detoxification metabolism. It has to be assumed that there is an influence on N metabolism of Pinus sylvestris caused by the deposition of environmentally relevant TCA concentrations.  相似文献   

13.
Sheep dip formulations containing organophosphates (OPs) or synthetic pyrethroids (SPs) have been widely used in UK, and their spreading onto land has been identified as the most practical disposal method. In this study, the impact of two sheep dip formulations on the microbial activity of a soil was investigated over a 35-d incubation. Microbial utilisation of [1-(14)C] glucose, uptake of (14)C-activity into the microbial biomass and microbial numbers (CFUs g(-1) soil) were investigated. In control soils and soils amended with 0.01% sheep dip, after 7d a larger proportion of added glucose was allocated to microbial biomass rather than respired to CO(2). No clear temporal trends were found in soils amended with 0.1% and 1% sheep dips. Both sheep dip formulations at 0.1% and 1% concentrations resulted in a significant increase in CFUs g(-1) soil and [1-(14)C] glucose mineralisation rates, as well as a decline in microbial uptake of [1-(14)C] glucose, compared to control and 0.01% SP- or OP-amended soils. This study suggests that the growth, activity, physiological status and/or structure of soil microbial community may be affected by sheep dips.  相似文献   

14.
Phytoremediation is of great interest to remediate soil contaminated with hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT). The ability of 4 agronomic plants (maize, soybean, wheat and rice) to take up these explosives and their fate in plants were investigated. Plants were grown for 42 days on soil contaminated with [(14)C]RDX or [(14)C]TNT. Then, each part was analyzed for its radioactivity content and the percentage of bound and soluble residues was determined following extractions. Extracts were analyzed by radio-HPLC. More than 80% of uptaken RDX was translocated to aerial tissues, up to 64.5 mgg(-1) of RDX. By contrast, TNT was little translocated to leaves since less than 25% of uptaken TNT was accumulated in aerial parts. Concentrations of TNT residues were 20 times lower than for RDX uptake. TNT was highly metabolized to bound residues (more than 50% of radioactivity) whereas RDX was mainly found in its parent form in aerial parts.  相似文献   

15.
Hoekstra EJ 《Chemosphere》2003,52(2):355-369
This paper reviews the concentrations of trichloroacetate (TCA) in the atmosphere-plant-soil system. Data originate mainly from Europe. The median TCA concentration in rainwater and canopy drip decreased until 1995. From then the median TCA concentration in rainwater remains rather constant while for canopy drip later data are not available. The same seems to hold for concentrations in air although a very limited data set is available. The median concentrations in coniferous needles and groundwater are constant for the period observed. The median TCA concentrations in soil decreased until 1992 and then remained constant.The TCA formation from chlorinated solvents in the atmosphere may explain a substantial percentage of the TCA amount in the atmosphere. The TCA concentrations in rainwater and canopy drip indicate that there will be other sources contributing to 10-50%. Waste incineration, biomass burning and natural formation in the marine boundary layer are potential candidate sources of TCA, but nothing can be said as yet on their TCA emission rates. Anthropogenic emissions of chlorine could also be a source.TCA can be formed from chlorinated solvents by biota. However, for coniferous trees the uptake of TCA from soil may be the predominant route. Biotic and abiotic reactions can cause to formation of TCA in soil, but also formation of TCA from chlorinated solvents by biota that excrete TCA, may contribute. Mass balance calculations of the bioactive soil top layer show that the production rate of TCA in certain soil types could be substantial. The mass balance calculations could not distinguish between natural and anthropogenic sources in soil.  相似文献   

16.
Phytoremediation is an emerging strategy to remediate soils contaminated with pollutants like explosives in which plants will uptake, degrade and/or accumulate pollutants. To implement this technology on a site contaminated with RDX, we chose rice, which is able to grow in lagoons, and we tested its ability to grow in soils with high levels of RDX and to decrease RDX concentrations in soil. Rice was grown for 40 days in soil contaminated with increasing [14C]RDX concentrations. Emergence and growth were not affected by RDX. Total chlorophyll content decreased with RDX concentrations of over 500 mg kg(-1). Amounts of chlorophyll were correlated with the appearance of necrosis in leaf extremities. After 40 days, rice translocated 89% of uptaken radioactivity to leaves with 90% in leaf extremities. Analyzes of leaf extracts showed that 95% of radioactivity was RDX in its parent form. Necrosis appears to be a phytotoxic symptom of RDX accumulation.  相似文献   

17.
Lee JK  Führ F  Kwon JW  Ahn KC 《Chemosphere》2002,49(2):173-181
In order to elucidate the long-term fate of the sulfonylurea herbicide cinosulfuron, the 14C-labelled chemical was applied to a clay loam soil, encased in two lysimeters, 22 days after rice (Oryza sativa L.) transplanting, and rice plants were grown for four consecutive years. Throughout the experimental period, leaching through soil profiles, absorption and translocation by rice plants, and distribution of 14C by downward movement in the soil layers were clarified. The total volume of leachates collected through the lysimeter soil over the four years amounted to 168 and 146 L in lysimeters I and II, respectively. The leachates contained 2.43% and 2.99% of the originally applied 14C-radioactivity, corresponding to an average concentration of 0.29 and 0.41 microg/L as the cinosulfuron equivalent in lysimeters I and II, respectively. The total 14C-radioactivity translocated to rice plants in the third and fourth year was 0.69% and 0.60% (lysimeter I), and 1.02% and 0.84% (lysimeter II) of the 14C applied, respectively. Larger amounts of cinosulfuron equivalents (0.54-0.75%) remained in the straw in the fourth year than in any other parts. The 14C-radioactivities distributed down to a depth of 70 cm after four years were 56.71-57.52% of the 14C applied, indicating the continuous downward movement and degradation of cinosulfuron in soil. The non-extractable residues were more than 88% of the soil radioactivity and some 45-48% of them was incorporated into the humin fraction. The 14C-radioactivity partitioned into the aqueous phase was nearly 30% of the extractable 14C, suggesting strongly that cinosulfuron was degraded into some polar products during the experimental period. It was found out in a supplemental investigation that flooding and constant higher temperature enhanced mineralization of [14C]cinosulfuron to 14CO2 in soil, indicating the possibility of chemical hydrolysis and microbial degradation of the compound in the flooded lysimeter soil.  相似文献   

18.
Norway spruce saplings [Picea abies (L.) Karst.] were exposed during four growing seasons to different ozone treatments in open-top chambers: charcoal filtered air (CF), non-filtered air (NF) and non-filtered air with extra ozone (NF+, 1.4xambient concentrations). The CF and NF+ ozone treatments were combined with phosphorous deficiency and drought stress treatments. The total biomass of the trees was harvested at different intervals during the experimental period. The ozone uptake to current-year needles of the Norway spruce saplings was estimated using a multiplicative stomatal conductance simulation model. There was a highly significant correlation between the reduction of total biomass and the estimated cumulative ozone uptake, which did not vary when different thresholds were applied for the rate of ozone uptake. The reduction of the total biomass was estimated to 1% per 10 mmol m(-2) cumulated ozone uptake, on a projected needle area basis.  相似文献   

19.
McCulloch A 《Chemosphere》2002,47(7):667-686
Suppositions that the trichloroacetic acid (TCA, CCl3C(O)OH) found in nature was a consequence solely of the use of chlorinated hydrocarbon solvents prompted this critical review of the literature on its environmental fluxes and occurrences. TCA is widely distributed in forest soils (where it was rarely used as an herbicide) and measurements suggest a soil flux of 160 000 tonnes yr(-1) in European forests alone. TCA is also produced during oxidative water treatment and the global flux could amount to 55 000 tonnes yr(-1) (from pulp and paper manufacture, potable water and cooling water treatments). By contrast, the yields of TCA from chlorinated hydrocarbon solvents are small: from tetrachloroethene 13 600 tonnes yr(-1) and from 1,1,1-trichloroethane 4300 tonnes yr(-1) on a global basis, at the atmospheric burdens and removal rates typical of the late 1990s. TCA is ubiquitous in rainwater and snow. Its concentrations are highly variable and the variations cannot be connected with location or date. However, there is no significant difference between the concentrations found in Chile and in eastern Canada (by the same analysts), or between Malawi and western Canada, or between Antarctica and Switzerland, nor any significant difference globally between the concentrations in cloud, rain and snow (although local enhancement in fog water has been shown). TCA is present in old ice and firn. At the deepest levels, the firn was deposited early in the 19th century, well before the possibility of contamination by industrial production of reactive chlorine, implying a non-industrial background. This proposition is supported by plume measurements from pulp mills in Finland. TCA is ubiquitous in soils; concentrations are very variable but there are some indications that soils under coniferous trees contain higher amounts. The concentrations of TCA found in plant tissue are region-specific and may also be plant-specific, to the extent that conifers seem to contain more than other species. TCA is removed from the environment naturally. There is abundant evidence that soil microorganisms dehalogenate TCA and it is lost from within spruce needles with a half-life of 10 days. There is also recent evidence of an abiotic aqueous decarboxylation mechanism with a half-life of 22 days. The supposedly widespread effects of TCA in conifer needles are not shown in controlled experiments. At concentrations in the needles of Scots pine similar to those observed in needles in forest trees, changes consequent on TCA treatment of field laboratory specimens were almost all insignificant.  相似文献   

20.
Aerobic biodegradation of dichloroethylenes in surface and subsurface soils   总被引:5,自引:0,他引:5  
Klier NJ  West RJ  Donberg PA 《Chemosphere》1999,38(5):1175-1188
Laboratory studies were conducted to examine the aerobic biodegradation of dichloroethylenes (cis-1,2-DCE, trans-1,2-DCE and 1,1-DCE) in soil and groundwater. Authentic surface and subsurface materials with no reported DCE exposure history were used. All DCE isomers were observed to biodegrade to varying degrees in the soils examined. Use of radiolabeled [14C] test chemicals allowed correlation of DCE disappearance with mineralization to 14CO2. Study results indicate that naturally occurring microorganisms in soil and groundwater are capable of degrading cis-1,2-, trans-1,2- and 1,1-DCE without laboratory supplementation of exogenous organic nutrients, or previous exposure history. The data further suggest that degradative potential may vary with soil type, DCE isomer structure, and concentration.  相似文献   

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