CN109626493A - A kind of application of surfactant-modified goethite in removal microcystic aeruginosa - Google Patents
A kind of application of surfactant-modified goethite in removal microcystic aeruginosa Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention provides application of the surfactant-modified goethite of one kind in removal microcystic aeruginosa.The surfactant includes hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide, cetalkonium chloride or Cetyltrimethylammonium bromide.Specifically surfactant is dissolved in the water, then goethite is added into lysate, is stirred, supernatant, freeze-drying are abandoned in centrifugation, and surfactant-modified goethite can be prepared in grinding.Product of the invention is during removing microcystic aeruginosa, positively charged carbochain can net catch and bond the frustule of negative electrical charge, alkyl chain penetrates frustule film, change the integrality of phospholipid bilayer, film is caused to rupture, it reacts with frond internal protein, nucleic acid, make the bridged bond relaxation between cellulosic molecule or inhibits the synthesis of protein.Goethite generates the free radical attack frustule of strong oxidizing property under the action of light, causes organic matter in frustule body to ooze out, inhibits frustule growth.
Description
Technical field
The present invention relates to a kind of surfactant-modified goethites, and are applied on removal microcystic aeruginosa, belong to
In technical field of water pollution control.
Background technique
It is higher and higher in the raw frequency of many national blue algae grey hairs at present, it has also become a global environmental problem.It is blue
The undue growth of algae makes color, smell and the toxin of water produce harm to the mankind, animal and aquatile, it is necessary to excessive raw
Long algae carries out in-situ control.Microcystic aeruginosa is a kind of well-known algae, it is in global freshwater lake and reservoir
Cause cyanobacteria algal tufa.Now common some processing methods have chemical algae removing agent, clay flocculating, ultrasound wave irradiation, large-scale aquatic plant
Object, biotechnology and ultraviolet light irradiation etc..
Effectively as one kind, economy and environmentally friendly material by extensive concern and apply to blue algae to its CLAY MINERALS AND THEIR SIGNIFICANCE
China's control.Since water flow movement leads to floccule body settling flux after traditional clay mineral and frustule flocculation, algae removal is influenced
Effect.At present with surfactant-modified mineral become research a big hot spot, it can not only reduce liquid, solid and gas it
Between surface and interface tension, the adhesive force for improving mineral reaches efficient removal effect, and metal oxide semiconductor exists
The living radical generated under the irradiation of light can aoxidize protein, lipid and nucleic acid in frustule, destroy cell membrane and cause
Frustule rupture.Wu Ting etc. is modified with Gemini surface active by vermiculite, montmorillonite, is sent out by the removal to Phaeocystis globosa
Removal rate is maximum for 24 hours when concentration is 6.5mg/L for existing modified vermiculite.Liu Guofeng etc. uses cetyl trimethylammonium bromide
(CTAB) modified clay not only makes cell aggregation also crack cell in flocculation process.
There is a large amount of ferriferous oxides in nature, and wherein goethite is widely present in the environment such as soil and deposit Jie
In matter, and with its environmentally friendly, reserves are big, chemical property is stable etc. has attracted the research of numerous scholars.
Summary of the invention
The present invention is modified goethite using 4 kinds of surfactants, the algae removal efficiency of modified material is analyzed, to property
Material that can be best carries out algae removal efficiency exploration under different physico chemical factors.Particular content is as follows:
The present invention provides application of the surfactant-modified goethite of one kind on removal microcystic aeruginosa.Including as follows
Step: being 7.5-9.5 in pH value, under the conditions of 20-30 DEG C and illumination are 1000-2500Lx, respectively into the culture medium to sterilize
Microcystic aeruginosa is added, adds surfactant-modified goethite, is put into illumination box 2-20d, removes microcystic aeruginosa.
The density of the microcystic aeruginosa is 1.0 × 106-1.0×107Cells/mL, microcystic aeruginosa include in pair
The frustule in number growth period and death phase.
The additive amount of the surfactant-modified goethite is 10mg/L-60mg/L.The surfactant packet
Include hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide, cetalkonium chloride, octadecyl
Any one in trimethylammonium bromide.
The surfactant-modified goethite the preparation method is as follows: surfactant is dissolved in 55-65 DEG C
Water in, then goethite is added into lysate, stirs, supernatant, vacuum drying are abandoned in centrifugation, and table can be prepared in grinding
The modified goethite of face activating agent.
The present invention analyzes surfactant-modified goethite to the removal effect of microcystic aeruginosa, 4 kinds of surfaces
In activating agent, the modified goethite of ODTMA is best to the removal effect of chlorophyll a.It is tested and is found by single factor test physico chemical factor,
ODTMA/ goethite reaction density is 50mg/L, temperature is 35 DEG C, the condition of 2000Lx illumination and reaction pH be faintly acid
It is maximum with chlorophyll a removal rate when neutrality.This is because ODTMA/ goethite is during removing microcystic aeruginosa, on the one hand
Positively charged carbochain can net catch and bond the frustule of negative electrical charge, alkyl chain penetrates frustule film, changes phospholipid bilayer
The integrality of layer, causes film to rupture, reacts with frond internal protein, nucleic acid, makes bridged bond relaxation or suppression between cellulosic molecule
The synthesis of protein processed.Another aspect goethite generates the free radical attack frustule of strong oxidizing property under the action of light, causes
Organic matter oozes out in frustule body, so that frustule be inhibited to grow.
Detailed description of the invention
Fig. 1 is removal rate (a) and its Zeta potential (b) of the goethite under different surfaces activating agent is modified to chlorophyll a.
Fig. 2 is the XRD diagram of ODTMA/ goethite sample.
Fig. 3 is that the SEM of sample schemes the natural goethite of (a)-(b)；(c)-(d) ODTMA/ goethite
Fig. 4 is influence (a) the ODTMA/ goethite dosage that physico chemical factor removes chlorophyll a to ODTMA/ goethite；(b)
Light intensity；(c) temperature；(d)pH.
Fig. 5 is influence (a) Chla- chlorophyll a and Caro- carotenoids of the ODTMA/ goethite to physical signs removal rate
Element；(b) PC- phycocyanin；APC- allophycocyanin and PE- phycoerythrin；(c) TSP- soluble protein；(d) MDA- the third two
Aldehyde.
Fig. 6 is before frustule SEM schemes the processing of (a)-(b) ODTMA/ goethite；(c)-(d) after the processing of ODTMA/ goethite.
Fig. 7 is before frustule flow cytometer figure (a) ODTMA/ goethite is handled；(b) after the processing of ODTMA/ goethite.
Fig. 8 is ODTMA/ goethite except TOC variation diagram in BG-11 culture medium after algae.
Specific embodiment
Realize that reagent used in technical solution of the present invention and instrument are as follows:
Major experimental reagent: hexadecyltrimethylammonium chloride (CTAC, Aladdin reagent, AR)；Cetyl trimethyl
Ammonium bromide CTAB, Aladdin reagent, AR)；Cetalkonium chloride (HDTMA, Aladdin reagent, AR)；18
Alkyl trimethyl ammonium bromide (ODTMA, Sigma Aldrich, AR)；Goethite (Sigma Aldrich, AR).
Major experimental instrument: superclean bench (SW-CJ-1F, Wujiang Wei Feng cleaning equipment Co., Ltd)；High pressure sterilization
Pot (SYQ-DSY-280B, Shenan Medical Appliances Factory, Shanghai)；(PGX-250B, Ningbo sea daybreak match Buddhist laboratory apparatus to illumination box
Factory)；Ultraviolet-visible spectrophotometer (UV-Vis DRS, Lambda25, the U.S.)；PH meter (Delta 320, Mettler-
Toledo, Shanghai Co., Ltd)；X-ray diffractometer (XRD, D/max2500, Rigaku, Japan)；Awkward silence at a meeting scanning electron microscopy
Mirror (SEM, JSM-7500F, JEOL, Japan)；Total organic carbon analyzer (TOC, Multi N/C 2000, Germany).
The preparation and characterization of ODTMA/ goethite
The preparation of ODTMA/ goethite: the ODTMA for weighing 0.48g is dissolved in 60 DEG C of water of 100mL, then into lysate
The goethite of 0.11g is added, is placed on magnetic stirring apparatus, stirs 72h, supernatant is abandoned in centrifugation, is dried in vacuo, grinding.According to phase
Tongfang method prepares the modified goethite of CTAC, CTAB, HDTMA.
The characterization of ODTMA/ goethite: using the crystalline form of X-ray diffractometer measurement ODTMA/ goethite, 2 θ ranges of scanning are
20°-60°；Its pattern is measured using awkward silence at a meeting scanning electron microscope.
Surfactant-modified goethite is tested except algae
It is 7.5 that pH value is controlled in technical solution of the present invention, and temperature is 25 DEG C, illumination 2000Lx.It goes out respectively to 200mL
The frustule in logarithmic growth phase of equivalent is added in the culture medium that bacterium crosses, so that initial algae density is 1.7 × 106cells/
mL.A certain amount of surfactant-modified goethite is weighed in algae solution, is put into illumination box reaction certain time.It is green with leaf
The removal rate of plain a is evaluation criterion, and 2 repetitions are arranged in each experimental group.
4 kinds of surfactant-modified goethites are except in algae experiment, the dosage of catalyst is 50mg/L；In order to investigate best table
The influence of the modified goethite reaction density of face activating agent, be provided with 0mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L,
50mg/L and 60mg/L；It is 0Lx (dark), 500Lx, 1000Lx, 1500Lx, 2000Lx that light intensity, which influences setting gradient,；It investigates
Temperature range: 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C and 35 DEG C, medium pH range is 6.5,7.5,8.5,9.5 and 10.5.Surface-active
Agent is modified goethite concentration, light intensity, temperature and pH experiment and is put into incubator experiment 1d.
Surfactant-modified goethite influences frustule physical signs to use ODTMA/ goethite in experiment, is put into light
1d is tested according to incubator.Measure the wherein chlorophyll a of frustule, carotenoid, phycobniliprotein, soluble protein and malonaldehyde
Content reflects that surfactant-modified needle iron damages algal grown, physiological status, cell metabolism and frustule film respectively
The influence of wound.
In addition, frustule pattern changes after changing except the total organic carbon (TOC) of culture medium during algae by monitoring, remove algae
And cell membrane integrity discloses surfactant-modified goethite to the removal mechanisms at work of frustule.
Index analysis method
The measurement (including chlorophyll a, carotenoid, soluble protein, malonaldehyde) of frustule physical signs, frustule
Surface texture and film integrality test.
The measurement of chlorophyll a and carotenoid content: taking 10mL algae solution 5000r/min to be centrifuged 5min, remove supernatant,
95% isometric ethyl alcohol is added into precipitating, is stayed overnight at 4 DEG C, then 5000r/min is centrifuged 5min, takes supernatant spectrophotometric
Value at 665,649 and 470nm of meter measurement.The calculation formula of chlorophyll a and carotenoid content is as follows:
Chla (mg/L)=13.7 × A665-5.76×A649
Caro (mg/L)=(1000 × A470-2.05×Chla)/245
The measurement of Phycobiliprotein Content: taking 5mL algae solution, and 10000r/min is centrifuged 10min, removes supernatant, and 5mL phosphorus is added
Acid buffer (0.05mol/L, pH value 7.0).The ultrasound 120s (working time 3s, off time 2s) on Ultrasonic Cell Disruptor, 4
At DEG C overnight, then 12000r/min is centrifuged 10min.Take the value at 650,620 and 565nm of supernatant spectrophotometric determination.
The calculation formula of phycocyanin (PC), allophycocyanin (APC) and phycoerythrin (PE) content is as follows:
PC=(A620-0.7×A650)/7.38
APC=(A650-0.19×A620)/5.65
PE=(A565-2.8×PC-1.34×APC)/1.27
The measurement of soluble protein and mda content: taking 20mL algae solution, and 10min is centrifuged under 5000r/min, and it is thin to collect algae
Born of the same parents are added the phosphate buffer 1mL (pH=7.8) of 0.05mol/L, utilize ultrasonic cell disruption instrument ice bath smudge cells
10min (work 5s, gap 20s therebetween), microscopy are without 10min, supernatant is centrifuged after intact cell under 12000r/min
Crude enzyme liquid.The protein content of Bioengineering Research Institute is built up in the measurement of soluble protein content and mda content referring to Nanjing
Assay kit (article No.: A045-2) and Malondialdehyde Kit (article No.: A003-1) specification carry out.
The measurement of dissolved oxygen: by BiBOr9/ fabric is added to the 2.0 × 10 of 200mL6It, will every 3d in cells/mL algae solution
Dissolved oxygen instrument probe, which is inserted into the algae solution of control group and processing group, measures dissolved oxygen content, measures 3 times, is averaged.
The detection of active specy: four conical flasks are taken, are added the 2.0 × 10 of 200mL in each conical flask6cells/mL
Algae solution and BiBOr9/ fabric.Be separately added into three conical flasks thereto again benzoquinones (BQ 1mM), isopropanol (IPA 1mM) and
Ethylenediamine tetra-acetic acid (EDTA 1mM) reacts 18d, takes a sample every 3d, measures chlorophyll a value.
Frustule surface texture observation: untreated blank algae solution and addition BiOBr/ fabric treating after taking 100mL to react
Algae solution be centrifuged 10min at 4000r/min, discard supernatant liquid, the glutaraldehyde that 1mL 2% is added into the frustule of collection is solid
Determine frustule 2h, is then cleaned 3 times with the phosphate buffer (pH=6.8) of 1mL 0.1mol/L, each 10min.Then 1mL is used
50%, 70%, 90% Gradient elution using ethanol 15min, 100% ethanol dehydration 2 times, each 30min, drying sample.Test sample
When sample is glued on sample stage with two-sided, observed simultaneously under Hitachi's scanning electron microscope with ion sputtering instrument to after sample gold-plated film
It takes pictures.
The test of frustule film integrality: propidium iodide is a kind of nuclei dyeing color reagent that can be dyed to DNA.It is a kind of
The analog of Ethidum Eremide discharges red fluorescence after being embedded in double-stranded DNA.PI cannot penetrate intact cell film, but dead cell and
Damaged state is presented in its cell membrane of cell in apoptosis advanced stage, and PI molecule can penetrate, and incarnadine nucleus.It takes
Microcystic aeruginosa liquid each 1mL, 4000r/min the centrifugation 5min of after BiOBr/ fabric treating and normal growth breeding, discards
Clear liquid is added ultrapure water and cleans 2 times, and centrifugation discards supernatant liquid, and 1mL ultrapure water is added to be uniformly mixed.Add the PI solution of 61 L
(1mg/mL), so that the ultimate density being added is 65.2mg/L.15min is dyed in dark, flow cytometer is detected using FL2
Device detection, data are analyzed using BD FACSuite Software software.
The measurement of TOC: the ODTMA/ goethite of 5mg is added in the algae solution of 100mL, takes 2mL algae solution through 0.22 μ daily
After m membrane filtration, supernatant is through total content of organic carbon in total organic carbon analyzer measurement sample.
The modified goethite of different cationic surfactants removes the expression activitiy of algae
Package modification is carried out to goethite using 4 kinds of cationic surfactants HDTMA, CTAC, CTAB and ODTMA, it is right
Microcystic aeruginosa chlorophyll a is gone shown in influence such as Fig. 1 (a) of division result.By Fig. 1 (a) it is found that using after surfactant-modified
Goethite its be significantly increased except algae efficiency, wherein the modified goethite activity of ODTMA improves maximum, and chlorophyll a is gone
From high to low successively except rate are as follows: ODTMA/ goethite (90.81%) > CTAB/ goethite (84.23%) > CTAC/ goethite
(81.20%) > HDTMA/ goethite (79.12%) > goethite (57.24%).Fig. 1 (b) give 4 kinds of modified goethites with
The Zeta potential of unmodified goethite changes, it can be found that the Zeta potential of modified goethite is all to positive charge from Fig. 1 (b)
Direction is mobile, wherein the Zeta potential of ODTMA/ goethite between 50.12mV~65.01mV, and HDTMA/ goethite,
CTAB/ goethite, CTAC/ goethite Zeta potential between 25.21mV~45.32mV, lower than the electricity of ODTMA/ goethite
Position.This is because the carbon chain length of the more other threes of ODTMA, the Zeta potential value after being modified goethite is bigger, and adsorption capacity is also got over
By force.In addition, the carbochain the long more is conducive to quaternary ammonium group and the effective coating modification of goethite surface progress, and it combines algae thin
The ability of after birth phospholipid bilayer is stronger, to more be readily adsorbed on frustule film, cell membrane function is caused to destroy, led
Cause chlorophyll a decline.
Therefore, goethite ODTMA modified in four kinds of quaternary cationics except algae effect it is best, and
Modified Zeta potential size is directly proportional to algae removal efficiency.So the goethite for selecting ODTMA modified is deep in follow-up study
Enter the various chemical factors that research acts on the removal of microcystic aeruginosa and influences to remove algae effect.
The characterization of ODTMA/ goethite
XRD
ODTMA/ goethite crystals purity passes through XRD characterization.As shown in Fig. 2, being 17.77 °, 21.24 °, 53.63 ° in 2 θ
The diffraction maximum of appearance is all corresponding with the diffraction maximum of natural goethite, and peak shape is more sharp, this illustrates ODTMA/ goethite
Better crystallinity degree, purity is high.Other diffraction maximums are had also appeared in the XRD spectrum of ODTMA/ goethite, this is because ODTMA packet
The reason of wrapping up in.
SEM
The pattern of ODTMA/ goethite is as shown in figure 3, Fig. 3 (a) and Fig. 3 (b) is the SEM figure of natural goethite, Cong Tuzhong
It was found that natural goethite is assembled by a large amount of acicular nanometer rods.Fig. 3 (c) and Fig. 3 (d) is that the SEM of ODTMA/ goethite schemes, from figure
Middle discovery surface of nanometer rods unlike natural goethite seems have a tunic to be wrapped in, i.e., ionic surface active agent is main
It is covered on the surface and edge of goethite.
ODTMA/ goethite removes the research of algae effect under different physico chemical factors
Shown in the influence result such as Fig. 4 (a) of the ODTMA/ goethite of various concentration to microcystic aeruginosa chlorophyll a.From figure
Middle discovery ODTMA/ goethite can effectively inhibit the growth of microcystic aeruginosa, and algae removal efficiency in a certain range with dosage
It is directly proportional.When the concentration of ODTMA/ goethite is less than 50mg/L, algae removal efficiency is directly proportional to concentration.When ODTMA/ goethite
When concentration is more than 50mg/L, algae removal efficiency tends to balance.The adsorption potential on goethite surface is increased after the modified goethite of ODTMA
Point, due to one timing of number of frustule, increases the use of ODTMA/ goethite when ODTMA/ goethite concentration is less than 50mg/L
The interaction with frustule can be improved in amount, thus increase removal efficiency, and when the dosage for continuing raising ODTMA/ goethite
When, the effect between frustule and ODTMA/ goethite tends to be saturated, so that inhibitory effect tends towards stability.Therefore, 50mg/ is selected
The ODTMA/ goethite of L is as reaction optium concentration.
Shown in the influence such as Fig. 4 (b) of intensity of illumination to ODTMA/ goethite algae removal efficiency.When no light, alga-killing rate is
42.18%, and with the enhancing of illumination, alga-killing rate is successively increased by 67.04% to 92.04%.This is mainly that goethite has
Photocatalytic activity, can be with stimulating activity species under the irradiation of light, and goethite has big specific surface area, in dark state
It is lower to be adsorbed with frustule, frustule is settled down using self gravity.After increasing light intensity, the active matter of goethite generation
The frustule film of kind attack absorption frustule, so that cell membrane is by destroying infection growth and breeding.
ODTMA/ goethite has efficient removal effect at different temperatures, as a result as shown in Fig. 4 (c), is being investigated
20 DEG C -35 DEG C within the scope of, alga-killing rate rises to 100% by 88.23% with the raising of temperature.Reason on the one hand be
The solubilization of ODTMA surfactant, temperature raising causes warm-up movement to aggravate, so that there are more spaces in micelle
Frustule, another aspect ODTMA/ goethite are heat absorptions except the entire reaction process of algae.The increase of temperature, so that ODTMA/ needle
The motion frequency of iron ore and microcystic aeruginosa is accelerated, and when microcystic aeruginosa is close to ODTMA/ goethite, they can be attached to material
On the surface of material, so that alga-killing rate be made to rise.15 DEG C of alga-killing rates reach 94.08%, are due to being not suitable for copper under 15 DEG C of low temperature
Therefore green Microcystis aeruginosa own growth causes alga-killing rate to rise.
The pH value of solution is one of most important parameter in adsorption process, because it influences the physical chemistry of catalyst surface
Property and surface binding site.ODTMA/ goethite under different pH environment is investigated to the removal capacity of microcystic aeruginosa, as a result
As shown in Fig. 4 (d).Within the scope of the pH investigated (6.5-10.5), the alga-killing rate of ODTMA/ goethite is in 71.01%-
Between 93.12%, wherein the alga-killing rate of pH=6.5 is up to 93.21%, in pH=7.5-10.5 as alkalinity enhances, removes
Algae rate is slightly decreased.
Zeta potential measurement result shows that ODTMA/ goethite surface in the range of pH=2-10 is all positively charged, and
Stablize in 55mV-65mV, when pH value < 6, there is a large amount of protons in solution, can be generated largely on goethite surface
Positive charge.Show that there are strong electrostatic attractions between ODTMA/ goethite and frustule, therefore is able to achieve under lower ph
High removal effect.When solution ph > 7, there is a large amount of hydroxide ions in solution, this can reduce ODTMA/ goethite table
The positively charged bit number of points in face and the quantity for increasing adsorbent surface anionic sites in number, so that negatively charged frustule adsorbs
Amount on ODTMA/ goethite surface is reduced.The removal efficiency of frustule chlorophyll a with hydroxide ion in solution increase
And be gradually reduced, show that high ph-values are unfavorable for the absorption of frustule, because excessive hydroxide ion and absorption algae are thin in solution
There are competitive relations between the activated adoption site of born of the same parents.
Influence of the ODTMA/ goethite to frustule physical signs
Chlorophyll a and carotenoid are the index for determining that photosynthetic rate is indispensable, the energy in photosynthesis
Capture and transfer in play an important role.Chlorophyll a and carotenoid are most important photosynthetic colors in microcystic aeruginosa
Element, and chlorophyll a and carotenoid content can also prove the primary productivity of water body.ODTMA/ goethite is to chlorophyll a
Shown in influence such as Fig. 5 (a) with carotenoid.With the progress of reaction, the removal rate of chlorophyll a and carotenoid is gradually
Increase, after reaction for 24 hours, the removal rate of chlorophyll a and carotenoid is respectively 90.33% and 81.34%.Mainly due to table
When face activating agent ODTMA/ goethite concentration is higher, the breeding of the biosynthesis block of chlorophyll a and carotenoid, cell is pressed down
System.
Photosynthesis is algae basis for the survival, phycobniliprotein need to utilize and absorb luminous energy promote in frustule biochemistry at
The synthesis divided, and the variation of biochemical composition reflects the physiological status of algae indirectly.Fig. 5 (b) is ODTMA/ goethite to algae gallbladder
The influence of albumen removal rate, in reaction process either its removal rate of phycocyanin, allophycocyanin or phycoerythrin all with
Time is directly proportional, and after reaction for 24 hours, removal rate is respectively 62.47%, 67.68% and 40.14%.This is because ODTMA/ needle iron
The effect of mine have stimulated II reaction center of PS, it is suppressed that photosynthetic primitive reaction hinders photoelectron from primary to secondary
The transmittance process of electron acceptor causes carbon sequestration and assimilation to weaken, has slowed down the synthesis of biochemical composition, therefore inhibit
The photosynthesis of frustule.
Soluble protein is not only urging for the important component of large biological molecule in frustule and biochemical reaction
Agent participates in various metabolic activities, is the important indicant of frustule metabolic condition.If Fig. 5 (c) is ODTMA/ goethite
Influence to soluble protein removal rate, with the extension of time, ODTMA/ goethite to the removal rate of soluble protein gradually
Enhancing.Removal rate reaches 30.22% after reaction for 24 hours.The CTAC and ODTMA of the researchs such as this result of study and Jin Guohua are to four tail grid
Algae is consistent with the variation tendency of soluble protein when the toxic effect of chlorella pyrenoidosa.Protein is organic as frustule body
Ingredient influences significantly enzymatic activity, is the material guarantee of frustule normal physiological function, the reduction of content influences leaf in turn
The normal function of green element, and then influence MDA content.
In order to study influence of the oxidative stress to microcystic aeruginosa oxidative damage, Lipid peroxidation metabolism is evaluated.Point
Product MDA is solved as a kind of biomarker, the oxidative damage being used to always in evaluation cell.ODTMA/ goethite is thin to algae
Influence such as Fig. 5 (d) of after birth damage, with the extension of reaction time, MDA content dramatically increases.React 18h after, MDA content by
Initial 5.20nmol.mg/TSP increases to maximum value 7.28nmol.mg/TSP, then starts to reduce, to MDA when reacting 1d
Content becomes 6.11nmol.mg/TSP.Alga cells film is made of unsaturated phosphatide, the influence vulnerable to active oxygen.It is reacting
When 18h, frustule MDA content is dramatically increased, and illustrates the abnormal lipids peroxidating of ODTMA/ goethite induction microcystic aeruginosa
Reaction, the oxide species that ODTMA/ goethite generates during the reaction cause serious oxidative stress to microcystic aeruginosa, and
Cell membrane polyunsaturated fatty acid is damaged.
Removal mechanisms at work of the ODTMA/ goethite to frustule
Structure of cell surface observation
Fig. 6 (a) and Fig. 6 (b) is the Microcystis aeruginosa Strains of normal growth breeding, and Fig. 6 (c) and Fig. 6 (d) are ODTMA/ needle
Iron ore treated Microcystis aeruginosa Strains it can be found that normal frustule surface is full, well-balanced, smooth from figure, and are located
Frustule surface after reason is deposited on cell membrane due to ODTMA/ goethite nano particle and the direct Physical interaction of frustule
On, so that film deforms, it is impaired that when ODTMA low concentration, will lead to frustule breeding, and the permeabilization of frustule film is induced in middle concentration, high
Frustule film is directly destroyed when concentration.Part cell is recessed inwardly by serious destruction, or even cracks, and then causes thin
After birth infiltration sexually revises, and influences metabolism.
ODTMA/ goethite particle can be observed from Fig. 6 (c) and Fig. 6 (d) to be attached on frustule, this is because band is just
The carbochain of charge can net catch and bond negative electrical charge frustule and other particles, cause frustule surface texture destroy, in portion
Dividing around the frustule of deformation has some substances in irregular shape that it is sticked together, thus it is speculated that is extracellular point of frustule
Secretion or the intracellular matter of cell rupture release.
Frustule apoptosis situation
In recent years, Flow Cytometry is widely applied for assessing the integrality in oxidation process to frustule vigor and film
It influences.With the help of nucleic acid staining agent, flow cytometer quickly can carry out quantitative and sensitive survey to each Cells of Blue-green Algae
Amount.Influence of the ODTMA/ goethite to frustule film integrality is as shown in Figure 7.Fig. 7 (a) is the verdigris micro-capsule of normal growth breeding
Algae, Fig. 7 (b) are Microcystis aeruginosa Strains after the processing of ODTMA/ goethite.Normal frustule is not since cell membrane is by broken
Bad, PI molecule cannot be introduced into the cell, have 98.03% frustule for living cells so negative status is presented, and Fig. 7 (b)
In, red area has 52.47% positive for being in PI, and 47.46% is in the negative status of PI, illustrates there is 52.47%
Frustule is dead or cell membrane is destroyed.
TOC variation
Extraneous BG-11 training is released to when the cell wall and damaged membrane of frustule will lead to organic matter in frustule
It supports in base, therefore in order to further study the damage situations of the cell wall of frustule and cell membrane, TOC's contains in measurement BG-11
Amount variation.ODTMA/ goethite is as shown in Figure 8 except the variation of TOC during algae.It can be found that being not affected by ODTMA/ needle from figure
The frustule of iron ore processing is because normal growth breeding TOC value is little with time change, and the processing of ODTMA/ goethite is added
Algae solution in TOC value increase with the increase in reaction time.This is because the oxygen that ODTMA/ goethite generates under illumination effect
Compound kind destroys the cell wall and cell membrane of frustule, and cytoplasm is caused to be revealed, and TOC value increases in BG-11 culture medium, thus
Prevent the growth and survival of microcystic aeruginosa.
Claims (6)
1. application of the surfactant-modified goethite in removal microcystic aeruginosa.
2. application according to claim 1, which is characterized in that the surfactant includes cetyl trimethyl chlorine
Change ammonium, cetyl trimethylammonium bromide, cetalkonium chloride, appointing in Cetyltrimethylammonium bromide
It anticipates one kind.
3. application according to claim 1, which is characterized in that the preparation method of surfactant-modified goethite is such as
Under: surfactant is dissolved in 55-65 °C of water, then goethite is added into lysate, stirred, supernatant is abandoned in centrifugation,
Surfactant-modified goethite can be prepared in vacuum drying, grinding.
4. application according to claim 1, which comprises the steps of: pH value be 7.5-9.5,20-30 DEG C
And under the conditions of illumination is 1000-2500 Lx, microcystic aeruginosa is added into the culture medium to sterilize respectively, it is living to add surface
Property the modified goethite of agent, be put into illumination box 2-20d, remove microcystic aeruginosa.
5. application according to claim 4, which is characterized in that the density of the microcystic aeruginosa is 1.0 × 106 -1.0
×107 Cells/mL, microcystic aeruginosa include the frustule in logarithmic growth phase and death phase.
6. application according to claim 4, which is characterized in that the additive amount of the surfactant-modified goethite is
10 mg/L-60 mg/L。
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