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1.
The effects of persistent organic pollutants on the aquatic environment still can hardly be assessed. Therefore, ready biodegradability is a desired key characteristic of chemicals. Accordingly, biodegradation testing is of utmost importance and is a vital part within the risk assessment for organic chemicals. In the closed bottle test (CBT; OECD 301D) the degree of biological degradation of a chemical is assessed by monitoring the oxygen consumption so far with a Clark electrode as standard method. However, this method is time‐consuming, laborious and led to frequent fluctuations of the test results, which limited their validity. Due to these shortcomings, an optical system that enables contact‐free measuring of the oxygen concentration in a closed bottle, based on dynamic luminescence quenching, was examined. The test results were compared to those obtained with the “classical” electrochemical technique (Clark electrode). At first, a basic standard for the handling of the new instrument in the laboratory was developed. Then possible influencing factors, reliability, comparability, and reproducibility of the test results were investigated by running the CBTs in parallel with the electrode and optode method. The findings proved the new optode method to be unambiguously superior to the electrode technique. The frequency of fluctuations of the test results and time and effort necessary for the test run could considerably be reduced. The degradation kinetics of the test substances could be followed easily in the CBT by increasing the measuring points without much additional effort.  相似文献   

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Catechol is one of the most abundant phenolic components of olive mill wastewaters. In this article, the mineralization of this compound in synthetic aqueous solutions by the Fenton and photo‐Fenton processes is studied. It has been found that for 1.44 mM catechol, the total organic carbon of solutions is reduced about 94.4% at best after 60 min of Fenton treatment at optimized conditions of pH 3.0, 0.2 mM Fe2+, 7.09 mM H2O2, and 25°C. A faster and overall mineralization is attained by applying photo‐Fenton with UVA irradiation. o‐Benzoquinone, 1,2,3‐trihydroxybenzene and 1,2,4‐trihydroxybenzene were identified by GC–MS as primary quinonic and polyhydroxylated derivatives. Small amounts of generated carboxylic acids like muconic, maleic, malonic, acetic, oxalic, and formic acids were detected by ion‐exclusion chromatography. The Fe(III) complexes of these acids persist in the medium under Fenton conditions, while their photolysis by UVA light and that of other by‐products account for by the faster degradation and total mineralization achieved in the photo‐Fenton process. A reaction sequence for catechol mineralization by Fenton and photo‐Fenton involving all intermediates detected is proposed.  相似文献   

4.
Most anti-tumour agents are known to be carcinogenic, mutagenic, teratogenic, embryotoxic or fetotoxic. Only little is known about the environmental impact of pharmaceuticals. Unmetabolized active substances are excreted and will show up in municipal wastewater. Therefore, we examined the biodegradability of the widely used anti-tumour agent 5-fluorouracil (5-FU), also as an example for assessing the impact of hospital effluent on the biodegradation of a test compound. The biodegradability of the structurally similar anti-tumour agents cytarabine and gemcitabine was also examined. Test systems used were the closed bottle test (OECD 301 D) and the modified Zahn-Wellens test (OECD 302 B). 5-FU was not biodegradable in the closed bottle test (CBT) nor in the Zahn-Wellens test (ZWT). At the highest concentration of 5-FU, with hospital effluent an inhibition of the degradation of substances present in hospital effluent was observed, probably as a result of a synergistic effect by 5-FU with antibiotics present in hospital sewage. Gemcitabine was biodegraded 42% in the CBT. The prolongation of the test period to 40 days only improved the result to 45%. In the ZWT, the biodegradation of gemcitabine was 50%. Cytarabine was partially biodegraded in the CBT (50%), but only after an adaptation period of 20 days. After a test prolongation to 40 days, the degree of biodegradation was 80%. In the ZWT, the biodegradability was > 95% after only a few days.  相似文献   

5.
Sulfonamides (SAs) are one of the most frequently used antibiotics. SAs have been found in various environmental compartments. If SAs are not degraded in the environment, they can affect bacteria by their antibiotic properties and contribute to bacterial antibiotic resistance. Therefore, the biodegradability of 11 SAs (sulfanilamide, sulfaguanidine monohydrate, sulfadiazine, sulfathiazole, sulfapyridine, sulfamerazine, sulfamethoxypyridazine, sulfachloropyridazine, sulfamethazine, sulfamethoxazole, and sulfadimethoxine) was studied. For this purpose, the Closed Bottle Test (CBT, OECD 301D) was performed, which includes a toxicity control. In order to monitor the environmental fate of the parent compound and to check for transformation products, a simple, efficient, and reliable HPLC–UV method for the simultaneous determination of these SAs has been developed. Acetonitrile and water (with 0.1% formic acid) were used as mobile phase solvents for gradient elution. The method was validated in terms of precision, detection and quantitation limits, selectivity, and analytical solution stability. In the CBT, none of these SAs was readily biodegradable. The HPLC–UV analysis confirmed that no degradation of any SA took place. In the toxicity control, these SAs showed no toxic effect in the used concentration of environmental bacteria applied in the test.  相似文献   

6.
The biodegradability of 5 different commercially available common photographic developers and their ingredients hydroquinone, isoascorbic acid, and its sodium salt was determined in parallel using the OECD-screening-test (OECD 301E). The results obtained from the degradation test on hydroquinone were compared with the results of other laboratories. Biodegradability of developers containing isoascorbic acid was in the same range as of comparable products containing hydroquinone.  相似文献   

7.
Biodegradation of the Photolysis Products of FeIIIEDTA Ethylenediaminetetraacetate (EDTA) is not biodegraded by activated sludge from a wastewater treatment plant. This work shows that after photolysis of FeIIIEDTA, easily degradable metabolites are formed. The OECD Test 302 B yielded a 53% bioelimination with a sunlight irradiation time of 6.5 hours followed by a 4-week incubation. After 20 hours of sunlight irradiation, EDTA is bioeliminated to 92%. One of the photolytic degradation products, ethylenediaminediacetate (EDDA), has been quantitatively eliminated within 14 days following a lag-phase of 2 weeks. The photolysis of the iron complexes of the phosphonates ATMP and DTPMP did not result in biologically degradable metabolites. With these results, the environmental impact of EDTA can be re-evaluated emphasizing the amount and fate of FeIIIEDTA in the environment. FeIIIEDTA was found to be present in effluents of wastewater treatment plants at fractions from 20 to 90% of the total EDTA. FeIIIEDTA has a half life of about 2 hours in sunlit waters. Complexes of EDTA with other metals do not exchange with iron and are photostable. Therefore, EDTA behaves like 2 different compounds: – FeIIIEDTA undergoes fast photolysis with biodegradation of the metabolites. – The other metal-EDTA complexes are persistent in the environment. Ecological arguments against the use of EDTA are therefore still valid for all EDTA-complexes except the one of Fe(III). However, Fe(III) complexes with the phosphonates ATMP and DTPMP do not exhibit such favorable properties over other metal-complexes, and so all arguments against the use of phosphonates are still valid.  相似文献   

8.
The primary degradation of a technical nonylphenol ethoxylate surfactant with an average chain length of 10 ethoxylate units (NPEO‐10) was studied in a flow‐through system by means of miniaturized biofilm reactors (mBFR) with bacteria from an activated sludge plant. 5 mg/L of the test compound (total EO concentration) were spiked in synthetic wastewater (SWW) and fed to the reactors continuously for 64 days. Compound removal and the formation of degradation products (DP) were monitored under both oxic and anoxic conditions. Solid‐phase extraction and RP‐HPLC with fluorescence detection were employed for sample preparation and analysis. Better removal of the parent compound was seen with the oxic reactors (50 to 70%) than with the anoxic reactors (30 to 50%). Compared to SWW organic matter, the test compound proved to be of refractory nature. The appearance of degradation products in the effluent was earlier with anoxic reactors despite their lower elimination efficiency. After extraction of biomass only minor amounts of NPEO‐10 and metabolites were found, indicating that small amounts were present in adsorbed or intracellular form. Ultimate biodegradation of NPEO‐10 and of octylphenol ethoxylates (OPEO‐9.5; average chain length of 9.5 EO units) was tested by means of manometric respirometry at a theoretical oxygen demand (ThOD) of 100 mg/L. Whereas NPEO‐10 was biodegraded by only 26%, at best, in 28 days, OPEO‐9.5 degradation amounted to (40 ± 5)%.  相似文献   

9.
The degradation of two pesticides: atrazine and metazachlor was investigated in aqueous solution under UV-irradiation with and without H2O2. Rate constants of the photochemical degradation were determined applying a first order kinetics and quantum yields of the processes were calculated. This approach leads to an apparent decrease of the quantum yield with increasing initial pesticide concentration. At low H2O2 initial concentrations, the pesticide degradation was shown to be much more efficient than the degradation under UV-irradiation only. However, at high H2O2 concentrations (>2 mmol L?1), the efficiency of the UV/H2O2 system dropped down and the quantum yields of degradation were lower than for the direct photolysis. In the absence of H2O2, no influence of the pH value on the photodegradation of the pesticides could be noticed in a range between pH 3 and pH 11. At low H2O2 initial concentrations, the photochemical degradation of the pesticides was much faster at pH 3 and pH 7 compared with the degradation at pH 11. The results emphasize the potential of optimized reaction conditions in advanced oxidation.  相似文献   

10.
Bacteria that degrade natural organic matter in groundwater contain oxygenase enzymes that can co‐oxidize trichloroethene (TCE). This degradation pathway is promising for large dilute plumes, but its evaluation is limited because the density of the bacteria with oxygenase enzymes has not been correlated to field scale rates of degradation. A 14C–TCE assay was developed to determine pseudo first‐order rate constants for the aerobic co‐oxidation of TCE in groundwater. The assay involved incubating 14C–TCE in samples of groundwater contained in 160 mL serum bottles, and monitoring the accumulation of radiolabel in degradation products. A first‐order rate constant for co‐oxidation was extracted from the rate of accumulation of 14C in products, accounting for volumetric changes in the serum bottles due to sampling and subsequent changes to the distribution of TCE between the aqueous and gaseous phases. Of the groundwater samples evaluated from 19 wells at five sites, eight samples at three sites had 14C product accumulation rates that exceeded the accumulation rate in filter‐sterilized groundwater controls. First‐order rate constants ranged from 2.65 to 0.0066 year?1, which is equivalent to half‐lives of 0.26 to 105 years. Groundwater samples from a few of the wells in which co‐oxidation occurred had volatile organic contaminants in addition to TCE; their presence may have induced the oxygenase enzymes that are needed for TCE co‐oxidation. 14CO2 represented ~37% to 97% of the 14C products that accumulated; the balance of the products was soluble and non‐volatile.  相似文献   

11.
This study investigated the degradation kinetics, formation of disinfection by‐products (DBPs), and degradation pathways during monochloramination of oxytetracycline (OTC). The degradation kinetics can be well described by a second‐order kinetic model, first‐order in monochloramine (NH2Cl), and first‐order in OTC. Reaction of OTC with NH2Cl shows a high reactivity, with the apparent rate constant of 17.64/M/s at pH 7. The apparent rate constant declined as pH increased from 5 to 10. Six DBPs were detected during monochloramination of OTC, including chloroform (CF), 1,1‐dichloro‐2‐propanone (1,1‐DCP), 1,1,1‐trichloro‐2‐propanone (1,1,1‐TCP), dichloroacetonitrile (DCAN), trichloronitromethane (TCNM), and N‐nitrosodimethlyamine (NDMA). CF, DCAN and NDMA had the maximum yields at neutral pH, while 1,1‐DCP and 1,1,1‐TCP had the maximum yields at pH 4. However, TCNM concentration increased as pH increased. Degradation pathways of OTC monochloramination were then proposed. Hydroxylation and Cl‐substitution are found to be the dominant mechanisms in monochloramination of OTC.  相似文献   

12.
The present work focuses on the performance of Fenton, sono‐Fenton, and sono‐photo‐Fenton processes for the oxidation of phenol present in aqueous solution. The effects of H2O2 concentration, Fe2+ concentration, pH, and initial phenol concentration on the oxidation of phenol were studied. The optimum Fe2+ and H2O2 concentrations for the Fenton process were 45 and 800 mg/L, respectively. For the sono‐Fenton process, the optimum Fe2+ and H2O2 concentrations were 30 and 800 mg/L, respectively. The optimal conditions for the sono‐photo‐Fenton process were found to be 20 mg/L of Fe2+ and 700 mg/L of H2O2. The optimum pH was found to be 3 for the processes investigated in the present study. The analysis of results showed that the sono‐photo‐Fenton method reduced the Fe2+ concentration by 30–50% and the H2O2 concentration by 12.5%. It was found that the sono‐photo‐Fenton technique showed better performance than the Fenton and sono‐Fenton processes for the oxidation of phenol. A lumped kinetic model was used to predict the chemical oxygen demand reduction and the model was found to fit the data.  相似文献   

13.
Photolysis rates of phenanthrene as a function of ionic strength (salinity), oxygen levels and humic acid concentrations were measured in aqueous solution over the range of conditions found in fresh to marine waters. Photolysis followed first order kinetics, with an estimated photodegradation half-life in sunlight in pure water of 10.3±0.7h, in the mid-range of published results. Photolysis rate constants decreased by a factor of 5 in solutions with humic acid concentrations from 0 to 10 mg C L(-1). This decrease could be modeled entirely based on competitive light absorption effects due to the added humics. No significant ionic strength or oxygen effects were observed, consistent with a direct photolysis mechanism. In the absence of significant solution medium effects, the photodegradation lifetime of phenanthrene will depend only on solar fluxes (i.e. temporal and seasonal changes in sunlight) and not vary with a freshwater to marine environment.  相似文献   

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15.
We test the acquisition of high‐resolution topographic and terrain data using hand‐held smartphone technology, where the acquired images can be processed using technology freely available to the research community. This is achieved by evaluating the quality of digital terrain models (DTM) of a river bank and an Alpine alluvial fan generated with a fully automated, free‐to‐use, structure‐from‐motion package and a smartphone integrated camera (5 megapixels) with terrestrial laser scanning (TLS) data used to provide a benchmark. To evaluate this approach a 16.2‐megapixel digital camera and an established, commercial, close‐range and semi‐automated software are also employed, and the product of the four combinations of the two types of cameras and software are compared. Results for the river bank survey demonstrate that centimetre‐precision DTMs can be achieved at close range (10 m or less), using a smartphone camera and a fully automated package. Results improve to sub‐centimetre precision with either higher‐resolution images or by applying specific post‐processing techniques to the smartphone DTMs. Application to an entire Alpine alluvial fan system shows the degradation of precision scales linearly with image scale, but that (i) the expected level of precision remains and (ii) difficulties in separating vegetation and sediment cover within the results are similar to those typically found when using other photo‐based techniques and laser scanning systems. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

16.
Large laboratory columns (15.2 cm diameter, 183 cm long) were fed with groundwater containing trichloroethylene (TCE), were biostimulated and bioaugmented, and were monitored for over 7.5 years. The objective of the study was to observe how the selection of the carbon and energy source, i.e., whey, Newman Zone® standard surfactant emulsified oil and Newman Zone nonionic surfactant emulsified oil, affected the rate and extent of dechlorination. Column effluent was monitored for TCE and its degradation products, redox indicators (nitrate‐N, Fe(II), sulfate), and changes in iron mineralogy. Total bacteria and Dehalococcoides mccartyi strains were quantified using q‐PCR. Complete dechlorination was only observed in the whey treated columns, occurring 1 year after bioaugmentation with addition of a culture known to dechlorinate TCE to ethene, and 3 years later in the non‐bioaugmented column. The addition of the emulsified oils with or without bioaugmentation resulted in dechlorination only through cis‐DCE and vinyl chloride. While Dehalococcoides mccartyi strains are the only known bacteria that can fully dechlorinate TCE, their presence, either natural or augmented, was not the sole determiner of complete dechlorination. The establishment of a supporting microbial community and biogeochemistry that developed with continuous feeding of whey, in addition to the presence of D. mccartyi, were necessary to support complete reductive dechlorination. Results confirm that careful selection of a biostimulant is critical to the success of TCE dechlorination in complex soil environments.  相似文献   

17.
Both laboratory experiments and numerical modelling were conducted to study the biodegradation and transport of benzene–toluene–xylenes (BTX) in a simulated semi‐confined aquifer. The factors incorporated into the numerical model include advection, hydrodynamic dispersion, adsorption, and biodegradation. The various physico‐chemical parameters required by the numerical model were measured experimentally. In the experimental portion of the study, BTX compounds were introduced into the aquifer sand. After the contaminants had been transported through the system, BTX concentrations were measured at 12 equally spaced wells. Subsequently, microorganisms obtained from the activated sludge of a sewage treatment plant and cultured in BTX mixtures were introduced into the aquifer through the 12 sampling wells. The distribution data for BTX adsorption by the aquifer sand form a nonlinear isotherm. The degree of adsorption by the sand varies, depending on the composition of the solute. The degradation time, measured from the time since the bacteria were added to the aquifer until a specific contaminant was no longer detectable, was 35–42 h for BTX. The dissolved oxygen, after degradation by BTX compounds and bacteria, was consumed by about 40–60% in the entire simulated aquifer; thus the aerobic conditions were maintained. This study provides insights for the biodegradation and transport of BTX in aquifers by numerical modelling and laboratory experiments. Experimental and numerical comparisons indicate that the results by Monod degradation kinetics are more accurate than those by the first‐order degradation kinetics. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   

18.
In 1988 and 1989, a natural gradient tracer test was performed in the shallow, aerobic and aquifer at Canadian Forces Base (CFB) Borden. A mixture of ground water containing dissolved oxygenated gasoline was injected below the water table along with chloride (Cl-) as a conservative tracer. The migration of BTEX, MTBE, and Cl was monitored in detail for 16 moths. The mass of BTEX compounds in the plume diminished significantly with time due to intrinsic aerobic biodegradation, while MTBE showed only a small decrease in mass over the 16-month period. In 1995/96, a comprehensive ground water sampling program was undertaken to define the mass of MTBE still present in the aquifer. Since the plume had migrated into an unmonitored section of the Borden Aquifer, numerical modeling and geostatistical methods were applied to define an optimal sampling grid and to improve the level of confidence in the results. A drive point profiling system was used to obtain ground water samples. Numerical modeling with no consideration of degradation pedicted maximum concentrations in excess of 3000 μg/L; field sampling found maximum concentrations of less than 200 μg/L. A mass balance for the remaining MTBE mass in the aquifer eight years after injection showed that only 3% of the original mass remained. Sorption, volatilization, a biotic degradation, and plant uptake are not considered significant attenuation processes for the field conditions. Therefore, we suggest that biodegradation may have played a major role in the attenuation of MTBE within the Borden Aquifer.  相似文献   

19.
Contamination of groundwater with chlorinated ethenes is common and represents a threat to drinking water sources. Standard anaerobic bioremediation methods for the highly chlorinated ethenes PCE and TCE are not always effective in promoting complete degradation. In these cases, the target contaminants are degraded to the daughter products DCE and/or vinyl chloride. This creates an additional health risk, as vinyl chloride is even more toxic and carcinogenic than its precursors. New treatment modalities are needed to deal with this widespread environmental problem. We describe successful bioremediation of a large, migrating, dilute vinyl chloride plume in Massachusetts with an aerobic biostimulation treatment approach utilizing both oxygen and ethene. Initial microcosm studies showed that adding ethene under aerobic conditions stimulated the rapid degradation of VC in site groundwater. Deployment of a full‐scale treatment system resulted in plume migration cutoff and nearly complete elimination of above‐standard VC concentrations.  相似文献   

20.
The degradation pathway for the oxidation of EDTA in the UV/H2O2-process was investigated. In absence of iron ions, the mineralization of EDTA is dominated by the reaction of the HO-radicals generated by the photolysis of H2O2. The organic degradation products iminodiacetate (IMDA), glycinate, oxamate, glyoxylate, oxalate and formate, and the inorganic degradation products carbon dioxide, ammonia, nitrate, nitrite, and cyanate were found. In the presence of iron ions, photolytic decarboxylation processes inside the complex get an important role during degradation, and the organic degradation products ethylenediaminetriacetate (ED3A), ethylenediaminediacetate (EDDA), ethylenediaminemonoacetate (EDMA) were also found. By combining product studies with balances of carbon and nitrogen, the degradation pathway in the UV/H2O2-process could be elucidated. The degradation of EDTA was fast (kdeg = 0.012 s–1), and no toxic degradation products were identified. Therefore, the process is well suited for the elimination of EDTA in water treatment.  相似文献   

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