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1.
Pharmaceutical and personal care products, biocides and iodinated contrast media (ICM) are persistent compounds, which appear in ng to μg L−1 in secondary effluents of sewage treatment plants (STPs). In this work, biogenic metals manganese oxides (BioMnOx) and bio-palladium (Bio-Pd) were applied in lab-scale membrane bioreactors (MBR) as oxidative and reductive technologies, respectively, to remove micropollutants from STP-effluent. From the 29 substances detected in the STP-effluent, 14 were eliminated in the BioMnOx-MBR: ibuprofen (>95%), naproxen (>95%), diuron (>94%), codeine (>93%), N-acetyl-sulfamethoxazole (92%), chlorophene (>89%), diclofenac (86%), mecoprop (81%), triclosan (>78%), clarithromycin, (75%), iohexol (72%), iopromide (68%), iomeprol (63%) and sulfamethoxazole (52%). The putative removal mechanisms were the chemical oxidation by BioMnOx and/or the biological removal by Pseudomonas putida and associated bacteria in the enriched biofilm. Yet, the removal rates (highest value: 2.6 μg diclofenac L−1 d−1) need to improve by a factor 10 in order to be competitive with ozonation. ICM, persistent towards oxidative techniques, were successfully dehalogenated with a novel reductive technique using Bio-Pd as a nanosized catalyst in an MBR. Iomeprol, iopromide and iohexol were removed for >97% and the more recalcitrant diatrizoate for 90%. The conditions favorable for microbial H2-production enabling the charging of the Pd catalyst, were shown to be important for the removal of ICM. Overall, the results indicate that Mn oxide and Pd coupled to microbial catalysis offer novel potential for advanced water treatment.  相似文献   

2.
Quintana JB  Weiss S  Reemtsma T 《Water research》2005,39(12):2654-2664
Laboratory degradation tests with five acidic pharmaceuticals using activated sludge as inocculum under aerobic conditions were performed and microbial metabolites were analysed by liquid chromatography-mass spectrometry (LC-MS). Ketoprofen was partly mineralized as a sole source of carbon and energy and the metabolites determined by LC-MS suggest microbial ketoprofen degradation to proceed along the pathway known for biphenyls and related compounds. Bezafibrate, naproxen and ibuprofen were degraded only cometabolically whereas no transformation was obtained for diclofenac. Some biodegradation intermediates in these batch tests could be tentatively identified by means of LC-MS. The first step in microbial bezafibrate degradation appears to be the hydrolytic cleavage of the amide bond, generating well degradable 4-chlorobenzoic acid as one of the hydrolysis products. As previously found for mammals, ether cleavage and formation of desmethylnaproxen was the initial step in microbial degradation of naproxen. Two isomers of hydroxy-ibuprofen were detected as intermediates in the mineralization of ibuprofen. Laboratory studies suggest that naproxen and ibuprofen can be fully mineralized whereas more stable metabolites occur in microbial ketoprofen and bezafibrate transformation, that may deserve further attention. A LC-MS method for the trace analysis of these metabolites in water was developed and applied to municipal wastewater. Municipal wastewater treatment by a membrane bioreactor may gradually improve the removal of these pharmaceuticals.  相似文献   

3.
The cost of a package plant membrane bioreactor   总被引:1,自引:0,他引:1  
Fletcher H  Mackley T  Judd S 《Water research》2007,41(12):2627-2635
The capital and operating costs associated with a small package plant MBR for small-scale domestic duty has been appraised based on a medium-strength municipal wastewater. The three main membrane configurations were considered, these being multi-tube, hollow fibre and flat sheet, with the most appropriate plant design chosen for each configuration. The analysis proceeded via a consideration of the estimated amortised capital costs of the plant individual components and their installation, coupled with operating costs based largely on energy demand and residuals management. Energy demand was calculated from aeration and pumping costs, with aeration based on a combination of empirical relationships for membrane aeration and mass balance, and the modified Activated Sludge Model version 2 used for estimating tank size and sludge generation. Results indicate that it is possible to produce a single household MBR at a capital cost similar to the current market cost for package treatment plants. Desludging and maintenance of these plants is similar but power requirements for an MBR are around 4 times that associated with more conventional package plants. Economies of scale exist from 6-20 p.e. plants but above 20 p.e. there is little cost difference per head, due to the design assumptions made. CAPEX and OPEX are to some extent interchangeable; reductions in CAPEX are associated with an increase in OPEX and vice versa. Whilst costs are high, the market for package MBRs is significantly influenced by the recycling potential of the effluent produced.  相似文献   

4.
More stringent legislation on dissolved organic matter (DOM) urges the drinking water industry to improve in DOM removal, especially when applied to water with high dissolved organic carbon (DOC) contents and low turbidity. To improve conventional processes currently used in drinking water treatment plants (DWTPs), the performances of a hybrid membrane bioreactor containing fluidised activated carbon were investigated at the DWTP of Rennes. Preliminary results showed that the residual DOC was the major part of the non-biodegradable fraction. In order to increase the global efficiency, an upstream oxidation step was added to the process. Ozone was chosen to break large molecules and increase their biodegradability. The first step consisted of carrying out lab-scale experiments in order to optimise the necessary ozone dose by measuring the process yield, in terms of biodegradable dissolved organic carbon (BDOC). Secondly, activated carbon adsorption of the DOC present in ozonated water was quantified. The whole process was tested in a pilot unit under field conditions at the DWTP of Rennes (France). Lab-scale experiments confirmed that ozonation increases the BDOC fraction, reduces the aromaticity of the DOC and produces small size organic compounds. Adsorption tests led to the conclusion that activated carbon unexpectedly removes BDOC first. Finally, the pilot unit results revealed an additional BDOC removal (from 0.10 to 0.15 mg L−1) of dissolved organic carbon from the raw water considered.  相似文献   

5.
The biodegradation of selected non-adsorbing persistent polar pollutants (P(3)) during wastewater (WW) treatment was studied by comparing a lab-scale membrane bioreactor (MBR) running in parallel to activated sludge treatment (AST). The investigated P(3) are relevant representatives or metabolites from the compound classes: pesticides, pharmaceuticals, insect repellents, flame retardants and anionic surfactants. Analyses of all these P(3) at low ng L(-1) levels with sufficient standard deviations was performed in WW influents and effluents. Non-degradable micropollutants, such as EDTA and carbamazepine were not eliminated at all during WW treatment by any technique. However, the MBR showed significant better removals compared to AST for the investigated poorly biodegradable P(3), such as diclofenac, mecoprop and sulfophenylcarboxylates. An application of such an in terms of sludge retention time optimised MBR may lead to a reduction of these P(3) in the watercycle.  相似文献   

6.
A combined strategy of a photo-Fenton pretreatment followed by a Sequencing Batch Biofilm Reactor (SBBR) was evaluated for total C and N removal from a synthetic wastewater containing exclusively 200 mg L−1 of the antibiotic Sulfamethoxazole (SMX). Photo-Fenton reaction was optimized at the minimum reagent doses in order to improve the biocompatibility of effluents with the subsequent biological reactor. Consequently, the pretreatment was performed with two different initial H2O2 concentrations (300 and 400 mg L−1) and 10 mg L−1 of Fe2+. The pre-treated effluents with the antibiotic intermediates as sole carbon source were used as feed for the biological reactor. The SBBR was operated under aerobic conditions to mineralize the organic carbon, and the Hydraulic Retention Time (HRT) was optimized down to 8 h reaching a removal of 75.7% of the initial Total Organic Carbon (TOC). The total denitrification of the NO3 generated along the chemical-biological treatment was achieved by means of the inclusion of a 24-h anoxic stage in the SBBR strategy. In addition, the Activated Sludge Model No. 1 (ASM1) was successfully used to complete the N balance determining the N fate in the SBBR.The characterization and the good performance of the SBBR allow presenting the assessed combination as an efficient way for the treatment of wastewaters contaminated with biorecalcitrant pharmaceuticals as the SMX.  相似文献   

7.
Fluoroquinolones (FQs) are a group of widely prescribed antibiotics and have been frequently detected in the aquatic environment. The reaction kinetics and transformation of seven FQs (ciprofloxacin (CIP), enrofloxacin (ENR), norfloxacin (NOR), ofloxacin (OFL), lomefloxacin (LOM), pipemidic acid (PIP) and flumequine (FLU)) and three structurally related amines (1-phenylpiperazine (PP), N-phenylmorpholine (PM) and 4-phenylpiperidine (PD)) toward chlorine dioxide (ClO2) were investigated to elucidate the behavior of FQs during ClO2 disinfection processes. The reaction kinetics are highly pH-dependent, can be well described by a second-order kinetic model incorporating speciation of FQs, and follow the trend of OFL > ENR > CIP ∼ NOR ∼ LOM > > PIP in reactivity. Comparison among FQs and related amines and product characterization indicate that FQs’ piperazine ring is the primary reactive center toward ClO2. ClO2 likely attacks FQ’s piperazinyl N4 atom followed by concerted fragmentation involving piperazinyl N1 atom, leading to dealkylation, hydroxylation and intramolecular ring closure at the piperazine moiety. While FQs with tertiary N4 react faster with ClO2 than FQs with secondary N4, the overall reactivity of the piperazine moiety also depends strongly on the quinolone ring through electronic effects. The reaction rate constants obtained in clean water matrix can be used to model the decay of CIP by ClO2 in surface water samples, but overestimate the decay in wastewater samples. Overall, transformation of FQs, particularly for those with tertiary N4 amines, could be expected under typical ClO2 disinfection conditions. However, the transformation may not eliminate antibacterial activity because of little destruction at the quinolone ring.  相似文献   

8.
Onesios KM  Bouwer EJ 《Water research》2012,46(7):2365-2375
Pharmaceuticals and personal care products (PPCPs) have been detected in bodies of water worldwide, yet their effects on the environment are not fully understood. Recent toxicity studies suggest that mixtures of PPCPs at low concentrations may be detrimental to exposed organisms, highlighting the need to remove PPCPs from wastewater treatment plant effluent before it is discharged to the environment. In this study, the utility of biofilm-based PPCP removal as a means to prevent environmental PPCP contamination was investigated. The removal of 14 PPCPs, each at an initial concentration of 10 μg/L, was studied in laboratory sand columns inoculated with wastewater treatment plant effluent. The examined PPCPs included biosol, biphenylol, p-chloro-m-cresol, p-chloro-m-xylenol, chlorophene, sodium diclofenac, gabapentin, gemfibrozil, 5-fluorouracil, ibuprofen, ketoprofen, naproxen, triclosan, and valproic acid. Ten of the PPCPs were removed by greater than 95% during column passage, while the four other compounds proved more recalcitrant. The effect of the concentration (either 50 or 1000 μg/L) of an easily degradable primary substrate (acetate) supplied along with the mixture of PPCPs was examined. Most of the tested PPCPs were removed consistently by the biofilms regardless of the concentration of acetate, although the extent of removal for three compounds showed dependence on acetate concentration, and two behaved with no reproducible pattern over time. Biofilm protein measurements indicated that the mixture of PPCPs supplied to columns suppressed biofilm growth, suggesting toxicity of the PPCPs to the biofilm communities. This laboratory-scale experiment suggests that biofilm-based water treatment strategies, such as soil aquifer treatment and slow sand filtration, may be well-suited for the removal of many PPCPs from impacted water.  相似文献   

9.
Removal of emerging contaminants of concern by alternative adsorbents   总被引:3,自引:0,他引:3  
The effective removal of emerging contaminants of concern (ECCs) such as endocrine-disrupting chemicals, pharmaceutically active compounds, personal care products, and flame retardants is a desirable water treatment goal. In this study, one activated carbon, one carbonaceous resin, and two high-silica zeolites were studied to evaluate their effectiveness for the removal of an ECC mixture from lake water. Adsorption isotherm experiments were performed with a mixture of 28 ECCs at environmentally relevant concentrations (200–900 ng/L). Among the tested adsorbents, activated carbon was the most effective, and activated carbon doses typically used for taste and odor control in drinking water (<10 mg/L) were sufficient to achieve a 2-log removal for most of the tested ECCs. The carbonaceous resin was less effective than the activated carbon because this adsorbent had a smaller volume of pores in the size range required for the adsorption of many ECCs (6–9 Å). For the removal of ECC mixture constituents, zeolites were less effective than the carbonaceous adsorbents. Because zeolites contain pores of uniform size and shape, a few of the tested ECCs with matching pore size/shape requirements were well removed, but the adsorptive removal of others was negligible, even at zeolite doses of 100 mg/L. The results of this study demonstrate that effective adsorbents for the removal of a broad spectrum of ECCs from water should exhibit heterogeneity in pore size and shape and a large pore volume in the 6–9 Å size range.  相似文献   

10.
Juang RS  Tsai SY 《Water research》2006,40(19):3517-3526
A polypropylene (PP) hollow fiber membrane contactor was used as a reactor to enhance the biodegradation of equimolar phenol and sodium salicylate (SA) by Pseudomonas putida CCRC 14365 at 30 degrees C and pH 7. Experiments were performed at a fixed initial cell density of 0.025 g/L and in the total substrate level range 5.32-63.8 mM. The degradation experiments by free cells were also studied for comparison. With pristine hydrophobic fibers, the degradation of SA was started only after phenol was completely consumed. Substrate inhibitory effect was avoided due to sufficiently low substrate levels in the cell medium; however, the biodegradation was time consuming. With ethanol-wetted fibers, both substrates were completely degraded much faster than the use of pristine fibers. Although the wetted fibers were unable to prevent movement of substrates through the pores, biofilm formed on the outer surfaces of the fibers could enhance the tolerance limit of substrate toxicity. This greatly extended the treatment range to high-level substrate mixtures, as long as the water was nearly neutral and free of concentrated inorganic salts.  相似文献   

11.
Lagoon systems are a common and effective method to purify communal sewage in rural areas. Low costs and high purification rates are some of their advantages. But mostly algae blooms in the lagoon cause a secondary pollution of the following stream. In order to tackle this problem, several tests have been carried out combining both lagoon and filtering system. This paper describes a 3 year study on the combination of a lagoon and a planted filter dam in one basin. This system has shown a high and continuous retention rate of algae, pH buffering and a further reduction of general sewage parameters. Furthermore, the effects of varying weather conditions (dry, wet) and seasonal aspects on this combined system will be presented.  相似文献   

12.
The occurrence and removal of phthalates in a trickle filter STW   总被引:2,自引:0,他引:2  
Oliver R  May E  Williams J 《Water research》2005,39(18):4436-4444
This study investigated the fate of phthalates in a trickle filter sewage treatment works. A wide variety of phthalates were researched of which only two were present in significant amounts. Mean concentrations of di-(2-ethylhexyl) phthalate (DEHP) and diethyl phthalate (DEP) measured throughout the system were 23.6 and 25.0 microg/l in raw sewage, 22.0 and 24.8 microg/l in primary, 14.6 and 0.60 microg/l in trickle filter, 18.6 and 0.10 microg/l in humus tank and 18.5 and 0.40 microg/l in reedbed effluents, respectively. Removal by the trickle filter was constantly high for DEP (94-99%) whereas DEHP was variable (<1-44%). Mean concentrations of DEHP and DEP in raw sludge were 30.2 and 1.60 microg/g dry wt, respectively. A mass balance for DEHP was calculated using data from field studies and estimates of sludge production at the works. The mass balance approach helped to provide information that could be used to improve the design and operation of sewage treatment works.  相似文献   

13.
Degradation of 2-chlorobenzoic acid (2-CBA), a model recalcitrant chlorinated organic compound, by pure cultures of Burkholderia cepacia strain DNT with (transformed B. cepacia) and without (untransformed B. cepacia) the bacterial hemoglobin (Vitreoscilla hemoglobin, VHb) gene, vgb, was investigated in parallel membrane bioreactors (MBRs). This was done aseptically to prevent contamination during the operation of the MBRs. The objective was to determine whether the degradation of 2-CBA by cometabolism, using acetate as a primary carbon source, under hypoxic conditions might be enhanced for vgb-bearing cells in MBRs. The 2-CBA removal efficiency of transformed B. cepacia (97-99%) was slightly higher than that of untransformed B. cepacia (95-99%) at all stages. The average amount of chloride released from 2-CBA by transformed cells was also higher than for untransformed cells, 92-96% compared to 64-84% of the maximum theoretical amount, the exact value depending on the operating conditions. These results indicate that 2-CBA degradation/transformation is not accompanied by the stoichiometric release of chloride for the untransformed strain. The difference between percentages of 2-CBA removal and chloride release by untransformed cells was attributed to persistence, under hypoxic conditions, of the 2-CBA chlorine atom in 2-CBA metabolites. Growth of transformed cells was also significantly enhanced under hypoxic conditions compared to untransformed cells. For varying media compositions, the transformed cells reached higher cell densities (3.2-5.4 g/L) relative to untransformed cells (2.8-4.7 g/L) at food to microorganism ratios ranging from 0.44-0.59 to 0.38-0.49 g COD/g biomass-d The observed yields thus ranged from 0.16-0.20 and 0.15-0.18 g TSS/g COD for untransformed and transformed cells, respectively. The value of the yield depended on medium composition. The MBR system using vgb-containing B. cepacia maintained a high biomass concentration without oxygen limitations and provided cell-free effluent. Hence, it may be useful for treating high volumes of water contaminated with low levels of recalcitrant organics.  相似文献   

14.
Rejection of micropollutants by clean and fouled forward osmosis membrane   总被引:1,自引:0,他引:1  
As forward osmosis (FO) gains attention as an efficient technology to improve wastewater reclamation processes, it is fundamental to determine the influence of fouling in the rejection of emerging contaminants (micropollutants). This study focuses on the rejection of 13 selected micropollutants, spiked in a secondary wastewater effluent, by a FO membrane, using Red Sea water as draw solution (DS), differentiating the effects on the rejection caused by a clean and fouled membrane. The resulting effluent was then desalinated at low pressure with a reverse osmosis (RO) membrane, to produce a high quality permeate and determine the rejection with a coupled forward osmosis - low pressure reverse osmosis (FO-LPRO) system. When considering only FO with a clean membrane, the rejection of the hydrophilic neutral compounds was between 48.6% and 84.7%, for the hydrophobic neutrals the rejection ranged from 40.0% to 87.5%, and for the ionic compounds the rejections were between 92.9% and 96.5%. With a fouled membrane, the rejections were between 44.6% and 95.2%, 48.7%-91.5% and 96.9%-98.6%, respectively. These results suggest that, except for the hydrophilic neutral compounds, the rejection of the micropollutants is increased by the presence of a fouling layer, possibly due to the higher hydrophilicity of the FO fouled membrane compared to the clean one, the increased adsorption capacity of hydrophilic compounds and reduced mass transport capacity, membrane swelling, and the higher negative charge of the membrane surface, related to the foulants composition, mainly NOM acids (carboxylic radicals) and polysaccharides or polysaccharide-like substances. However, when coupled with RO, the rejections in both cases increased above 96%. The coupled FO-LPRO system was an effective double barrier against the selected micropollutants.  相似文献   

15.
介绍了膜生物反应器的发展历程,对膜生物反应器的分类以及工艺特点作了阐述,并讨论了膜生物反应器在生活污水、工业废水中的应用,对其发展前景进行了展望.  相似文献   

16.
膜生物反应器在水处理中的应用与发展   总被引:3,自引:0,他引:3  
崔丽英  杨成永  武红霞 《山西建筑》2003,29(18):103-104
介绍了国内外膜生物反应器的研究及应用进展,结合膜生物反应器的特点与分类,就其应用现状作了阐述,并指出膜生物反应器技术是一种高效废水处理工艺,具有广阔的应用前景。  相似文献   

17.
Wang P  He YL  Huang CH 《Water research》2011,45(4):1838-1846
Tetracyclines (TCs) are a group of widely used antibiotics that have been frequently found in the aquatic environment. The potential reactions of TCs with common water disinfection oxidants such as chlorine dioxide (ClO2) and free available chlorine (FAC) have not been studied in depth and are the focus of this study. The oxidation kinetics of tetracycline, oxytetracycline, chlorotetracycline and iso-chlorotetracycline by ClO2 and FAC are very rapid (with large apparent second-order rate constants kapp = 2.24 × 105-1.26 × 106 M−1 s−1 with ClO2 and kapp = 1.12 × 104-1.78 × 106 M−1 s−1 with FAC at pH 7.0) and highly dependent on pH. Species-specific rate constants are obtained by kinetic modeling that incorporates pH-speciation of TCs and the oxidants (for FAC), and reveal that TCs primarily react with ClO2 and FAC by their unprotonated dimethylamino group and deprotonated phenolic-diketone group. The modest difference in reactivity among the four TCs toward the oxidants is consistent with expectation and can be explained by structural influences on the two reactive moieties. Product evaluation shows that oxidation of TCs by ClO2 leads to (hydr)oxylation and breakage of TC molecules, while oxidation of TCs by FAC leads to chlorinated and (hydr)oxylated products without any substantial ring breakage. Results of this study indicate that rapid transformation of TCs by oxidants such as ClO2 and FAC under water and wastewater treatment conditions can be expected.  相似文献   

18.
The goal of this study was to determine the effect of a long sludge retention time on the biodegradation of the endogenous residue in membrane digestion units receiving a daily feed of sludge and operated under either aerobic or intermittently aerated (22 h off-2 h on) conditions. The mixed liquor for these experiments was generated in a 10.4 day sludge retention time membrane bioreactor fed with a synthetic and completely biodegradable influent with acetate as the sole carbon source. It had uniform characteristics and consisted of only two components, heterotrophic biomass XH and endogenous residue XE. Membrane digestion unit experiments were conducted for 80 days without any sludge wastage except for some sampling. The dynamic behaviour of generation and consumption of filtered organic digestion products was characterized in the membrane digestion unit systems using three pore filter sizes. Results from this investigation indicated that the colloidal matter with size between 0.04 μm and 0.45 μm was shown to contain a recalcitrant fraction possibly composed of polysaccharides bound to proteins which accumulated in the membrane digestion unit under both conditions. Modelling the membrane digestion unit results by considering a first-order decay of the endogenous residue allowed to determine values of the endogenous residue decay rate of 0.0065 and 0.0072 d−1 under fully aerobic and intermittently aerated conditions, respectively. The effect of temperature on the endogenous decay rate was assessed for the intermittently aerated conditions in batch tests using thickened sludge from tests gave an endogenous decay rate constant of 0.0075 d−1 at 20 °C and an Arrhenius temperature correction factor of 1.033.  相似文献   

19.
Degradation of paracetamol in aqueous solutions by TiO2 photocatalysis   总被引:1,自引:0,他引:1  
Yang L  Yu LE  Ray MB 《Water research》2008,42(13):3480-3488
In this study, photo/photocatalytic oxidation of common analgesic and antipyretic drug, paracetamol (acetaminophen), was investigated to determine the optimal operating conditions for degradation in water. UVA (365 nm) radiation alone degraded negligible amount of paracetamol, whereas paracetamol concentration decreased substantially under an irradiation of UVC (254 nm) with marginal changes in total organic carbon (TOC). In the presence of TiO2, much faster photodegradation of paracetamol and effective mineralization occurred; more than 95% of 2.0mM paracetamol was degraded within 80 min. The degradation rate constant decreased with an increase in the initial concentration of paracetamol, while it increased with light intensity and oxygen concentration. The degradation rate also increased with TiO2 loading until a concentration of 0.8 g L(-1). The degradation rate slowly increased between pH 3.5 and 9.5, but significantly decreased with increasing pH between 9.5 and 11.0. Based on the experimental data, a kinetic equation describing paracetamol photocatalytic degradation with various process parameters is obtained.  相似文献   

20.
The paper describes the aerobic degradation of carbamazepine (CBZ), an anti-epileptic drug widely found in aquatic environment, from Erlenmeyer flask to bioreactor by the white-rot fungus Trametes versicolor. In Erlenmeyer flask, CBZ at approximately 9 mg L−1 was almost completely eliminated (94%) after 6 d, while at near environmentally relevant concentrations of 50 μg L−1, 61% of the contaminant was degraded in 7 d. Acridone, acridine, 10,11-dihydro-10,11-dihydroxy-CBZ, and 10, 11-epoxy-CBZ were identified as major metabolites, confirming the degradation of CBZ. The degradation process was then carried out in an air pulsed fluidized bioreactor operated in batch and continuous mode. Around 96% of CBZ was removed after 2 days in batch mode operation, and 10,11-dihydro-10,11-epoxycarbamazepine was found as unique metabolite. In bioreactor operated in continuous mode with a hydraulic retention time of 3 d, 54% of the inflow concentration (approx. 200 μg L−1) was reduced at the steady state (25 d) with a CBZ degradation rate of 11.9 μg CBZ g−1 dry weight d−1. No metabolite was detected in the culture broth. Acute toxicity tests (Microtox) indicated that the final culture broth in both batch and continuous mode operation were non toxic, with 15 min EC50 values of 24% and 77%, respectively.  相似文献   

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