CN114034788B - Method for detecting sulfur-containing organic compounds in marine sediments - Google Patents
Method for detecting sulfur-containing organic compounds in marine sediments Download PDFInfo
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Abstract
The invention discloses a method for detecting sulfur-containing organic compounds in marine sediments, belongs to the technical field of pesticide analysis and detection, and particularly relates to biochar, wherein corn straw powder, straw cellulose, starch and aluminum citrate containing aluminum element are mixed, the mixture is calcined under the action of a phosphoric acid solution to obtain biochar, and the biochar is used for detecting sulfur-containing compounds such as endosulfan in the marine sediments, so that the biochar has the following beneficial effects: the specific surface area of the biochar is large, and is 700-900m2(ii)/g; the diameter of the pores of the biochar is small, and the diameter of the pores is 2.5-3.5 nm; the biochar has a good adsorption effect on endosulfan or endosulfan, and is used in a chromatographic column, and then the chromatographic column is used in the method for detecting sulfur-containing compounds in marine sediments, so that the detection recovery rate and the precision are good.
Description
Technical Field
The invention belongs to the technical field of pesticide analysis and detection, and particularly relates to a method for detecting sulfur-containing organic compounds in marine sediments.
Background
Persistent Organic Pollutants (POPs) which are environmental Organic Pollutants and potentially threaten the environment and human health have the characteristics of high lipid solubility, so that the POPs can enter organisms from the environment to be enriched through different media, and the POPs also have the characteristics of environmental persistence and semi-volatility, so that the POPs can be transported and migrated in a long distance in a global range through different environmental media, and finally cause serious harm to the ecological environment and human health. Common POPs mainly comprise organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and Polycyclic Aromatic Hydrocarbons (PAHs). The basic environmental characteristics of persistent organic pollutants include high toxicity, environmental persistence, bioaccumulation, and long-range mobility.
Because the persistent organic pollutant has stronger degradation resistance, the persistent organic pollutant can not be completely degraded in the environment, and the degradation speed is also restricted by external factors. Pesticides such as organochlorines, once introduced into the environment, can be present in environmental media such as water, sediments, and organisms for months to years, and even decades.
Endosulfan is also widely noticed as a novel POPs, and the main metabolites of endosulfan after degradation in the environment are endosulfan diol and endosulfan sulfate. The toxicity of endosulfate in the hydrolysate is greater than that of endosulfan glycol, and the mixture of endosulfan and endosulfan is called endosulfan (total). Therefore, it is important to develop a pretreatment and detection method for efficiently extracting, enriching and quantifying endosulfan and derivatives from seawater and sediments.
Disclosure of Invention
The invention aims to provide a biochar which has large specific surface area, small pore diameter and high adsorption rate to endosulfan and endosulfan sulfate.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the invention aims to provide a method for detecting sulfur-containing compounds in marine sediments by using aluminum-containing biochar as a chromatographic column filler.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method for detecting sulfur-containing organic compounds in marine sediments, comprising:
s1, a preparation method of the biochar;
s2, extracting the sulfur-containing compounds in the marine sediments by using an extracting agent to obtain extract liquid of the sulfur-containing compounds; the sulfur-containing compound is endosulfan and/or endosulfan.
S3, purifying the extraction liquid chromatographic column of the sulfur-containing compound and detecting by adopting GC-mu ECD; the chromatographic column contains the biochar prepared by the method.
Preferably, the extractant is a mixed solution of acetone and dichloromethane.
Preferably, the marine sediment is sonicated by adding copper powder prior to adding the extractant.
Preferably, the biochar is obtained by calcining a mixture of corn straw powder, straw cellulose, starch and aluminum citrate as a carbon source, and adding a phosphoric acid solution into the mixture before calcining.
More preferably, the amount of aluminum citrate used is 5-25wt% of the corn stover powder.
More preferably, the mass fraction of phosphoric acid in the phosphoric acid solution is 40 to 60 wt%.
More preferably, the specific surface area of the biochar is 700-900m2/g。
Preferably, in the pretreatment of the marine sediment, the marine sediment is subjected to vacuum freeze drying, grinding and sieving to obtain the pretreated sediment.
Preferably, in the extraction of the sulfur-containing compound, an extracting agent is added into the pre-treated sediment, copper powder is added, the mixture is mixed for 2-10min, ultrasonic extraction is carried out for 30-90min, an organic phase is centrifugally separated, the extraction step is repeated for more than 2 times, the centrifugally separated organic phases are combined, rotary evaporation and concentration are carried out until the organic phase is nearly dry, and n-hexane is added, so that an extraction liquid of the sulfur-containing compound is obtained.
More preferably, the extractant is a mixed solution of acetone and dichloromethane, and the volume ratio of acetone to dichloromethane in the extractant is 1: mixing at a ratio of 0.5-3.
More preferably, the amount of the pretreated sediment is 40-60wt% of the extractant.
More preferably, the amount of copper powder used is 30-60wt% of the pretreated deposit.
More preferably, n-hexane is used in an amount to bring the near dry concentrate to 2-3 mL.
Preferably, the chromatographic column is filled with deactivated alumina, biochar, deactivated silica gel, biochar, sulfuric acid silica gel and anhydrous sodium sulfate from bottom to top in sequence.
More preferably, the loading height of the deactivated alumina is 3-5 cm.
More preferably, the packing height of the biochar deactivating the upper layer of alumina is between 1 and 3 cm.
More preferably, the loading height of the deactivated silica gel is 2-4 cm.
More preferably, the packing height of the bio-char on the upper layer of the deactivated silica gel is 1-3 cm.
More preferably, the filling height of the sulfuric acid silica gel is 2-4 cm.
More preferably, the filling height of the anhydrous sodium sulfate is 1-2 cm.
Preferably, in the preparation of the pretreated biochar, the biochar is placed in pretreatment liquid, ultrasonic treatment is carried out for 20-60min at the temperature of 50-65 ℃, and drying is carried out to obtain the pretreated biochar.
More preferably, the pretreatment solution is a solution of ammonium lactate and ammonium oxalate, the content of ammonium lactate in the pretreatment solution is 2-6wt%, and the content of ammonium oxalate in the pretreatment solution is 1-4 wt%. After the biochar is pretreated by ammonium lactate and ammonium oxalate, the desorption performance of the biochar is better, and after a sulfur-containing compound such as endosulfan or endosulfan sulfate is adsorbed, endosulfan or endosulfan sulfate can be better desorbed under elution of an eluent, so that the recovery rate and the precision of a detection method are improved.
More preferably, the pretreated biochar is used as a biochar to deactivate the upper layer of alumina.
Preferably, in the purification and detection of the sulfur-containing compound, an n-hexane solution of the sulfur-containing compound is purified by a chromatographic column, a leacheate is used for pre-leaching before sampling, then the eluent is used for elution, the eluent is collected to obtain a purified solution of the sulfur-containing compound, high-purity nitrogen is used for purging and concentrating to 1mL, GC-mu ECD detection is carried out, and the content of the sulfur-containing compound is calculated according to a standard curve.
More preferably, the leacheate is n-hexane.
More preferably, the eluent is a mixed solution of n-hexane and dichloromethane, and the mass ratio of n-hexane to dichloromethane in the eluent is 1: mixing at a ratio of 0.3-2, and eluting at a rate of 1-5 mL/min.
The invention aims to provide a biochar which has large specific surface area, small pore diameter and high adsorption rate to endosulfan and endosulfan sulfate.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a biochar, comprising: the biological carbon is obtained by calcining a mixture of corn straw powder, straw cellulose, starch and aluminum citrate as a carbon source; the mixture is added to a phosphoric acid solution prior to calcination. The surfaces of the corn straw powder, the straw cellulose and the starch are provided with a large amount of functional groups, after phosphoric acid is added, the phosphoric acid interacts with the functional groups of the raw materials to generate phosphoric acid bonds and polyphosphoric acid bonds, so that the raw materials are mutually connected, a large amount of mesopore and micropore structures are generated in the calcining process, the aluminum citrate also contains a large amount of functional groups, and the aluminum citrate can improve the stability of the composite structure of the raw materials in the interaction with the corn straw powder, the straw cellulose, the starch and the phosphoric acid due to the existence of aluminum elements, has excellent retaining effect after calcining, greatly improves the specific surface area of the biochar, reduces the pore diameter of the biochar, and has high adsorption rate and high adsorption capacity when used for adsorbing sulfur-containing compounds such as endosulfan and/or endosulfan.
Preferably, the aluminum citrate is used in an amount of 5-25wt% of the corn stalk powder.
Preferably, the mass fraction of phosphoric acid in the phosphoric acid solution is 40-60 wt%.
Preferably, the specific surface area of the biochar is 700-900m2/g。
The invention aims to provide a preparation method of biochar with large specific surface area, small pore diameter and high adsorption rate to endosulfan and endosulfan sulfate.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method for preparing biochar, comprising:
s1, preparing the straw cellulose from the corn straw powder in a cellulose extracting solution through an extraction process;
s2, mixing the corn straw powder, the straw cellulose, the starch and the aluminum citrate, adding a phosphoric acid solution, and calcining to obtain the biochar.
Preferably, the cellulose extracting solution is a mixed solution of nitric acid and ethanol.
Preferably, in the preparation of the corn stalk powder, the corn stalk is cut into small sections, washed for more than 2 times by distilled water, dried, crushed and sieved to obtain the corn stalk powder.
Preferably, in the preparation of the straw cellulose, the corn straw powder is added into the cellulose extracting solution, reflux condensation is carried out for 3-12h at the heating temperature of 100-130 ℃, suction filtration is carried out to remove the filtrate, the residue is washed by the cellulose extracting solution, the residue is washed to be neutral by distilled water, and finally, the residue is washed by absolute ethyl alcohol and dried to obtain the straw cellulose.
More preferably, the cellulose extracting solution is a mixed solution of nitric acid and ethanol, and the mass ratio of nitric acid to ethanol in the cellulose extracting solution is 1: mixing at a ratio of 0.2-0.8.
More preferably, the corn stalk powder is used in an amount of 3-9wt% of the cellulose extract.
Preferably, in the preparation of the biochar, the corn straw powder, the straw cellulose, the starch and the aluminum citrate are mixed, added with a phosphoric acid solution, and calcined at the temperature of 300-500 ℃ for 2-6h to obtain the biochar.
More preferably, the straw cellulose is used in an amount of 20-50wt% of the corn straw powder.
More preferably, the starch is used in an amount of 10-40wt% of the corn stover powder.
More preferably, the aluminum citrate is used in an amount of 5-25wt% of the corn stalk powder.
More preferably, the mass fraction of phosphoric acid in the phosphoric acid solution is 40 to 60 wt%.
More preferably, the phosphoric acid solution is used in an amount of 80-320wt% of the corn stalk powder.
Use of biochar containing aluminum element in detecting endosulfan and/or endosulfan sulfate in marine sediments.
The invention adopts the corn straw powder and the straw celluloseThe starch and the aluminum citrate containing the aluminum element are mixed and calcined under the action of phosphoric acid solution to obtain the biochar, and the biochar is used for detecting sulfur-containing compounds such as endosulfan in marine sediments, so that the method has the following beneficial effects: the specific surface area of the biochar is large, and is 700-900m2(ii)/g; the diameter of the pores of the biochar is small, and the diameter of the pores is 2.5-3.5 nm; the biochar has a good adsorption effect on endosulfan or endosulfan sulfate, and is used in a chromatographic column, and then the chromatographic column is used in the method for detecting the sulfur-containing compounds in the marine sediments, so that the detection recovery rate and the detection precision are good. Therefore, the invention relates to a method for detecting sulfur-containing compounds in marine sediments by using aluminum-containing biochar as a chromatographic column filler.
Drawings
FIG. 1 is a graph of the specific surface area of biochar;
FIG. 2 is a graph of pore diameters of biochar;
FIG. 3 is a plot of endosulfan adsorption rates of biochar;
FIG. 4 is a chart showing the adsorption rate of endosulfan to charcoal;
FIG. 5 is a graph of recovery for endosulfan detection;
FIG. 6 is a RSD plot of endosulfan detection;
FIG. 7 is a graph of recovery of endosulfan detection;
FIG. 8 is a graph of RSD in endosulfan assay.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a method for preparing biological carbon, which comprises the following steps,
preparing corn straw powder: cutting corn stalk into small segments, washing with distilled water for 3 times, drying, pulverizing, and sieving to obtain corn stalk powder.
Preparing straw cellulose: adding corn stalk powder into the cellulose extracting solution, refluxing and condensing for 6h at the heating temperature of 120 ℃, carrying out suction filtration, removing the filtrate, washing the residue with the cellulose extracting solution, washing the residue to be neutral with distilled water, finally washing with absolute ethyl alcohol, and drying to obtain the stalk cellulose. The cellulose extracting solution is a mixed solution of nitric acid and ethanol, and the mass ratio of the nitric acid to the ethanol in the cellulose extracting solution is 1: mixing at a ratio of 0.4; the usage amount of the corn stalk powder is 7wt% of the cellulose extracting solution.
Preparing biochar: mixing the corn straw powder, straw cellulose, starch and aluminum citrate, adding a phosphoric acid solution, and calcining at the temperature of 400 ℃ for 4 hours to obtain the biochar. The using amount of the straw cellulose is 40wt% of the corn straw powder, the using amount of the starch is 30wt% of the corn straw powder, the using amount of the aluminum citrate is 10wt% of the corn straw powder, the mass fraction of the phosphoric acid in the phosphoric acid solution is 50wt%, and the using amount of the phosphoric acid solution is 150wt% of the corn straw powder.
Example 2:
a method for preparing biological carbon, which comprises the following steps,
compared with the embodiment 1, the difference of the embodiment is only that the aluminum citrate is used in 18wt% of the corn stalk powder in the preparation of the biochar.
Example 3:
a method for detecting sulfur-containing organic compounds in marine sediments,
pretreatment of marine sediments: and (4) carrying out vacuum freeze drying, grinding and sieving on the marine sediments to obtain the pretreated sediments.
Extraction of sulfur-containing compounds: adding an extracting agent into the pretreated sediment, adding copper powder, mixing for 10min, performing ultrasonic extraction for 60min, performing centrifugal separation on an organic phase, repeating the extraction step for 3 times, combining the centrifugally separated organic phases, performing rotary evaporation and concentration to be nearly dry, and adding n-hexane to obtain an extract containing a sulfur compound. The extraction agent is a mixed solution of acetone and dichloromethane, and the volume ratio of acetone to dichloromethane in the extraction agent is 1: 1, the usage amount of the pre-treatment sediment is 50wt% of the extracting agent, the usage amount of the copper powder is 40wt% of the pre-treatment sediment, and the usage amount of the n-hexane is that the volume of the near-dry concentrate is 2 mL. The amount of the pretreated sludge used was 10 g.
The chromatographic column is filled with deactivated alumina, biochar, deactivated silica gel, biochar, silica gel sulfate and anhydrous sodium sulfate from bottom to top in sequence. The filling height of the deactivated alumina is 4cm, the filling height of the biochar on the upper layer of the deactivated alumina is 3cm, the filling height of the deactivated silica gel is 3cm, the filling height of the biochar on the upper layer of the deactivated silica gel is 2cm, the filling height of the sulfuric acid silica gel is 4cm, and the filling height of the anhydrous sodium sulfate is 2 cm. Biochar was derived from example 1.
Purification of sulfur-containing compounds: purifying the normal hexane solution containing the sulfur compounds by a chromatographic column, pre-leaching with a leaching solution before sampling, eluting with an eluent, collecting the eluent to obtain a purified solution containing the sulfur compounds, purging and concentrating the purified solution to 1mL by high-purity nitrogen, detecting by GC-mu ECD, and calculating the content of the sulfur compounds according to a standard curve. The eluent is n-hexane, the eluent is a mixed solution of n-hexane and dichloromethane, and the mass ratio of n-hexane to dichloromethane in the eluent is 1: 1, and the elution speed was kept at 3mL/min during elution.
GC- μ ECD detection conditions:
a chromatographic column: DB-1701P (30 m × 0.25mm × 0.25 μm);
carrier gas: 99.999% high purity nitrogen;
flow rate: 1.5mL/min in a constant current mode;
temperature of the gasification chamber: 250 ℃;
detector temperature: 250 ℃;
column temperature procedure: maintaining at 100 deg.C for 1 min; heating to 180 deg.C at 10 deg.C/min, and keeping for 3 min; heating to 280 deg.C at 10 deg.C/min, and maintaining for 5 min;
and (3) sample introduction mode: no-shunt sample introduction; sample introduction amount: 1 μ L.
The standard curve was prepared as follows:
diluting 5.0mg/mL endosulfan standard solution with n-hexane, preparing endosulfan standard solutions with mass concentrations of 10, 50, 100, 250, 500 and 1000 mug/L step by step, detecting, and obtaining a standard substance curve according to the result. And (4) making a standard curve by using the detection peak area to the concentration.
Diluting 5.0mg/mL endosulfan standard solution with n-hexane, preparing into endosulfan standard solutions with mass concentrations of 10, 50, 100, 250, 500 and 1000 μ g/L step by step, detecting, and obtaining a standard substance curve according to the result. And (4) making a standard curve by using the detection peak area to the concentration.
Example 4:
a method for detecting sulfur-containing organic compounds in marine sediments,
this example is compared to example 3, with the only difference that the biochar in the chromatography column originates from example 2.
Example 5:
a method for detecting sulfur-containing organic compounds in marine sediments,
pretreatment of marine sediments: and (4) carrying out vacuum freeze drying, grinding and sieving on the marine sediments to obtain the pretreated sediments.
Extraction of sulfur-containing compounds: adding an extracting agent into the pretreated sediment, adding copper powder, mixing for 10min, performing ultrasonic extraction for 60min, performing centrifugal separation on an organic phase, repeating the extraction step for 3 times, combining the centrifugally separated organic phases, performing rotary evaporation and concentration to be nearly dry, and adding n-hexane to obtain an extract containing a sulfur compound. The extraction agent is a mixed solution of acetone and dichloromethane, and the volume ratio of acetone to dichloromethane in the extraction agent is 1: 1, the usage amount of the pre-treatment sediment is 50wt% of the extracting agent, the usage amount of the copper powder is 40wt% of the pre-treatment sediment, and the usage amount of the n-hexane is that the volume of the near-dry concentrate is 2 mL. The amount of the pretreated sludge used was 10 g.
Preparation of pretreated biochar: and (3) putting the biochar into a pretreatment solution, performing ultrasonic treatment at the temperature of 60 ℃ for 30min, and drying to obtain the pretreated biochar. The pretreatment liquid is a solution of ammonium lactate and ammonium oxalate, the content of the ammonium lactate in the pretreatment liquid is 3wt%, and the content of the ammonium oxalate in the pretreatment liquid is 2 wt%.
The chromatographic column is filled with deactivated alumina, pretreated biochar, deactivated silica gel, biochar, silica gel sulfate and anhydrous sodium sulfate from bottom to top in sequence. The filling height of the deactivated alumina is 4cm, the filling height of the pretreated biochar is 3cm, the filling height of the deactivated silica gel is 3cm, the filling height of the biochar on the upper layer of the deactivated silica gel is 2cm, the filling height of the sulfuric acid silica gel is 4cm, and the filling height of the anhydrous sodium sulfate is 2 cm. Biochar was derived from example 2.
Purification of sulfur-containing compounds: purifying the normal hexane solution containing the sulfur compounds by a chromatographic column, pre-leaching with leacheate before sampling, eluting with eluent, collecting the eluent to obtain a purified solution containing the sulfur compounds, purging and concentrating the purified solution to 1mL by high-purity nitrogen, detecting by GC-mu ECD, and calculating the content of the sulfur compounds according to a standard curve. The eluent is n-hexane, the eluent is a mixed solution of n-hexane and dichloromethane, and the mass ratio of n-hexane to dichloromethane in the eluent is 1: 1, and the elution speed was kept at 3mL/min during elution.
GC- μ ECD detection conditions:
a chromatographic column: DB-1701P (30 m.times.0.25 mm.times.0.25 μm);
carrier gas: 99.999% high purity nitrogen;
flow rate: 1.5mL/min in a constant current mode;
temperature of the gasification chamber: 250 ℃;
detector temperature: 250 ℃;
column temperature procedure: maintaining at 100 deg.C for 1 min; heating to 180 deg.C at 10 deg.C/min, and keeping for 3 min; heating to 280 deg.C at 10 deg.C/min, and keeping for 5 min;
and (3) sample introduction mode: no shunt sampling; sample introduction amount: 1 μ L.
The standard solution was prepared as follows:
diluting 5.0mg/mL endosulfan standard solution with n-hexane, preparing endosulfan standard solutions with mass concentrations of 10, 50, 100, 250, 500 and 1000 mug/L step by step, detecting, and obtaining a standard substance curve according to the result. And (4) making a standard curve by using the detection peak area to the concentration.
Diluting 5.0mg/mL endosulfan standard solution with n-hexane, preparing into endosulfan standard solutions with mass concentrations of 10, 50, 100, 250, 500 and 1000 μ g/L step by step, detecting, and obtaining a standard substance curve according to the result. And (4) making a standard curve by using the detection peak area to the concentration.
Example 6:
a method for detecting sulfur-containing organic compounds in marine sediments,
this example is different from example 5 only in that the pretreatment liquid contained 4wt% of ammonium lactate and 3wt% of ammonium oxalate in the pretreatment liquid in the preparation of pretreated biochar.
Comparative example 1:
this comparative example differs from example 2 only in that no aluminum citrate was used in the biochar preparation.
Comparative example 2:
this comparative example is compared to example 4, except that the biochar is derived from comparative example 1.
Test example:
1. specific surface area and pore size distribution
Test samples: biochar prepared in examples 1-2 and comparative example 1.
The test method comprises the following steps: the adsorption effect of the biochar sample on high-purity liquid nitrogen is measured at the liquid nitrogen temperature (77K), the biochar sample is degassed at the temperature of 150 ℃ for 24 hours before being measured, the specific surface area of the activated carbon is calculated by adopting a BET method, and the pore size distribution is made by adopting a BJH method.
The specific surface area test of the biochar prepared by the invention is shown in figure 1, wherein the specific surface area of the biochar prepared in example 1 is 837.9 m2(g), the specific surface area of the biochar prepared in example 2 is 860.5 m2(g), the specific surface area of the biochar prepared in comparative example 1 was 546.4 m2The results of examples 1-2 compared with comparative example 1 show that in the preparation of biochar according to the present invention, corn straw powder, straw cellulose, starch and aluminum citrate are mixed, and a phosphoric acid solution is added, and finally, biochar is obtained by calcination, and the aluminum citrate is used, such that the specific surface area of the obtained biochar is substantially increased, and the aluminum citrate is used in the preparation of biochar, such that the aluminum citrate has an excellent effect of increasing the specific surface area of biochar. Comparison between example 1 and example 2 shows that the effect of the change in the amount of aluminum citrate used on the increase in the specific surface area of the biochar is not significant.
The specific surface area of the biochar prepared by the invention is 700-900m2/g。
The pore diameter test of the biochar prepared by the present invention is shown in fig. 2, wherein the pore diameter of the biochar prepared in example 1 is 3.26 nm, the pore diameter of the biochar prepared in example 2 is 2.97 nm, the pore diameter of the biochar prepared in comparative example 1 is 4.81 nm, and the comparison of examples 1-2 with comparative example 1 shows that in the biochar prepared by the method of the present invention, corn straw powder, straw cellulose, starch and aluminum citrate are mixed and added with a phosphoric acid solution, and finally calcined to obtain biochar, the use of aluminum citrate reduces the pore diameter of the biochar, which shows that the use of aluminum citrate in the method of preparing biochar has an effect of reducing the pore diameter of biochar. Comparison between example 1 and example 2 shows that the effect of the change in the amount of aluminum citrate used on the reduction of the pore diameter of the biochar is not significant.
The diameter of the pores of the biochar prepared by the method is 2.5-3.5 nm.
2. Study on adsorption characteristics of biochar on pesticide
Test samples: biochar prepared in examples 1-2 and comparative example 1.
The test method comprises the following steps: adding 200mg of biochar into 100mL of 1mg/L pesticide aqueous solution, stirring and adsorbing for 5min, centrifuging, and taking supernatant for GC-mu ECD detection.
GC- μ ECD detection conditions:
a chromatographic column: DB-1701P (30 m × 0.25mm × 0.25 μm);
carrier gas: 99.999% high purity nitrogen;
flow rate: 1.5mL/min in a constant current mode;
temperature of the gasification chamber: 250 ℃;
temperature of the detector: 250 ℃;
column temperature procedure: maintaining at 100 deg.C for 1 min; heating to 180 deg.C at 10 deg.C/min, and keeping for 3 min; heating to 280 deg.C at 10 deg.C/min, and keeping for 5 min;
and (3) sample introduction mode: no shunt sampling; sample introduction amount: 1 μ L.
Diluting 5.0mg/mL endosulfan standard solution with n-hexane, preparing endosulfan standard solutions with mass concentrations of 10, 50, 100, 250, 500 and 1000 mug/L step by step, detecting, and obtaining a standard substance curve according to the result.
The standard curve is drawn by the detection peak area to the concentration: y =286.45 x-3129.16; r2=0.9993。
Diluting 5.0mg/mL endosulfan standard solution with n-hexane, preparing into endosulfan standard solutions with mass concentrations of 10, 50, 100, 250, 500 and 1000 μ g/L step by step, detecting, and obtaining a standard substance curve according to the result.
The standard curve is drawn by the detection peak area to the concentration: y =234.18 x-2651.7; r2=0.9991。
The adsorption test of the biochar prepared by the invention on endosulfan is shown in fig. 3, wherein the adsorption rate of the biochar prepared by the example 1 on endosulfan is 85.15%, the adsorption rate of the biochar prepared by the example 2 on endosulfan is 91.59%, the adsorption rate of the biochar prepared by the comparative example 1 on endosulfan is 78.27%, and the comparison of the examples 1-2 with the comparative example 1 shows that in the biochar prepared by the method of the invention, the corn straw powder, the straw cellulose, the starch and the aluminum citrate are mixed, the phosphoric acid solution is added, and finally the biochar is obtained by calcining, and the aluminum citrate is used, so that the adsorption rate of the biochar on endosulfan is greatly improved, and the aluminum citrate is used in the method for preparing the biochar and has the effect of improving the adsorption rate of the biochar on endosulfan. Comparison between example 1 and example 2 shows that the higher the amount of aluminum citrate used, the higher the effect of the biochar in increasing the rate of adsorption of endosulfan.
The adsorption test of the biochar prepared by the invention on the endosulfan is shown in fig. 4, wherein the adsorption rate of the biochar prepared by the example 1 on the endosulfan sulfate is 81.32%, the adsorption rate of the biochar prepared by the example 2 on the endosulfan sulfate is 88.62%, and the adsorption rate of the biochar prepared by the comparative example 1 on the endosulfan sulfate is 73.48%, compared with the comparative example 1, the results of the examples 1-2 show that in the biochar prepared by the method of the invention, the corn straw powder, the straw cellulose, the starch and the aluminum citrate are mixed, the phosphoric acid solution is added, and finally the biochar is obtained by calcination, and the aluminum citrate is used, so that the adsorption rate of the biochar on the endosulfan sulfate is greatly improved, and the aluminum citrate is used in the method for preparing the biochar and has the effect of improving the adsorption rate of the biochar on the endosulfan sulfate. Comparison between example 1 and example 2 shows that the higher the amount of aluminum citrate used, the higher the effect of increasing the adsorption rate of endosulfan sulfate by biochar.
3. Recovery and precision of the assay
Blank sample: the marine sediment without the sulfur compound is taken, the sulfur compound is added to make the mass concentration reach 100 mu g/L, and the GC-mu ECD detection of the sulfur compound is carried out according to the method of the example 4, the example 6 and the comparative example. The sulfur-containing compound is endosulfan or endosulfan sulfate.
The results of the recovery rate of endosulfan detection by the method of the present invention are shown in fig. 5, wherein the detection recovery rate of endosulfan detection by the detection method of example 3 is 87.53%, the detection recovery rate of endosulfan detection by the detection method of example 4 is 88.42%, and the detection recovery rate of endosulfan detection by the detection method of comparative example 2 is 85.11%, and the adsorption test of the biochar to endosulfan shows that the biochar has excellent adsorption performance to endosulfan, and the comparison of examples 3-4 with comparative example 2 shows that the biochar prepared by aluminum citrate is used in the biochar prepared by the method of the present invention, and the biochar is used in the method of the present invention for detecting sulfur-containing compounds, and the recovery rate of endosulfan detection by the detection method of the present invention is increased; comparing examples 5-6 with example 4, it is shown that the recovery rate of endosulfan is improved by applying the pretreated biochar to the detection of endosulfan sulfate after the biochar is pretreated by the solution of ammonium lactate and ammonium oxalate.
The results of the relative standard deviation of the method of the invention for detecting endosulfan are shown in fig. 6, wherein the detection method of example 3 for endosulfan has a RSD of 6.3, the detection method of example 4 for endosulfan has a RSD of 5.9, and the detection method of comparative example 2 for endosulfan has a RSD of 7.8, and the adsorption test of biochar for endosulfan shows that biochar has a better adsorption performance for endosulfan, and the comparison of examples 3-4 with comparative example 2 shows that biochar prepared from aluminum citrate is used in the method of the invention for detecting sulfur-containing compounds, and the detection method of the invention for endosulfan has a better precision; compared with the example 4, the comparison of the examples 5-6 shows that after the biochar is pretreated by the solution of the ammonium lactate and the ammonium oxalate, the pretreated biochar is applied to the detection of the endosulfan, so that the detection precision of the endosulfan is improved.
The recovery rate results of the detection of endosulfan by the method of the present invention are shown in fig. 7, wherein the detection recovery rate of endosulfan by the detection method of example 3 is 83.34%, the detection recovery rate of endosulfan by the detection method of example 4 is 84.76%, the detection recovery rate of endosulfan by the detection method of comparative example 2 is 79.82%, the adsorption test of biochar to endosulfan shows that biochar has excellent adsorption performance to endosulfan, and the comparison of examples 3-4 with comparative example 2 shows that biochar prepared by aluminum citrate is used in the preparation of biochar by the method of the present invention, and the recovery rate of endosulfan by the detection method of the present invention is increased when the biochar is used in the detection method of sulfur-containing compounds by the present invention; comparing examples 5-6 with example 4, it is shown that the application of the pretreated charcoal in the detection of endosulfan sulfate improves the recovery rate of endosulfan sulfate after the charcoal is pretreated with the solution of ammonium lactate and ammonium oxalate.
The relative standard deviation results of the method for detecting the endosulfan are shown in fig. 8, wherein the detection method of the embodiment 3 has the detection RSD of 6.9 for endosulfan sulfate, the detection method of the embodiment 4 has the detection RSD of 6.6 for endosulfan sulfate, and the detection method of the comparative example 2 has the detection RSD of 7.4 for endosulfan sulfate, and the adsorption test of the biochar to endosulfan sulfate shows that the biochar has better adsorption performance for endosulfan sulfate, and compared with the comparative example 2, the embodiments 3-4 show that the biochar prepared by using the aluminum citrate is used in the biochar prepared by the method of the invention, and the detection method of the invention for sulfur-containing compounds has better precision for the detection results of endosulfan sulfate; compared with the example 4, the results show that the detection precision of the endosulfan is improved by applying the pretreated biochar to the detection of endosulfan after the biochar is pretreated by the solution of ammonium lactate and ammonium oxalate.
The above embodiments are merely illustrative, and not restrictive, of the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (7)
1. A method for detecting sulfur-containing organic compounds in marine sediments, comprising:
extracting a sulfur-containing compound in the marine sediments by using an extracting agent to obtain an extract liquid of the sulfur-containing compound; the sulfur-containing compound is endosulfan and/or endosulfan;
purifying an extraction liquid chromatographic column containing a sulfur compound and detecting by adopting GC-mu ECD; the chromatographic column contains biochar, the biochar is porous biochar containing an aluminum element, and the aluminum element is derived from aluminum citrate;
the biochar is obtained by calcining a mixture of corn straw powder, straw cellulose, starch and aluminum citrate as a carbon source, wherein a phosphoric acid solution is added into the mixture before calcination, the calcination temperature is 300-500 ℃, and the calcination time is 2-6 h;
the using amount of the aluminum citrate is 5-25wt% of the corn straw powder; the mass fraction of phosphoric acid in the phosphoric acid solution is 40-60wt%, and the usage amount of the phosphoric acid solution is 80-320wt% of the corn straw powder; the using amount of the straw cellulose is 20-50wt% of the corn straw powder; the usage amount of the starch is 10-40wt% of the corn stalk powder.
2. The method of claim 1, wherein the method comprises the steps of: the extractant is a mixed solution of acetone and dichloromethane.
3. The method of claim 1, wherein the method comprises the steps of: copper powder is added into the marine sediments before the extracting agent is added into the marine sediments for ultrasonic treatment.
4. The method of claim 1, wherein the method comprises the steps of: the specific surface area of the biochar is 700-900m2/g。
5. A method for preparing biochar, comprising:
s1, preparing the straw cellulose from the corn straw powder in a cellulose extracting solution through an extraction process;
s2, mixing the corn straw powder, the straw cellulose, the starch and the aluminum citrate, adding a phosphoric acid solution, and calcining to obtain biochar; the calcining temperature is 300-500 ℃, and the calcining time is 2-6 h;
the using amount of the aluminum citrate is 5-25wt% of the corn straw powder; the mass fraction of phosphoric acid in the phosphoric acid solution is 40-60wt%, and the usage amount of the phosphoric acid solution is 80-320wt% of the corn straw powder; the using amount of the straw cellulose is 20-50wt% of the corn straw powder; the usage amount of the starch is 10-40wt% of the corn stalk powder.
6. The method for preparing biochar according to claim 5, which is characterized in that: the cellulose extracting solution is a mixed solution of nitric acid and ethanol.
7. Use of biochar containing aluminum element prepared by the preparation method of claim 5 in detecting endosulfan and/or endosulfan sulfate in marine sediments.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462720A (en) * | 2009-01-16 | 2009-06-24 | 国家海洋环境监测中心 | Preparation of modified active carbon |
| CN104258812A (en) * | 2014-10-24 | 2015-01-07 | 江苏省农业科学院 | Metal element improved biochar-based nitrate radical adsorbent and preparation method thereof |
| CN107175072A (en) * | 2017-06-16 | 2017-09-19 | 中国环境科学研究院 | The preparation and its application in typical organochlorine pesticides in removing water environment of a kind of biological carbon based material |
| KR102015327B1 (en) * | 2018-04-30 | 2019-08-28 | 경상대학교산학협력단 | Method for inhibiting uptake into plant of organochlorine pesticide present in soil using biochar |
| CN110947361A (en) * | 2019-11-27 | 2020-04-03 | 南通大学 | Wheat straw biochar adsorbing material for removing fluorine in water and preparation method thereof |
| CN113457622A (en) * | 2021-06-09 | 2021-10-01 | 南京融众环境工程研究院有限公司 | Preparation of aluminum-manganese composite modified biochar and application of aluminum-manganese composite modified biochar in phosphorus removal |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212080B (en) * | 2017-12-12 | 2019-05-31 | 江苏省农业科学院 | A kind of preparation method and application of composite modified stalk active particle charcoal adsorbent material |
-
2021
- 2021-11-01 CN CN202111280795.2A patent/CN114034788B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462720A (en) * | 2009-01-16 | 2009-06-24 | 国家海洋环境监测中心 | Preparation of modified active carbon |
| CN104258812A (en) * | 2014-10-24 | 2015-01-07 | 江苏省农业科学院 | Metal element improved biochar-based nitrate radical adsorbent and preparation method thereof |
| CN107175072A (en) * | 2017-06-16 | 2017-09-19 | 中国环境科学研究院 | The preparation and its application in typical organochlorine pesticides in removing water environment of a kind of biological carbon based material |
| KR102015327B1 (en) * | 2018-04-30 | 2019-08-28 | 경상대학교산학협력단 | Method for inhibiting uptake into plant of organochlorine pesticide present in soil using biochar |
| CN110947361A (en) * | 2019-11-27 | 2020-04-03 | 南通大学 | Wheat straw biochar adsorbing material for removing fluorine in water and preparation method thereof |
| CN113457622A (en) * | 2021-06-09 | 2021-10-01 | 南京融众环境工程研究院有限公司 | Preparation of aluminum-manganese composite modified biochar and application of aluminum-manganese composite modified biochar in phosphorus removal |
Non-Patent Citations (5)
| Title |
|---|
| 渔业环境沉积物中硫丹及其代谢物残留的气相色谱分析;叶玫 等;《福建水产》;20120625;第34卷(第03期);摘要，第1.1节 * |
| 灰分对挺水植物生物炭吸附硫丹的影响;何琦等;《中国环境科学》;20180620(第06期);第316-322页 * |
| 玉米秸秆中纤维素的低温提取方法;宋贺明等;《湖北农业科学》;20200910(第17期);第121-123页 * |
| 生物炭的制备及其镁改性对污染物的吸附行为研究;杨雪等;《环境科学学报》;20180612(第10期);第249-260页 * |
| 碳酸钾添加比例对玉米秸秆生物炭表面特性的影响;祝凌等;《土壤学报》;20171130(第06期);第1508-1515页 * |
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