Trichloroacetic acid cycling in Sitka spruce saplings and effects on sapling health following long term exposure

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.     

Size and spatial structure in deep versus shallow populations of the Mediterranean gorgonian <Emphasis Type="Italic">Eunicella singularis</Emphasis> (Cap de Creus,northwestern Mediterranean Sea)

In the Western Mediterranean Sea, the gorgonian Eunicella singularis (Esper, 1794) is found at high densities on sublittoral bottoms at depths from 10 to 70 m. Shallow colonies have symbiotic zooxanthellae that deeper colonies lack. While knowledge of the ecology of the shallow populations has increased during the last decades, there is almost no information on the ecology of the deep sublittoral populations. In October and November 2004 at Cap de Creus (42°19′12″ N; 03°19′34″ E), an analysis of video transects made by a remotely operated vehicle showed that shallow populations (10–25 m depth) were dominated by small, non-reproductive colonies, while deep sublittoral populations (50–67 m depth) were dominated by medium-sized colonies. Average and maximum colony heights were greater in the deeper populations, with these deeper populations also forming larger patch sizes and more extensive regions of continuous substrate coverage. These results suggest that shallow habitats are suitable for E. singularis, as shown by the high recruitment rate, but perturbations may limit or delay the development of these populations into a mature stage. This contrasts with the deep sublittoral habitats where higher environmental stability may allow the development of mature populations dominated by larger, sexually mature colonies.     

Fluxes of trichloroacetic acid through a conifer forest canopy

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.     

Potentially toxic metals in ombrotrophic peat along a 400 km English-Scottish transect

Four samples of ombrotrophic peat were collected from each of 10 upland locations in a transect from the southern Pennines to the Highland Boundary Fault, a total distance of ca. 400 km. Bulk compositions and other properties were determined. Total contents of Al and heavy metals (Ni, Cu, Zn, Cd, Pb) were determined following digestion with hydrofluoric acid, and concentrations of metals extractable with dilute nitric acid were also measured. Supernatants obtained from aqueous extractions of the peat samples were analysed for pH, major cations and anions, dissolved organic carbon and dissolved metals, and concentrations of free metal ions (Al(3+), Ni(2+), etc.) were estimated by applying a chemical speciation model. Both total and HNO(3)-extractable metal concentrations varied along the transect, the highest values being found at locations close to industrial and former mining areas. The HNO(3)-extractable soil metal contents of Ni, Cu and Cd were appreciably lower than lowest-observed-effect-concentrations (LOEC) for toxicity towards microorganisms in acid, organic rich soils. However, the contents of Zn at two locations, and of Pb at five locations exceeded LOECs, suggesting that they may be exerting toxic effects in the peats. Soil solution concentrations of free heavy metal ions (Cu(2+), Zn(2+), Cd(2+), Pb(2+)) were substantially lower than LOECs for toxicity towards vascular plants, whereas concentrations of Al(3+) were near to toxic levels at two locations.     

Addressing analytical uncertainties in the determination of trichloroacetic acid in soil

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.