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1.
Vetter W  Luckas B 《Chemosphere》2000,41(4):499-506
Enantiomer separation of chiral toxaphene components in biological samples was studied by application of different chiral stationary phases based on modified cyclodextrins. Several pairs of enantiomers were resolved on permethylated beta-cyclodextrin (beta-PMCD), among them 2-endo,3-exo,5-endo,6-exo,8,8,9,10-octachlorobornane (B8-1412), which was not enantiomerically resolved on tert-butyldimethylsilylated beta-cyclodextrin (beta-BSCD). The latter column was applied to determine the enantiomer ratios (ERs) of 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P-26) in brain tissue of three seal species. The ER of B8-1413 (P-26) in brain was virtually racemic as well as those of the two persistent and chiral components of technical chlordane, 1-exo,2,2,4,5,6,7,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7-metha noindane (trans-nonachlor III or MC 6) and 1-exo,2-endo,3-exo,4,5,6,8,8-octachloro-3a,7,7a-tetrahydro-4,7- methanoindane (U82). In contrast, B8-1412 and 2-exo,5,5,8,9,9,10,10-octachlorobornane (B8-2229 or P-44) were significantly enantiomerically enriched in several samples of high trophic level biota. 2,2,5,5,8,9,9,10,10-Nonachlorobornane (B9-1025 or P-62), a chlorobornane metabolisable by seals and the presumable precursor of B8-2229 (P-44), was also enantiomerically enriched in seal blubber. These results confirm the assumption that some less persistent toxaphene components may be significantly degraded in biological samples. Enantioselective gas chromatography provides the information that such a degradation is happening by the characteristic change of the ratio of the two enantiomers in the respective tissues.  相似文献   

2.
In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.  相似文献   

3.
Three environmentally significant chlorinated bomane (CHB) congeners were extracted from Arviat ringed seal blubber and identified by using gas chromatography/mass spectrometry (HRGC/HRECNIMS (CH4), low resolution EIMS, and linked field scanning). They are referred to as TS2 (Parlar#39, B8-531) [2-exo,3-endo,5-exo,6,6,8b,9c,10c (or 10a)-octachlorobonane], TS3 (Parlar#40, B8-1414) [2-endo,3-exo,5-endo,6-exo,8c,9b,10a,10c (or 10b)-octachlorobornane] and TS4 (Parlar#42, Toxicant A, B8-806/809) [2-exo,3-endo,6,6,8b,8c,9c,10c (or 10a)-octachlorobonane/2-exo,3-endo,6,6,8b,9b,9c,10a (or 10b)-octachlorobonane]. This is the first time Toxicant A, known to be the most toxic CHB congener in technical toxaphene, has been found in any significant concentration in a marine mammal.  相似文献   

4.
Witte J  Büthe A  Ternes W 《Chemosphere》2000,41(4):529-539
A method for the congener-specific analysis of toxaphene in eggs of seabirds from a monitoring program from the northern part of Germany was carried out. The method was optimized in most steps of the procedure: injection temperature, HRGC with an HT-8 column, ion source temperature and the MS detection mode NCI/SIM measuring the isotope clusters of [M] , [M-Cl]-, [M-HCl]- and [M-2Cl]-. The suitability of 1,4-exo, 7,8,9,10,10-heptachloro-5-methoxytricyclo [5,2,1,0(2,6)]dec-3,8-diene as internal standard was demonstrated. 14 toxaphenes with Parlar numbers and more than 60 unknown toxaphenes could be identified. Spatial and temporal trends of toxaphene contamination are presented by using the Parlar 22 components standard for quantification.  相似文献   

5.
Sorption is a natural process that takes place in sediments or soils and changes the mobility and availability of hydrophobic organic compounds, such as toxaphene pesticide in the environment. The sorption of the 2-exo,3-endo,5-exo,8,9,10,10-heptachlorobornane (B7-1450), used as a model compound of the toxaphene heptachlorobornane congeners found in sediments, was investigated for the first time through a series of batch sorption experiments. The losses of B7-1450 due to adsorption onto glass walls and to evaporation occurring during analytical treatment steps were corrected. The study showed that these specific losses ranged from 2% to 3.5% for the glass walls adsorption and can be as high as 15% for the evaporation treatment. The sorption coefficients, K(d) and K(oc), of B7-1450 could be overestimated by >30%, particularly for low-concentration samples, if the losses were not corrected. Loss correction equations were established, validated and applied to determine sorption coefficients for the B7-1450 congener. The K(oc) values for B7-1450 determined over a gradient of concentrations ranged from 3.5x10(4) to 6.5x10(4)mlg(-1), revealing a strong affinity of B7-1450 for marine sediments.  相似文献   

6.
A new potential toxaphene congener 3-endo,5-endo-dichloro-7,7-bis-chloromethyl-4-dichloromethyl-tricyclo[2.2.1.0(2,6)]heptane 2 has been isolated from reaction mixture obtained by the chlorination of 2-exo, 10,10-trichlorobornane 1. The X-ray structural analysis of 2 revealed an unusual tricyclic structure, where the two chlorine atoms occupying endo-positions are in close spatial proximity with each other and near to the neighbouring CHCl2 group. Further, it revealed that the symmetry of the molecule is distorted. The 1H and 13C NMR spectra of 2 have been assigned by means of 1H, 1H double-quantum filtered correlation spectroscopy (DQF COSY), PFG 1H, 13C HMQC (pulsed field gradient heteronuclear multiple-quantum coherence), 1H, 13C heteronuclear multiple bond correlation (HMBC) experiments, and computer aided 1H NMR spectral analysis. The asymmetry of 2 is also discernible on the 1H NMR parameters. In addition, gas chromatographic (GC) properties and electron impact (EI) mass spectrum of 2 has been studied. Ab initio Hartree-Fock (HF) method with the basis set 6-31G(d) has been used for the optimization of the equilibrium geometry and calculation of total energy for 2. The optimized geometry is in good agreement with the crystal structure. According to the rotation energy profile calculated at the HF/6-31G(d) level, rotation of the chloromethyl and dichloromethyl groups are highly unlikely at the room temperature.  相似文献   

7.
The gas-photocatalytic degradation of trichloroethylene without water   总被引:1,自引:0,他引:1  
The photocatalytic degradation of gaseous trichloroethylene (TCE) without water has been studied. The degradation products were determined to be CO2, HCl and Cl2, and the reaction stoichiometry, was described as . The degradation rate was found to be linear with 0.16 power of the illumination intensity. When the TCE concentration was low (1014 mol L−1 or a little more), its degradation rate model could be considered as first order kinetics. A mechanism of valence band hole oxidation was proposed.  相似文献   

8.
A series of novel synthetic monohydroxy polychlorinated biphenyls (OH-PCBs) (5 trichloro-, 5 tetrachloro- and 5 pentachloro-compounds) have been characterized (1H and 13C NMR and high resolution MS) and their estrogenic and thyroid hormone activities assessed using a yeast two-hybrid assay, both with and without possible metabolic activation by rat liver S9 preparation. Moderate estrogenic activity was found for 2,3,4(')-trichlorobiphenyl-4-ol (compound 5) but this was eliminated when exposed to the S9 mix. 2,2('),3('),4,6-Pentachlorobiphenyl-3-ol (13) and 2('),3,3('),6-tetrachlorobiphenyl-4-ol (10) both showed weak estrogenicity in the absence of the S9 mix. The estrogenicity of compound (10) was enhanced 10-fold by exposure to S9 metabolic activation but that of compound (13) remained unchanged. 2('),4,5('),6-Tetrachlorobiphenyl-2-ol (6) showed strong thyroid hormonal activity (5% of that of T4) whereas 3('),4,6-trichlorobiphenyl-3-ol (4), compound (10) and 2,3('),4,5('),6-pentachlorobiphenyl-3-ol (14) showed moderate activity, and 2('),3,3('),5-tetrachlorobiphenyl-2-ol (8) and 3,3('),5,5('),6-pentachlorobiphenyl-2-ol (11) showed weak activity. The activity of (4) was eliminated by S9 metabolic activation whereas those of (6) and (14) were weakened and that of (10) remained unchanged.  相似文献   

9.
The rate coefficient for the reaction of nitrite with hypochlorite and hypochlorous acid has been studied using spectrophotometric measurements. The reaction rate has been determined in a wide range of H(+) concentration (5< or =-log[H(+)]< or =11). The kinetics were carried out as a function of NO(2)(-), H(+) and total hypochlorite ([HOCl](total)=[HOCl]+[ClO(-)]+[ClNO(2)]) concentrations. The observed overall rate law is described by: -d[HClO](T)dt=[a[NO(2)(-)](2)+b[NO(2)(-)]][H(+)](2)c+d[H(+)]+e[NO(2)(-)][H(+)](2)[HOCl](total)At T=298 K and in Na(2)SO(4) at an ionic strength (I=1.00 M), we obtained using a nonlinear fitting procedure: a=(1.83+/-0.36)x10(7) s(-1), b=(1.14+/-0.23)x10(5) Ms(-1), c=(1.12+/-0.17)x10(-13) M, d=(1.43+/-0.29)x10(-6) M(2) and e=(1.41+/-0.28)x10(3) M where the errors represent 2sigma. According to the overall rate law, a/b=k(1)/k(3), b/e=k(3), c=K(w), d/c=K(a), d=K(a)K(w) and e=K(1)K(a). In Na(2)SO(4) at an ionic strength (I=1.00 M), the values of K(1) and K(a) are (1.1+/-0.1)x10(-4) and 1.28x10(7) M(-1), respectively. A mechanism is proposed for the NO(2)(-) oxidation which involves the reversible initial step: NO(2)(-)+HOCl left harpoon over right harpoon ClNO(2)+OH(-) (K(1)), while ClNO(2) undergoes the two parallel reactions: attack by NO(2)(-) (k(1)) and hydrolysis (k(3)). ClNO(2) and N(2)O(4) are proposed as important intermediates as they control the mechanism. The rate coefficients k(1) and k(3) have been determined at different ionic strengths in NaCl and Na(2)SO(4). The influence of the ionic strength and ionic environment has been studied in this work.  相似文献   

10.
Three novel halogenated organic compounds (HOCs) have been identified in the blubber of marine mammals from coastal New England with the molecular formulae C(9)H(3)N(2)Br(6)Cl, C(9)H(3)N(2)Br(7), and C(9)H(4)N(2)Br(5)Cl. They were identified using high and low resolution gas chromatography mass spectrometry (GCMS) and appear to be highly brominated analogues of Q1, a heptachlorinated HOC suspected to be naturally produced. These compounds were found in Atlantic white sided dolphin (Lagenorhynchus acutus), bottlenose dolphin (Tursiops truncatus), common dolphin (Delphinus delphis), Risso's dolphin (Grampus griseus), harbor porpoise (Phocoena phocoena), beluga whale (Delphinapterus leucas), fin whale (Balaenoptera physalus), grey seal (Halichoerus grypus), harp seal (Phoca groenlandica) and a potential food source (Loligo pealei) with concentrations as high as 2.7 microg/g (lipid weight). The regiospecificity of C(9)H(3)N(2)Br(6)Cl is suggestive of a biogenic origin. Debromination of C(9)H(3)N(2)Br(6)Cl may be significant in the formation of C(9)H(4)N(2)Br(5)Cl.  相似文献   

11.
In the context of leaching of surface-applied nitrate fertilizer to runoff, this paper evaluates the performance of five simple predictive models, based upon: (1) field capacity; (2) uniform displacement; (3) wetting front; (4) by-passing (preferential) flow; and (5) soil-water domains. Predicted behaviour and observed on an 85-cm depth soil are compared for leaching depth and outflow response. Predictive success of outflow by the models for 40 monitored rainfall events were: (1) 60%; (2) 52%; and (3) 76%. For the by-passing flow model (4), simple prediction of pedal excess flow (4a) gave a success of 80%; where calculations of the operational volume in preferential flow were involved (4b), variations from 20 to 100% success occurred for a range of operational volumes, the lowest volumes giving the greatest success (4c). The soil-water domain model (5) is a simple, predictive scheme involving the classification of outflow events according to antecedent soil moisture (θa); the method uses the mobile: retained water content (θr) at 2 bars and field capacity (θfc). Using soil-water domains alone was of limited success but when the domains were combined with rainfall intensity, the scheme specified outflow exactly. Thus, for θa < θr, no soil-water outflow occurred, even at high rainfall intensity; for θa >θfc outflow always occurred, even at low rainfall intensity and for θa >θr < θfc the simple by-passing model (4a) achieved 100% predictive success. The implications for fertilizer application are discussed.  相似文献   

12.
The molecular structures of individual HBCD stereoisomers are not elucidated yet. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and tentatively assigned their relative configurations. Herein we report on the isolation of enantiomerically pure (+) and (-) beta-HBCDs, both obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations determined from X-ray diffraction analysis. The absolute configuration of (+) beta-HBCD was found to be (1S,2S,5S,6R,9S,10R), while the one of (-) beta-HBCD was assigned to (1R,2R,5R,6S,9R,10S). The given structural information allows, for the first time, the unambiguous identification of these two important HBCD stereoisomers, which are typically found in technical products at proportions of about 3-5% for each enantiomer.  相似文献   

13.
鸟粪石结晶法去除垃圾渗滤液中NH_4~+-N的效果研究   总被引:1,自引:0,他引:1  
研究了鸟粪石结晶法对经混凝预处理后的垃圾渗滤液中NH4+-N的去除效果,考察了不同影响因素对NH4+-N去除效果的影响,并进行了磷酸铵镁(MgNH4PO4·6H2O,简称MAP)沉淀的表征及成分分析,并提出了反应后溶液中Mg2+、PO43-及MAP的回收利用办法。结果表明,反应的最佳条件为:pH8.5~9.5,Mg2+∶NH4+∶PO34-(摩尔比)=1.1∶1.0∶1.3,反应温度30℃,反应时间为25 min时,此时NH4+-N的去除率达94.70%;最佳沉淀剂投加组合为MgCl2.6 H2O与Na2HPO4·12H2O;pH为9.0时生成的沉淀符合典型MAP沉淀的晶体结构,生成的沉淀大部分为MAP,且没有氰化物、酚等有害物质的检出,而pH为10.5时生成的沉淀由许多疏松的微小沉淀颗粒组成,排列较杂乱,影响了沉淀的纯度。利用鸟粪石结晶法去除混凝预处理后的垃圾渗滤液中NH4+-N技术可行,经济效益合理,具有广阔的应用前景。  相似文献   

14.
A biofilter using granular activated carbon with immobilized Paracoccus sp. CP2 was applied to the elimination of 10–250 ppm of trimethylamine (TMA), dimethylamine (DMA), and methylamine (MA). The results indicated that the system effectively treated MA (>93%), DMA (>90%), and TMA (>85%) under high loading conditions, and the maximum degradation rates were 1.4, 1.2, and 0.9 g-N kg−1 GAC d−1. Among the three different amines treated, TMA was the most difficult to degrade and resulted in ammonia accumulation. Further study on TMA removal showed that the optimal pH was near neutral (6.0–8.0). The supply of high glucose (>0.1%) inhibited TMA removal, maybe due to substrate competition. However, complete TMA degradation was achieved under the co-immobilization of Paracoccus sp. CP2 and Arthrobacter sp. CP1 (96%). Metabolite analysis results demonstrated that the metabolite concentrations decreased by a relatively small 27% while the metabolite apparently increased by heterotrophic nitrification of Arthrobacter sp. CP1 in the co-immobilization biofilter.  相似文献   

15.
Lu M  Mulholland JA 《Chemosphere》2001,42(5-7):625-633
Aromatic hydrocarbon growth from indene (C9H8), which contains the five-membered ring cyclopentadienyl moiety, was investigated experimentally in a 4 s flow reactor over a temperature range 650-850 degrees C. Major products observed were three C18H12 isomers (chrysene, benz[a]anthracene and benzo[c]phenanthrene), two C17H12 isomers (benzo[a]fluorene and benzo[b]fluorene), and two C10H8 isomers (naphthalene and benzofulvene). Reaction pathways to these products are proposed. Indenyl radical addition to indene produces a resonance-stabilized radical intermediate which further reacts by one of two routes. Rearrangement by intramolecular addition produces a bridged structure that leads to the formation of C17H12 and C10H8 products. Alternatively, beta scission produces biindenyl, which leads to the formation of C18H12 products by a ring condensation mechanism analogous to that proposed for cyclopentadiene-to-naphthalene conversion. Temperature dependencies of both the partitioning between these two routes and the product isomer distributions are consistent with thermochemical modeling using semi-empirical molecular orbital methods. The results further illustrate the role of resonance-stabilized radical rearrangement in aromatic growth and condensation of systems with cyclopentadienyl moieties.  相似文献   

16.
Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.  相似文献   

17.
合成了H3PMo12O40、H4SiW12O40、H3PW12O40、H4PMo11VO40、H5PMo10V2O40和H6PMo9V3O406种杂多酸,分别采用红外光谱(FT-IR)和X射线衍射(XRD)表征杂多酸的结构,并采用气相色谱仪对6种杂多酸水溶液进行脱硫实验测试。实验结果表明:制备的6种杂多酸具有良好的Keggin型结构;H3PMo12O40、H3PW12O40和H4SiW12O40的3种水溶液中,磷钼杂多酸的脱硫性能最好,脱硫率在120 min时可达到16.38%;不同比例的多原子也会使杂多酸有不同的脱硫性能,脱硫性能顺序为:H6PMo9V3O40〉H5PMo10V2O40〉H4PMo11VO40;且6种杂多酸的脱硫稳定性的顺序为:H4PMo11VO40〉H6PMo9V3O40〉H3PMo12O40〉H5PMo10V2O40〉H4SiW12O40≈H3PW12O40。  相似文献   

18.
Yamamoto T  Yasuhara A 《Chemosphere》2002,46(8):1215-1223
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.  相似文献   

19.
煤基腐殖酸对外源砷胁迫下玉米生长及生理性状的影响   总被引:1,自引:0,他引:1  
为了筛选用于砷污染土壤治理的煤基腐殖酸,采用盆栽实验研究了施用不同种类和浓度的煤基腐殖酸及EDTA对外源砷胁迫下玉米株高、株鲜重、株干重、根干重、砷积累量、叶片抗氧化酶(POD,SOD和CAT)活性和脯氨酸含量的影响。结果表明,11种供试煤基腐殖酸均促进了玉米生长,提高了叶片POD、SOD和CAT活性。其中6和10号腐殖酸可降低土壤砷活性和显著抑制玉米吸收和积累砷,而8和9号腐殖酸增加了土壤活性砷和显著促进了玉米对砷的吸收和累积,且不同程度地强于EDTA。除8和9号外,其余腐殖酸均可明显降低玉米叶片脯氨酸的含量。EDTA可显著促进玉米吸收和积累砷,且加剧了砷对玉米的危害。因此,8和9号供试煤基腐殖酸可以替代EDTA活化土壤砷,与植物配合以提高砷污染土壤的植物修复速度和效果,而6和10号供试煤基腐殖酸则可用于土壤砷钝化剂,以保证作物产品的安全。  相似文献   

20.
对城市污泥填埋场填埋气集气井收集系统进行了优化研究,考察了城市污泥水平方向的渗透系数(以下简称污泥渗透系数)对集气井影响半径的影响、集气井抽气负压随填埋时间的变化规律、填埋气的经济收集年限。结果表明,当抽气负压为25000~30000Pa时,污泥渗透系数分别取1.04×10-7、2.60×10-8、1.04×10-8m2/(Pa.s)时,集气井的影响半径分别为10.0~11.0、6.0~7.0、5.0~5.5m,过小的污泥渗透系数会严重影响集气井的集气效率,因此污泥渗透系数最好不应小于1.00×10-8m2/(Pa.s);随城市污泥填埋时间的增加,集气井抽气负压总体呈指数型降低趋势,从第8年起,抽气负压由起初的25000Pa降低到5000Pa以下,此时CH4产率约为2kg/(m3.a),到第20年时CH4产率接近于零,故从城市污泥填埋后第8年起,对填埋气继续进行收集的意义已经不大。  相似文献   

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