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.     

Mass balance of trichloroacetic acid in the soil top layer

Since the ban on the use of trichloroacetic acid (TCAA) as a herbicide in several countries, TCAA is still found ubiquitously in the environment. The presence of TCAA nowadays is suggested to originate mainly from the atmospheric degradation of tetrachloroethene. Our mass balance calculations indicate that this may be true for the presence of TCAA in the atmosphere. However, our mass balance calculations also provide tentative evidence for the formation of TCAA in soil. If our calculated production fluxes are realistic estimates, a very large source of TCAA in soil has been identified.     

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.     

Non-isothermal gaseous exchange between soil and atmosphere

The theoretical and experimental basis of a non-isothermal rotary gas exchange (NRGE) between soil and atmosphere is given. A method of measurement for the NRGE intensity in porous media, including soil, is given and its validity is examined. The global NRGE of selected gases is determined. Relatively high NRGE intensities are found to exist for some gases. The heat transfer determination method is given. An electrical scheme for simulating the NRGE process is also described.     

Photosonochemical degradation of trichloroacetic acid in aqueous solution

The degradation of trichloroacetic acid (TCA) was studied with ultraviolet (UV) photolysis, ultrasound (US) sonolysis and their combination. It was found that the degradation in the combined processes was more significant than in the UV photolysis or sonolysis alone. The effects of pH and dissolved gases on the rate of photosonochemical degradation of TCA were investigated and the degradation kinetics, mechanism and possible degradation products were discussed in detail.     

Perfluorinated compounds in water, sediment, soil and biota from estuarine and coastal areas of Korea

Soil, sediment, water, and biota collected from the western coast of Korea were analyzed to determine occurrence and sources of perfluorinated compounds (PFCs). PFCs were significantly concentrations of PFCs were measured in some water and biological samples, while concentrations of PFCs in soils and sediments were relatively low. The most widely detected compound was found to be perfluorooctanesulfonate (PFOS), with a maximum concentration in water of 450 ng/L and in fish of 612 ng/g, dw. PFOS concentrations in water and biota were both less than those thought to cause toxicity. However, in both cases concentrations were within a factor of 10 of the toxicity threshold concentration. Concentrations of PFCs were significantly greater downstream than those upstream on the same river, suggesting point sources. Overall, the detection of PFCs at relatively great concentrations in various environmental matrixes from this region of Korea suggests that further studies characterizing PFCs and their potential risk to both humans and wildlife are needed.     

三氯乙酸与其他有机物在活性炭上的竞争吸附

通过等温吸附实验,考察了三氯乙酸(TCAA)与十二烷基苯磺酸钠(DBS)、腐殖酸(HA)在活性炭(GAC)上的竞争吸附现象。结果表明,GAC对TCAA的吸附符合Langmuir模型,对DBS和HA的吸附均符合Freudlich模型;在GAC上,DBS和HA对TCAA构成竞争吸附,大分子HA阻塞GAC的微孔,使得TCAA与DBS难以进入微孔;GAC对3种物质的吸附能力由大到小依次为DBS、TCAA和HA;离子型表面活性剂DBS憎水性一端与TCAA竞争吸附位,亲水性一端与TCAA形成吸附,使GAC总饱和吸附量有所加大。     

Impact of gold mining associated with mercury contamination in soil,biota sediments and tailings in Kenya

This work considered the environmental impact of artisanal mining gold activity in the Migori–Transmara area (Kenya). From artisanal gold mining, mercury is released to the environment, thus contributing to degradation of soil and water bodies. High mercury contents have been quantified in soil (140 μg kg^?1), sediment (430 μg kg^?1) and tailings (8,900 μg kg^?1), as expected. The results reveal that the mechanism for transporting mercury to the terrestrial ecosystem is associated with wet and dry depositions. Lichens and mosses, used as bioindicators of pollution, are related to the proximity to mining areas. The further the distance from mining areas, the lower the mercury levels. This study also provides risk maps to evaluate potential negative repercussions. We conclude that the Migori–Transmara region can be considered a strongly polluted area with high mercury contents. The technology used to extract gold throughout amalgamation processes causes a high degree of mercury pollution around this gold mining area. Thus, alternative gold extraction methods should be considered to reduce mercury levels that can be released to the environment.     

中国台湾地区土壤及地下水污染整治管理与经验

中国台湾地区土壤及地下水污染整治基金管理会自2001年成立以来,不断完善管理架构和管理体系,发布相关领域的法律法规、行政规则和公告,有效运行污染整治基金的财务筹措和使用等经济管理机制。开展了一系列行之有效的预防、监测、调查、评估等管理工作,为污染场地的识别和筛选奠定了坚实的基础。对于污染场地的整治工作,采用标准和风险评估相结合的验收方式,推行场地可持续利用的绿色修复技术。重点研究台湾地区土壤及地下水污染整治工作的管理政策、模式和措施,总结相关经验,为中国土壤及地下水污染防治工作提供借鉴和参考。     

Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

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.     

In vitro cytogenetic assessment of trichloroacetic acid in human peripheral blood lymphocytes

Trichloroacetic acid (TCA), a common water disinfection byproduct and a persistent metabolite of trichloroethylene (TCE), has been examined for its genotoxic potential in human lymphocytes. Chromosomal aberration (CA) and cytokinesis-block micronucleus (CBMN) assay were employed to assess the toxicity of TCA. Lymphocytes obtained from three healthy donors were exposed to 25, 50, and 100 μg/ml concentration of TCA separately. TCA exposure resulted in chromosomal anomalies and the formation of micronuclei in lymphocytes. Chromosome analysis revealed the dose-dependent and significant induction of CA. Chromatid break/chromosome break, fragments, and chromatid exchanges were commonly observed. Exposure of higher concentration (50 and 100 μg/ml) significantly inhibited mitotic index. Data obtained with CBMN assay indicated that the induction of micronucleus (MN) formation was greater than that of CA. At 25 μg/ml, TCA induced significant frequencies of MN as compared to control cells. Significant induction of MN at the lowest concentration indicates TCA may also interact with mitotic spindles. Lower percentage of CA and MN at 100 μg/ml as compared to 50 μg/ml indicates occurrence of severe cytotoxicity on exposure of 100 μg/ml TCA in lymphocytes. Collectively, results of both cytogenetic assays indicate that exposure of TCA can induce significant genotoxic and cytotoxic effects.     

Airborne trichloroacetic acid and its deposition in the catchment area of the Caspian Sea

The main sources of pollution discharge into the Caspian Sea are metal and oil processing plants in the catchment areas of the Ural and Volga rivers, as well as the coastal and offshore oil industry in the countries bordering the sea. The high evaporation from the surface of this largest inland sea introduces highly volatile C₂-chlorohydrocarbons into the atmosphere. Subsequent reactions with OH radicals and other oxidants results in the formation of secondary pollutants, such as phytotoxic trichloroacetic acid (TCA), which are then delivered by the air or rain into the neighbouring ecosystems of various vegetation zones. Biomonitoring investigations in the catchment area of the Caspian Sea have revealed that differences in pollution levels in the southern Russian area between the Black Sea and the Caspian Sea, resulting from TCA originating in the atmosphere, are attributable to climatic conditions and the geographical position of the measuring sites. ©     

Trace elements in soil and biota in confined disposal facilities for dredged material

We studied the relation of trace element concentrations in soil to those in house mice (Mus musculus), common reed (Phragmites australis) and ladybugs (Coccinella septempunctata at five disposal facilities for dredged material. The sites had a wide range of soil trace element concentrations, acid soils and a depauperate fauna. They were very poor wildlife habitat because they were dominated by the common reed. Bioassay earthworms exposed to surface soils from three of the five sites died, whereas those exposed to four of five soils collected a meter deep survived, presumably because the deeper, unoxidized soil, was not as acid. Concentrations of Ni and Cr in the biota from each of the sites did not seem to be related to the concentrations of the same elements in soil. Although Pb, Zn and Cu concentrations in biota were correlated with those in soil, the range of concentrations in the biota was quite small compared to that in soil. The concentrations of Pb detected in mice were about as high as the concentrations previously reported in control mice from other studies. Mice from the most contaminated site (530 ppm Pb in soil) contained only slightly more Pb (8 ppm dry wt) than did mice (2-6 ppm dry wt) from sites containing much less Pb (22-92 ppm in soil). Despite the acid soil conditions, very little Cd was incorporated into food chains. Rather, Cd was leaching from the surface soil. We concluded that even the relatively high concentrations of trace elements in the acid dredged material studied did not cause high concentrations of trace elements in the biota.     

Input of trichloroacetic acid into the vegetation of various climate zones--measurements on several continents

Trichloroacetic acid (TCA, CCl(3)COOH) is a phytotoxic chemical. Although TCA salts and derivates were once used as herbicides to combat perennial grasses and weeds, they have since been banned because of their indiscriminate herbicidal effects on woody plant species. However, TCA can also be formed in the atmosphere. For instance, the high-volatile C(2)-chlorohydrocarbons tetrachloroethene (TECE, C(2)Cl(4)) and 1,1,1-trichloroethane (TCE, CCl(3)CH(3)) can react under oxidative conditions in the atmosphere to form TCA and other substances. The ongoing industrialisation of Southeast Asia, South Africa and South America means that use of TECE as solvents in the metal and textile industries of these regions in the southern hemisphere can be expected to rise. The increasing emissions of this substance--together with the rise in the atmospheric oxidation potential caused by urban activities, slash and burn agriculture and forest fires in the southern hemisphere--could lead to a greater input/formation of TCA in the vegetation located in the lee of these emission sources. By means of biomonitoring studies, the input/formation of TCA in vegetation was detected at various locations in South America, North America, Africa, and Europe.     

The exchange of nitric oxide, nitrogen dioxide and ozone between pasture and the atmosphere

Fluxes of NO, NO2 and O3 were determined over a drained marshland pasture in south-east England by using flux-gradient techniques. Nitric oxide was found to be emitted at rates of up to 40 ng m(-2) s(-1), the rate of emission being related to the magnitude of the eddy diffusivity. Nitrogen dioxide deposited at rates of up to 90 ng m(-2) s(-1) under the control of stomatal resistance, a clear diurnal cycle being observed. Minimum canopy resistance was of the order of 80 s m(-1). Ozone deposition was also controlled by stomatal resistance, the minimum canopy resistance being around 100 s m(-1) and fluxes reaching a maximum of 220 ng m(-2) s(-1). Corrections made to NO and NO2 fluxes to compensate for chemical reactions showed flux divergences of the order of 30% for NO and NO2, but these were not statistically significantly different from the measured fluxes. The pasture was found to be a net sink for nitrogen in the form of NOx.     

SEAR技术修复土壤和地下水中NAPL污染的研究进展

就SEAR技术修复土壤及地下水中NAPL污染的原理及发展现状进行了综述.SEAR技术可以快速有效地去除土壤和地下水中的NAPL污染源,适于多种污染物.该技术通过增溶和增流2种途径提高NAPL污染物的去除率.表面活性剂的选择和微乳液体系的调配是SEAR技术实施的关键环节.将SEAR技术用于高浓度NAPL污染源的治理,并与生物修复和自然降解相结合,是经济高效的治理方案.     

纳米天然黄铁矿对土壤和地下水中铬的原位固定技术

采用机械球磨活化方法制备了纳米级黄铁矿,将其作为可渗透反应屏障中的介质材料,用于原位固定土壤和地下水中的Cr(Ⅵ),通过柱实验研究了黄铁矿对Cr(Ⅵ)动态反应(吸附)和解吸附的性能,并结合高分辨率透射电子显微镜(TEM)、X射线衍射(XRD)等对黄铁矿材料进行了表征,同时对反应机理进行了探讨。结果表明：在纳米天然黄铁矿填充的PRB反应器中,FeS₂能够有效地处理含铬废水并将Cr(Ⅵ)原位固定在土壤中;在反应过程中,1 g黄铁矿可处理50 mg·L⁻¹的含铬废水1 854.4 mL,2 g的纳米级天然黄铁矿介质固定了约69.458 mg的Cr(VI);当铬溶液到达穿透点时,Cr(Ⅵ)去除率达到了99.9%。本研究成果可为纳米级天然黄铁矿处理土壤和地下水中Cr(Ⅵ)以及原位固定其他的重金属提供参考。     

SEAR技术修复土壤和地下水中NAPL污染的研究进展

就SEAR技术修复土壤及地下水中NAPL污染的原理及发展现状进行了综述.SEAR技术可以快速有效地去除土壤和地下水中的NAPL污染源,适于多种污染物.该技术通过增溶和增流2种途径提高NAPL污染物的去除率.表面活性剂的选择和微乳液体系的调配是SEAR技术实施的关键环节.将SEAR技术用于高浓度NAPL污染源的治理,并与生物修复和自然降解相结合,是经济高效的治理方案.     

Mineralisation studies of 14C-labelled metsulfuron-methyl, tribenuron-methyl, chlorsulfuron and thifensulfuron-methyl in one Danish soil and groundwater sediment profile.

Bacterial mineralisation of four sulfonylurea herbicides at 20 microg kg(-1) in a sandy soil from nine different depths in a sandy soil horizon (5-780 cm) was investigated in laboratory studies. Metsulfuron-methyl, chlorsulfuron, and tribenuron-methyl were 14C-labelled in the sulfonamide ring, while thifensulfuron-methyl was labelled in the thiophene ring. The highest mineralised amount in 126 days was observed for metsulfuron-methyl (40%) followed by tribenuron-methyl (25%), and thifensulfuron-methyl (11%). Chlorsulfuron showed low mineralisation in all the soils tested (<4%). Mineralisation of the herbicides metsulfuron-methyl and tribenuron-methyl varied according to soil depth (upper profile: 5-70 cm, and lower profile: 165-780 cm) and were proven faster in soil taken from depths 5-7 and 30-35 cm, and slower in depths 45-50 and 70-75 cm. Mineralisation was absent in the lower profile (165-780 cm). As an indicator of microbial activity bacterial counts were taken at the experimental start; these counts grouped in three levels: highest in the surface layer (5-7 cm), slightly lower in the depths 30-75 cm, and lowest in the lower profile (165-780 cm). Residual concentrations of metsulfuron-methyl correlated to the accumulated amount mineralised, with high residual concentrations in soil showing low mineralisation. Also chlorsulfuron showed high residual concentrations with increasing depth in the upper profile, but the relatively high dissipation at 30-35 cm and lower one at 45-50 cm could not be related with the lack of mineralisation. This shows that hydrolysis occurs, but mineralisation of the chloro-substituted sulfonamide is restricted. Tribenuron-methyl and thifensulfuron-methyl could not be detected due to interference with other compounds.     

北京某染料厂污染地块土壤和地下水6种氯苯类化合物的分布特征及迁移转化分析

针对染料化工企业用地存在多种氯苯类化合物污染的问题,以北京某染料厂污染地块为研究对象,采集并测定土壤样品260个、地下水样品6个,研究了地块包气带和饱和带中6种氯苯类化合物的分布特征,分析了6种物质的来源与迁移过程。结果表明,6种氯苯类化合物主要分布在生产区及污水处理区等重污染区的包气带中,低氯苯类化合物遍布地下水中。推断四氯苯、五氯苯和六氯苯主要由生产原料(二氯苯和三氯苯)在高温等工艺条件下发生氯化反应转化而成,而氯苯是由深层厌氧环境中的CBs经微生物还原脱氯生成。氯苯自深层厌氧区迁移扩散,部分向上扩散进入包气带再挥发至空气中;其它5种污染物在重污染区进入包气带,主要受淋溶以及重力作用向下迁移,汇集于包气带的黏粉~粉黏层,其中的二氯苯和三氯苯穿透包气带进入地下水并扩散至整个厂区。本研究结果可为染料化工污染地块的调查及修复工程提供参考。