CN107064040A - The efficiently concentrating and separation method of traces of antibiotic in water environment - Google Patents
The efficiently concentrating and separation method of traces of antibiotic in water environment Download PDFInfo
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- CN107064040A CN107064040A CN201710490969.5A CN201710490969A CN107064040A CN 107064040 A CN107064040 A CN 107064040A CN 201710490969 A CN201710490969 A CN 201710490969A CN 107064040 A CN107064040 A CN 107064040A
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- 230000003115 biocidal effect Effects 0.000 title claims abstract description 74
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- 238000000926 separation method Methods 0.000 title claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 138
- 238000010521 absorption reaction Methods 0.000 claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
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- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 claims abstract description 30
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- 229960002180 tetracycline Drugs 0.000 claims description 42
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- 239000000243 solution Substances 0.000 claims description 40
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The efficiently concentrating and separation method of traces of antibiotic in water environment of the present invention, study absorption property of the magnetic graphene under different adsorption conditionses to tetracycline antibiotics, and the change of antibiotic concentration in front and rear solution is adsorbed with UV spectrophotometer measuring, so as to calculate its corresponding adsorption rate and magnetic graphene adsorption capacity.Influence of the different factors to antibiotic absorption property is investigated, optimal adsorption condition is drawn, suction-operated mechanism is analyzed, and adsorption dynamics adsorption kinetics, Adsorption thermodynamics etc. are inquired into.The present invention is using quadracycline TC as research object, under the different factors such as system research pH value of solution, temperature, Dissolved Organic Matter (by taking humic acid as an example), MGO is to TC characterization of adsorption, high spot reviews adsorption dynamics adsorption kinetics and Adsorption thermodynamics of the MGO to TC.
Description
Technical field
The present invention relates to the processing method of antibiotic waste water, in particular to traces of antibiotic in a kind of water environment
Efficiently concentrating and separation method.
Background technology
Tetracycline antibiotics are a kind of broad-spectrum antibiotics produced by streptomycete, are polycyclic aphthacene Carboxylamide parent nucleus
Derivative.Tetracycline antibiotics can be divided into natural product and the class of semi-synthetic two, and wherein semi-synthetic is also known as the second generation four
Ring element, is combined by the 30S subunits with ribosome, the combination of aminoacyl tRNA and ribosome is then prevented, so as to produce
Raw effect pharmacologically.
The existing antibiosis of tetracycline antibiotics has antiinflammatory action again, therefore largely uses the antibiotic both at home and abroad, and
Counted as usage amount maximum and utilize one of widest antibiotic kind.Summer nineteen twenty-eight Fleming luckily be found that mould
Element, up to now antibiotic be widely used and continue to develop, be that the prevention and treatment of human diseases are made that huge contribution.
Secondly in terms of animal husbandry, antibiotic equally exists substantial amounts of application.
The harm of antibiotic：Tetracycline antibiotics are also widely used in agricultural, fishery cultivating field, in feed and
The tetracycline antibiotics of doses are added in breeding water body, not only can be with disease preventing and treating, moreover it is possible to promote poultry, domestic animal and water
The growth of product etc..Tetracycline antibiotics wherein more than half are in animal digestive system and without metabolism, most
Environment is discharged into by excrement afterwards.Swill, the animal wastes on farm etc. turn into organic fertilizer after microbial action, are taken
The antibiotic of band is constantly enriched with after entering soil, after a period of time, antibiotic is permeated the ground water by the eluviation of soil,
Or enter surface water system with rainwash, the soil erosion.
Further, since tetracycline antibiotics can accelerate the growth of water body animals and plants, aquaculture industry is also commonly used
Tetracycline antibiotics, antibiotic can be gathered in water body deposit, and with the flowing of water body, be diffused near water body or
In soil, the face of antibiotic is caused to pollute.
At present, global growing interest has the shadow that the continuous propagation of the pathogen of antibiotic resistant in the environment is brought
Ring, and tackle one of effective measures of this predicament, waste water is produced and containing such material to tetracycline antibiotics
Water body carries out appropriate processing.And the domestic research for tetracycline antibiotics removal is also very limited, existing processing skill
Art is also not enough to realize this target of removal tetracycline antibiotics, the especially research of its pollution mechanism and processing method completely
It is ripe not enough.The processing method comparative maturity of antibiotic waste water has chemical method, bioanalysis, physical-chemical process and group at present
It is legal etc..
(1) chemical treatment method
It is that chemical substance is added into antibiotic waste water in chemical treatment method, it is occurred chemistry with pollutant anti-
Should, so that pollutant is removed, while COD can be reduced.Isil Akmehmet B etc. carry out ozone oxidation to 3 kinds of antibiotic waste waters
Processing, have studied the influence to treatment effect such as pH, influent COD value and hydrogen peroxide addition.Wang et al. researchs are found
Ozone can effectively degrade tetracycline antibiotics, and after ozone oxidation nearly half an hour, the bio-toxicity of water body nearly reaches percent
Hundred, but after a period of time, the bio-toxicity of water body is essentially 0.Chen et al. have studied MnO oxidation tetracyclines and aureomycin
Product afterwards, it is found that tetracycline and aureomycin after aoxidizing lose the antibacterial action as antibiotic, therefore reduce anti-
Influence of the raw element to environment.
The secondary pollution of water body is easily produced in the processing procedure of chemical method, while it is also limitationization that processing cost is too high
The reason for one of oxidizing treatment popularization is important.
(2) bioremediation
1. Aerobic Process for Treatment method
Aerobic method has for wastewater organic pollutant and preferably gone as a kind of very important method in biochemical treatment
Except rate.During to antibiotic pharmacy wastewater treatment, because content of organics is higher in waste water, and with bio-toxicity,
Therefore need after being pre-processed to waste water, antibiont waste water could be handled using aerobic method, so as to obtain good processing
Effect.
Open the research such as system to find, first adjust the pH of water body and add a certain amount of pulverized limestone, carry out materialization to water body locates in advance
Reason, then Aerobic Process for Treatment is carried out to waste water by SBR techniques, with regard to the COD value of water outlet can be made to control in 300mg/L or so.Liu Xiuyan
It is found that SBR techniques and contact oxidation technology carry out series connection processing tetracycline wastewater Deng research, in practice it has proved that, the group technology
Use, the COD clearances of waste water can be made stable more than 85%, while sbr reactor device load can reach 2.7kg COD/ (m3·
d).Qiao Hongqi etc. handles tetracycline wastewater using biomembrance process, and to the COD of waste water, clearance can in 2d after domestication for microorganism
76% is reached, then coordinates flyash to filter, COD clearances are up to 88%.
But, COD concentration can not be entered in more than 10g/L high concentrated organic wastewater with conventional aerobic process activated sludge process
Row processing, just needs to carry out former antibiotic waste water ten times or even hundred times of dilution, it is therefore desirable to consume substantial amounts of clear water during water inlet,
Power consumption simultaneously is also very big, causes processing cost very high, therefore aerobic method is in practice using less.
2. Anaerobic Treatment method
Anaerobic Treatment method is mainly degraded by anaerobe to the pollutant in sewage, and the process need not expose
Gas, operation is easy to operate, saves power consumption, and excess sludge production is small.
But the antibiotic organic wastewater of high concentration is after Anaerobic Treatment, and effluent color dilution is higher, and COD value does not reach far
Waste water after mark, Anaerobic Treatment need to carry out Aerobic Process for Treatment again, to ensure the qualified discharge of water outlet.When handling antibiotic waste water,
Due to containing a large amount of noxious materials in waste water, there is a certain degree of inhibitory action to the bioactivity of anaerobe, so that
Cause reduction of the reaction tank to organic matter removal efficiency, therefore typically do not use anaerobic process to handle antibiotic waste water.
3. Aerobic-anaerobic combined method
Combined method combines the advantage of aerobic method and anaerobic process.Wherein Anaerobic Treatment uses efficient anaerobic technique, with appearance
The advantage that product load is high, COD removal efficiency is high, impact load is high, reduces dilution water and can significantly reduce COD, and recyclable natural pond
Gas, while Aerobic Process for Treatment can ensure standard water discharge.In addition, for nitrogenous effluent and high organic wastewater, passing through the group technology
It may also reach up the purpose of denitrogenation.
Wang Peijing etc. have studied the combined method of UASB anaerobic techniques and SBR aerobic process to the terramycin wastewater of high concentration
Treatment effect, the ad hoc preaeration tank of the experiment, not only stripping CO2、H2The reducing substanceses such as S, and precipitated in anaerobic effluent
Sludge.
(3) physical chemistry processing method
1. coagulation
A kind of technique that coagulation is pre-processed as physico-chemical process, mainly use coagulant remove waste water in suspended particulate with
And colloidal substance, so as to reduce the concentration of suspension and COD in waste water.
Bend the research clouding such as pavilion it is solidifying-sand filtration-microfiltration systems can effectively remove solid suspension, most turbidity of raw water
It is removed, reduces the contaminated risk of microfiltration membranes and qualified water inlet is provided for follow-up reverse osmosis process.
2. air supporting
Bubble-floating Method is used for the processing of suspension and the more antibiotic waste water of colloidal content, relatively low especially for density
Waste water, then need to pre-process it using Bubble-floating Method.
Li Ying is handled antibiotic production wastewater using air supporting-biology-ozone air-float process integration, and research shows,
When the COD of water inlet is in 8000mg/L or so, the COD after processing is less than 200mg/L, and clearance reaches
More than 97.5%.
3. adsorb
Application and research relatively conventional, tetracycline compound higher hydrophobicity and Tetracyclines of the absorption method in waste water
The planes of molecules structure of material, which result in the material and adsorbent, larger Van der Waals force；On the other hand, Tetracyclines molecule
On group easily reacted with the structure on sorbing material so that promote absorption.
Wu Wei et al. have studied activated carbon powder foot couple and take acidum nalidixicum, terramycin, the suction of the typical antibiotic of three kinds of lincomycin
Attached performance, as a result shows that the dosage of Powdered Activated Carbon is respectively when acidum nalidixicum, terramycin, lincomycin concentration are 1mg/L
115mg/L, 75mg/L, 25mg/L, clearance is more than 99%.Zou's magnitude using montmorillonite be adsorbent to tetracycline and terramycin
Adsorption test is carried out, influence of the factors such as water pH value and cationic strength to antibiotic absorption property is have studied.Simultaneously
Figueroa researchs find that absorption of the ionic strength to two kinds of adsorbents to tetracycline compound has little to no effect.The persons such as Ji
Take multi-walled carbon nanotube, single-walled carbon nanotube and active carbon etc. as adsorbent, have studied their tetracycline adsorptions
Performance.
Absorption method have the advantages that in wastewater treatment it is easy to operate, stably, in the absence of secondary pollution, still, absorption method
Equally there is also drawback, after tetracycline adsorption pollutant, it is impossible to which adsorbent is effectively recycled, institute
To cause processing cost larger, this is to influence the principal element of its application.
The property of graphene and application：
The cellular two dimensional crystal that graphene (graphene) is made up of individual layer hexagonal primitive unit cell carbon atom, is to build other
The elementary cell of dimension carbonaceous material.Because graphene only has 1 carbon atom thickness, the specific surface area for making it possess super large is preferable
Individual layer GR specific surface area it is huge, be almost 2 times of normal activated carbon specific surface area so that GR turn into water process in potentiality
Huge sorbing material.
GR graphene oxides obtained by oxidation treatment (graphene oxide, GO), good hydrophily can be very
It is scattered in the aqueous solution well, is used widely in water environment as sorbing material.
(1) absorption of heavy metal
In recent years, heavy metal pollution turns into the very important problem of environmental pollution of a class, the spy with strong toxicity, difficult degradation
Property, into organism after be difficult a large amount of discharge, eventually cause slow poisoning.Graphene and its composite heavy metal ion tool
There is higher affinity, numerous studies personnel are based on carrying out further investigation in this respect.
Hao etc. prepares SiO2/ graphene composite material is used to quickly remove the Pb in solution2+, test result indicates that, it is inhaled
Attached capacity is 113.6mg/g, with pure SiO2Significantly improved compared to adsorption capacity, research finds it main reasons is that electrostatic is mutual
Effect.Tan etc. prepares three-dimensional grapheme/layered double-hydroxide composite by situ synthesis, due to its Large ratio surface
Product and special pore structure, the maximum adsorption capacity to uranium (VI) is 277.8mg/g, as a result infers the function of graphenic surface
Group and UO2+Stable complex is formed to strengthen absorption property.Xing Haitao has synthesized four ammonia of triethylene-magnetizing reduction oxidation stone
Black alkene composite, the saturation magnetization of the material reaches 42.13emu/g, and the presence of magnetic to separate after absorption more square
Just and reuse can be realized.Wang Bo has prepared ethylene diamine-modified graphite oxide by carrying out modification to graphene oxide
The composites such as alkene, the graphene oxide of dendritic interphase modification, GO/EDA reaches to the maximal absorptive capacity of Pb (II)
413.22mg/g, GO/tPAMAMs reach 568.2mg/g to Pb (II) maximal absorptive capacity, and power of regeneration is strong, can repeat to make
With.Liu's yarn yarn etc. is by Silanization reaction in the acid of GO surface graft chelating functional groups N- (trimethoxy silicon propane) ethylenediamine three
(EDTA-Si), to modified graphene oxide (GO-EDTA), simulation finds Pb2+And Na+Adsorb to the oxygen-containing of graphene oxide
Around functional group's carboxyl, with respect to Na+Ion, Pb2+Ion is easier to be gathered in COO-Around, 2 oxygen atoms are formed to 1 Pb2+
The aggregated structure of ion, equal power gesture shows compared to Ca2+And Na+Ion, Pb2+Ion is more easy to mutually tie with carboxyl in graphene oxide
Conjunction forms ion pair, and ion pair is difficult dissociation.
(2) absorption of dyestuff
Waste water from dyestuff complicated component, colourity are deep, salinity is high, COD is high, bio-refractory, become in wastewater treatment
Weight difficult point.At present, in ripe processing method, the characteristics of absorption method has selective enrichment has spy in field of waste water treatment
Different status, and GO has good absorption property to most of dyestuffs.
The report such as Zhang shows that the charcoal of graphene coating is not only to polycyclic aromatic hydrocarbons (PAH) through batch adsorption experiment result
There is higher adsorption capacity, the adsorption capacity to methylene blue is equally up to 174mg/g, 20 times of left sides higher than unmodified charcoal
It is right.Bradder etc. handles malachite green using GO, and its adsorption capacity is 248mg/g, compared with graphite and activated carbon, finds
GO adsorption capacity is more much higher than other 2 kinds of sorbing materials.Lv Shasha etc. is by studying the carboxylated graphene (G- synthesized
COOH) to the absorption property of 4 kinds of ionic dyes such as crystal violet, dimethyl diaminophenazine chloride in the aqueous solution, NaOH/EtOH mixed solutions are used in discovery
Crystal violet is eluted, eluting rate is close to 90%, and the G-COOH after elution is recycling；G-COOH reaches to the saturated extent of adsorption of crystal violet
700mg/g is arrived；And the magnificent yellow and alizarin red of anionic dye is advantageous for the progress of absorption in acid condition.Wei Jinzhi etc. is adopted
Prepare magnetic triethylene tetramine graphene oxide (M-T-GO) first with constant temperature paddling process and hydro-thermal method, research shows M-T-GO pairs
The saturated extent of adsorption of anionic dye tartrazines (TY) and dye of positive ion methylene blue (MB) be respectively 157.23mg/g and
169.49mg/g, optimal adsorption pH value is respectively 1.0 and 12.0, and M-T-GO is to ionic dyes not only advantages of good adsorption effect, simultaneously
There is quick separating and easily regenerate.Jiang Yan is compound using coprecipitation synthesis chitosan magnetic/graphene oxide
Material (MCGO), the material is gradually decreased to the adsorption capacity of methyl orange with the increase of solution initial pH value；MCGO is to first
The absorption of base orange is rapid, and adsorption process meets plan second-order kinetics model, and its isothermal adsorption can meet Langmuir adsorption isotherms
Model, maximum adsorption capacity is 398.08mg/g；Meanwhile, MCGO reusing is very high.
With reference to Research Literature in recent years in terms of graphene and its composite, table 1 is domestic and international grapheme material
Study on adsorption properties is in progress.
The grapheme material Study on adsorption properties of table 1 is in progress
Table 1 Research Progress on Adsorption Properties of GO
(3) absorption of antibiotic
The environmental problem of current antibiotic pollution is paid attention to by many developed countries, while social concerns are increasing,
Related basic research is also a large amount of to be carried out.There is stable, difficult degradation relatively, strong toxicity for antibiotic pollution, have accumulation
The features such as effect, graphene absorption method removes antibiotic because the advantages of its cost is low, efficiency high, feasibility are good as a kind of
Effective ways.
Zhao etc. is carried out with porous GO- chitosans aeroge (PGO-CS) as adsorbent to the absorption property of tetracycline
Investigation, finds its adsorption capacity up to 1470mg/g, carries out adsorbent reactivation research to PGO-CS using hydrochloric acid washing method, as a result
Show, PGO-CS is recycled 4 times, and its adsorption capacity is still close to 1470mg/g.The graphite that Chao etc. is modified with molybdenum disulfide
Alkene material process fortimicin, compared with molybdenum disulfide, it is found that the graphene composite adsorbing material shows higher absorption
Capacity.Luo etc. uses Fe3O4Modified graphene magnetic composite effectively extracts the sulfa antibiotics in water sample, solves
The problem that nano-powder adsorbent is not readily separated, extends application of the graphene in terms of analytical chemistry, and research shows a variety of anti-
Raw element, such as tetracycline, fortimicin, sulfa antibiotics produce phase interaction by pi-pi bond with graphene-based composite
With.The graphene oxide (KOH-GO) that Feng Dongyan is activated with KOH is studied the absorption property of tetracycline as adsorbent, is ground
Study carefully and show that pH is bigger, OH-More, active oxidation graphene is better to the absorption property of tetracycline；Pass through KOH graphene oxide
Non-activated graphene oxide is significantly larger than to the absorption property of tetracycline, KOH-GO is to the maximum adsorption capacity of tetracycline
525.64mg/g.Li Ya etc. prepares graphene oxide using improved hummer methods, and using GO as presoma, ferric chloride hexahydrate is
Source of iron, passes through solvent-thermal method one-step synthesis RGO/Fe2O3Material, the material is 783.53mg/g to TC static saturated capacity, is put down
The equal rate of recovery is 99.1%~99.6%, and relative standard deviation (RSD) is 5.2%~6.0%.
The content of the invention
By consulting lot of documents, it is known that MGO is good for the absorption property of heavy metal and dyestuff, and TCs pollution is outstanding
It is that aureomycin, terramycin, quadracycline rarely have research.The present invention overcomes the shortcomings of existing treatment technology, and there is provided one kind warp
The magnetic graphene sorbent treatment that Ji is efficient, operation is simple and stable and environmentally safe, friendly is anti-containing Tetracyclines
The method of raw element water body.The content of tetracycline antibiotics in water body is reduced, tetracycline antibiotics are reduced to aquatile, people
The harm of body and ecological environment.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：1st, traces of antibiotic in a kind of water environment
Efficiently concentrating and separation method, it is characterised in that：
(1) foundation of standard curve；
(2) under certain condition, MGO is added into antibiotic solution, is placed in constant temperature oscillator and vibrates, in different absorption
Difference filtering and sampling in time, the absorbance of sample is measured with ultraviolet specrophotometer, then calculates remaining according to standard curve
TC concentration, finds corresponding time of equilibrium adsorption；
(3) into certain antibiotic concentration solution, MGO is added, under certain condition, respectively in constant temperature oscillation to corresponding
Equilibration time, filtering and sampling measures the absorbance of sample with ultraviolet specrophotometer, then calculates residue TC according to standard curve
Concentration, analysis ionic strength presence under conditions of, influence of the temperature to MGO adsorption effects, find optimal adsorption temperature；
(4) TC solution is mixed with MGO powder, regulation pH, which is placed in constant temperature oscillator, to be shaken to corresponding equilibration time,
Filtering and sampling, absorbance is determined with ultraviolet specrophotometer in respective certain wave strong point.
The efficiently concentrating and separation method of traces of antibiotic in above-mentioned water environment, it is further characterized by, the mark
The foundation of directrix curve：
Quadracycline storing solution is prepared, full wave scanning is carried out under ultraviolet specrophotometer, it is optimal to determine
Absworption peak；Storing solution is configured to certain density standard liquid with distilled water diluting, and adds sodium chloride to ensure stabilization
Ionic strength；Using ultraviolet specrophotometer maximum absorption wave strong point bioassay standard solution absorbance and record, to extinction
Degree and concentration carry out linear regression analysis, obtain corresponding TC standard curves.
The mass concentration of tetracycline in solution is calculated according to antibiotic standard curve, and calculates MGO unit adsorbance
(Qt) and antibiotic eliminating rate of absorption (r)：
In formula：C0And CtInitial in solution respectively and during absorption t after remaining antibiotic concentration, mg/L；V is solution body
Product, takes 30mL；M is adsorbent MGO quality, mg.
The efficiently concentrating and separation method of traces of antibiotic in above-mentioned water environment, it is further characterized by：
At 25 DEG C, under conditions of 180r/min, 5mg is added into the antibiotic solution that antibiotic concentration is 10mg/L
MGO, is placed in constant temperature oscillator and vibrates, and filtering and sampling is distinguished in different adsorption times, and sample is measured with ultraviolet specrophotometer
The absorbance of product, then calculates residue TC concentration according to standard curve, finds corresponding time of equilibrium adsorption.
Be respectively to antibiotic concentration 5mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L solution in, throw
Plus 5mg MGO, under conditions of 180r/min, respectively 10, at 20,40 DEG C constant temperature oscillation to corresponding equilibration time, filtering
Sampling, the absorbance of sample is measured with ultraviolet specrophotometer, and residue TC concentration is then calculated according to standard curve, and analysis exists
Under conditions of ionic strength is present, optimal adsorption temperature is found in influence of the temperature to MGO adsorption effects.
30mL 10mg/L TC solution is mixed with 5mg MGO powder, regulation pH is respectively 2,3.3,5,7.69,9,
9.69th, 10, it is placed in constant temperature oscillator and is shaken to corresponding equilibration time under the conditions of 298K, rotating speed is set to 180r/min, mistake
Leaching sample, determines absorbance, each pH does 3 Duplicate Samples with ultraviolet specrophotometer in respective certain wave strong point.
From 0.1mol/L HCl solution as the eluant, eluent to tetracycline, at 25 DEG C, under conditions of 180r/min, to
Concentration is placed in constant temperature oscillator and vibrated, in time of equilibrium adsorption to add 5mg graphene in 10mg/L tetracycline
Interior filtering and sampling, the absorbance of sample is measured with ultraviolet specrophotometer, is determined the concentration of remaining tetracycline, is utilized HCl solution
The MGO cleaned after stirring test, carries out repeating experiment.
Beneficial effect：
The present invention using quadracycline TC as research object, system research pH value of solution, temperature, Dissolved Organic Matter (with
Exemplified by humic acid) etc. under different factors, MGO is to TC characterization of adsorption, high spot reviews adsorption dynamics adsorption kinetics and absorption of the MGO to TC
Thermodynamics.Main result and conclusion are as follows：
(1) MGO meets TC adsorption process second- order reaction kinetics rule, and coefficient correlation is close to 1.
(2) MGO meets TC adsorption process Freundlich adsorption isotherms, and coefficient correlation is close to 1；Adsorption process is
One spontaneous endothermic process, high temperature is beneficial to absorption.
(3) pH influences existing forms of the TC in water, and then influences its absorption property, quadracycline during pH=3.3
Adsorption effect is best.
(4) after 4 adsorption-desorption circulation experiments, MGO is to the adsorption rate of tetracycline still greater than 60%.
Brief description of the drawings
Fig. 1 is the MGO hysteresis curve figures of the embodiment of the present invention.
Fig. 2 is the MGO surfaces Zeta potential figure of the embodiment of the present invention.
Fig. 3 is the uv-spectrogram figure of the quadracycline of the embodiment of the present invention.
Fig. 4 is the canonical plotting of the quadracycline of the embodiment of the present invention
Fig. 5 is that the concentration of the embodiment of the present invention changes with time figure.
Fig. 6 is that the adsorbance of the embodiment of the present invention changes with time figure.
Fig. 7 is the dynamic curve diagram of the graphene tetracycline adsorption of the embodiment of the present invention.
Fig. 8 is the influence schematic diagram that is adsorbed to quadracycline of temperature of the embodiment of the present invention.
Fig. 9 is the adsorption isotherm schematic diagram of the graphene tetracycline adsorption of the embodiment of the present invention.
Figure 10 is the adsorbance of the embodiment of the present invention with pH variation diagram.
Figure 11 is influence schematic diagram of the MGO regeneration cycles number of times of the embodiment of the present invention to absorption property.
Embodiment
The present invention is further elaborated below in conjunction with the drawings and specific embodiments.
Absorption property of the main research magnetic graphene of the invention under different adsorption conditionses to tetracycline antibiotics, and
The change of antibiotic concentration in front and rear solution is adsorbed with UV spectrophotometer measuring, so as to calculate its corresponding adsorption rate and magnetic
Property graphene adsorption capacity.Influence of the different factors to antibiotic absorption property is investigated, optimal adsorption condition, analysis absorption is drawn
Mechanism of action, and adsorption dynamics adsorption kinetics, Adsorption thermodynamics etc. are inquired into.Related invention content is as follows：
(1) Study on adsorption properties of the magnetic graphene to tetracycline antibiotics.
(2) dynamics research of magnetic graphene tetracycline adsorption class antibiotic.
(3) thermodynamic study of magnetic graphene tetracycline adsorption class antibiotic.
Experiment reagent：
Reagent needed for the present embodiment as shown in table 2, mainly there is a quadracycline, auxiliary reagent have concentrated hydrochloric acid, sodium hydroxide,
Humic acid etc..
Table 2 tests agents useful for same
Table 2 Reagents used in the experiments
Laboratory apparatus：
Instrument is as shown in table 3 needed for the present embodiment.
Table 3 tests key instrument equipment
Table 3 Main instruments used in experiments
The preparation of adsorbent and sign：
The adsorbent MGO, prepared MGO that the present embodiment is used are as follows to the absorption property of tetracycline antibiotics.
1. MGO magnetometric analysis
Magnetometric analysis is to utilize VSM magnetic measurement systems, using electromagnetic induction principle measurement at one group of search coil center
Make the magnetic moment of the sample of micro-vibration with fixed frequency and amplitude.Saturation magnetization is higher, and the magnetic of material is stronger.
The present embodiment uses vibrating specimen magnetometer (7410, Lake Shore companies of the U.S.), it is possible to achieve very high
The measurement of sensitivity, maximum field is 2.4T, and the range limit of magnetic moment measurement is carried out with VSM and can reach 0.1Am2Or it is higher.
Adsorption method：
(1) foundation of standard curve
10mg/L quadracycline storing solution is prepared, full wave scanning is carried out under ultraviolet specrophotometer, with true
Fixed optimal absworption peak.By 10mg/L storing solution be configured to distilled water diluting concentration for 2,4,6,8,10,12,20mg/L
Standard liquid, and add 0.02mol/L sodium chloride to ensure stable ionic strength.Inhaled using ultraviolet specrophotometer in maximum
The absorbance and record that this 7 kinds of standard liquids are determined at wavelength are received, absorbance and concentration are linearly returned with Origin softwares
Return analysis, obtain corresponding TC standard curves.
The mass concentration of tetracycline in solution is calculated according to antibiotic standard curve, and calculates MGO unit adsorbance
(Qt) and antibiotic eliminating rate of absorption (r)：
In formula：C0And CtInitial in solution respectively and during absorption t after remaining antibiotic concentration, mg/L；V is solution body
Product, takes 30mL；M is adsorbent MGO quality, mg.
(2) adsorption dynamics adsorption kinetics researchs of the MGO to TC
The present embodiment will do three groups of parallel laboratory tests, at 25 DEG C, under conditions of 180r/min, be 10mg/L to antibiotic concentration
Antibiotic solution in add 5mg MGO, be placed in constant temperature oscillator vibrate, in different adsorption times distinguish filtering and sampling,
The absorbance of sample is measured with ultraviolet specrophotometer, residue TC concentration is then calculated according to standard curve, is found corresponding
Time of equilibrium adsorption.
(3) Adsorption thermodynamics researchs of the MGO to TC
The present embodiment will do 3 groups of parallel laboratory tests, to antibiotic concentration be respectively 5mg/L, 10mg/L, 20mg/L, 30mg/L,
In 40mg/L, 50mg/L solution, 5mg MGO are added, under conditions of 180r/min, constant temperature shakes 10, at 20,40 DEG C respectively
Swing to corresponding equilibration time, filtering and sampling, the absorbance of sample is measured with ultraviolet specrophotometer, then according to standard curve
Residue TC concentration is calculated, analysis is under conditions of ionic strength presence, influence of the temperature to MGO adsorption effects, find optimal
Adsorption temp.
(4) pH adsorbs TC influence to magnetic graphene
30mL 10mg/L TC solution is mixed with 5mg MGO powder, regulation pH is respectively 2,3.3,5,7.69,9,
9.69th, 10, it is placed in constant temperature oscillator and is shaken to corresponding equilibration time under the conditions of 298K, rotating speed is set to 180r/min, mistake
Leaching sample, determines absorbance, each pH does 3 Duplicate Samples with ultraviolet specrophotometer in respective certain wave strong point.
Sorbent regeneration process：
The present embodiment selects 0.1mol/L HCl solution as the eluant, eluent to tetracycline, in 25 DEG C, 180r/min bar
Under part, to concentration to add 5mg graphene in 10mg/L tetracycline, it is placed in constant temperature oscillator and vibrates, in absorption
Filtering and sampling in equilibration time, the absorbance of sample is measured with ultraviolet specrophotometer, is determined the concentration of remaining tetracycline, is utilized
MGO after HCl solution cleaning stirring test, carries out repeating experiment.
Magnetometric analysis：In order to analyze the magnetic characteristic of adsorbent, (298K) determines adsorbent to the present embodiment at room temperature
Hysteresis curve, typical S types are presented in as shown in Figure 1 (MGO hysteresis curves figure), hysteresis curve, and saturation magnetization is
18.15emu/g, the Magneto separate that remanent magnetization tends to 0, MGO is very capable, it is easy to profit is reclaimed from adsorption reaction system
With.
Surface Zeta potential：This experiment determines the Zeta potential of adsorbent under (298K) at room temperature, and dispersant is goes
Ionized water, (MGO surfaces Zeta potential figure) as shown in Figure 2, MGO Zeta potential is 17.4mV, and deviation is 5.39mV, electrical conductivity
For 0.034mS/cm.
The standard curve of antibiotic：To 2,4,6,8,10,12,20mg/L antibiotic solution carries out ultraviolet spectra wave band and sweeps
Retouch, corresponding uv-spectrogram can be obtained.
Fig. 3 is the uv-spectrogram figure of quadracycline, and Fig. 4 is the canonical plotting of quadracycline.
It can be obtained by Fig. 3, the corresponding wavelength of ultraviolet characteristic absorption peak of quadracycline is 276nm and 355nm, takes 355nm
Scanning wavelength used, above-mentioned solution is respectively placed in the condition of 355nm wavelength during for this measuring quadracycline wavelength
Lower its absorbance of measure, each water sample makees three groups of Duplicate Samples, draws out the standard curve of quadracycline, you can obtain absorbance
A and quadracycline mass concentration c equation of linear regression, matched curve is as shown in Figure 4.
Adsorption dynamics adsorption kinetics research of the magnetic graphene to antibiotic：
Adsorption dynamics adsorption kinetics is the subject of a research adsorption and desorption speed and various influence factors, commonly uses pseudo-first-order and moves
Mechanical equation, pseudo-second order kinetic equation are fitted, and wherein pseudo-second order kinetic equation can predict equilibrium adsorption capacity.
Pseudo-first-order kinetics equation is a kind of kinetics equation for being usually used in sunykatuib analysis sloid-liq-uid adsorption system, the equation
Linear representation is：
ln(qe-qt)=lnqe-k1t (1)
Or
In formula：qeAdsorbance during for balance, mg/g；qtFor the adsorbance of t, mg/g；k1Be defined primary adsorption speed
Constant, min-1。
In most cases, pseudo-first-order kinetics equation can not be applied to whole adsorption process.Meanwhile, accurate two grades are moved
Mechanical model is widely used in the adsorption dynamics adsorption kinetics process of metal ion, and the description that it is provided is than pseudo-first-order kinetics equation
It is more accurate.The linear representation of quasi- second order rate equation is：
In formula：qeAdsorbance during for balance, mg/g；qtFor the adsorbance of t, mg/g；k2The secondary absorption that is defined speed
Constant, g/ (mgmin-1)。
Respectively with log (qe-qt) to t,T is mapped, entered with pseudo-first-order kinetics equation and pseudo-second order kinetic equation
Row fitting, if straight line can be obtained, illustrates that its adsorption mechanism meets the model.
Result according to measured by experimental procedure, Fig. 5 is the influence adsorbed to tetracycline the time, and Fig. 6 is tetracycline absorption
Equilibration time curve.
From Fig. 5 (concentration change with time figure) and Fig. 6 (adsorbance change with time figure), deposited in ionic strength
Graphene is as follows to the absorption situation of 10mg/L quadracycline solution under the conditions：0-5h tetracycline concentrations rapidly under
Drop to the rate of adsorption after certain numerical value, 5h to decline, be slow absorption phase, after absorption 8h, basically reach balance, therefore choosing
It is time of equilibrium adsorption to take 8h.
With reference to absorption Research Literature in recent years in terms of antibiotic, sorbing material and suction of the table 4 for domestic and international antibiotic
Attached Advance of Properties Research.
Sorbing material and the Study on adsorption properties progress of the antibiotic of table 4
Table 4 Research Progress on adsorption materials and adsorption
properties of antibiotics
Using adsorption time t as abscissa, make (25 DEG C) of same temperature by ordinate of ln (Qe-Qt) and t/Qt respectively different
The firsts and seconds kinetic curve of mass concentration graphene tetracycline adsorption, as shown in Figure 7 (graphene tetracycline adsorption it is dynamic
Force diagram figure), wherein：(a) first order kinetics curve map, (b) second-order kinetics illustraton of model.
It is fitted obtained relevant parameter as shown in table 5.
The kinetic model of table 5 and relevant parameter
Table 5 Dynamic model and related parameters
As shown in Table 5, under conditions of ionic strength presence, the R of second-order kinetics2More than the R of first order kinetics2, graphite
Absorption of the alkene to quadracycline relatively meets second-order kinetics curvilinear equation.
Adsorption isotherm of the magnetic graphene to antibiotic：
Under the conditions of certain temperature, the adsorbance at certain moment and the relation curve of adsorption density in etching solution when this are referred to as
Adsorption isotherm, the power that adsorbent and adsorbate are acted on is may determine that by the changing rule of adsorption isotherm, and according to
Physico-chemical theories are assumed and model, obtain Langmuir and Freundlich Tellurium determinations, data can be asked after fitting
Go out some model constants, these constants have corresponded to the contents such as absorption mechanism, adsorbed layer structure.
Choose common Langmuir, Freundlich adsorption isotherm model to study this adsorption experiment, to experiment
Data carry out linear fit, with the coefficient R of the corresponding equation of each model2Examine fitting result.
Langmuir Adsorption Models are based on assuming that adsorption site quantity is limited, and adsorption site is distributed evenly in absorption
Agent surface, between mono layer adsorption, and adsorbate without interaction.Its isotherm model is：
In formula：qeAdsorbance during for balance, mg/g；qmFor maximal absorptive capacity, mg/g；KLFor Langmuir constants, with suction
The attached dose of affinity between adsorbate is relevant.qmAnd KLValue can be tried to achieve by the slope and intercept of equation.
Freundlich Adsorption Models assume that the surface nature of adsorbent is different, and distribution and the inequality of adsorption site
It is even, imperfection absorption and multilayer absorption for different surfaces.Its isotherm model is：
In formula：Ce is equilibrium concentration, mg/L；qeAdsorbance during for balance, mg/g；KFFor Freundlich constants, with suction
The relevant parameter of attached dose of adsorption capacity；N is adsorption exponent, the parameter relevant with adsorbent surface action intensity with binding molecule.
KFIt can be tried to achieve with n values by the slope and intercept of equation.
The result measured is tested as shown in figure 8, the influence schematic diagram that temperature is adsorbed to quadracycline.
As shown in Figure 8, at 10 DEG C, 25 DEG C, adsorbed respectively at 40 DEG C of three temperature, the absorption effect of tetracycline at 40 DEG C
It is really best.Therefore, for tetracycline, between 10 DEG C -40 DEG C, with the rise of temperature, adsorption effect is become better and better.
What fitting was obtained waits kelvin relation as shown in Figure 9 (the adsorption isotherm schematic diagram of graphene tetracycline adsorption), fitting
Obtained relevant parameter is as shown in table 6.In Fig. 9, (a) Langmuir adsorption isotherm line charts, (b) Freundlich adsorption isotherms
Figure.
The thermodynamical model of table 6 and relevant parameter
Table 6 Thermodynamic model and related parameters
As shown in Fig. 9 and table 6, under conditions of ionic strength presence, absorption of the graphene to quadracycline more meets
Freundlich adsorption isotherms, coefficient correlation (R2)Close to 1.N belongs to favourable absorption in the range of 1-10.
Adsorption thermodynamics of the magnetic graphene to antibiotic：
Fuel factor in adsorption process is referred to as heat of adsorption.By studying Adsorption thermodynamics, not only it will be seen that absorption journey
Degree and driving force, can also analyse in depth Influencing Mechanism of the various factors to absorption.
Gibbs free energy change (△ G) in adsorption process can be calculated by following formula to be obtained：
Δ G=-RT ln K (6)
In formula：△ G are gibbs free energy change, kJ/mol；T is Kelvin absolute temperature, K；R is gas constant, is taken
8.314J·mol-1·K-1；K is the Adsorption thermodynamics equilibrium constant.
Enthalpy change in adsorption process can be calculated by following formula to be obtained：
In formula：△ H are standard enthalpy change, kJ/mol；△ S are standard entropy change, Jmol-1·K-1.△ H and △ S value can be with
Pass through lnK pairsMapping is obtained.
Under identical concentration, time, pH etc., the temperature conditionss of different temperatures, according to adsorption isothermal curve,
Freundlich adsorption isotherms, Adsorption thermodynamics behaviors of the research MGO to quadracycline.
Using 1/T as abscissa, lnK is ordinate, is fitted obtained specific data as shown in table 7.
The thermodynamic parameter of the quadracycline of table 7
Table 7 The thermodynamic parameters of tetracycline hydrochloride
As shown in Table 7, gibbs free energy change △ G at three temperatures are respectively less than zero, and with the rise of temperature,
△ G reduce, and it is a spontaneous process to the adsorption process of quadracycline thus to illustrate MGO.Drawn by enthalpy change △ H more than zero
The adsorption process belongs to endothermic process, and high temperature is beneficial to absorption.
PH adsorbs the influence of antibiotic to magnetic graphene：(adsorbance is with pH's as shown in Figure 10 for the result that experiment is measured
Variation diagram).
As shown in Figure 10, pH=3.3 is that graphene is adsorbed most to quadracycline under conditions of ionic strength presence
Good pH.Graphene presents first to increase to the adsorption effect of quadracycline between pH 2-10 subtracts the trend increased again afterwards.Be probably by
Change in pH, quadracycline form generation changes, so as to influence its absorption property.
Parse influence such as Figure 11 (MGO regeneration cycle of the different cycle-indexes of MGO of regeneration to the clearance of quadracycline
Influence schematic diagram of the number of times to absorption property).Quadracycline regeneration cycle experiment in, first three time cycle efficieny compared with
Height, compared with substance system, clearance does not have bigger difference, and after the 4th time circulates, clearance is first 71.9%.
Result above shows that magnetic oxygenated graphene can be with desorption and regeneration, and can be recycled with high efficiency.
Above content described in description of the invention is only that examples of the invention is illustrated.Skill belonging to of the invention
The technical staff in art field can be made various modifications to described specific embodiment or be replaced using similar mode, as long as not
Deviate the content of description of the invention or surmount scope defined in the claims, the protection model of the present invention all should be belonged to
Enclose.
Claims (8)
1. the efficiently concentrating and separation method of traces of antibiotic in a kind of water environment, it is characterised in that：
(1) foundation of standard curve；
(2) under certain condition, MGO is added into antibiotic solution, is placed in constant temperature oscillator and vibrates, in different adsorption times
Interior filtering and sampling respectively, the absorbance of sample is measured with ultraviolet specrophotometer, then calculates residue TC's according to standard curve
Concentration, finds corresponding time of equilibrium adsorption；
(3) into certain antibiotic concentration solution, MGO is added, under certain condition, respectively in constant temperature oscillation to corresponding balance
Time, filtering and sampling measures the absorbance of sample with ultraviolet specrophotometer, then calculates the dense of residue TC according to standard curve
Degree, analysis is under conditions of ionic strength presence, and optimal adsorption temperature is found in influence of the temperature to MGO adsorption effects；
(4) TC solution is mixed with MGO powder, regulation pH, which is placed in constant temperature oscillator, to be shaken to corresponding equilibration time, filtering
Sampling, absorbance is determined with ultraviolet specrophotometer in respective certain wave strong point.
2. the efficiently concentrating and separation method of traces of antibiotic in water environment according to claim 1, it is characterised in that institute
State the foundation of standard curve：
Quadracycline storing solution is prepared, full wave scanning is carried out under ultraviolet specrophotometer, to determine optimal absorption
Peak；Storing solution is configured to certain density standard liquid with distilled water diluting, and adds sodium chloride to ensure stable ion
Intensity；Using ultraviolet specrophotometer maximum absorption wave strong point bioassay standard solution absorbance and record, to absorbance and
Concentration carries out linear regression analysis, obtains corresponding TC standard curves.
3. the efficiently concentrating and separation method of traces of antibiotic in water environment according to claim 2, it is characterised in that：
The mass concentration of tetracycline in solution is calculated according to antibiotic standard curve, and calculates MGO unit adsorbance (Qt) and it is anti-
The eliminating rate of absorption (r) of raw element：
<mrow>
<msub>
<mi>Q</mi>
<mi>t</mi>
</msub>
<mo>=</mo>
<mfrac>
<mrow>
<mo>(</mo>
<msub>
<mi>C</mi>
<mn>0</mn>
</msub>
<mo>-</mo>
<msub>
<mi>C</mi>
<mi>t</mi>
</msub>
<mo>)</mo>
<mo>&times;</mo>
<mi>V</mi>
</mrow>
<mi>m</mi>
</mfrac>
<mo>-</mo>
<mo>-</mo>
<mo>-</mo>
<mrow>
<mo>(</mo>
<mn>8</mn>
<mo>)</mo>
</mrow>
</mrow>
<mrow>
<mi>r</mi>
<mo>=</mo>
<mfrac>
<mrow>
<mo>(</mo>
<msub>
<mi>C</mi>
<mn>0</mn>
</msub>
<mo>-</mo>
<msub>
<mi>C</mi>
<mi>t</mi>
</msub>
<mo>)</mo>
</mrow>
<msub>
<mi>C</mi>
<mn>0</mn>
</msub>
</mfrac>
<mo>&times;</mo>
<mn>100</mn>
<mi>%</mi>
<mo>-</mo>
<mo>-</mo>
<mo>-</mo>
<mrow>
<mo>(</mo>
<mn>9</mn>
<mo>)</mo>
</mrow>
</mrow>
In formula：C0And CtInitial in solution respectively and during absorption t after remaining antibiotic concentration, mg/L；V is liquor capacity, is taken
30mL；M is adsorbent MGO quality, mg.
4. the efficiently concentrating and separation method of traces of antibiotic in water environment according to claim 1, it is characterised in that：
At 25 DEG C, under conditions of 180r/min, to antibiotic concentration to add 5mgMGO in 10mg/L antibiotic solution, it is placed on
Vibrated in constant temperature oscillator, filtering and sampling is distinguished in different adsorption times, the extinction of sample is measured with ultraviolet specrophotometer
Degree, then calculates residue TC concentration according to standard curve, finds corresponding time of equilibrium adsorption.
5. the efficiently concentrating and separation method of traces of antibiotic in water environment according to claim 1, it is characterised in that：
Be respectively to antibiotic concentration 5mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L solution in, add
5mg MGO, under conditions of 180r/min, 10, at 20,40 DEG C, constant temperature oscillation, to corresponding equilibration time, is filtered to take respectively
Sample, the absorbance of sample is measured with ultraviolet specrophotometer, and residue TC concentration is then calculated according to standard curve, analyze from
Under conditions of sub- intensity is present, optimal adsorption temperature is found in influence of the temperature to MGO adsorption effects.
6. the efficiently concentrating and separation method of traces of antibiotic in water environment according to claim 1, it is characterised in that：
30mL 10mg/L TC solution is mixed with 5mg MGO powder, regulation pH is respectively 2,3.3,5,7.69,9,9.69,
10, it is placed in constant temperature oscillator and is shaken to corresponding equilibration time under the conditions of 298K, rotating speed is set to 180r/min, filters to take
Sample, determines absorbance, each pH does 3 Duplicate Samples with ultraviolet specrophotometer in respective certain wave strong point.
7. the efficiently concentrating and separation method of traces of antibiotic, its feature in the water environment according to one of claim 1 to 6
It is：
From HCl solution as the eluant, eluent to tetracycline, under certain condition, graphene is added into tetracycline, put
Vibrated in constant temperature oscillator, the filtering and sampling in time of equilibrium adsorption, the absorbance of sample measured with ultraviolet specrophotometer,
The concentration of remaining tetracycline is determined, the MGO cleaned using HCl solution after stirring test carries out repeating experiment.
8. the efficiently concentrating and separation method of traces of antibiotic in water environment according to claim 7, it is characterised in that：
From 0.1mol/L HCl solution as the eluant, eluent to tetracycline, at 25 DEG C, under conditions of 180r/min, to concentration
To add 5mg graphene in 10mg/L tetracycline, it is placed in constant temperature oscillator and vibrates, the mistake in time of equilibrium adsorption
Leaching sample, the absorbance of sample is measured with ultraviolet specrophotometer, is determined the concentration of remaining tetracycline, is cleaned using HCl solution
MGO after stirring test, carries out repeating experiment.
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