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.     

Review of concentrations and chemistry of trichloroacetate in the environment

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.     

PCBs and chlorinated hydrocarbon pesticides in Antarctic atmosphere and hydrosphere

PCBs and chlorinated hydrocarbon pesticides such as DDTs and HCHs (BHCs) were measured in air, water, ice and snow samples collected around the Japanese research stations in Antarctica and adjacent oceans during December 1980 to March 1982. The atmospheric concentrations of chlorinated hydrocarbons decreased in the transport process from northern lands to Antarctica, but the compositions of PCBs, DDT compounds and HCH isomers were relatively uniform throughout this process. Regional and seasonal variations were found in aerial concentrations of these pollutants at Syowa Station and adjacent seas in Antarctica. Chlorinated hydrocarbons were also detected in snow, ice, lake water and sea water samples, in which rather high concentrations were found in snow and ice samples. This suggests that snow and ice serve as media of supply of these pollutants into Antarctic marine environment. Most interestingly, the concentrations of DDTs and higher chlorinated biphenyls were much lower in sea water under fast ice than in that from outer margin of pack ice. This indicates that the active removal of these pollutants is occurred in the sea under fast ice, and that is strongly associated with high primary productivity. It is, therefore, presumed that the concentrations of PCBs and DDTs in marine organisms living under fast ice in Antarctica could be lower than those in other oceans.     

Spatial and seasonal variations of elemental composition in Mt. Everest (Qomolangma) snow/firn

In May 2005, a total of 14 surface snow (0–10 cm) samples were collected along the climbing route from the advanced base camp to the summit (6500–8844 m a.s.l.) on the northern slope of Mt. Everest (Qomolangma). A 108 m firn/ice core was retrieved from the col of the East Rongbuk Glacier (28.03°N, 86.96°E, 6518 m a.s.l.) on the north eastern saddle of Mt. Everest in September 2002. Surface snow and the upper 3.5 m firn samples from the core were analyzed for major and trace elements by inductively coupled plasma mass spectroscopy (ICP-MS). Measurements show that crustal elements dominated both surface snow and the firn core, suggesting that Everest snow chemistry is mainly influenced by crustal aerosols from local rock or prevalent spring dust storms over southern/central Asia.There are no clear trends for element variations with elevation due to local crustal aerosol inputs or redistribution of surface snow by strong winds during the spring. Seasonal variability in snow/firn elements show that high elemental concentrations occur during the non-monsoon season and low values during the monsoon season. Ca, Cr, Cs, and Sr display the most distinct seasonal variations. Elemental concentrations (especially for heavy metals) at Mt. Everest are comparable with polar sites, generally lower than in suburban areas, and far lower than in large cities. This indicates that anthropogenic activities and heavy metal pollution have little effect on the Mt. Everest atmospheric environment. Everest firn core REE concentrations are the first reported in the region and seem to be comparable with those measured in modern and Last Glacial Maximum snow/ice samples from Greenland and Antarctica, and with precipitation samples from Japan and the East China Sea. This suggests that REE concentrations measured at Everest are representative of the background atmospheric environment.     

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.     

Environmental risk assessment of airborne trichloroacetic acid--a contribution to the discussion on the significance of anthropogenic and natural sources

In environmental risk assessments the question has to be answered, whether risk reduction measures are necessary in order to protect the environment. If the combination of natural and anthropogenic sources of a chemical substance leads to an unacceptable risk, the man-made emissions have to be reduced. In this case the proportions of the anthropogenic and natural emissions have to be quantified. Difficulties and possible solutions are discussed in the scope of the OECD- and EU-risk assessments of trichloroacetic acid (TCA) and tetrachloroethylene.In the atmosphere, TCA is formed by photo-oxidative degradation of tetrachloroethylene (PER) and 1,1,1-trichloroethane. The available data on atmospheric chemistry indicate that tetrachloroethylene is the more important pre-cursor. With its high water solubility and low volatility, TCA is adsorbed onto aerosol particles and precipitated during rainfalls. Extended monitoring in rainwater confirmed the global distribution of airborne TCA. TCA reaches soils by dry and wet deposition. In addition formation of TCA from tetrachloroethylene in plants was observed. Consequently, high concentrations were detected in needles, leaves and in forest soil especially in mountain regions.The effect assessment revealed that plants exposed via soil are the most sensitive species compared to other terrestrial organisms. A PNECsoil of 2.4 microg/kg dw was derived from a long-term study with pine and spruce seedlings. When this PNEC is compared with the measured concentrations of TCA in soil, in certain regions a PEC/PNEC ratio >1 is obtained. This clearly indicates a risk to the terrestrial ecosystem, with the consequence that risk reduction measures are deemed necessary.To quantify the causes of the high levels of TCA in certain soils, and to investigate the geographical extent of the problem, intensive and widespread monitoring of soil, air and rainwater for TCA and tetrachloroethylene would be necessary to be able to perform a full mass balance study at an appropriate number of sites. In addition, measurements of the 14C content in TCA isolated from soil could clarify whether a significant proportion of the TCA occurs from natural sources. The possible formation of TCA in soil can also be tested by incubation of isotope enriched inorganic chloride with subsequent mass spectrometry of TCA.     

Regional variation of selected polyaromatic and chlorinated hydrocarbons over the South Island of New Zealand, as indicated by their content in Pinus radiata needles

We analysed needles of Pinus radiata along three transects through the South Island of New Zealand for chlorinated hydrocarbons ( alpha- and gamma-HCH, HCB and PCB) and PAH (fluoranthene, 3,4-benzopyrene, benzo(ghi)perylene and indenopyrene). At rural sites we also collected samples of moss (Wijkia extenuata) and lichens (Usnea sp.) in order to compare the pollutant concentrations within these plants. A principal component analysis confirmed findings from moss and snow studies in Europe that the PAH concentrations vary regionally in the same way. The pattern of the principal component loadings of the chlorinated hydrocarbons reflects their heterogeneous immission and their different chemodynamics. The regional pattern indicates an increase of gamma-HCH from remote areas to those used intensively for agriculture and gardening, followed by a decrease towards the inner city of Christchurch. In contrast, PCB and PAH show their highest levels of contamination in the city. The regional distribution of PAH in Christchurch correlates well with traffic density, and particularly with the pattern of smoke from domestic fires. Our study demonstrates that needles of P. radiata can be better monitors of atmospheric pollution in New Zealand than mosses or lichens.     

Heavy metal pollution and forest health in the Ukrainian Carpathians

The Ukrainian Carpathians are characterized by high air pollution caused by emissions from numerous industries. We have been monitoring the state of forests in this region since 1989. The highest levels of tree defoliation (>30%) are found close to industrial emission sources and in the upper mountain forests of the Ivano-Frankivsk and Chernivtsi regions. This is caused by a combination of strong anthropogenic influences (pollution, illegal uses, recreation) as well as poor site and climatic conditions. In the Ivano-Frankivsk region, Cd and Mo accumulate in forest soils; Cr, Mo and Zn soil concentrations are higher than their limit levels; and Pb concentrations exceed toxic levels close to industrial areas (10% of the region territory). Local background levels of heavy metals are greatly exceeded in snow close to industrial regions. Analysis of correlation matrices shows that the chemical elements Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V and Zn occur at pollution levels in natural ecosystems in the Ukrainian Carpathians. Maximum concentrations of toxic elements occur in the oak forest zone; the most industrially developed area of the region. Toxic heavy metals in the Ukrainian Carpathians forests enter with precipitation and dustfall, then become fixed in soil and accumulate in leaves, needles of vascular plants and mosses. Concentrations of these metals decrease with altitude: highest in the oak forests, less in beech, and lowest in the spruce forest zones. However, some chemical elements have the highest concentrations in spruce forests; V in needles, As in snow, and Ba and Al in soils.     

Reproductive success and chlorinated hydrocarbon contamination in tree swallows (Tachycineta bicolor) nesting along rivers receiving pulp and paper mill effluent discharges

The insectivorous tree swallow was chosen as an indicator species to investigate the uptake of pulp mill-related chlorinated hydrocarbons from emergent aquatic insects. Nest box populations were monitored for reproductive success at locations upstream and downstream of pulp mills on two river systems in British Columbia, Canada. Also, 16-day-old nestlings were collected and analysed for polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), pesticides, chlorophenols and chloroguaiacols. Most reproductive parameters were not different between populations at upstream and downstream locations, and were equivalent to or greater than those recorded for other tree swallow populations. Chlorinated hydrocarbon contamination of nestlings was low at all sites. The highest tissue concentrations were detected downstream of pulp mills on the Fraser River, where PCDD and PCDF patterns along with the presence of pentachlorophenol (PCP) suggested that the primary source of contaminants was past use of PCP for timber preservation. Although the absolute tissue concentration of contaminants was less, the toxic concentration (as estimated with I-TEQs) was greatest in nestlings downstream of a pulp mill on the Thompson River. The proportionately larger contributions from 2,3,7,8-TCDF and PCB-77 elevated these TEQs in comparison to other populations. Nest success was the one reproductive measure that showed substantial reductions in downstream populations on both rivers; however, there was little indication that nest failures were the direct result of contamination. Failures were largely due to parental abandonment, and, while poor parental attentiveness and nest abandonment have been associated with chlorinated hydrocarbon tissue concentrations in other studies, our 1-year assessment was insufficient to establish any link with pulp mill effluent exposure. Nestling growth models showed some subtle differences in growth patterns between nest box populations on the two rivers, but an association with pulp mill effects on aquatic insect prey availability was not established.     

Haloacetic acids,phytotoxic secondary air pollutants

Haloacetic acids are atmospheric oxidation products of airborne C₂-halocarbons which are important solvents and propellants. Levels of trichloroacetate (TCA) in conifer needles from mountain ranges in Germany (Black Forest, Erzgebirge) and from two sites in Finland are compared; TCA is present in conifer needles at concentrations up to 0.7 μmol/kg, MCA up to 0.2 μmol/kg. At the Finnish sites, TCA-concentrations and branch degeneration symptoms of Scots pine are correlated. Monochloroacetate (MCA) has been determined in needle samples from Southern Germany in concentrations exceeding its phytotoxicity threshold towards photoautotrophic organisms. Data on atmospheric chloroacetate levels in Germany are also given; ambient air levels of chloroacetic acids range from about 2 pmol/m³ (TCA) to 390 pmol/m³ (MCA). TCA and dichloroacetic acid (DCA) arise from atmospheric oxidation of airborne C₂-chlorocarbons, while the source of MCA is not yet known; several tentative pathways are suggested.     

Bioremediation trial on aged PCB-polluted soils—a bench study in Iceland

Polychlorinated biphenyls (PCBs) pose a threat to the environment due to their high adsorption capacity to soil organic matter, stability and low reactivity, low water solubility, toxicity and ability to bioaccumulate. With Icelandic soils, research on contamination issues has been very limited and no data has been reported either on PCB degradation potential or rate. The goals of this research were to assess the bioavailability of aged PCBs in the soils of the old North Atlantic Treaty Organization facility in Keflavík, Iceland and to find the best biostimulation method to decrease the pollution. The effectiveness of different biostimulation additives (N fertiliser, white clover and pine needles) at different temperatures (10 and 30 °C) and oxygen levels (aerobic and anaerobic) were tested. PCB bioavailability to soil fauna was assessed with earthworms (Eisenia foetida). PCBs were bioavailable to earthworms (bioaccumulation factor 0.89 and 0.82 for earthworms in 12.5 ppm PCB soil and in 25 ppm PCB soil, respectively), with less chlorinated congeners showing higher bioaccumulation factors than highly chlorinated congeners. Biostimulation with pine needles at 10 °C under aerobic conditions resulted in nearly 38 % degradation of total PCBs after 2 months of incubation. Detection of the aerobic PCB degrading bphA gene supports the indigenous capability of the soils to aerobically degrade PCBs. Further research on field scale biostimulation trials with pine needles in cold environments is recommended in order to optimise the method for onsite remediation.     

Polynuclear aromatic hydrocarbons in the United Kingdom environment: a preliminary source inventory and budget

This paper presents the first attempt to quantify the production, cycling, storage and loss of PAHs in the UK environment. Over 53 000 tonnes of sigmaPAHs (sum of 12 individual compounds) are estimated to reside in the contemporary UK environment, with soil being the major repository. If soils at contaminated sites are included, this estimate increases dramatically. Emission of PAHs to the UK atmosphere from primary combustion sources are estimated to be greater than 1000 tonnes sigmaPAHs per annum, with over 95% coming from domestic coal combustion, unregulated fires and vehicle emissions. It is estimated that approximately 210 tonnes of sigmaPAH are delivered to terrestrial surfaces each year via atmospheric deposition. Therefore, inputs of PAHs to the UK atmosphere outweigh the outputs by a factor of over 4. This may be explained by enhanced particulate deposition near point sources, PAH degradation in the atmosphere and transport away from the UK with prevailing winds. Disposal of waste residues is estimated to contribute a further 1000 tonnes of sigmaPAH per year to the terrestrial environment. It is illustrated that the use of creosote has the potential to release considerable quantities of PAHs to the UK environment. Temporal trends in PAH cycling are then considered. There is good evidence to suggest that air concentrations and fluxes to the UK surface are now lower than at any time throughout this century. Nonetheless, the UK sigmaPAH burden is still increasing at the present time, principally through retention by soils. However, there are marked differences in the behaviour of individual compounds: there is evidence, for example, that phenanthrene concentrations in soils have declined since the 1960s, although soil concentrations of benzo[a]pyrene and other heavier PAHs have continued to increase through this century. Volatilisation of low molecular weight PAHs accumulated in soils over previous decades may be making an important contribution to the current atmospheric burden. The major uncertainties identified by data on this budget are: (1) the lack of PAH concentrations in some environmental matrices; (2) the possible importance of contaminated soils as a major repository and source of PAHs; (3) the lack of emission data (especially vapour phase releases) for some PAH sources; (4) the importance of biodegradation and volatilisation as loss mechanisms for low molecular weight PAHs in soils; and (5) the importance of creosote use in the PAH cycle.     

Persistent toxic substances in soils and waters along an altitudinal gradient in the Laja River Basin, Central Southern Chile

In this study the levels and distribution of some persistent toxic substances (PTS) were investigated in soils, superficial water, and snow along an altitudinal gradient in the Laja River Basin (South Central Chile). The principal objective was to establish the basin's contamination status. The working hypothesis was that PTS levels and distribution in the basin are dependent on the degree of anthropogenic intervention. Fifteen PAHs, seven PCBs congeners, and three organochlorine pesticides were studied in superficial soil and water samples obtained along the altitudinal gradient and from a coastal reference station (Lleu-Lleu River). Soil samples were extracted using accelerated solvent extraction with acetone/cyclohexane (1:1) for PAHs and organochlorine compounds. Contaminants were extracted from water and snow samples by liquid-liquid extraction (LLE). PAH and organochlorine compound quantification was carried out by HPLC with fluorescence detection and GC-MS, respectively. PCBs in soils presented four different profiles in the altitudinal gradient, mainly determined by their chlorination degree; these profiles were not observed for the chlorinated pesticides. In general, the detected levels for the analyzed compounds were low for soils when compared with soil data from other remote areas of the world. Higher summation operator PAHs levels in soils were found in the station located at 227 masl (4243 ng g-1 TOC), in a forestry area and near a timber industry, where detected levels were up to eight times higher than the other sampling sites. In general, PAH levels and distribution seems to be dependent on local conditions. No pesticides were detected in surface waters. However, congeners of PCBs were detected in almost all sampling stations with the highest levels being found in Laja Lake waters, where 1.1 ng/l were observed. This concentration is two times higher than values reported for polluted lakes in the Northern Hemisphere. The presence of organochlorine compound in snow sampled at the highest elevation point of the basin is indicative of the transport and atmospheric deposition phenomena of alpha-HCH, gamma-HCH and PCB 52, with values being similar to the levels reported in Canadian snow samples. We conclude that environmental PTS substance levels are in general relatively low, although PAHs may be of concern in some areas of the basin.     

Long-term mercury dynamics in UK soils

A model assuming first-order losses by evasion and leaching was used to evaluate Hg dynamics in UK soils since 1850. Temporal deposition patterns of Hg were constructed from literature information. Inverse modelling indicated that 30% of 898 rural sites receive Hg only from the global circulation, while in 51% of cases local deposition exceeds global. Average estimated deposition is 16 μg Hg m⁻² a⁻¹ to rural soils, 19 μg Hg m⁻² a⁻¹ to rural and non-rural soils combined. UK soils currently hold 2490 tonnes of reactive Hg, of which 2140 tonnes are due to anthropogenic deposition, mostly local in origin. Topsoil currently releases 5.1 tonnes of Hg⁰ per annum to the atmosphere, about 50% more than the anthropogenic flux. Sorptive retention of Hg in the lower soil exerts a strong control on surface water Hg concentrations. Following decreases in inputs, soil Hg concentrations are predicted to decline over hundreds of years.     

Chlorinated short chain aliphatic hydrocarbons in pine needles by purge and trap gas chromatography/mass spectrometry

The concentrations of volatile chlorinated short chain aliphatic hydrocarbons in pine needles have been measured using purge and trap GC/MS. The concentrations of dichloromethane, chloroform, dichloroethene and tetrachloroethene in the needles were calculated. The concentrations of dichloromethane and tetrachloroethene were highest. As a rule the concentrations were higher in the older needles. The needle samples were collected from five sampling points in an area situated in the Southern Finland in the vicinity of a metal scrab plant. Reference needles were collected in the Central Finland. Needles originated from years 1991, 1992 and 1993.     

Effects of trichloroacetic acid on the nitrogen metabolism of Pinus sylvestris--a 13C/15N tracer study

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.     

Contaminant risks from biosolids land application: contemporary organic contaminant levels in digested sewage sludge from five treatment plants in Greater Vancouver,British Columbia

This study examines the potential for environmental risks due to organic contaminants at sewage sludge application sites, and documents metals and various potential organic contaminants (volatile organics, chlorinated pesticides, PCBs, dioxins/furans, extractable petroleum hydrocarbons, PAHs, phenols, and others) in current production biosolids from five wastewater treatment plants (WWTPs) within the Greater Vancouver Regional District (GVRD). There has been greater focus in Europe, North America and elsewhere on metals accumulation in biosolids-amended soil than on organic substances, with the exception of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. Another objective, therefore, was to evaluate the extent to which management of biosolids re-use based on metal/metalloid levels coincidentally minimizes environmental risks from organic contaminants. Historical-use contaminants such as chlorophenols, PCBs, and chlorinated pesticides were not detected at environmentally relevant concentrations in any of the 36 fresh biosolids samples, and appear to have virtually eliminated from sanitary collection system inputs. The few organic contaminants found in freshly produced biosolids samples that exhibited high concentrations relative to British Columbia and Canadian soil quality benchmarks included p-cresol, phenol, phenanthrene, pyrene, naphthalene, and heavy extractable petroleum hydrocarbons (HEPHs--nCl9-C34 effective carbon chain length). It was concluded that, with the exception of these petroleum hydrocarbon constituents or their microbial metabolites, the mixing of biosolids with uncontaminated soils during land application and based on the known metal concentrations in biosolids from the Greater Vancouver WWTPs investigated provides adequate protection against the environmental risks associated with organic substances such as dioxins and furans, phthalate esters, or volatile organics. Unlike many other organic contaminants, the concentrations of petroleum hydrocarbon derived substances in biosolids has not decreased within the last decade or more in the WWTPs studied, and--unlike persistent chlorinated compounds--the associated PAHs and other hydrocarbon constituents merit careful consideration, especially in the context of repeated land-application of biosolid.     

Investigation of uptake, translocation and fate of trichloroacetic acid in Norway spruce (Picea abies/L./Karst.) using 14C-labelling.

[1,2-14C]TCA of a high specific activity (3.7 GBq/mmol) and appropriate radioindicator techniques were used, to study the effect of trichloroacetic acid (TCA) on conifers. Easy uptake of TCA from soil through spruce roots and its further translocation by the transpiration stream up to the needles (where damage of the photosynthetic apparatus occurs) has been proved. During the growth period, after one-shot load of TCA, the uptake was most intensive in current-year needles at first; over an extended period a decrease in the level of [1,2-14C]TCA-derived radioactivity was found in the current-year needles while in older needles (C + 2), the level rose. Symptoms of TCA biodegradation and/or metabolism were found in the plant/soil system under study. During an eight-week exposure significant losses of radioactivity into the atmosphere were noticed, at least a part of them in the form of carbondioxide. The results of these more or less preliminary experiments demonstrated the suitability and advantages of the radioisotopic technique used.     

Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils

In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-β-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is required using soils from a range of hydrocarbon contamination sources in order to develop robust assays for predicting bioremediation endpoints in the field.     

Shouldn’t snowpacks be sources of monocarboxylic acids?

We report the first measurements of the mixing ratios of acetic (CH₃COOH) and formic (HCOOH) acids in the air filling the pore spaces of the snowpacks (firn air) at Summit, Greenland and South Pole. Both monocarboxylic acids were present at levels well above 1 ppbv throughout the upper 35 cm of the snowpack at Summit. Maximum mixing ratios in Summit firn air reached nearly 8 ppbv CH₃COOH and 6 ppbv HCOOH. At South Pole the mixing ratios of these acids in the top 35 cm of firn air were also generally >1 ppbv, though their maximums barely exceeded 2.5 ppbv of CH₃COOH and 2.0 ppbv of HCOOH. Mixing ratios of the monocarboxylic acids in firn air did not consistently respond to diel and experimental (fast) variations in light intensity, unlike the case for N oxides in the same experiments. Air-to-snow fluxes of CH₃COOH and HCOOH apparently support high mixing ratios (means of (CH₃COOH/HCOOH) 445/460 and 310/159 pptv at Summit and South Pole, respectively) in air just above the snow during the summer sampling seasons at these sites. We hypothesize that oxidation of carbonyls and alkenes (that are produced by photo- and OH-oxidation of ubiquitous organic compounds) within the snowpack is the source of the monocarboxylic acids.