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。     

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.     

Comparison of a mass balance and an ecosystem model approach when evaluating the carbon cycling in a lake ecosystem

Carbon budgets are frequently used in order to understand the pathways of organic matter-in ecosystems, and they also have an important function in the risk assessment of harmful substances. We compared two approaches, mass balance calculations and an ecosystem budget, to describe carbon processing in a shallow, oligotrophic hardwater lake. Both approaches come to the same main conclusion, namely that the lake is a net autotrophic ecosystem, in spite of its high dissolved organic carbon and low total phosphorus concentrations. However, there were several differences between the carbon budgets, e.g. in the rate of sedimentation and the air-water flux of CO2. The largest uncertainty in the mass balance is the contribution of emergent macrophytes to the carbon cycling of the lake, while the ecosystem budget is very sensitive towards the choice of conversion factors and literature values. While the mass balance calculations produced more robust results, the ecosystem budget gave valuable insights into the pathways of organic matter transfer in the ecosystem. We recommend that when using an ecosystem budget for the risk assessment of harmful substances, mass balance calculations should be performed in parallel in order to increase the robustness of the conclusions.     

Mercury in the Mediterranean. Part 2: processes and mass balance

Mass balance of contaminants can provide useful information on the processes that influence their concentrations in various environmental compartments. The most important sources, sinks and the equilibrium or non-equilibrium state of the contaminant in individual environmental compartments can also be identified. Using the latest mercury speciation data, the results of numerical models and the results of recent studies on mercury transport and transformation processes in the marine environment, we have re-evaluated the total mercury (HgT) mass balance in the Mediterranean Sea. New calculations have been performed employing three distinct marine layers: the surface layer, the thermocline and the deep sea. New transport mechanisms, deep water formation and density-driven sinking and upwelling, were included in the mass balance calculations. The most recent data have even enabled the calculation of an approximate methylmercury (MeHg) mass balance. HgT is well balanced in the entire Mediterranean, and the discrepancies between inputs and outputs in individual layers do not exceed 20 %. The MeHg balance shows larger discrepancies between gains and losses due to measurement uncertainties and gaps in our knowledge of Hg species transformation processes. Nonetheless, the main sources and sinks of HgT (deposition and evasion) and MeHg (fluxes from sediment, outflow through the Gibraltar Strait) are in accordance with previous studies on mercury in the Mediterranean Basin. Mercury in the Mediterranean fish harvest is the second largest MeHg sink; about 300 kg of this toxic substance is consumed annually with sea food.     

Assessing the risk of N leaching from forest soils across a steep N deposition gradient in Sweden

Nitrogen leaching from boreal and temporal forests, where normally most of the nitrogen is retained, has the potential to increase acidification of soil and water and eutrophication of the Baltic Sea. In parts of Sweden, where the nitrogen deposition has been intermediate to high during recent decades, there are indications that the soils are close to nitrogen saturation. In this study, four different approaches were used to assess the risk of nitrogen leaching from forest soils in different parts of Sweden. Nitrate concentrations in soil water and C:N ratios in the humus layer where interpreted, together with model results from mass balance calculations and detailed dynamic modelling. All four approaches pointed at a risk of nitrogen leaching from forest soils in southern Sweden. However, there was a substantial variation on a local scale. Basing the assessment on four different approaches makes the assessment robust.     

Electrochemical dechlorination of chloroacetic acids (CAAs) using hemoglobin-loaded carbon nanotube electrode

Hemoglobin (Hb) was immobilized on carbon nanotube (CNT) electrode to catalyze the dechlorination of chloroacetic acids (CAAs), and the electrocatalytic behaviors of the Hb-loaded electrode for the dechlorination of trichloroacetic acid (TCAA) were studied by cyclic voltammetry and constant-potential electrolysis technique. An Hb-loaded packed-bed flow reactor was also constructed for bioelectrocatalytic dechloriantion of CAAs from drinking water. The results showed that the reduced heme of Hb immobilized on CNT electrode was easily regenerated, and Hb exhibited a stable and high activity for reductive dechlorination of CAAs with significant lowering of overpotential. TCAA could be reduced at -0.450 V (vs. saturated calomel electrode (SCE)) with catalysis of Hb-loaded electrode and its dechlorination was stepwise, following the pathway of TCAA-->dichloroacetic acid (DCAA)-->monochloroacetic acid (MCAA)-->acetic acid. It was also found that all CAAs, e.g., TCAA, DCAA and MCAA, could be dechlorinated completely at -0.450 V. The removal of 30.0 mM TCAA and DCAA is ca. 40% and 31%, respectively, with electrolysis for 100 min at -0.600 V (vs. SCE) using the Hb-loaded packed-bed flow reactor. The dechlorination activities of CAAs follow the decreasing order: TCAA>DCAA>MCAA, and the average current efficiency is over 90%.     

Validation of Mobile Source Emission Estimates Using Mass Balance Techniques

Air quality models must consider error in the emissions estimates as well as in the model itself. Currently, the accepted method for determining emission factors for mobile sources is through the use of the EPA model MOBILE₃. In this paper, emission factor calculations from a technique based on the conservation of mass are presented from experimental data. These emission factors are then compared to MOBILE₃ simulations using the experimental conditions and two different methods of obtaining the vehicle scenario. In both cases, the mass balance gave emission factors that were from 1.5 to 2.2 times those predicted by MOBILE₃. Next, mass balance and MOBILE₃ emission factors were used in the dispersion models CALINE3 and TXLINE in an effort to predict the observed CO concentrations. In both models, enhanced performance was observed when mass balance data were implemented.     

Haloacetic acid removal by sequential zero-valent iron reduction and biologically active carbon degradation

An innovative haloacetic acid (HAA) removal process was developed. The process consisted of a zero-valent iron (Fe⁰) column followed by a biologically active carbon (BAC) column that were efficient in degrading tri- and di-HAAs, and mono- and di-HAAs, respectively. The merit of the process was demonstrated by its performance in removing trichloroacetic acid (TCAA). An empty bed contact time of 10 min achieved nearly complete removal of 1.2 μM TCAA and its subsequent products, dichloroacetic acid (DCAA) and monochloroacetic acid (MCAA). HAA removal was a result of chemical dehalogenation and biodegradation rather than physical adsorption. Preliminary kinetic analyses were conducted and the pseudo-first-order rate constants were estimated at ambient conditions for Fe⁰ reduction of TCAA and biodegradation of DCAA and MCAA by BAC. This innovative process is highly promising in removing HAAs from drinking water, swimming pool water, and domestic or industrial wastewater.     

Environmental risk appraisement of disinfection by-products (DBPs) in plant model system: Allium cepa

The organic toxicants formed in chlorinated water cause potential harm to human beings, and it is extensively concentrated all over the world. Various disinfection by-products (DBPs) occur in chlorinated water are genotoxic and carcinogenic. The toxicity is major concern for chlorinated DBPs which has been present more in potable water. The purpose of the work was to evaluate genotoxic properties of DBPs in Allium cepa as a plant model system. The chromosomal aberration and DNA laddering assays were performed to examine the genotoxic effect of trichloroacetic acid (TCAA), trichloromethane (TCM), and tribromomethane (TBM) in a plant system with distinct concentrations, using ethyl methanesulfonate (EMS) as positive control and tap water as negative control. In Allium cepa root growth inhibition test, the inhibition was concentration dependent, and EC₅₀ values for trichloroacetic acid (TCAA), trichloromethane (TCM), and tribromomethane (TBM) were 100 mg/L, 160 mg/L, and 120 mg/L respectively. In the chromosome aberration assay, root tip cells were investigated after 120 h exposure. The bridge formation, sticky chromosomes, vagrant chromosomes, fragmented chromosome, c-anaphase, and multipolarity chromosomal aberrations were seen in anaphase–telophase cells. It was noticed that with enhanced concentrations of DBPs, the total chromosomal aberrations were more frequent. The DNA damage was analyzed in roots of Allium cepa exposed with DBPs (TCAA, TCM, TBM) by DNA laddering. The biochemical assays such as lipid peroxidation, H₂O₂ content, ascorbate peroxidase, guaiacol peroxidase, and catalase were concentration dependent. The DNA interaction studies were performed to examine binding mode of TCAA, TCM, and TBM with DNAs. The DNA interaction was evaluated by spectrophotometric and spectrofluorometric studies which revealed that TCAA, TCM, and TBM might interact with Calf thymus DNA (CT- DNA) by non-traditional intercalation manner.

     

Predictive model for disinfection by-product in Alexandria drinking water, northern west of Egypt

Chlorine has been utilized in the early stages of water treatment processes as disinfectant. Disinfection for drinking water reduces the risk of pathogenic infection but may pose a chemical threat to human health due to disinfection residues and their by-products (DBP) when the organic and inorganic precursors are present in water. In the last two decades, many modeling attempts have been made to predict the occurrence of DBP in drinking water. Models have been developed based on data generated in laboratory-scale and field-scale investigations. The objective of this paper is to develop a predictive model for DBP formation in the Alexandria governorate located at the northern west of Egypt based on field-scale investigations as well as laboratory-controlled experimentations. The present study showed that the correlation coefficient between trihalomethanes (THM) predicted and THM measured was R ²?=?0.88 and the minimum deviation percentage between THM predicted and THM measured was 0.8 %, the maximum deviation percentage was 89.3 %, and the average deviation was 17.8 %, while the correlation coefficient between dichloroacetic acid (DCAA) predicted and DCAA measured was R ²?=?0.98 and the minimum deviation percentage between DCAA predicted and DCAA measured was 1.3 %, the maximum deviation percentage was 47.2 %, and the average deviation was 16.6 %. In addition, the correlation coefficient between trichloroacetic acid (TCAA) predicted and TCAA measured was R ²?=?0.98 and the minimum deviation percentage between TCAA predicted and TCAA measured was 4.9 %, the maximum deviation percentage was 43.0 %, and the average deviation was 16.0 %.     

Mass balance and long-term fate of PCDD/Fs in a lagoon sediment and paddy soil, Niigata, Japan

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in a sediment core and in samples of surface sediment and paddy soil collected from the Toyano lagoon and Kameda basin in Niigata, Japan, were analyzed to elucidate the temporal trends of their concentrations in the lagoon sediment and the relationship between the sediment and the paddy soil. The mass balance of these pollutants was also estimated to determine their long-term fate in surface waters. An analysis by chemical mass balance identified the agrochemicals pentachlorophenol and 2,4,6-trichlorophenyl 4-nitrophenyl ether as the major sources of PCDD/Fs. On the basis of the findings regarding the mass balance in the Kameda basin over the last 40 years, we estimate that more than half the input of PCDD/Fs to the Kameda basin has disappeared. We suggest that the PCDD/Fs that flowed out from the paddy fields have been transferred to the lower basin.     

Biodegradation of haloacetic acids by bacterial enrichment cultures

Haloacetic acids (HAAs) are toxic organic chemicals that are frequently detected in surface waters and in drinking water distribution systems. The aerobic biodegradation of HAAs was investigated in serum bottles containing a single HAA and inoculated with washed microorganisms obtained from enrichment cultures maintained on either monochloroacetic acid (MCAA) or trichloroacetic acid (TCAA) as the sole carbon and energy source. Biodegradation was observed for each of the HAAs tested at concentrations similar to those found in surface waters and in drinking water distribution systems. The MCAA culture was able to degrade both MCAA and monobromoacetic acid (MBAA) with pseudo-first order rate constants of 1.06 x 10(-2) and 1.13 x 10(-2) l(mg protein)(-1) d(-1), respectively, for concentrations ranging from 10(-5) to 2 mM. The pseudo-first order rate constant for TCAA degradation by the TCAA culture was 6.52 x 10(-3) l(mg protein)(-1) d(-1) for concentrations ranging from 5.33 x 10(-5) to 0.72 mM. The TCAA culture was also able to degrade MCAA with the rate accelerating as incubation time increased. Experiments with radiolabeled HAAs indicated that the 14C was primarily converted to 14CO2 with minor incorporation into cell biomass. The community structure of the enrichment cultures was analyzed by both cultivation-dependent and cultivation-independent approaches. Denaturing gradient gel electrophoresis (DGGE) of the PCR-amplified 16S rRNA gene fragments showed that each of the two enrichment cultures had multiple bacterial populations, none of which corresponded to HAA-degrading bacteria cultivated on HAA-supplemented agar plates. This research indicates that biodegradation is a potential loss mechanism for HAAs in surface waters and in drinking water distribution systems.     

Degradation of 4-fluorobiphenyl in soil investigated by 19F NMR spectroscopy and 14C radiolabelling analysis

The incubation of the model pollutant [U-14C]'-4-fluorobiphenyl (4FBP) in soil, in the presence and absence of biphenyl (a co-substrate), was carried out in order to study the qualitative disposition and fate of the compound using 14C-HPLC and 19F NMR spectroscopy. Components accounted for using the radiolabel were volatilization, CO2 evolution, organic solvent extractable and bound residue. Quantitative analysis of these data gave a complete mass balance. After sample preparation. 14C-HPLC was used to establish the number of 4FBP related components present in the organic solvent extract. 19F NMR was also used to quantify the organic extracts and to identify the components of the extract. Both approaches showed that the composition of the solvent extractable fractions comprised only parent compound with no metabolites present. As the 14C radiolabel was found to be incorporated into the soil organic matter this indicates that metabolites were being generated, but were highly transitory as incorporation into the SOM was rapid. The inclusion of the co-substrate biphenyl was to increase the overall rate of degradation of 4FBP in soil. The kinetics of disappearance of parent from the soil using the data obtained were investigated from both techniques. This is the first report describing the degradation of a fluorinated biphenyl in soil.     

Behavior of perfluorinated compounds in soils during leaching experiments

Perfluorinated compounds (PFCs) can be detected worldwide in both, soil and water. In order to study the leaching behavior of this heterogeneous group of compounds in soil, flow-through column experiments have been conducted. Ten perfluoro carboxylates and four perfluoro sulfonates ranging from C4 to C14 in chain length, and contaminated sewage sludge, have been used to spike a standard soil. The aqueous column effluent was analyzed using liquid chromatography tandem mass spectrometry (LC-MS/MS) with direct injection. The observed percolation velocity seems to be strongly correlated with the length of the perfluorinated chain. Other factors that additionally contribute to the leaching behavior are the functional group of the PFC, the organic carbon content of the soil and the presence of other adsorbates. A mass balance calculation showed that perfluorobutanoic acid can adsorb strongly to the soil, when no PFC with longer carbon chain are present. Only about 60% of the added perfluorobutanoic acid could be detected in the percolate water. The missing amount started to elute again when longer chain PFC or stearate were added to the soil. Thus it would appear that larger and more lipophilic molecules can displace shorter PFC from their binding sites in the soil.The results of a monitoring study using 32 surface water samples and 150 groundwater samples confirm that the PFC with the highest concentrations in groundwater are the short chain PFC with less than 7 (fluorinated) carbon atoms. The dominating PFC in surface waters are perfluorooctanoic acid and perfluorooctane sulfonic acid.     

Ambient concentrations and source apportionment of PCBs and trace elements around an industrial area in Izmir, Turkey

Atmospheric concentrations of polychlorinated biphenyls (PCBs) and trace elements were measured at two sites (Industrial and Urban) located around the Aliaga industrial region, Izmir, Turkey. Average sigma 36PCB concentrations were 3136+/-824 and 1371+/-642 pg m(-3) for summer and winter periods, respectively in the Industrial site and they were 314+/-129 and 847+/-610 pg m(-3) in the Urban site. The elemental content showed that the PM(10) measured at the Industrial site was dominated by terrestrial elements and trace elements emitted by the iron-steel plants (Fe, Zn and Pb). The elemental profile at the Urban site was typical for Aegean Region that was dominated by terrestrial elements (Ca, Al, Mg) and sea salt (Na). Sources of particle-phase PCBs and trace elements were identified using factor analysis (FA) and were apportioned by chemical mass balance (CMB) model. FA suggested that the steel industry, fuel oil combustion, or the nearby vinyl chloride process in the petrochemical plant, and soil were significant PCB sources. CMB results showed that at the Industrial site, the contribution of steel industry and soil to particle-phase PCBs were 71% and 22%, respectively, while at the Urban site, the contributions were 33% and 49%, respectively. Steel industry was also the dominant contributor for trace elements around the site. Fugacity calculations in air and soil showed that the soil acts as a secondary source to the atmosphere for low molecular weight PCBs especially in summer and as a sink for the higher molecular weight ones.     

Fluxes of trichloroacetic acid between atmosphere,biota, soil,and groundwater

Trichloroacetic acid (TCA), in former times used as a herbicide in agriculture, is now ubiquitous and almost evenly distributed in precipitations of the Northern and Southern Hemisphere, despite larger emissions of the possible precursors tetrachloroethene and 1,1,1-trichloroethane in the Northern Hemisphere. The permanent input of a herbicidal compound into most vulnerable ecosystems might lead to adverse effects to biota (plants, microorganisms, etc.). TCA soil levels of coniferous forests in mountainous regions of Central Europe are significantly elevated. Mass balance calculations show that precipitation as sole source of TCA in soil seems to be of minor importance and provide evidence for a natural formation of TCA within soil itself. In addition, the isolation of a chlorinating enzyme in soil and laboratory experiments with humic acid, iron and halide point to an omnipresent chlorinating capability of nature producing polyhalogenated organic compounds such as TCA.In this paper we present an overview of TCA levels in the environment and provide a new estimate about the extent of a natural TCA formation, especially in soil.     

Assessment of Uncertainty in Long-Term Mass Balances for Acidification Assessments: A MAGIC Model Exercise

Long-term (1860–2010) catchment mass balance calculations rely on models and assumptions which are sources of uncertainty in acidification assessments. In this article, we report on an application of MAGIC to model acidification at the four Swedish IM forested catchments that have been subject to differing degrees of acidification stress. Uncertainties in the modeled mass balances were mainly associated with the deposition scenario and assumptions about sulfate adsorption and soil mass. Estimated base cation (BC) release rates (weathering) varied in a relatively narrow range of 47–62 or 42–47 meq m⁻² year⁻¹, depending on assumptions made about soil cation exchange capacity and base saturation. By varying aluminum solubility or introducing a dynamic weathering feedback that allowed BC release to increase at more acidic pHs, a systematic effect on predicted changes in acid neutralizing capacity (ΔANC ca. 10–41 μeq l⁻¹) and pH (ca. ΔpH = 0.1–0.6) at all sites was observed. More robust projections of future changes in pH and ANC are dependent on reducing uncertainties in BC release rates, the timing, and extent of natural acidification through BC uptake by plants, temporal changes in soil element pools, and fluxes of Al between compartments.     

Soil climate and decomposer activity in Sub-Saharan Africa estimated from standard weather station data: a simple climate index for soil carbon balance calculations

Soil biological activity was calculated on a daily basis, using standard meteorological data from African weather stations, a simple soil water model, and commonly used assumptions regarding the relations between temperature, soil water content, and biological activity. The activity factor r(e_clim) is calculated from daily soil moisture and temperature, thereby taking the daily interaction between temperature and moisture into account. Annual mean r(e_clim) was normalized to 1 in Central Sweden (clay loam soil, no crop), where the original calibration took place. Since soils vary in water storage capacity and plant cover will affect transpiration, we used this soil under no crop for all sites, thereby only including climate differences. The Swedish r(e_clim) value, 1, corresponds to ca. 50% annual mass loss of, e.g., cereal straw incorporated into the topsoil. African mean annual r(e_clim) values varied between 1.1 at a hot and dry site (Faya, Chad) and 4.7 at a warm and moist site (Brazzaville, Congo). Sites in Kenya ranged between r(e_clim) = 2.1 at high altitude (Matanya) and 4.1 in western Kenya (Ahero). This means that 4.1 times the Swedish C input to soil is necessary to maintain Swedish soil carbon levels in Ahero, if soil type and management are equal. Diagrams showing daily r(e_clim) dynamics are presented for all sites, and differences in within-year dynamics are discussed. A model experiment indicated that a Swedish soil in balance with respect to soil carbon would lose 41% of its soil carbon during 30 y, if moved to Ahero, Kenya. If the soil was in balance in Ahero with respect to soil carbon, and then moved to Sweden, soil carbon mass would increase by 64% in 30 y. The validity of the methodology and results is discussed, and r(e_clim) is compared with other climate indices. A simple method to produce a rough estimate of r(e_clim) is suggested.     

Release of uranium from rock matrix—a record of glacial meltwater intrusions?

Uranium release observed in a rock matrix around water-carrying fractures was studied using U-series disequilibrium (USD) modelling and mass balance calculations. Several release scenarios were tested, with specific attention to the glacial aspects. The release appears to have occurred in two or three violent episodes during the last 300 ky. A release after the last glaciation can be excluded on mass flow grounds. Continuous release for more than 300 ky can be excluded on radioactive disequilibrium grounds. Repeated inflows of oxic glacial meltwater seem to have triggered the release episodes.     

Release of uranium from rock matrix--a record of glacial meltwater intrusions?

Uranium release observed in a rock matrix around water-carrying fractures was studied using U-series disequilibrium (USD) modelling and mass balance calculations. Several release scenarios were tested, with specific attention to the glacial aspects. The release appears to have occurred in two or three violent episodes during the last 300 ky. A release after the last glaciation can be excluded on mass flow grounds. Continuous release for more than 300 ky can be excluded on radioactive disequilibrium grounds. Repeated inflows of oxic glacial meltwater seem to have triggered the release episodes.