CN103558059B

CN103558059B - A kind of chitosan gel rubber Passive sampler during for Heavy Metal Pollution in Water Environment of China thing controlled

Info

Publication number: CN103558059B
Application number: CN201310544841.4A
Authority: CN
Inventors: 汪磊; 张启钧; 孙红文; 唐雪娇
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2013-11-04
Filing date: 2013-11-04
Publication date: 2016-06-08
Anticipated expiration: 2033-11-04
Also published as: CN103558059A

Abstract

The invention discloses a kind of with chitosan gel rubber for accepting phase, to mix calcium silica dioxide gel as controlling phase, can be used for monitoring Heavy Metal Pollution in Water Environment of China thing in one period and exist new type of passive sampling apparatus and the correlation technique of situation. Be positioned over successively in the glass tube of both ends open mixing calcium silica dioxide gel and chitosan gel rubber, connect glass tube upper end with emulsion tube, and mineralized liquid is injected to emulsion tube. Sampler is vertically fixed in monitored water body, the heavy metal contaminants in water environment is carried out to passive collection. By changing mineralized liquid concentration, can regulate the mineralization rate of controlling phase gel, thereby realize the control of accepting the effective enrichment time of relative target contaminant. After passive sampling finishes, use dilution heat of sulfuric acid to carry out wash-out processing to the heavy metal in accepting mutually, and heavy metal contaminants in eluent is carried out to Instrumental Analysis. Simulated experiment result shows, chitosan gel rubber is accepted the heavy metal Hg of being on good terms in effective enrichment aqueous solution, in controlling mutually by adjusting, the concentration of sodium carbonate in the concentration of calcium ion and mineralized liquid, can realize this passive sampling apparatus to the control of Concentration Sampling time of Heavy Metal Pollution in Water Environment of China thing.

Description

A kind of chitosan gel rubber Passive sampler during for Heavy Metal Pollution in Water Environment of China thing controlled

Technical field

The present invention relates to one taking chitosan gel rubber as filler, in order to gather Heavy Metal Pollution in Water Environment of China thing in monitoring special timeThere is the passive sampling new equipment of level.

Background technology

In water environment, exist a large amount of heavy metal contaminants, and heavy metal has stronger bio-toxicity effect. Therefore, rightThe environmental monitoring work of Heavy Metal Pollution in Water Environment of China thing, very important to ensureing human health and safeguarding that environmental ecology all hasMeaning.

There is many limiting factors in sampling monitoring method initiatively, and for example, collection volume of water sample is limited, cycles of concentration is not high, interferenceThe removal complex steps of material, somewhat expensive, analysis result often can only represent the transient state of organic pollution in water environment.Therefore, can the continuous acquisition sampling period in the passive sampling technology of pollutant IC in surrounding medium, be widely usedIn the monitoring and environmental process research of Environmental Trace pollutant. But, be directed at present organic pollution passive sampling technologyWhat develop is rapider, and typical passive sampling technology has semipermeable membrane devices (SPMDs) and polar organic matter comprehensively sampling device(POCIS) technology such as; Compared with studying with the passive sampling of organic pollution, the passive sampling of Heavy Metal Pollution in Water Environment of China thingIt is less that study on monitoring is carried out.

Shitosan (Chitosan) is de-acetyl chitin and a kind of boiomacromolecule of obtaining is the Main Derivatives of chitin.Shitosan is that chitin is hydrolyzed under alkali condition, makes its part deacetylation, and the solubility in diluted acid is with deacetylation journeyThe increase of degree and increasing, when deacetylation reaches 70% when above, in the hydrochloric acid of spirit of vinegar or 0.5mol/L-1.0mol/L allCan well be dissolved into colloidal solution. De-second degree is white in color or ecru crystalline powder or sheet at the shitosan of 80%-90%Solid. Shitosan can by molecule-HN₂,-the functional groups such as OH and Hg²⁺、Cd²⁺、Ni²⁺、Cu²⁺、Ag⁺、Au⁺、Mn²⁺、Pb²⁺Form stable chelate etc. heavy metal ion.

Summary of the invention

The present invention aim to provide a kind of taking without calcium chitosan gel rubber as accepting phase, calcic silica dioxide gel is to control phase, canFor monitoring the new type of passive sampler of Heavy Metal Pollution in Water Environment of China substrate concentration in the regular period. Thereby in reflection special time periodThe level of pollution of Heavy Metal Pollution in Water Environment of China thing.

Passive sampler structure provided by the invention is as follows: Passive sampler entirety is by the glass tube of filled chitosan gel and be equipped withEmulsion tube two parts composition of mineralized liquid. Glass pipe range 3cm, external diameter 10mm, internal diameter 8mm; Latex pipe range 12cm, outerFootpath 9mm, internal diameter 7mm (as shown in Figure 1). In glass tube, fill successively two sections of gels from top to bottom, upper end is that shitosan is solidifyingGlue (accepting phase), length 2cm, weight 1g, lower end is calcic silica dioxide gel (control phase), length 1cm, weight0.5g. (as shown in Figure 1). Emulsion tube is connected to glass tube upper end. When passive sampling, device vertical suspension is placed in water body,Can fix by support. In the time starting to sample, mineralized liquid is injected in emulsion tube by top, by adjusting mineralized liquid concentration, controlSystem sampling duration. This passive sampling apparatus design parameter and use and sample treatment mode are as follows:

1. the sampler phase of accepting used---the preparation method of chitosan gel rubber is: get 0.8g shitosan in beaker, add 1%Acetum 40mL, fully stir until chitosan particle disappear, form white thickness colloidal liquid, then add 20mLTetramethoxy-silicane (TMOS) is to this solution, and vigorous stirring 30 minutes is until layering thoroughly disappears and TMOS is evenly dividedLoose, to place after 30 minutes, white translucent gels basically forms, and covers preservative film and put into refrigerator to leave standstill above gel12 hours for subsequent use.

2. sampler control phase used---the preparation method who mixes calcium silica dioxide gel is: by 1% acetum of 30mL andThe CaCl of the 0.01mol/L of 10mL₂Solution fully stirs, then adds 20mL tetramethoxy-silicane (TMOS) to this solutionIn, vigorous stirring 30 minutes, until layering thoroughly disappears and make TMOS dispersed, is placed 30 minutes, forms white semi-transparentBright gel, above beaker, cover preservative film and put into refrigerator leave standstill 12 hours for subsequent use.

3. by chitosan gel rubber with mix calcium silica dioxide gel and insert long 3cm by glass tube two ends, external diameter 10mm, internal diameter 8mmGlass tube in, making the height of chitosan gel rubber is 2cm, the height of mixing calcium silica dioxide gel is 1cm. At the shell of glass tubeOne section of connecting length of glycan gel is 12cm, external diameter 9mm, the emulsion tube of internal diameter 7mm. Install for subsequent use 4 DEG C of refrigerations.

4. before passive sampling, 2mL sodium carbonate mineralized liquid is injected to emulsion tube, mineralized liquid concentration is 0-0.5mol/L. By wholeDevice vertically hangs in the water body that will monitor, passive sampling prison can realize the control to Heavy Metals in Waters pollutant timeSurvey.

5. Passive sampler is accepted the pre-treating method of phase and is: after sampler reclaims, gel outer surface is wiped with clean absorbent cottonDry. Chitosan gel rubber is proceeded in centrifuge tube, add the 0.1mol/L sulfuric acid solution of 10mL, strongly shake one hour, withCentrifugal 5 minutes of the rotating speed of 1500r/m, shifts out supernatant to be measured, then adds the 0.1mol/L sulfuric acid solution of 10mL to repeatAforesaid operations. The content of heavy metal contaminants in eluent is carried out to Instrumental Analysis.

Brief description of the drawings

Fig. 1 two-period form gel Passive sampler schematic diagram

The passive enrichment kinetic curve of mercury in Fig. 2 chitosan gel rubber Passive sampler

The passive enrichment kinetic curve of chitosan gel rubber to mercury when Fig. 3 uses variable concentrations mineralized liquid

For better understanding content of the present invention, below by embodiment, the present invention is further illustrated, but the cited case is notLimit the scope of the invention.

Embodiment 1: contain in the aqueous solution that mercury (Hg2+) concentration is 1mg/L at 4L, put into 8 cover chitosan gel rubbers passiveSampling apparatus, adds deionized water in the emulsion tube of device. Sampling apparatus is vertically statically placed in and in the aqueous solution, carries out passive sampling.In the time that the sampling time is 0.5h, 1h, 3h, 6h, 12h, 24h, 48h, 168h, take out sampling apparatus respectively, use clear waterRinse sampler, gel outer surface is dried with clean absorbent cotton. Chitosan gel rubber is proceeded in plastic centrifuge tube, add 10mL0.1mol/L sulfuric acid solution, concuss one hour, with the rotating speed of 1500r/m centrifugal 5 minutes, supernatant is shifted out,Add again the 0.1mol/L sulfuric acid solution of 5mL to repeat said extracted process, after extract is merged, analyze. Record samplingIn cycle, in sampler, the concentration of target compound is:

Sampling time (h)	0	0.5	1	3	6	12	24	48	168
										Equilibrium concentration (μ g/g)	0.00	8.25	19.61	29.10	32.15	39.80	40.73	41.23	41.04

Embodiment 2: carry out passive sampling experiment in system same as Example 1, and to add concentration at Passive sampler be 0.01The mineralized liquid of mol/L. Sampler sample treatment is same as Example 1. Record in the sampling period target compound in samplerConcentration is:

Sampling time (h)	0	0.5	1	3	6	12	24	48	168
										Equilibrium concentration (μ g/g)	0.00	8.40	13.57	24.97	27.37	33.47	38.69	38.55	37.47

Embodiment 3: carry out passive sampling experiment in system same as Example 1, and to add concentration at Passive sampler be 0.05The mineralized liquid of mol/L. Sampler sample treatment is same as Example 1. Record in the sampling period target compound in samplerConcentration is:

Sampling time (h)	0	0.5	1	3	6	12	24	48	168
										Equilibrium concentration (μ g/g)	0.00	7.36	14.18	22.20	27.39	32.98	35.95	34.22	33.88

Embodiment 4: carry out passive sampling experiment in system same as Example 1, and to add concentration at Passive sampler be 0.1The mineralized liquid of mol/L. Sampler sample treatment is same as Example 1. Record in the sampling period target compound in samplerConcentration is:

Sampling time (h)	0	0.5	1	3	6	12	24	48	168
										Equilibrium concentration (μ g/g)	0.00	8.16	13.53	19.06	23.93	25.97	33.35	29.31	27.87

Embodiment 5: carry out passive sampling experiment in system same as Example 1, and to add concentration at Passive sampler be 0.5The mineralized liquid of mol/L. Sampler sample treatment is same as Example 1. Record in the sampling period target compound in samplerConcentration is:

Sampling time (h)	0	0.5	1	3	6	12	24	48	168
										Equilibrium concentration (μ g/g)	0.00	6.30	12.79	17.39	19.05	19.98	21.68	20.05	18.56

Prove the passive sampling apparatus that uses chitosan gel rubber to set up, ore deposit not in the microcosm system of laboratory through laboratory researchThe chitosan gel rubber Passive sampler of changing can be realized effective enrichment (Fig. 2) to heavy metal Hg. Add the ore deposit of different concentration of sodium carbonateChange liquid and carry out passive sampling enrichment, result shows along with the concentration of mineralized liquid raises, control the calcium gel mineralization velocity of mixing of phase and accelerate,Thereby can realize the control (Fig. 3) of chitosan gel rubber being accepted to heavy metal acquisition time in relative water.

Claims

1. during for Heavy Metal Pollution in Water Environment of China thing controlled, a chitosan gel rubber Passive sampler, is characterized in thatTaking chitosan gel rubber as accepting phase, to mix calcium silica dioxide gel as controlling the passive sampling apparatus of phase, in order to enrichmentHeavy metal contaminants in monitoring water environment in certain period, described Passive sampler is by filled chitosan gel successivelyWith the glass tube and emulsion tube two parts composition that mineralized liquid is housed, mineralized liquid in emulsion tube of mixing calcium silica dioxide gelFor sodium carbonate liquor;

The structural parameters of described Passive sampler are as follows:

(1) glass pipe range 3cm, external diameter 10mm, internal diameter 8mm; Latex pipe range 12cm, external diameter 9mm, internal diameter 7mm;

(2) glass tube is filled two sections of gels successively, and calcium silica dioxide gel is mixed mutually for controlling in bottom, length 1cm,Weight 0.5g; Upper end is for accepting phase chitosan gel rubber, length 2cm, weight 1g;

(3) mineralized liquid taking up in emulsion tube is aqueous sodium carbonate 2.5mL, concentration 0～0.5mol/L.

2. Passive sampler according to claim 1, is characterized in that, described Passive sampler processing methodFor: use dilution heat of sulfuric acid to accept to carry out mutually multiple oscillation extraction to the chitosan gel rubber of sampler, will repeatedly extractLiquid is analyzed after merging.