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1.
The Humic Lake Acidification Experiment (HUMEX) was launched in 1988 to study the role of humic substances in the acidification of surface waters and the impacts of acidic deposition on the chemical and biological properties of humic substances. This subproject was designed to determine the contribution of organic acids to the acidity of Lake Skjervatjern (the HUMEX Lake) and the impacts of the acidification on the characteristics of organic carbon. In order to get an empirical measure for organic acidity, dissolved organic carbon (DOC) was fractionated, isolated, and base-titrated from each half of Lake Skjervatjern. Hydrophobic acids were the dominant organic carbon fraction; the total organic acid content was generally greater than 80% of the DOC. The reliability of the fractionation procedure was tested with synthetic acids and the Nordic Fulvic acid. The DOC fractions did not show high variation over the 1.5-y acidification period. Hydrophilic acids had consistently greater exchange acidities compared to hydrophobic acids, averaging 12.9 μeq/mg DOC vs. 10.9 μeq/mg DOC, respectively. The dissociation of organic acids during acid-base titrations clearly increased with increasing pH. The high organic anion contribution to the ion balances indicates that humic matter is an important acidity source in Lake Skjervatjern. There are slight signs that the contribution of organic acids to overall lake acidity has decreased since acidification was initiated.  相似文献   

2.
The combined XAD-8 and XAD-4 resin procedure for the isolation of dissolved organic solutes from water was found to isolate 85% or more of the organic solutes from Lake Skjervatjern in Norway. Approximately 65% of the dissolved organic carbon (DOC) was first removed on XAD-8 resin, and then an additional 20% of the DOC was removed on XAD-4 resin. Approximately 15% of the DOC solutes (primarily hydrophilic neutrals) were not sorbed or concentrated by the procedure. Of the 65% of the solutes removed on XAD-8 resin, 40% were fulvic acids, 16% were humic acids, and 9% were hydrophobic neutrals. Approximately 20% of the hydrophilic solutes that pass through the XAD-8 resin were sorbed solutes on the second resin, XAD-4 (i.e., they were hydrophobic relative to the XAD-4 resin). The fraction sorbed on XAD-4 resin was called XAD-4 acids because it represented approximately 85–90% of the hydrophilic XAD-8 acid fraction according to the original XAD-8 fractionation procedure. The recovery of hydrophobic acids (fulvic acids and humic acids) and the hydrophobic neutral fraction from XAD-8 resin was essentially quantitative at 96%, 98%, and 86%, respectively. The recovery of XAD-4 acids from the XAD-4 resin was only about 50%. The exact reason for this moderately low recovery is unknown, but could result from π-π bonding between these organic solutes and the aromatic matrix of XAD-4. The hydrophobic/hydrophilic solute separation on XAD-8 resin for water from background Side A and Side B of the lake was almost identical at 65 and 67%, respectively. This result suggested that both sides of the lake are similar in organic chemical composition even though the DOC variation from side to side is 20%.  相似文献   

3.
Total organic halogen (TOX) was evaluated as a means to detect contamination of groundwater by halogenated organics. Groundwater samples from monitoring wells at 10 Canadian landfill sites were analyzed for carbon adsorbable TOX, total organic carbon and volatile organics. Low concentrations of TOX (range, ND-44; median 8 μg Cl L?1) were found at nine sites, and elevated TOX levels (?2072 μg Cl L?1) at the tenth site. This latter site was studied in greater detail, and TOX and GC-MS analyses were carried out for volatile, base neutral, and acid extractable fractions of the water in six monitoring wells at this site. The TOX and GC-MS techniques were found to provide complementary information. GC-MS analysis detected high concentrations of 1,2-dichloroethylene, trichloroethylene, toluene, and ethylbenzene in some of the wells. TOX measurements, however, indicated the presence of halogenated contaminants in the base-neutral and acid extractable fractions, which had not been detected by GC-MS.  相似文献   

4.
The study concerns the possible changes in the molecular characteristics of humic materials isolated from the same source as a function of time. A great deal of data has been reported concerning the contrast in molecular characteristics of humic substances isolated from different environments. This has primarily been an attempt to identify source-specific molecular characteristics. However, data presented in this paper suggests that humic substances isolated from a single catchment have significant changes in molecular characteristics over time. Two naturally occurring peat pools (X and Y) situated upon a small organic catchment on Great Dun Fell, Cumbria, UK were sampled monthly between November 1994 and November 1996. Dissolved organic matter (DOM) from the pool water samples was fractionated using macroporous nonionic resins (XAD8 and 4), and the humic, fulvic and hydrophilic acids were collected. These fractions were analysed for elemental composition (C, H and N), weight average molecular weight, functional group content and adsorption (340 nm) of a 1 g l(-1) solution measured in a 1-cm spectrophotometer cell. The molecular characteristics were compared to those of natural DOM described by Scott et al. (1998). Scott et al. reported that drought conditions and seasonal climatic changes could have appreciable effects upon molecular characteristics of natural DOM. Results showed that the atomic H/C ratio of the humic substances increased immediately after strong drought conditions experienced in the summer of 1995. This change was temporary with atomic H/C ratio decreasing gradually over the following months. A similar decrease was observed in the carboxyl group content of the isolated compounds. The data set suggested that atomic H/C ratio in the fulvic and hydrophilic fractions exhibited seasonal characteristics of higher ratios during the late summer/early autumn months. This was not observed in the humic fraction. Humic acids exhibited a seasonal pattern of higher weight average molecular weight during the summer months. These trends were explained in terms of summer production of DOM in the catchment soils, their sequestering in the soil due to limited soil water movement during the summer months and their relative ease of dissolution when rainfall and soil water movement increased during the late summer/early autumn period. The results were found to support seasonal and long-term patterns observed in natural DOM as reported by Scott et al. (1998).  相似文献   

5.
Carcinogenic and mutagenic compounds, which were extracted from the particulates that adhered to inner surfaces of diesel and gasoline engine mufflers, were quantified by the series method of Soxhlet extraction, liquid-liquid partition, thin-layer chromatography, and spectrofluorometry. Mutagenic activity of their neutral and acidic fractions was tested in the improved Ames assay by the preincubation method with Salmonella typhimurium TA98 in the presence and absence of metabolic activation system (S-9 mix). The average content levels (μg/g tar) of polycyclic aromatic hydrocarbons from gasoline engine cars were greater than those from diesel engine vehicles. However, the levels of nitro derivatives of PAHs and polycyclic quinones from the diesel engines were greater than from the gasoline engines. Mutagenic activity of the diesel acidic fraction was the highest among the diesel and gasoline fractions, and was significantly higher in the absence of the S-9 mix. Furthermore, the relative value (Rc = 0) of infrared absorption of carbonyl stretching vibration to that of methylene asymmetric stretching vibration of the diesel acidic fraction was the highest among the diesel and gasoline fractions. These results strongly suggest that highly direct-acting mutagens in the acidic fraction are at higher levels in diesel emission particulates than those from gasoline, and that these mutagens are carboxylic acid, aldehyde, and alcohol derivatives of PAHs and NPAHs.  相似文献   

6.
研究了不同水文期条件下长三角某典型河流型水源地源水有机物种类分布特性及其与消毒副产物关系。结果表明,该水源地源水有机污染特性呈现出丰水期>平水期>枯水期的特点,水体腐殖化程度依次降低。经树脂富集分离后水样溶解性有机物(DOM)各组分占总有机碳(DOC)的比例有所不同。丰水期:疏水性有机酸(HPO A,38%)>亲水性有机物(HPI,26%)>过渡亲水性有机酸(TPI A,16%)>疏水性有机中性物质(HPO N,12%)>过渡亲水性中性物质(TPI N,8%);平水期:HPO A(32%)>HPO N(22%)>TPI A(20%)>HPI(18%)>TPI N(8%);枯水期:HPO A(28%)>TPI A(24%)>HPO N(20%)>HPI(19%)>TPI N(9%)。DOM中仅HPI组分比紫外吸光度值(SUVA)低于原水,其余均高于原水,其中HPO A组分SUVA值最高,是原水的177倍。各水文期条件下,疏水性有机物(疏水性有机酸和疏水性中性物质)对三卤甲烷和卤乙酸生成的贡献,分别超过全部有机物氯化后消毒副产物生成量的60%和65%,表明疏水性有机物是最主要的消毒副产物前体物,应当作为水处理工艺重点去除的有机物组分。各水文期源水有机物特性与消毒副产物生成潜能的关系变化不大,三卤甲烷生成潜能(STHMFP)与SUVA的线性相关度较高,卤乙酸生成潜能(SHAAFP)与SUVA的线性相关度一般。因此,可用水样SUVA值间接反映三卤甲烷生成潜能,以利于在实际生产中快速监控水中消毒副产物前体物的变化趋势  相似文献   

7.
A sample of contaminated groundwater was analyzed using a combination of wet techniques to obtain geochemical information on the mobile species of 60Co, 125Sb, 137Cs and 241Am. The techniques were combined in a scheme to determine the predominant character of the radionuclides in negative or positive fractions, size separation by ultrafiltration, and their association with natural organic matter (NOM). The analyses indicated that the radionuclides of interest were predominantly in the negative fraction. Most of the 60Co and 125Sb were in the small size fraction (<5000 Da), and 137Cs and 241Am were found with the larger, colloidal-sized material. Antimony-125 and 60Co were predominantly in the hydrophilic fraction, while 137Cs and 241Am were found in hydrophobic fractions. Our analysis indicated that 137Cs is found in the same fraction as the large-sized colloidal (hydrophobic) material, suggesting an association with NOM. The results suggested that 60Co and 241Am were associated with NOM, in different size fractions, suggesting that these two nuclides are bound to different sites. Finally, the 125Sb results were inconclusive, whether this nuclide is associated with NOM, or it is inorganic.  相似文献   

8.
Pollutants which are capable of being extracted into nonpolar solvent such as hexane have received the greatest attention in environmental monitoring. However, the polar fraction, inherently more difficult to analyze, is currently undergoing closer scrutiny. Sampling methods specifically designed to entrap polar particles and vapors are compared. Ion-exchange and reversed-phase liquid chromatography columns are examples of such specific sampling techniques. Various extraction schemes are presented with their individual problems and capabilities. Although there are numerous papers on the analysis of polar organic pollutants, few report actual measurements of ambient air samples. Current reports on polar organic pollutants measured in air samples are summarized. Polar organics are generally divided into three categories: acidic, basic, and neutral. Analytical methods relating to the following categories of polar organic compounds are reviewed: (1) phenols, mono- and dicarboxylic acids, and sulfonic acids, (2) aliphatic and aromatic amines, and (3) alcohols, aldehydes and ketones, phthalate esters, isocyanates and N-nitrosamines. Derivatization techniques, such as ester formation, are compared to the analysis of the unsubstituted compound. The formation of such derivatives is often the best way to trace specific compounds at very low levels.  相似文献   

9.
Direct field toxicity tests were performed in two Louisiana waterways, Bayous Trepagnier and St. John, on sediments containing organic/heavy metal mixtures. Our approach involved bioluminescent bacterial toxicity assays (using DeltaTox, which qualitatively identifies polluted areas, and Microtox, which quantifies toxicity). Samples were more completely analyzed in our laboratory using inductively coupled plasma atomic emission spectroscopy (ICP-AES) and gas chromatography/mass spectrometry (GC/MS). Results indicate that lead is the primary toxic metal at the sites examined, though concentrations of metals fluctuate due to spatial variation and the dynamic nature of the waterways. Polycyclic aromatic hydrocarbons (PAHs) are the most abundant group of organics measured and appear to contribute to the overall toxic response. DeltaTox located toxic hotspots where there was an average light loss of 53-100%. Toxicity results from both assays agree but are well correlated with concentration measurements only for certain sediment fractions. Overall, the DeltaTox/Microtox approach appears to be rapid and cost effective for on-site hotspot identification, and may increase understanding of hazards associated with heavy metal and organic contaminants in these waterways.  相似文献   

10.
Mass transfer plays a significant role in the ozonation process. The prediction models associated with the volumetric overall mass transfer coefficient (KLa) and initial fractional ozone absorption (FOA0) during the ozonation process were developed through the use of dimensional analysis. It was found that the volumetric overall mass transfer coefficient is the function of diffusivity, agitation speed, and gas flow rate, and the parameters in the KLa equation are determined. Application of the prediction models for KLa and FOA0 would yield information to choose the most practically feasible operating parameters. The removability of total organic carbon (TOC) can be estimated based on the mass balance relationship and kinetic expression of TOC oxidation, during continuous laboratory ozonation of humic acid solution. The reaction rate constant averaged 0.0291 L/mg·min. The developed model in combination with the mass transfer and reaction kinetics can be used successfully in forecasting the most efficient agitation speed to control the formation of organic compounds. Also, the critical value of ozone partial pressure to achieve the highest TOC removability can be determined through the use of the above developed model.  相似文献   

11.
The removal and transformation of natural organic matter were monitored in the different stages of the drinking water treatment train. Several methods to measure the quantity and quality of organic matter were used. The full-scale treatment sequence consisted of coagulation, flocculation, clarification by flotation, disinfection with chlorine dioxide, activated carbon filtration and post-chlorination. High-performance size-exclusion chromatography separation was used to determine the changes in the humic substances content during the purification process; in addition, a UV absorbance at wavelength 254 nm and total organic carbon amount were measured. A special aim was to study the performance and the capacity of the activated carbon filtration in the natural organic matter removal. Four of the activated carbon filters were monitored over the period of 1 year. Depending on the regeneration of the activated carbon filters, filtration was effective to a degree but did not significantly remove the smallest molar mass organic matter fraction. Activated carbon filtration was most effective in the removal of intermediate molar mass compounds (range 1,000-4,000 g/mol). Regeneration of the carbon improved the removal capacity considerably, but efficiency was returned to a normal level after few months.  相似文献   

12.
Removal of NOM in the different stages of the water treatment process   总被引:5,自引:0,他引:5  
Natural organic matter (NOM) is abundant in natural waters in Finland and in many ways affects the unit operations in water purification. In this study, the organic matter content in water in different stages of a full-scale treatment process over 1 year was measured. The full-scale treatment sequence, studied at the Rusko water treatment plant in Tampere, Finland, consisted of coagulation, flocculation, clarification by sedimentation or flotation, activated carbon (AC) filtration, and disinfection. High-performance size exclusion chromatography (HPSEC) was used for separation to determine changes in the humic substances content during the purification process. In addition, total organic carbon (TOC), KMnO4-number, and UV-absorbance at wavelength 254 nm (UV254) were measured. High molecular weight (HMW) matter was clearly easier to remove in coagulation and clarification than low molecular weight (LMW) matter. Furthermore, depending on the regeneration of the activated carbon filters, activated carbon filtration was effective to a degree but did not remove most of the lowest molecular weight compounds. Significant correlation was established among HPSEC, KMnO4, UV254 absorbance, and TOC. HPSEC proved to be a fast and relatively easy method to estimate NOM content in water and, in fact, gave more information than traditional methods on the type of NOM in a water sample. It also helped the process performance follow-up.  相似文献   

13.
Dissolved organic matter (DOM) in freshwaters is present at concentrations ranging from 0.5 to 50 mg L?1, and consists of various organic compounds, including humic substances (HS). HS exert a variety of direct and indirect biological effects, including interaction with the aryl hydrocarbon receptor (AhR). AhR is a cytosolic receptor that binds various hydrophobic organic compounds (HOCs) and mediates some of their toxic effects. In vitro effects of binary mixtures of various DOM (mainly HS) with various HOCs on AhR-mediated responses were studied by use of H4IIE-luc cells. Six out of 12 DOM activated the AhR even at environmentally relevant concentrations (17 mg L?1). In simultaneous exposures of H4IIE-luc cells to DOM (17 mg L?1) and each of the model compounds, 2,3,7,8-TCDD, PCB126, PCB169, benzo[a]pyrene, benzo[a]anthracene, dibenz[a,h]anthracene, fluoranthene, a mixture of persistent organic pollutants (POPs), a mixture of polycyclic aromatic hydrocarbons (PAHs), and a mixture of all HOCs, either significant additive or facilitative effects were observed when compared to activities of single HOCs. No significant decrease of effects due to possible sorption of HOCs to DOM was observed, even in subsequent experiments when HOCs+DOM mixtures were preincubated for six days before exposure to H4IIE-luc. Thus, DOM does not seem to protect organisms against AhR-mediated toxic effects of HOCs (as usually predicted due to sorption of HOCs on DOM), but it can actually enhance their potency for AhR-mediated effects in some situations.  相似文献   

14.
《Environment international》1999,25(2-3):191-207
The FA and HA fractions represent 20 to 50% of the DOC of the original samples, depending on the origin, and serve as reference materials. The original aqueous samples and the aqueous solutions of the reference materials were characterized with methods suited for measuring samples at natural concentrations. The DOC normalized values of the spectral absorbances (λ = 254 nm; λ = 436 nm) in the original water samples were highest for the brown water and brown coal water and lowest for the secondary effluents. The FA fractions were similar in the UV-absorbance with the exception of the low-absorbing groundwater FA, reflecting a low density of double bonds. The DOC-normalized proton capacity of the FA fractions (10 to 20 μmol/mg) was highest for the brown coal, brown water, and soil-derived samples and again lowest for the groundwater FA. The high values are due to a higher contribution of the weak acids of phenolic type. Specific data for copper complexation capacity (0.5 to 2.5 μmol/mg) went parallel to the proton capacity. The characterization of the FAs by gel chromatography with organic carbon detection revealed three major fractions. The refractory part at short retention time dominated in the brown water and soil-derived samples, whereas the fractions for the lower molecular mass acids at long retention times were dominant in the secondary effluent and the brown coal isolate. Comparison with UV-detected chromatograms revealed a strong decrease in the specific absorbance of the secondary effluent. Up to 3% of the total mass of the FAs could be identified as hydrolyzable amino acids with the highest yield in the sample from secondary effluent and the lowest one in the groundwater sample. The nitrogen content was always higher in the FAs compared to the HAs of the same origin. The application of gel chromatography fluorescence and fluorescence decay time distribution analysis turned out to be a useful tool to differentiate between the different fractions of NOM, the isolates obtained by different methods (e.g., XAD-8, membrane separation) and the fractions of the samples from different origin and age. This is of special value, for the information can also be obtained for samples with natural NOM concentrations, even though further investigations required for full understanding of the data. This work is part of a multi-disciplinary research program (ROSIG: Refraktäre Organische Säuren in Gewässern), funded by the German Research Association (DFG).  相似文献   

15.
High-resolution liquid chromatography is being applied to the characterization of refractory organic compounds present in coal conversion streams at concentrations as low as a few micrograms per liter. The chromatographic system, which was previously developed for the analysis of the molecular biochemical constituents in human body fluids, is capable of analyzing for compounds that are u.v.-absorbing and/or oxidizable with sulfatoceric acid. Aqueous samples from various coal-liquefaction experiments have been collected, concentrated when necessary, and chromatographed. The chromatographic fractions have then been subjected to a multiple-analytical identification procedure utilizing, in sequence, UV-spectrometry, gas chromatography, and mass spectrometry. With this procedure, 18 organics were identified and 15 were quantified in the effluent from the product scrubber of a bench-scale hydrocarbonization unit. In addition, numerous unknown constituents have been characterized with respect to gas chromatographic and mass spectrometric properties.  相似文献   

16.
Natural organic matter, such as humic and fulvic acids and humin, plays a key role in determining the fate and mobility of radioiodine in soil and sediments. The radioisotope 129I is continuously produced and released from nuclear fuel reprocessing plants, and as a biophilic element, its environmental mobility is strongly linked to organic matter.Due to its long half-life (15.7 million years), 129I builds up in the environment and can be traced since the beginning of the nuclear era in reservoirs such as soils and marine sediments. Nevertheless, partition of the isotope between the different types of organic matter in soil and sediment is rarely explored. Here we present a sequential extraction of 129I and 127I chemical forms encountered in a Danish soil, a soil reference material (IAEA-375), an anoxic marine sediment from Southern Norway and an oxic sediment from the Barents Sea. The different forms of iodine are related to water soluble, exchangeable, carbonates, oxides as well as iodine bound to humic acid, fulvic acid and to humin and minerals. This is the first study to identify 129I in humic and fulvic acid and humin. The results show that 30-56% of the total 127I and 42-60% of the total 129I are associated with organic matter in soil and sediment samples. At a soil/sediment pH below 5.0-5.5, 127I and 129I in the organic fraction associate primarily with the humic acid while at soil/sediment pH > 6 129I was mostly found to be bound to fulvic acid. Anoxic conditions seem to increase the mobility and availability of iodine compared to oxic, while subaerial conditions (soils) reduces the availability of water soluble fraction compared to subaqueous (marine) conditions.  相似文献   

17.
The sorption characteristics of 10 organic chemicals, categorized as pharmaceuticals, estrogens and phenols, onto synthetic suspended particle (i.e., alumina) coated with humic acid were investigated according to their octanol-water partition coefficient (K(ow)). Chemical analyses were performed with gas chromatography and mass spectrometry (GC/MS) and high performance liquid chromatography (HPLC). The effects of particles on the toxicity reduction were evaluated using bioassay tests, using Daphnia magna and Vibrio fisheri for phenols and pharmaceuticals, and the human breast cancer cell MCF-7 for estrogens. Sorption studies revealed that 22 and 38% of octylphenol and pentachlorophenol, respectively, were removed by suspended particle, whereas 2,4-dichlorophenol was not removed, which was directly proportional to the logK(ow) value. Similar to the sorption tests, suspended particles significantly reduced the acute toxicities of octylphenol and pentachlorophenol to D. magna and V. fisheri (p<0.01), but there was no significant difference in the toxicity of 2,4-dichlorophenol to D. magna (p=0.8374). Pharmaceuticals, such as ibuprofen, gemfibrozil and tolfenamic acid, showed no discernible sorption to the suspended particle, with the exception of diclofenac, which revealed 11% sorption. For estrogens, such as estrone, 17beta-estradiol and 17alpha-ethynylestradiol, the results indicated no reduction in the sorption test. This may be attributed to the polar interaction by functional groups in sorption between pharmaceuticals and estrogens and suspended particles. In the bioassays, presence of suspended particles did not significantly modify the toxicity of pharmaceuticals (regardless of their K(ow) values) to D. magna, V. fisheri or E-screen.  相似文献   

18.
The humic substances extracted from different soil depths are separated into humic (HA) and fulvic (FA) acids, and characterized for their chemical composition, proton exchange capacity, spectroscopic characteristics and binding properties to the europium ion. The chemical and spectroscopic results show that FA compared to HA has a relatively high O/C ratio, high acidic functional group contents and low aromatic contents. The synchronous fluorescence spectroscopic results show that the stability constant (K) of the soil humic substances with Eu(III) ion tends to increase as the soil depth becomes deeper, and HA has a slightly stronger binding ability than FA. The measured total site concentrations (C(L)) reveal that Eu(III) ion is loaded onto HA by 62-77% of the total acid sites, but FA is only approximately 50% covered by Eu(III) ion. Information could be useful in understanding the migration of radionuclides in soil layer.  相似文献   

19.
It is well known that dissolved organic matter in soil solution may affect the toxicity or bioavailability of heavy metals to plants, but existing information on various organic substances is insufficient for treating problems with heavy metal-contaminated soils. To clarify how dissolved organic matter alters the toxicity and bioavailability of metals, we germinated lettuce seeds exposed to solutions containing Cu and several kinds of dissolved organic matters. Low molecular weight organic acids (citric, malic, and oxalic acids) increased the toxicity and bioavailability of Cu, but low concentrations of the synthetic chelators ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine penta-acetic acid (DTPA) decreased the toxicity and bioavailability of Cu. In contrast, humic acid appeared to be the most effective organic substance for detoxifying Cu, even though it did not significantly decrease the bioavailability of Cu. Consequently, the bioavailability and toxic effects of Cu in soil depend on the nature of coexisting organic substances in the soil solution.  相似文献   

20.
Instrumentation and procedures were developed for gross and detailed characterization of oily wastewaters. The methodology was applied to the assessment of effectiveness of a centralized oily waste treatment facility. Generated data included total, dissolved, and suspended organic content and detailed chemical characteristics of oily water samples.The usefulness of the methodology was demonstrated in a real-life field study involving operation of a centralized oily waste treatment facility operated by the U.S. Army at Fort Eustis, Virginia, in 1976. It was found that the concentration of suspended organics ranged between 5 and 335 ppm and dissolved organics between 14 and 156 ppm in untreated bilge water.Treated bilge waste effluents contained essentially no suspended oil, but rather high (769–1262 ppm) amounts of dissolved organic matter.It was determined that physical methods of waste treatment based on gravity separation and coalescence are effective in removal of suspended petroleum, and that prolonged contact between an oil film and water results in water solubilization of petroleum, leading to very high concentrations of dissolved organic material in the treated effluent.  相似文献   

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