Chlorination of bisphenol A in aqueous media: formation of chlorinated bisphenol A congeners and degradation to chlorinated phenolic compounds

The chlorination of bisphenol A (BPA) in aqueous media was investigated in order to describe the degradation profile of this compound and the formation of chlorinated products. Aqueous solutions of BPA (approx. 1 mg/l) were chlorinated by sodium hypochlorite solution at room temperature and under weakly alkaline conditions. Chlorinated compounds were extracted with dichloromethane and determined by gas chromatography/mass spectrometry (GC/MS). BPA was consumed completely within 5 min of chlorination, when the initial chlorine concentration was 10.24 mg/l (molar ratio to BPA, 58.7). On the other hand, when the initial chlorine concentration was 1.03 mg/l (molar ratio, 6.56), 9.3% of BPA still remained after 60 min chlorination. Five chlorinated BPA congeners, 2-chlorobisphenol A (MCBPA), 2,6-dichlorobisphenol A (2,6-D2CBPA), 2,2'-dichlorobisphenol A (2,2'-D2CBPA), 2,2',6-trichlorobisphenol A (T3CBPA) and 2,2', 6,6'-tetrachlorobisphenol A (T4CBPA) were formed in the earlier stages of chlorination. Several chlorinated phenolic compounds, 2,4,6-trichlorophenol (T3CP), 2,6-dichloro-1,4-benzoquinone (D2CBQ), 2,6-dichloro-1,4-hydroquinone (D2CHQ), C9H10Cl2O2, C9H8Cl2O and C10H12Cl2O2, were also formed by further chlorination.     

Histological alternation and vitellogenin induction in adult rare minnow (Gobiocypris rarus) after exposure to ethynylestradiol and nonylphenol

Adult rare minnow (Gobiocypris rarus) were exposed to 0, 1, 5, and 25 ng/l (nominal concentrations) of 17alpha-ethynylestradiol (EE2) and 3, 10, and 30 microg/l (nominal concentrations) of 4-nonylphenol (NP) under flow-through conditions for a period of 28 d. Low mortality was observed at 5 and 25 ng/l EE2 and the growth of fish reduced significantly at 25 ng/l EE2 compared to controls. However, the gonadosomatic indices (GSI) of male fish were significantly higher in 1 ng/l EE(2) treatments and in 10 and 30 microg/l NP treatments (p<0.05). Renal somatic indices (RSI) of male fish in EE2 treatments were significantly higher than those in controls (p<0.05). In contrast, significantly decreased GSI and RSI of female fish could only be observed in 5 and 25 ng/l EE(2) treatments (p<0.05). Hepatosomatic indices (HSI) of male fish were significantly higher in 25 ng/l EE(2) treatments. However, significantly increased of HSI of female fish could only be observed in 1 ng/l EE(2) treatments. Plasma vitellogenin (VTG) induction could be observed in males after exposed to different concentrations of EE2 and NP, and plasma VTG concentrations in females exposed to 5 and 25 ng/l EE(2) were also significantly higher than in controls (p<0.05). At level higher than 5 ng/l EE2 or 30 microg/l NP, hepatic tissue and renal tissue impairment of males could be observed. The pathological male liver was associated with a hypertrophy of hepatocytes and damages to cellar structure and accumulated eosinophilic material. Renal tissue showed different pathological effects which was reflected by accumulated eosinophilic material, hemorrhages within the kidney tubules and hypertrophy of the tubular epithelia. Also at these levels of exposure, feminization of male fish could be noticed and parts of males manifested the testis-ova phenomenon. Ovaries of female rare minnow in 25 ng/l EE2 treatment group were degenerated. Therefore when exposed to EE2 and NP even at environmental observed concentrations, adverse effects could occur in the reproductive system of adult fishes. The observed hepatic tissue and renal tissue impairment should be due to the induction and accumulation of VTG in organs, especially in males.     

Surfactant-assisted UV-photolysis of nitroarenes

Photochemical transformations (lambda-254 nm) of 2,4-dinitrotoluene (2,4-DNT) in aqueous solutions containing the cationic surfactant cetyltrimethylammonium (CTA) and the anionic nucleophile borohydride (BH4-) were investigated. The overall decay rate was enhanced at CTA concentrations above the critical micelle concentration (cmc) when stoichiometric excess BH4- was present in solution. A kinetic model that separates the overall reaction rate into micellar and aqueous pseudo-phase components indicates transformation in micelles is 17 times faster that in the homogeneous water phase under those conditions investigated. Intermediate products were identified by comparing the HPLC retention times and ultraviolet-visible absorption spectra of product peaks to those of analytical standards. 2-Methyl-5-nitroaniline, 4-nitrotoluene, 2-nitrotoluene, 4-methyl-3-nitroaniline, 2,4-diaminotoluene, o-toluidine, 1,3-dinitrobenzene, 3-nitroaniline, p-cresol, and 2,4-diaminophenol were identified as photo-transformation intermediates or products.     

Hydrodechlorination of dichlorobiphenyls over Ni-Mo/Al2O3 catalysts prepared by spray-drying method

The hydrodechlorination (HDCl) process of 2,3-, 2,4- and 2,5-dichlorobiphenyls was studied over a sulphided Ni-Mo/Al(2)O(3) catalyst in a stirred autoclave at a hydrogen pressure of 3 MPa. The catalysts were prepared by spray-drying. They were characterized by N(2) adsorption, thermogravimetry and scanning electron microscopy with X-ray microanalysis. The reaction temperature of the catalytic HDCl process was varied in the range of 230-290 degrees C. Polychlorinated biphenyls (PCBs) free transformer oil was used as reaction medium. The HDCl degree of dichlorobiphenyl isomers was in the range of 82-93%. The efficiency in the chlorine removal was found to be related to the position of the substituted chlorine atom and decreased as follows 2,4-dichlorobiphenyl approximately 2,5-dichlorobiphenyl>2,3-dichlorobiphenyl. For comparison, the HDCl process of 2,3-dichlorobiphenyl (2,3-PCB) without catalyst was also studied. The chlorine removal was 85% for the catalytic HDCl of 2,3-PCB whereas non-catalytic process led only to 16% of dechlorination in the same operating conditions, i.e. at 290 degrees C after 120 min. Monodichlorobiphenyls were not detected in the reaction products. The data for both catalytic and non-catalytic conversion of 2,3-PCB fit to a first-order model. Kinetic constants and the activation energy of the overall HDCl reaction of 2,3-PCB to biphenyl were evaluated. Compared to non-catalytic process, a nearly threefold decrease in the activation energy was observed in the presence of Ni-Mo/Al(2)O(3) catalyst prepared by spray-drying (48 kJ mol(-1) vs. 124 kJ mol(-1)).     

Fe0-C微电解去除地下水中2,4-DNT的影响因素

采用批实验研究初始pH值、溶解氧（DO）和地下水中常见的阴、阳离子等因素对Fe0-C微电解对地下水中2,4-二硝基甲苯（2,4-DNT）去除率的影响,并分析Fe0-C降解2,4-DNT的产物。结果表明,在pH=7,DO=0.23 mg·L-1的条件下,Fe0-C去除溶液中2,4-DNT有明显的效果,反应200 min时,去除率达到83.09%,比Fe0和C的去除率提高了74.56%和9.89%;酸性条件下有利于2,4-DNT去除,初始pH=5的条件下,溶液中2,4-DNT的去除率为82%,而初始pH=10时,2,4-DNT的去除率分别为64%;反应体系中含有较高浓度的溶解氧有利于2,4-DNT的去除,在DO=9.26 mg·L-1条件下,2,4-DNT的去除率比 DO=0.23 mg·L-1时提高了9.5%;地下水中一定浓度的阴（Cl-、SO2-4）、阳离子（Ca2+、Mg2+、Na+、K+）可以提高2,4-DNT的去除率,提高率小于10%。反应过程中2,4-DNT降解的产物包括2-氨基-4-硝基甲苯（2A4 NT）、4-氨基-2-硝基甲苯（4A2 NT）和2,4-二氨基甲苯（2,4-DAT）。     

Photolysis of vinclozolin

Following photolysis of vinclozolin in methanol five products were detected and identified: 3,5-dichlorophenylisocyanate, 3,5-dichloroaniline, methyl 3,5-dichlorophenylcarbamate, 3-(3-chlorophenyl)-5-methyl-5-vinyl-oxazolidine-2,4-dione and methyl (3,5-dichlorophenyl) (2-hydroxy-2-methyl-1-oxo-buten-3-yl) carbamate. The major component identified from photolysis in benzene solution, 3-(3-chlorobiphenyl)-5-methyl-5-vinyl-oxazolidine-2,4-dione, was produced by replacement of one chlorine atom by a solvent molecule.     

Hydrogen peroxide-assisted UV photodegradation of Lindane

Aqueous solutions of gamma-hexachlorocyclohexane (Lindane) were photolyzed (lambda=254 nm) under a variety of solution conditions. The initial concentrations of hydrogen peroxide (H(2)O(2)) and Lindane varied from 0 to 20 mM and 0.21 to 0.22 microM, respectively, the pH ranged from 3 to 11, and several concentration ratios of Suwannee River humic acid and fulvic acid were dissolved in the irradiated solutions. Lindane rapidly reacted, and the maximum reaction rate constant (9.7 x 10(-3) s(-1)) was observed at pH 7 and initial [H(2)O(2)]=1 mM. Thus, 90% of the Lindane is destroyed in approximately 4 min under these conditions. In addition, within 15 min, all chlorine atoms were converted to chloride ion, indicating that chlorinated organic by-products do not accumulate. The reactor was characterized by measuring the photon flux (7.04 x 10(-6) E s(-1)) and the cumulative production of *OH during irradiation. The cumulative *OH production during irradiation was fastest at an initial [H(2)O(2)]=5 mM (k=0.77 micro M s(-1)).     

Detoxification of hexachlorobenzene by dechlorination with potassium-sodium alloy

Dechlorination of hexachlorobenzene (HCB) was achieved by a liquid potassium–sodium (K–Na)-alloy. HCB in a cyclohexane/benzene solution (22 mmol/l, 4.67 g/l as chlorine) was dechlorinated by almost 100% after a 30-min reaction, indicating high reactivity of K–Na alloy and high proton donating power of cyclohexane. Decreasing orders of chlorobenzenes identified after a 15-min reaction, by amount were 1,2,3,4- > 1,2,3,5- > 1,2,4,5- for tetrachlorobenzenes, 1,2,4- > 1,2,3- > 1,3,5- for trichlorobenzenes, and 1,4- > 1,3- > 1,2- for dichlorobenzenes. It was hypothesized that once one chlorine atom in HCB was replaced with a proton, the adjacent chlorine atom to the proton tended to be replaced with another hydrogen atom. A total of 63 PCBs formed via the Wurtz–Fittig reaction were identified as by-products in the sample after a 15-min reaction. Among PCBs found, 2,3^′,4^′,5-tetrachlorobiphenyl, which was a product from 1,2,4-trichlorobenzene formed via the Wurtz–Fittig reaction, was detected in relatively high concentration (48.9 nmol/ml). The sample obtained from a reaction mixture after 30 min contained only 14 PCBs in trace amounts, indicating that the PCBs formed were also further dechlorinated by K–Na alloy. Non-chlorinated compounds––such as methylbenzene, dimethylbenzene, dimer of tetrahydrofuran, and dicyclohexyl (dimer of cyclohexane)––were also identified in the samples. A method using K–Na alloy developed in the present study dechlorinated satisfactorily HCB at room temperature.     

二价铁活化过硫酸盐降解土壤中十溴联苯醚

研究了Fe2+活化过硫酸钠产生的硫酸根自由基降解土壤中十溴联苯醚（PBDE-209）的效果,分别考察了Na2S2O8的用量、初始pH值、Na2S2O8与Fe2+摩尔比例、反应时间4个因素对降解效果的影响。通过正交实验确定了降解污染物的最优条件。结果表明,在Na2S2O8用量为0.8 mmol·kg-1,初始pH为5,Na2S2O8与Fe2+摩尔比为2：1,反应时间为30 min的最优条件下,降解率达96.36%。分子探针竞争实验表明体系中产生了硫酸根自由基。Fe2+活化过硫酸钠降解PBDE-209反应过程符合一级反应动力学。     

Reactions of the amine-containing drugs fluoxetine and metoprolol during chlorination and dechlorination processes used in wastewater treatment

The reactivities of the amine-containing pharmaceuticals fluoxetine and metoprolol with hypochlorite were studied using conditions that simulate wastewater disinfection including neutral pH (7.0), a range of reaction times (2–60 min), and a molar excess of hypochlorite relative to the pharmaceutical concentration (5.7 times). The reactions were monitored using liquid chromatography (LC) with several detection modes including ultraviolet absorbance (UV), mass spectrometry (MS), and post-column reaction/reductive electrochemistry (EC) for determining active chlorine products. At levels of 10 μM, both compounds reacted rapidly (<2 min) to form principally N-chloramine products that were stable in aqueous solution for at least 1 h. The reaction was also studied in wastewater, and similar reactivity was noted. These results demonstrate that the cations fluoxetine and metoprolol are likely to be rapidly transformed into neutral N-chloramines during wastewater disinfection. The reactivity of the N-chloramines was also studied with sulfite to simulate dechlorination, which is often employed in wastewater treatment. Both N-chloramines reacted slowly with sulfite. In the pure water dechlorination experiments, it was estimated that 70% and 10% of the peak areas remained after 2 min reaction time for fluoxetine and metoprolol, respectively. At longer reaction times both N-chloramines had been completely reduced by sulfite, and the product of the sulfite reduction reaction was the parent pharmaceutical amine. Since typical dechlorination times in wastewater treatment are on the order of seconds, this suggests the chloramines formed from these two basic drugs might evade dechlorination and be released into the environment. The implications of chloramine release are discussed.     

有机膨润土负载纳米零价铁还原-类芬顿氧化降解2,4-二氯苯酚

目前,虽然有很多关于纳米零价铁(NZVI)通过吸附、还原和氧化作用去除各种污染物的报道,但关于如何联合这些方法来提高污染物的去除率仍然不是很清楚。本实验研究了联合有机膨润土DK1(十六烷基三甲基铵盐改性,d(001)=2.2 nm)吸附、NZVI还原、类芬顿氧化作用来去除溶液中2,4-二氯苯酚(2,4-DCP)的方法。在反应前30分钟,有机膨润土DK1负载NZVI(NZVI/DK1)通过吸附还原作用去除溶液中2,4-DCP,2,4-DCP和COD的去除率分别为16.1%和7.8%,说明了吸附还原作用对2,4-DCP的去除效果是有限的。接着向溶液中滴加适量的H2O2,在5 min内2,4-DCP的去除率由16.1%提高到了99%以上,COD的去除率达到了64.1%,这可能是由于NZVI腐蚀形成铁的氧化物缓慢释放出Fe2+和Fe3+,增强了芬顿反应对2,4-DCP和降解产物的氧化去除效果。通过SEM,EDS,UV-Vis和GC-MS等分析方法佐证了上面的结果。最后提出了联合吸附、还原和Fenton氧化去除2,4-DCP的机制。     

气田高浓度含硫废水的化学氧化处理

采用亚硫酸钠(Na2SO3)氧化法对气田高含硫废水进行了实验研究.考察了硫化物初始浓度、Na2SO3/Na2S(摩尔比)、初始pH值和反应时间对Na2SO3氧化去除硫化物效果的影响,进行了对氧化产物的元素分析.结果表明,在Na2SO3/Na2S(摩尔比)为0.7、初始pH值为5和反应时间为5 min时,硫化物从1 100 mg/L降至1.80 mg/L,去除率高达99.84%,达到了气田回注水水质标准.元素分析发现,氧化产物中C、N、S、H和O元素的含量分别为0.11%、0.06%、98.73%、0.90%和1.10%,且其产率达到90.59%.     

Assessment of the importance of sorption for steroid estrogens removal during activated sludge treatment

Distribution coefficients (K(d)) between water and activated sludge particles (f(oc)=27.7+/-0.1%) were measured for the steroid estrogens (SE), estrone (E1), 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in batch experiments. Experimental concentration levels ranged from environmentally realistic low ng/l to the high microg/l. In this range K(d)s were independent of their water concentration. The experimentally obtained K(d)s (with 95% confidence intervals) were 402+/-126 l/kg, 476+/-192 l/kg and 584+/-136 l/kg for E1, E2 and EE2, respectively. K(d)s were used to estimate the fraction of the total SE concentration that is expected to be sorbed in the activated sludge treatment tanks of a typical STP assuming equilibrium conditions. Assuming a suspended solids concentration of 4 g/l dissolved solids (ds), it was estimated that 61+/-9%, 66+/-13% and 70+/-6% of the total concentration of E1, E2 and EE2, respectively, would be sorbed during activated sludge treatment. The fraction of the SEs that was expected to be sorbed to suspended sludge particles in the effluents from a typical Danish STP was estimated to be only 0.20+/-0.06%, 0.24+/-0.10% and 0.29+/-0.07% of the total concentration of E1, E2 and EE2, respectively, at a suspended solids concentration of 5 mg/lds. For a typical STP the removal of steroid estrogens with excess sludge was estimated to be only 1.5-1.8% of the total loading if equilibrium conditions exists. Sorption is therefore not important for the fate of SEs in STPs compared to biodegradation.     

Formation of chlorinated estrones via hypochlorous disinfection of wastewater effluent containing estrone

Chlorinated derivatives of estrone (E1) in the effluent of a municipal sewage treatment plant located in Shizuoka prefecture, Japan were detected by gas chromatography/mass spectrometry using electron impact in selected ion monitoring (GC/MS-EI-SIM) analysis. The concentrations of E1, 2-chloroestrone, 4-chloroestrone and 2,4-dichloroestrone in the effluent sample collected in December 2005 were 60.0 ng l(-1), 4.0 ng l(-1), 14.5 ng l(-1), and 9.8 ng l(-1), respectively. In the effluent sample taken in June 2005, 2,4-dichloroestrone was detected at 5.6 ng l(-1) along with 17.6 ng l(-1) of E1. However, only E1 was detected at 5.9 ng l(-1) in the sample in May 2005. To elucidate the behavior of E1 during the disinfection process with sodium hypochlorite in the sewage treatment plant, we carried out a reaction of E1 with sodium hypochlorite in buffer solutions at pH 7 and 9. As E1 was consumed rapidly, chlorinated estrones were produced and relatively fast formation of 2-chloroestrone, 4-chloroestrone, and 2,4-dichloroestrone was observed. Furthermore, 1,4-estradiene-3,17-dione derivatives were formed from the reaction between 2,4-dichloroestrone and sodium hypochlorite.     

Comparison of the removal of 2,4-dichlorophenol and phenol from polluted water, by peroxidases from tomato hairy roots, and protective effect of polyethylene glycol

Multiple efforts have been directed towards optimized processes in which enzymes, like peroxidases, are used to remove phenolic compounds from polluted wastewater. Here we describe the use of peroxidase isoenzymes from tomato hairy roots, which were able to oxidise 2,4-dichlorophenol (2,4-DCP) and phenol from aqueous solutions. This could be an interesting alternative for the removal of these compounds from contaminated sites. We used different enzyme fractions: total peroxidases (TP), ionically bound to cell wall peroxidases (IBP), basic (BP) and acidic peroxidases (AP). We analyzed the optimum conditions of removal, the effect of Polyethyleneglycol (PEG-3350) on the process and on the enzyme activities, to obtain the maximum efficiency. The optimal H2O2 concentrations for 2,4-DCP and phenol removal were 1 and 0.1mM, respectively. TP, IBP and BP showed better removal efficiencies than AP, for both contaminants. The addition of different concentrations (10-100mg l(-1)) of PEG-3350 to solutions containing 2,4-DCP showed no effect on the removal efficiencies of the isoenzymes. However, PEG (100mg l(-1)) increased the removal efficiency of phenol by BP and IBP fractions. On the other hand, peroxidase activities from BP and IBP fractions were 3 and 13 times higher, respectively, than those detected for the same fractions in phenol treated solutions without PEG. The protective effect of PEG, which depends on the contaminant as well as of the enzyme fraction used, would be important to improve the removal efficiency of phenol by some peroxidase isoenzymes.     

Removal of dinitrotoluenes from water via reduction with iron and peroxidase-catalyzed oxidative polymerization: a comparison between Arthromyces ramosus peroxidase and soybean peroxidase

A two-step process for the removal of dinitrotoluene from water is presented: zero-valent iron reduction is coupled with peroxidase-catalyzed polymerization of the resulting diaminotoluenes (DAT). The effect of pH was examined in the reduction step: at pH 6 the reaction occurred much more rapidly than at pH 8. In the second step, optimal pH and substrate ratio, minimal enzyme concentration and effect of polyethylene glycol (PEG) as an additive for greater than 95% conversion of DAT, over a 3h reaction period were determined using high performance liquid chromatography. Two enzymes were investigated and compared: Arthromyces ramosus peroxidase (ARP) and soybean peroxidase (SBP). The optimal pH values were 5.4 and 5.2 for ARP and SBP, respectively, but SBP was more resistant to mild acid whereas ARP was more stable in neutral solutions. SBP was found to have a greater hydrogen peroxide demand (optimal peroxide/DAT molar ratio for SBP: 2.0 and 3.0 for 2,4-diaminotoluene (2,4-DAT) and 2,6-diaminotoluene (2,6-DAT), respectively; for ARP: 1.5 and 2.75 for 2,4-DAT and 2,6-DAT, respectively) but required significantly less enzyme (0.01 and 0.1 U ml(-1) for 2,4-DAT and 2,6-DAT, respectively) to convert the DAT than ARP (0.4 and 1.5 U ml(-1) for 2,4-DAT and 2,6-DAT, respectively). PEG was shown to have no effect upon the degree of substrate conversion for either enzyme.     

Biotransformation of ethinylestradiol by microalgae

The capability of biotransformation of 11 microalgae strains was tested on ethinylestradiol (EE). Seven strains were ineffective whilst Selenastrum capricornutum, Scenedesmus quadricauda, Scenedesmus vacuolatus and Ankistrodesmus braunii biotransformed the substrate. EE was converted by S. capricornutum in three products (ethinylestradiol glucoside, 3-β-d-glucopyranosyl-2-hydroxyethinylestradiol, and 3-β-d-glucopyranosyl-6β-hydroxyethinyl estradiol) in 40%, 5%, and 5% yields, respectively. S. quadricauda transformed EE into 17-ethinyl-1,4-estradien-10,17β-diol-3-one (12%) and A. braunii transformed EE into 6--hydroxy-ethinylestradiol (25%).

It is noteworthy that EE is converted in 92% yield in ethinylestradiol glucoside by S. capricornutum when using optimal algal density conditions.     

Fe(Ⅱ)活化过硫酸钠去除水中三氯生

采用Fe2+活化过硫酸钠（SPS）对水中三氯生（TCS）的去除进行了研究,考察了Fe2+、SPS的投加量、TCS初始浓度、pH值和腐殖酸（HA）等对TCS去除的影响,GC-MS鉴定识别了降解产物。结果表明Fe2+活化SPS工艺能有效去除TCS,2,4-二氯苯酚（2,4-DCP）为其主要降解产物,SPS浓度为1.0 mmol·L-1,Fe2+的投加量为0.4 mmol·L-1时,初始浓度为460 μg·L-1的TCS 2 min后去除率可达93.87％,TCS慢速反应阶段的降解符合一级反应动力学方程,其动力学常数K=0.140 min-1。TCS的去除随Fe2+浓度的增加先增大后减小,高浓度的Fe2+不利于2,4-DCP的降解,适量提高SPS浓度有利于TCS的去除和2,4-DCP的降解,TCS去除随初始浓度增大而降低,酸性环境有利于TCS的去除,腐殖酸对TCS的去除具有抑制作用,低浓度腐殖酸不利于2,4-DCP的降解。     

酪氨酸氯化过程中光谱变化特征及消毒副产物的生成规律

考察酪氨酸在不同投氯量条件下氯化后的余氯,紫外吸光度值和荧光光谱,以及消毒副产物对羟基苯乙腈(4-HBC)的生成特性。结果表明,随着投氯量的增加,余氯呈现先增加再减小再增加的趋势。在投氯量为0～0.5 mmolCl2/L时,增加投氯量可提高氯化后溶液的UV254、UV274和UV280值以及4-HBC的生成量,表明低投氯量时氯化可提高溶液中不饱和键的含量;而投氯量为0.5～1 mmol Cl2/L时,增加投氯量降低UV254、UV274和UV280值以及4-HBC的生成量,表明过量的氯亦可破坏溶液中的不饱和键。荧光光谱测试实验亦发现:在投氯量为0.05 mmol Cl2/L时,酪氨酸溶液氯化后的荧光峰强度明显增加,表明氯化可生成荧光强度较高的产物。过量的氯(0.5～1 mmol Cl2/L)则可破坏溶液中的荧光结构,降低荧光峰强度直至未检出。