The concentrations and input/output fluxes of trichloroacetic acid (TCA) were measured in all relevant media for one year at a 0.86 km2 upland conifer plantation and moorland catchment in SW Scotland (n > 380 separate samples analyzed). Annual wet precipitation to the catchment was 2.5 and 0.4 m for rain and cloud, respectively. TCA input to the catchment for the year was 2100 g, predominantly in rainwater (86%), with additional input via cloudwater (13%) and gas plus particle dry deposition (1%). There were no seasonal trends in TCA deposition, and cloudwater concentration was not enhanced over rainwater. TCA in precipitation exceeded concentrations estimated using currently accepted routes of gas-phase oxidation from anthropogenic chlorinated hydrocarbon precursors, in agreement with previous studies. Export of TCA from the catchment in streamwater totalled 1970 g for the year of study. The TCA concentration in streamwater at outflow (median 1.2 microg L(-1)) was significantly greater than that before the stream had passed through the conifer plantation. To well-within measurement uncertainties, the catchment is currently at steady-state with respect to TCA input/output. The catchment reservoir of TCA was dominated by soils (approximately 90%), with the remainder distributed in forest litter (approximately 9%), forest branchwood and stemwood (approximately 0.7%), forest foliage (approximately 0.5%), and moorland foliage (approximately 0.1%). Although TCA is clearly taken up into foliage, which consequently may be important for the vegetation, this was a relatively minor process for TCA at the catchment scale. If it is assumed, on the basis of laboratory extraction experiments, that only approximately 20% of "whole soil" TCA measured in this work was water extractable, then total mass of TCA in the catchment is reduced from approximately 13 to approximately 3.5 kg. Comparing the latter value with the annual flux yields an average steady-state residence time for TCA in the catchment of approximately 1-2 y, if all TCA is involved in catchment turnover. Considering that other evidence indicates the lifetime of TCA in soil and biota is considerably shorter than this (weeks rather than years), the magnitude of the TCA reservoir is suggested to be strong evidence for net natural TCA production in soils and/or that the majority of TCA in the reservoir is not involved with external fluxes.
Controlled-dosing experiments with conifer seedlings have demonstrated an above-ground route of uptake for trichloroacetic acid (TCA) from aqueous solution into the canopy, in addition to uptake from the soil. The aim of this work was to investigate the loss of TCA to the canopy in a mature conifer forest exposed only to environmental concentrations of TCA by analysing above- and below-canopy fluxes of TCA and within-canopy instantaneous reservoir of TCA. Concentrations and fluxes of TCA were quantified for one year in dry deposition, rainwater, cloudwater, throughfall, stemflow and litterfall in a 37-year-old Sitka spruce and larch plantation in SW Scotland. Above-canopy TCA deposition was dominated by rainfall (86%), compared with cloudwater (13%) and dry deposition (1%). On average only 66% of the TCA deposition passed through the canopy in throughfall and stemflow (95% and 5%, respectively), compared with 47% of the wet precipitation depth. Consequently, throughfall concentration of TCA was, on average, approximately 1.4 x rainwater concentration. There was no significant difference in below-canopy fluxes between Sitka spruce and larch, or at a forest-edge site. Annual TCA deposited from the canopy in litterfall was only approximately 1-2% of above-canopy deposition. On average, approximately 800 microg m(-2) of deposited TCA was lost to the canopy per year, compared with estimates of above-ground TCA storage of approximately 400 and approximately 300 microg m(-2) for Sitka spruce and larch, respectively. Taking into account likely uncertainties in these values ( approximately +/- 50%), these data yield an estimate for the half-life of within-canopy elimination of TCA in the range 50-200 days, assuming steady-state conditions and that all TCA lost to the canopy is transferred into the canopy material, rather than degraded externally. The observations provide strong indication that an above-ground route is important for uptake of TCA specifically of atmospheric origin into mature forest canopies, as has been shown for seedlings (in addition to uptake from soil via transpiration), and that annualized within-canopy elimination is similar to that in controlled-dosing experiments.
Soil is an important compartment in the environmental cycling of trichloroacetic acid (TCA), but soil TCA concentration is a methodologically defined quantity; analytical methods either quantify TCA in an aqueous extract of the soil, or thermally decarboxylate TCA to chloroform in the whole soil sample. The former may underestimate the total soil TCA, whereas the latter may overestimate TCA if other soil components (e.g. humic material) liberate chloroform under the decarboxylation conditions. The aim of this work was to show that extraction and decarboxylation methods yield different TCA concentrations because the decarboxylation method can also determine "bound" TCA. Experiments with commercial humic acid solutions showed there was no additional chloroform formation under decarboxylation conditions, and that all TCA in a TCA-humic acid mixture could be quantitatively determined (108 +/- 13%). Anion exchange resin was used as a provider of solid-phase TCA binding; only 5 +/- 1% of a TCA solution mixed with the resin was present in the aqueous extract subsequently separated from the resin, yet the decarboxylation method yielded mass balance (123 +/- 22%) with TCA remaining in the resin. In aqueous extraction of a range of soil samples (with or without added TCA spike), the decarboxylation method was able to satisfactorily account for TCA in the extractant + residue post-extraction, compared with whole-soil TCA (+ spike) pre-extraction: e.g. mass balances for unspiked soil from Sikta spruce and larch forest were 99 +/- 8% and 93 +/- 6%, respectively, and for TCA-spiked forest and agricultural soils were 114 +/- 13% and 102 +/- 2%. In each case recovery of TCA in the extractant was substantially less than 100%(<20% for unspiked soils, <55% for spiked soils). Extraction efficiencies were generally lower in more organic soils. The results suggest that analytical methods which utilise aqueous extraction may underestimate whole-soil TCA concentrations. Application of both methodologies together may enhance insight into TCA behaviour in soil.
A major flux of trichloroacetic acid (TCA) to forests is via wet deposition, but the transfer of TCA into tree foliage may occur by an above-or below-ground pathway. To investigate the routes and kinetics of TCA uptake, two groups of 10 Sitka spruce saplings (with an equivalent number of controls) were exposed to a single application of 200 µg TCA in solution, either to the soil only, or sprayed as a mist to the foliage only. The needle foliage was subsequently analysed regularly for TCA for 3 months during the growing season. Significant uptake into current year (C) needles was observed from both routes just a few days after application, providing direct evidence of an above-ground uptake route. Uptake of TCA was also observed in the previous year needle class (C+1). Kinetic modelling of the data indicated that the half-life for within-needle elimination (during the growing season) was ~50 ± 30 days. Most of the applied TCA appeared to be degraded before uptake, either in the soil, or externally on the sapling foliage.
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