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1.
The thermal oxidation degradation of styrene–butadiene rubber (SBR) was investigated by in situ FTIR, 2D-FTIR, and programming heating DSC. The results of analyses suggest that the degradation reaction is an autocatalytic process and mainly occurs on the aliphatic part instead of benzene pendants. Based on the results of in situ FTIR and 2D-FTIR, the oxidation process can be divided into three stages. In stage one, just two carbonyl peaks appear, namely 1,697 cm?1 (conjugate carbonyls) and 1,727 cm?1 (saturated carbonyls), and the generation speed is 1,697 > 1,727 cm?1. Yet the peaks appearing at 1,777 cm?1 belonged to peresters and anhydrides generating in stages two and three. The generation sequences are: 1,698 > 1,727 > 1,777 cm?1 for stage two; and 1,698 < 1,727 < 1,777 cm?1 for stage three. According to DSC results, the thermal oxidation of SBR contains four steps. The first step is the generation of alkyl radicals and the accumulation of hydroperoxide species. The second step is initial oxidation stage mainly producing conjugate carbonyls. The third step is deep oxidation process generating diverse carbonyls. The fourth is chain termination reaction, in which step the generation rates of anhydrides and peresters are the fastest due to bi-radical termination of alkoxy radicals and the consumption of conjugate carbonyl. Furthermore, crosslinking reactions occur during the whole thermal oxidation.  相似文献   

2.
《Analytical letters》2012,45(7):1171-1181
Nitrate removal and nitrate removal velocity rate were determined for Mississippi River deltaic plain forested-tupelo dominated wetland, and a floating emergent freshwater marsh. Nitrate removal rate from floodwater was 19.45 and 48.90 mg N m?2 d?1 for two forested-tupelo wetland sites and 48.41 and 46.98 mg N m?2 d?1 at two floating emergent freshwater marsh sites. The removal velocity constants (k) of NO3-N ranged from 0.44 to 1.44 per day for the four site studies. Removal velocity of nitrate from the water column was faster in the floating emergent marsh cores than from the forested wetland course, which contained more sediment. Results demonstrated that removal velocity is an important parameter when estimating nitrate removal from floodwater. Results also demonstrated the two freshwater wetland habitats had a high capacity for processing any nitrate entering the wetlands from adjacent agriculture area. Removal was attributed to denitrification and diffusion.  相似文献   

3.
Nature and population of Li+ cationic sites in MCM-22 zeolite and its pillared form (MCM-36) were investigated by means of adsorption of CO as a probe molecule. CO stretching frequency and adsorption heat were measured by FTIR spectroscopy and adsorption microcalorimetry. Intrazeolitic carbonyl complexes on Li+ cations in MCM-22 and MCM-36 are characterized by two main vibrational bands at 2,195 and 2,188 cm?1. Band at higher wavenumbers is ascribed to carbonyls on Li+ ions coordinated only to two oxygen atoms at the intersection of 10-ring channels and interacting with CO molecule by energy around 45 kJ mol?1. Band at 2,188 cm?1 was assigned to the carbonyls on Li+ cations located on top of 5 or 6-rings on the channel walls and coordinated to three or four oxygen atoms, interacting with CO molecule by energy 33–36 kJ mol?1. Effect of pillaring and layered form of zeolite on nature and population of Li+ cationic sites is also discussed, as well as the formation of dicarbonyl complexes.  相似文献   

4.
The anaerobic treatment of raw vinasse in a combined system consisting in two methanogenic reactors, up-flow anaerobic sludge blanket (UASB) + anaerobic packed bed reactors (APBR), was evaluated. The organic loading rate (OLR) was varied, and the best condition for the combined system was 12.5 kg COD m?3day?1 with averages of 0.289 m3 CH4 kg COD r?1for the UASB reactor and 4.4 kg COD m?3day?1 with 0.207 m3 CH4 kg COD r?1 for APBR. The OLR played a major role in the emission of H2S conducting to relatively stable quality of biogas emitted from the APBR, with H2S concentrations <10 mg L?1. The importance of the sulphate to COD ratio was demonstrated as a result of the low biogas quality recorded at the lowest ratio. It was possible to develop a proper anaerobic digestion of raw vinasse through the combined system with COD removal efficiency of 86.7% and higher CH4 and a lower H2S content in biogas.  相似文献   

5.
The objective of this study was to develop a simple, efficient and reliable method for routine quantitative analysis for Psoralea corylifolia L. An ultra performance liquid chromatography with DAD detector system was employed for simultaneous quantification of ten compounds. The chromatographic analysis was performed by UPLC with C18 column and gradient elution of 0.05% formic acid aqueous solution and acetonitrile in 16 min. All calibration curves were linear (R 2 ≥ 0.9990) over the tested ranges. The LOD and LOQ were lower to 13.07 and 39.22 ng mL?1 with 2 μL of injection volume, respectively. The intra- and inter-day precisions as determined from sample solutions were below 4.1 and 4.2%. The average recoveries were ranged from 94.2 to 108.8% with RSDs ≤ 4.6%. This validated method was applied for the analysis of ten analytes in P. corylifolia L. from different origins. The variation of the content of ten compounds was remarkable among the tested samples: psoralenoside increased from 7.42 to 17.04 mg g?1, isopsoralenoside from 6.05 to 14.34 mg g?1, psoralen from 2.37 to 3.90 mg g?1, isopsoralen from 2.53 to 3.65 mg g?1, neobavaisoflavone from 1.59 to 2.96 mg g?1, bavachin from 1.02 to 2.35 mg g?1, psoralidin from 0.45 to 1.91 mg g?1, isobavachalcone from 1.33 to 4.71 mg g?1, corylifol A from 1.02 to 2.40 mg g?1 and bakuchiol from 28.10 to 63.89 mg g?1.  相似文献   

6.
For the real-time measurements of volatile organic compounds (VOCs) in vehicle exhaust, we employed a vacuum ultraviolet single-photon ionization time-of-flight mass spectrometer (VUV-SPI-TOFMS). Exhaust measurements from gasoline and diesel engine vehicles were performed using a chassis dynamometer. Hydrocarbons such as alkylbenzenes, alkenes, alkanes, and dienes were the major organic compounds present in both gasoline and diesel engine exhaust. The concentrations of organic compounds in gasoline exhaust were higher under running conditions than during idling. The VOC concentrations in diesel exhaust were higher during idling than during running conditions. The VUV-SPI-TOFMS measured composition and emission profiles of many hydrocarbons, including aliphatics and aromatics, in vehicle exhaust simultaneously with real time response.  相似文献   

7.
An analytical method based on TD-GC/MS was developed and validated for the determination of volatile organic compounds (VOCs), including linear and cyclic volatile methylsiloxanes (VMSs), in biogas. Biogas was first sampled in Supel? Inert Film bags and subsequently dynamically sampled onto multisorbent bed tubes (Carbotrap, Carbopack X and Carboxen 569) using portable pump equipment. Two sample volumes, 100 and 250 ml, were evaluated. Desorption efficiency values for both volumes are in the range of 99–100% for almost all studied compounds while breakthrough values (%VOC on sample tube back section) are below 1% for most evaluated VOCs. However, acetaldehyde, carbon disulphide, ethanol and 1,3-butadiene have breakthrough values higher than 5%. Method detection limits were in the range of 0.01–0.8 ng per sample. The most abundant VOCs in biogas were terpenes with concentrations between 500 and 700 mg m?3. Other important families were ketones, aromatic hydrocarbons and alkanes, with concentrations in the range of 36–46 , 20–35 and 14–16 mg m?3, respectively. VMSs presented average concentrations of 4.9 ± 0.4 mg m?3. Additionally, the Supel? Inert Film bags were evaluated for stability for 4 days at room temperature. Although several VOC families’ concentrations in the bag increased or decreased significantly (t-test; p ≤ 0.01, = 5) 2 days after collection, recoveries were around 70–130% for most studied VOCs. The results shown demonstrate that the presented methodology is reliable and satisfactory for the evaluation of VOCs in biogas and presents an alternative to the currently existing biogas analytical techniques.  相似文献   

8.

A method has been developed to measure aldehydes and ketones associated with atmospheric particles. Carbonyl compounds from particulate material collected on Teflon-coated glass-fiber filters were simultaneously extracted and derivatized with an appropriate 2,4-dinitrophenylhydrazine (2,4-DNPH) solution. The efficiency of this procedure utilizing various 2,4-DNPH concentrations and solvent compositions was studied for 13 carbonyl compounds of atmospheric importance. These include formaldehyde, acetaldehyde, acetone, dicarbonyls such as glyoxal and methylglyoxal, and biogenic carbonyls such as pinonaldehyde and nopinone. An extraction solution containing 3 × 10?2 M 2,4-DNPH, in 60% acetonitrile/40% water, and pH 3 was most efficient in extracting and derivatizing these aldehydes and ketones (83-100% recovery). Improved sample enrichment and 2,4-DNPH purification methods were developed that afforded detection limits of 0.009-5.6 ng m?3. The relative standard deviation for replicate analyses were 1.9-10.1%. Carbonyl compounds in ambient particulate samples were quantified during a recent field study. Median values for nine carbonyl species ranged from 0.01-33.9 ng m?3 during the study.  相似文献   

9.
The electrodegradation of azithromycin was studied by its indirect oxidation using dimensionally stable Ti/RuO2 anode as catalyst in the electrolyte containing methanol, 0.05 M NaHCO3, sodium chloride and deionized water. The optimal conditions for galvanostatic electrodegradation for the azithromycin concentration of 0.472 mg cm?3 were found to be NaCl concentration of 7 mg cm?3 and the applied current of 300 mA. The differential pulse voltammetry using glassy carbon electrode was performed for the first time in the above-mentioned content of electrolyte for the nine concentration of azithromycin (0.075–0.675 mg cm?3) giving the limits of azithromycin detection and of quantification as: LOD 0.044 mg cm?3 and LOQ 0.145 mg cm?3. The calibration curve was constructed enabling the electrolyte analysis during its electrodegradation process. The electrolyte was analyzed by high-performance liquid chromatography and electrospray ionization time-of-flight mass spectrometry. The electrooxidation products were identified and after 180 min there was no azithromycin in the electrolyte while TOC analysis showed that 79% of azithromycin was mineralized. The proposed degradation scheme is presented.  相似文献   

10.
An anaerobic sequencing batch reactor containing immobilized biomass (AnSBBR) was used to produce biomethane by treating the effluent from another AnSBBR used to produce biohydrogen from glucose- (AR-EPHG) and sucrose-based (AR-EPHS) wastewater. In addition, biomethane was also produced from sucrose-based synthetic wastewater (AR-S) in a single AnSBBR to compare the performance of biomethane production in two steps (acidogenic and methanogenic) in relation to a one-step operation. The system was operated at 30 °C and at a fixed stirring rate of 300 rpm. For AR-EPHS treatment, concentrations were 1,000, 2,000, 3,000, and 4,000 mg chemical oxygen demand?(COD)?L?1 and cycle lengths were 6 and 8 h. The applied volumetric organic loads were 2.15, 4.74, 5.44, and 8.22 g COD L?1 day?1. For AR-EPHG treatment, concentration of 4,000 mg COD L?1 and 4-h cycle length (7.21 g COD L?1 day?1) were used. For AR-S treatment, concentration was 4,000 mg COD L?1 day?1 and cycle lengths were 8 (7.04 g COD L?1 day?1) and 12 h (4.76 g COD L?1 day?1). The condition of 8.22 g COD L?1 day?1 (AR-EPHS) showed the best performance with respect to the following parameters: applied volumetric organic load of 7.56 g COD L?1 day?1, yield between produced methane and removed organic material of 0.016 mol CH4?g COD?1, CH4 content in the produced biogas of 85 %, and molar methane productivity of 127.9 mol CH4?m?3 day?1. In addition, a kinetic study of the process confirmed the trend that, depending on the biodegradability characteristics of the wastewaters used, the two-step treatment (acidogenic for biohydrogen production and methanogenic for biomethane production) has potential advantages over the single-step process.  相似文献   

11.
Adsorption of CO as a probe molecule on K-FER zeolites differing in Si/Al ratio was investigated. Successful determination of adsorption heats of individual adsorption complexes formed upon adsorption of CO molecules on K-FER zeolites at 300 K by combination of IR spectroscopy with adsorption microcalorimetry is reported. Adsorption heat of bridged carbonyl complexes, where CO molecule interacts with two nearby extraframework K+ cations, was experimentally determined for the first time. It was found that bridged complexes on dual cationic sites exhibit adsorption heat of 34.8 kJ mol?1, whereas monodentate carbonyls on single isolated K+ cation exhibit adsorption heat of only 26.2 kJ mol?1 and adsorption heat of isocarbonyls was 21.5 kJ mol?1.  相似文献   

12.
A sensor is described for the detection of propionaldehyde in the gas phase. The sensing scheme is based on the blue cataluminescence (CTL) emission that results from the catalytic oxidation of propionaldehyde on the surface of nanosized zirconium dioxide. The sensor displays high sensitivity to propionaldehyde, a response time of 3 s, and a recovery time of 8 s. Under optimized conditions, the intensity of CTL is linearly related to the concentration of propionaldehyde in the 2.5–1,300 mg·m?3 concentration range, with a limit of detection of 0.6 mg·m?3 (at an SNR of 3) and a relative standard deviation (for n?=?6) of 2.2 % at a level of 80 mg·m?3 of propionaldehyde. Relatively weak interference is observed for ethanol, acetone and acetaldehyde. The method was applied to analyze environmental air samples containing propionaldehyde, and data were compared with those obtained by GC-MS. The results were in good agreement, thereby indicating the utility of the sensor for routine monitoring. A possible mechanism for the catalytic oxidation of propionaldehyde on the ZrO2 surface is discussed on the basis of the chromatograms of the reaction products.
Figure
A gas sensor for propionaldehyde was fabricated based on the cataluminescence (CTL) emission generated by the catalytic oxidation of propionaldehyde on a nanosized ZrO2 surface. The sensor showed highly sensitivity and good selectivity to propionaldehyde with a response time of less than 3 s and a recovery time of under 20 s  相似文献   

13.
Summary In this investigation an analytical procedure for the determination of different organobromine compounds in motor car exhaust gases is developed in order to obtain a total balance of these compounds in this type of exhaust gas. For this purpose, adsorption sampling on Tenax GC combined with thermal desorption and a fast cold trap injection into the GC column system is used. A special capillary cold trap/thermodesorption system for a fast injection within 1 s is developed. The chromatographically separated fractions are identified by their retention times and elementspecific detection with a microwave plasma detector. Methyl bromide, 1,2-dibromoethane, and vinyl bromide are analysed in exhaust gases in cases where the gasoline contains 1,2-dibromoethane as an additive (leaded gasoline). The analysed bromine contents, which correspond to these organobromine compounds, are in the range of 90–190 g/m3, 15–85 g/m3, and 5–20 g/m3, respectively. The portion of the organobromine compounds is 22–44% of the total bromine which is emitted by the exhaust gases. The other portion contains mainly inorganic particulate bromide, which can be separated by filters. The concentration of the organobromine compounds decreases with increasing motor temperature. After conversion into 2-bromocyclohexanol and after gas chromatographic separation HBr is detected to be 5.8 g bromine per m3 exhaust gas, which corresponds to approximately 1% of the total bromine emission. 1,2-Dichloroethane is analysed in the range of 5–35 g Cl/m3, whereas the concentration of tetraalkyl lead in the exhaust gases is less than the detection limit of 6.7 g Pb/m3. The average bromine/lead ratio found in the filterable portion of the exhaust gases is 0.30 (by weight); the same ratio calculated for total bromine emission including the organobromine compounds is 0.47. Compared with the bromine/ lead ratio in gasoline of 0.39 this means that at least 17% of the total lead in the gasoline is not directly emitted with the motor car exhaust gases.
Analyse von bromorganischen Verbindungen und HBr in Autoabgasen mit einem GC/Mikrowellenplasma-System
  相似文献   

14.
This work aimed to characterize two native microalgal strains newly isolated from South Mediterranean areas and identified as Chlorella sorokiniana ES3 and Neochloris sp. AM2. The growth properties and biochemical composition of these microalgae were evaluated in different culture media (Algal, BG-11, f/2, and Conway). Among the tested media, nitrate- and phosphate-rich Algal medium provided the maximum biomass productivities (85.5 and 111.5 mg l?1 day?1 for C. sorokiniana and Neochloris sp., respectively), while the nitrate- and phosphate-deficient f/2 medium resulted in the highest lipid productivities (24.1 and 35.8 mg l?1 day?1 for C. sorokiniana and Neochloris sp., respectively). The physiological state of both microalgae was investigated under different light and temperature levels using the pulse amplitude-modulated fluorometry. The better photosynthetic efficiency of C. sorokiniana was obtained at 23 °C with a light saturation of 156 μE m?2 s?1, while that of Neochloris sp. was achieved at 15 °C with a light saturation of 151 μE m?2 s?1. The analysis of fatty acid profile and biodiesel parameters revealed that C. sorokiniana, cultivated in Algal and f/2 media, can be considered as a suitable candidate for high-quality biodiesel production.  相似文献   

15.
Hypericum perforatum L. (St. John’s Wort) is an important medicinal plant which is widely used in the treatment for depression and irritable bowel syndrome. It is also used as a dietary supplement. Major bioactive phytochemicals of H. perforatum are phenolics and flavonoids. Quality of these phytochemicals is dramatically influenced by environmental and biological factors in the field grown plants. As an alternative, we have developed adventitious root cultures in large-scale bioreactors for the production of useful phytochemicals. Adventitious roots of H. perforatum were cultured in 500 l pilot-scale airlift bioreactors using half-strength Murashige and Skoog medium with an ammonium and nitrate ratio of 5:25 mM and supplemented with 1.0 mg l?1 indole butyric acid, 0.1 mg l?1 kinetin, and 3 % sucrose for the production of bioactive phenolics and flavonoids. Then 4.6 and 6.3 kg dry biomass were realized in the 500 l each of drum-type and balloon-type bioreactors, respectively. Accumulation of 66.9 mg g?1 DW of total phenolics, 48.6 mg g?1 DW of total flavonoids, 1.3 mg g?1 DW of chlorogenic acid, 0.01 mg g?1 DW of hyperin, 0.04 mg g?1 DW of hypericin, and 0.01 mg g?1 DW of quercetin could be achieved with adventitious roots cultured in 500 l balloon-type airlift bioreactors. Our findings demonstrate the possibilities of using H. perforatum adventitious root cultures for the production of useful phytochemicals to meet the demand of pharmaceutical and food industry.  相似文献   

16.
The effect of different abiotic elicitors [jasmonic acid, copper sulphate (CuSO4) and salicyclic acid] at varying concentrations on the stimulation of biomass and bacoside production in in vitro Bacopa monnieri shoot culture was studied. A systematic study conducted over a period of 35 days indicated that the maximum bacoside production (6.74 mg g? 1 dry weight (DW)) was obtained after a lag of 7 days and thereafter, the content decreased gradually to again increase at 28 days (5.91 mg g? 1 DW). Therefore, elicitation experiments were carried out over a period of 3, 6 and 9 days. The shoot cultures treated with 45 mg L? 1 of CuSO4 exhibited the highest bacoside content of 8.73 mg g? 1 DW (~1.42-fold higher) than in control cultures (6.14 mg g? 1 DW). This study indicates the effectiveness of abiotic elicitation on bacoside production in in vitro shoot cultures of this medicinally important herb known for its memory-enhancing properties.  相似文献   

17.
An anaerobic sequencing batch biofilm reactor (AnSBBR—total volume 7.5 L; liquid volume 3.6 L; treated volume per cycle 1.5 L) treated sucrose-based wastewater to produce biohydrogen (at 30 °C). Different applied volumetric organic loads (AVOL of 9.0, 12.0, 13.5, 18.0, and 27.0 kg COD m?3 day?1), which were varied according to the influent concentration (3,600 and 5,400 mg COD L?1) and cycle length (4, 3, and 2 h), have been used to assess the following parameters: productivity and yield of biohydrogen per applied and removed load, reactor stability, and efficiency. The removed organic matter (COD) remained stable and close to 18 % and carbohydrates (sucrose) uptake rate remained between 83 and 97 % during operation. The decrease in removal performance of the reactor with increasing AVOL, by increasing the influent concentration (at constant cycle length) and decreasing the cycle lengths (at constant influent concentrations), resulted in lower conversion efficiencies. Under all conditions, when organic load increased there was a predominance of acetic, propionic, and butyric acid as well as ethanol. The highest concentration of biohydrogen in the biogas (24–25 %) was achieved at conditions with AVOL of 12.0 and 13.5 kg COD m?3 day?1, the highest daily production rate (0.139 mol H2?day?1) was achieved at AVOL of 18.0 kg COD m?3 day?1, and the highest production yields per removed and applied load were 2.83 and 3.04 mol H2?kg SUC?1, respectively, at AVOL of 13.5 kg COD m?3 day?1. The results indicated that the best productivity tends to occur at higher organic loads, as this parameter involves the “biochemical generation” of biogas, and the best yield tends to occur at lower and/or intermediate organic loads, as this parameter involves “biochemical consumption” of the substrate.  相似文献   

18.
Mycelial growth in a defined medium by submerged fermentation is a rapid and alternative method for obtaining fungal biomass of consistent quality. Biomass, exopolysaccharides (EPS) and intracellular polysaccharides (IPS) production were optimised by response surface methodology in Lentinula edodes strain LeS (NCBI JX915793). The optimised conditions were pH 5.0, temperature 26°C, incubation period of 25 days and agitation rate of 52 r/min for L. edodes strain LeS. Under the calculated optimal culture conditions, biomass production (5.88 mg mL? 1), EPS production (0.40 mg mL? 1) and IPS production (12.45 mg g? 1) were in agreement with the predicted values for biomass (5.93 mg mL? 1), EPS (0.55 mg mL? 1) and IPS production (12.64 mg g? 1). Crude lentinan exhibited highest antibacterial effects followed by alcoholic, crude and aqueous extracts. The results obtained may be useful for highly effective yield of biomass and bioactive metabolites.  相似文献   

19.
The total metal concentration and bioaccessible concentration of Cr, Mn, Fe, Cu, Zn, Se in Momordica charantia, Asparagus racemosus, Terminalia arjuna and Syzyzium cumini were measured by instrumental neutron activation analysis and by inductively coupled plasma mass spectrometry analysis (ICP-MS). The bioaccessible concentrations were determined in the gastrointestinal digest obtained after treating dried powdered samples sequentially in gastric and intestinal fluid of porcine origin at physiological conditions. The bioaccessible concentration of Fe was in the range of 58–67 mg kg?1, Mn was 10.2–14.6 mg kg?1, Cu was 3.7–4.8 mg kg?1 and Zn was 10.6–18.4 mg kg?1, were within the safety limits set for vegetable food stuff set by Joint FAO/WHO. The bioaccessibility of Zn, an essential element, was high (40–50 %) in M. charantia and in S. cumini. In addition, the total metal contents and bioaccessible concentration of Ni, Se, Cd and Pb in these samples were measured by ICP-MS. The total Cd content in S. cumini (2.6 ± 0.2 mg kg?1) and its bioaccessible concentration (0.6 mg kg?1) were strikingly high as compared to the other samples. Though total Hg contents were determined by ICP-MS, but their bioaccessible concentrations were below the detection limit (0.036 mg kg?1).  相似文献   

20.
Trifloxystrobin and tebuconazole are used for control of Sigatoka leaf spot disease of banana. This study was conducted to evaluate residue persistence of the fungicides in/on banana fruit, other edible parts and soil after spray application of the combination formulation, Nativo 75 WG, at the standard dose, 87.5 + 175 and double dose, 175 + 350 g a.i. ha?1. The fungicides were extracted from banana and soil with acetone, partitioned into dichloromethane and cleaned-up using activated charcoal for trifloxystrobin and primary/secondary amine (PSA) for tebuconazole samples. The limit of quantification of the method was 0.05 mg kg?1 for both fungicides. Initial residues of trifloxystrobin were 0.444 and 0.552 mg kg?1 in/on banana with peel (whole fruit), which reached <0.05 and 0.065 mg kg?1 after 30 days from treatment at the standard and double doses, respectively. Tebuconazole residues were 0.636 and 960 mg kg?1 initially and reduced to 0.066 and 0.101 mg kg?1 after 30 days. Trifloxystrobin and tebuconazole degraded with the half-life of about 11 days. Trifloxystrobin or its metabolite was not detected in the fruit pulp. Tebuconazole being systemic in nature moved to the fruit pulp which was highest on the 3rd day (0.103 and 0.147 mg kg?1) and remained for 15 days. Matured banana fruit, flower, pseudostem and field soil were free from fungicide residues. For consumption of raw banana 43 days pre-harvest interval (PHI) is required after treatment of the combination formulation. Therefore application of the fungicides towards maturity stage of the fruits may be avoided.  相似文献   

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