Application of Passive Sampling Technique for Organic Pollutant and its Comparison with Convention Sampling Technique

doi:10.21203/rs.3.rs-2079589/v1

Pesticides are present at minute concentration are the cause for poor water parameter. The concentration can vary dynamically, due to the probably distribution of pesticide pollution. Thus the characterization of pesticide residue present in water carries important monitoring analytic challenges quantitation of limited type of pesticide present in water sample. As there are no. of pesticides present we have selectively represent some pesticide coefficient of the pesticide sample with the passive sample. In this study we have use the polymer- Low Density Polyethylene (LPDE) which is mostly used to target hydrophobic organic contaminants & can monitor water pollution.

Here we have selected 6 pesticide compound to show the adsorption of selected pesticides. The equilibrium reach is found on 4 pesticide compound i.e. Adrin, Chloropyrifos, Quinalfos, λ-cyhalothrin and where it was found that the Fluchorin and Profenofos doesn’t reach the equilibrium. These is been done by water- polymer partioning. Thus passive sampler has potential for effective use in water sample and can help quality managers to rationalize the fate of pesticide in future.

The aim of research study was provide a proof of concept for the use of simple passive samplers for the detection in water sample. This study will help of passive samplers against conventional sampling monitoring.

Passive sample

LDPE

Pesticides

water pollution

Adsorption

One of the important source of life is water. Water is both in surface water and underground water. As the distribution of water is seen uneven. India having only 4% of globe fresh water. Whereas 80% of water is been used in agriculture purpose central ground water board says most of ground water blocks are been overexploited. Since agricultural sector, is important in country India, and about 55% of population depends on agriculture. Thus variation in irrigation intensity is due to varied geographical condition in different part of country. Several region in the country could suffer water stress.

With the green revolution in the 2^nd half of twentieth century farmer started to use of advance technologies to enhance yield by using synthetic fertilizers, pesticides and herbicides are common around the globe. These chemicals were developed in the laboratory and this is been exercise great control over plants so that they grow by enriching the immediate response. Such environmental cost ex- pollution of streams, rivers, ponds, lakes, and also the coastal areas. As there organic pollutant run off into nearby water ways.

Farmers use chemicals to prevent crops from disease, thus chemical are runoff into water bodies. Agriculture water pollution is mostly caused by, farm animal wastes, pesticides and fertilizers. Research finding indicates that the insignificant of fertilizers pollute the water through the leaching nitrate from nitrogenous pesticide and fertilizers. The various type of insecticides and pesticides in agriculture cause water pollution.

PESTICIDE- Pesticide is a chemical substance, biological agent, disinfectant, antimicrobial or chemical use against any pest. Pest includes insects, plant pathogen weeds, bird mammals, fish mollucus, memotodes and microbe that decrease the property, enhance disease or caused nuisance.

As FAO 2002 define pesticide is any substance/compound or mixture of substances/compound intended for destroying preventing, repealing or migrating any pest, includes vectors of animal disease or humans, unwanted species of different plant or animal causing harm during or otherwise.

SAMPLING- Sampling is process of selecting units from a large population of interest so that by studying the sample we may generalize our results back to population from which we had chosen.

Sampling is of different type.

Types of conventional sampling

Grab sample- A grab sample is a discrete sample which is collected at a specific point time. If an environment medium varies spatially or temporally then a single grab sample is not representative and more samples are need to be collected. `
Composite sample- A composite sample is made by thoroughly mixing several grab samples. The whole composite may be measured or random samples from the composite may be withdrawn and measured

Passive sampling of environmental analysis.

Passive sampling is environmental monitoring technique which involves the use of collecting medium- for the chemical pollutant in environment. This a contrast with grab sample as in this sampling average chemical concentration are calculated over a device’s deployment time by samplers. Passive samplers have been developed and deployed to detect some PAH, PCBs, radionuclides, toxic metal, pesticides and other organic pollutant, while some can detect hazardous substance.

Passive sampling in water- different types of passive sampling devices exist for the monitoring pollution in water medium and also can monitor water pollution.

Chemcatcher- Inorganic & organic.
Diffusive gradient in thin films
Peepers
Polar organic chemical integrative sample.(POCIS)
Semipermeable membrane device.(SPMDS)
Stabilized liquid membrane devices.(SLMDs)

Passive sampling in air – passive sampling can be accomplished for contaminants in air, including hazardous vapor and gases. Ex- sorbent tubes.

Passive sampling in sediments- sampling in sediments monitor the pollutants in sediment. To assess the adverse effect of sediment contaminant on aquatic ecosystem.

POM- polyoxymethylene.
PDMS- polydimethysiloxane.
LDPE- low density polyethylene.
DGT- diffusive gradient in thin films.

Passive sampling with low density polyethylene (LDPE).

Principle- Passive sampling can be defined as any sampling technique based on free flow of analyte molecule from sampled medium to a receiving phase in a sampling device as the difference between the chemical potentials of analyte in two media. Sufficient time is needed to reach equilibrium.

As name suggest, the analyte are accumulated in the device until the concentration in the sample is in equilibrium with bulk concentration.

All samples goes through the kinetic stages but in the equilibrium stage is not reached at specific time depending upon the compound. Some can take day to week and some can weeks to month. Thus the smaller logK_ow value the shorter the chances to reaching the equilibrium state, it also depend upon the polymer type, thickness, environmental condition, temperature, etc. The large amount of water shorten the equilibrium state.

Equilibrium is been achieved particularly slowly for the strongly hydrophobic compounds (e.g., log K_ow>6). While not always is the case, many available passive samplers require days to weeks or weeks to months and even years to reach equilibrium for high K_ow target contaminants. Low log K_ow contaminants (i.e., log K_ow < 4) will reach to equilibrium more rapidly.

Table 1 - Partition coefficient of octanol water of targeted compound.

Compound	Log K ow
Aldrin	6.5
Chloropyrifos	4.96
Profenofos	4.68
Lambda cyhalothrin	5.3- 5.6
Fluchloralin	5.07
Quinalphos	4.4

Passive Sampler Advantages Disadvantages

Low density polyethylene- Inexpensive polymer,
Robust and rugged,
Easy to work with,
Simple to deploy and recover,
Not limited by sample mass (greater analytical sensitivity),
Will stretch during deployment before it rips,
Increasing use globally,
Good for both water column and sediment deployment.

For standardization of technique in situ analysis is been done for passive sampling. Using Passive sampling technique monitoring of hydrophobic compound in water.

Targeted Compounds:

Pesticides analyzed- Organophosphates, sp’s and 1 herbicide which are Aldrin, Chloropyrifos, Fluchlorin, Profenofos, Quinalphos, λ cyhalothrin.

Materials and equipment’s

GC, Fuming hood, Rota evaporator- concentration assembly, Flat bottom flask, Beaker, Polymer- LDPE, Separating funnel, Glass funnel, Forceps, Volumetric flask, Conical flask, Inserts, Vials, Micro-syringes, Micropipette, Shaker.

Chemical and reagents

Acetone, N- hexane Dichloromethane-DCM, Isooctane, Sodium chloride (Nacl), anhydrous sodium sulphate (Na₂So₄), Pesticide reference standard

Experimental procedure of the passive sampler.

In this section follows a detailed description of preparation and extraction of passive samplers used in the experimental work of this project.

1. Preparation of sheets

Cut LDPE strips in 2.5cm × 5cm long.
Submerged the polymer in acetone solvent for some time.
Then removed it.

2. Preparation of PRC’s

Preparation of standard mixture of 5 compounds (chloropyrifos + profenofos + lambda cyhalothrin+ fluchorin + quinalphos) and one individual compound Aldrin in 1ppm standard.
Make a mixture of standard in 5 ml volumetric flask.
Then PRC solution is ready of 1ppb of standard mixture and 4 ppb of aldrin.

Table 2- preparation of PRCs

PESTICIDES	STOCK SOLUTION CONCENTRATION	FINAL CONCENTRATION	VOLUME
Λ-CYHALOTHRIN	100PPM	1PPM	0.04ml or 40µL
PROFENOFOS	50PPM	1PPM	0.1ml or 100µL
CHLOROPYRIFOS	10PPM	1PPM	0.05ml or 50µL
QUINALFOS	10PPM	1PPM	0.5ml or 500µL
FLUCHLORIN	50PPM	1PPM	0.1ml or 100µL
ALDRIN	10PPM	4PPB	0.04ml or 40µL

3. Initial

Extraction
Concentration
Instrumentation.

4. Deployment

Take 100 ml distilled water in the conical flask.
Add LDPE strips (2.5cm × 5cm) from acetone solvent to the distilled water.
Make triplets of the standards and standard mixture.
Spike 1ppb STD mixture in triplet set and 4ppb also to triplet sets.
Keep it on shaker. The speed of shaker is 100rpm. The standard mix was kept for 20 hours and aldrin was kept for 24hours.
After completion of deployment proceed for the further analysis.

5. Preparation of extraction of polymer and water

(A) Extraction of water

Take 100 ml of water sample in 250ml separating funnel.
Add of Sodium Chloride (NaCl) and shake well till get dissolved. Nacl will help in making weaker bond of organic compound present.
Extract the sample thrice with 30ml of dichloromethane(10:10:10)
Shake for 3-4 minutes each time with periodic vetting and frequently remove the pressure.
Allow the aqueous and organic layer separate.
Elute the organic layer after settle of sample for 10 min. Repeat thrice
Collected the sample in pre-rinsed conical flask
Add Na₂So₄ to final volume (30ml) collected.
Concentration and micro concentration.

(B)Extraction of polymer

Take conical flask of 100 ml.
Add 30 ml of DCM to the conical flask.
Rinsed polymer with using distilled water and then add to DCM contain flask.
Using forescep add polymer to the flask and keep it on shaker for at least 4 to 6hrs, with the speed of 100 rpm.
Then concentration and micro-concentration.

6. Preparation of concentration of polymer and water

(A) Concentration of water samples

Take round flask. Clean it with acetone
Put anhydrous sodium sulphate (Na₂So₄) in the sample for the absorption of water molecules.
Take funnel & filter with whatman filter paper. Rinse the conical flask again with DCM and put it in round flask.
Keep it in Rota evaporator till it get concentrated and put that concentrated samples in vial and makeup with solvent.
For standard mixture- isooctane used; Aldrin standard- n-hexane used.
Make the vial of 0.2ml in insert.
Put that sample from vial to insert and sealed that with Teflon.

(B) Concentration of polymer

Take 40 ml extracted sample of polymer
Rinsed polymer with DCM
Removed polymer with forescep and add Na₂So₄
Then concentrate it till 0.2ml. Make that in vial and transfer in insert. Sealed with Teflon.
Stored in refrigerator. Then instrumentation.

7. GC analysis

After micro concentration of solvent, final volume is make up by isooctane and analyzed using GC. 1µl of solvent is injected in GC using auto sampler. The sequence of injection was followed as- solvent run, standard mixture run samples run again solvent run. The chromatogram is observed with retention time against peak area. Thus different pesticides have different retention time distinguished peaks will obtain according to the concentration of pesticides. The concentration of pesticides can be calculated by comparing the sample chromatogram with standard chromatogram.

Reference standard compound

Standard mixture of Organophosphate, Organochlorine and herbicides GC chromatography study: 1 microliters of reference standards were injected in GC to resolve and to establish the retention time which presented in table-3.

Table 3

Standard mixture GC results
Compound name	Concentration	Retention time	Area
Aldrin	0.1µl	19.255	8134.4
Fluchlorin	0.1 µl	15.852	3025.4
Chloropyrifos	0.1 µl	19.494	1073.48
Profenofos	0.1 µl	23.024	319.91
Quinalphos	0.1 µl	21.235	3597.10
λ –cyhalothrin	0.1 µl	30.325	7789.88

The amounts of PRCs fraction that remains in the samplers after deployment indicates sampling rate presented Table-4. Equilibrium reach is found in 4 compound i.e., Aldrin, Chloropyrifos, Quinalfos, λ-Cyhalothrin. With spike concentration of 1ppb and 4ppb. The remaining compound Fluchlorin and Profenofos doesn’t reach equilibrium as the compound remained in water sample. This has been carried out by water-polymer partitioning.

Performance Reference Compounds (PRCs) that had an Octonol -water partition coefficient log K_ow > 6 will deplete slow for hydrophobic compound. Where Octonol-water partition coefficient log K_ow < 4 will deplete more rapidly. The outcomes revealed the least sampling rate in Profenofos and Fluchlorin compound. The highest sampling rate found in Aldrin, Chloropyrifos, Quinalfos, λ- Cyhalothrin

Table 4

Results of amounts of PRCs fraction in water and polymer.
Compounds- in water sample	Conc. in ppb	Compounds – polymer	Conc. in ppb
Aldrin	0.0433	Aldrin	1.7746
Fluchlorin	0.3167	Fluchlorin	0.1442
Chloropyrifos	0.1012	Chloropyrifos	0.3898
Profenofos	0.5269	Profenofos	0.1158
Quinalphos	0.1109	Quinalphos	0.8860
λ cyhalothrin	0.0354	λ cyhalothrin	0.4841

Acknowledgement:

The authors is thankful to the Dr. Muthukumar Muthuchamy, Professor & Head, Department of Environmental Science, Central University of Kerala for granting permission to attend and present the paper.

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No competing interests reported.

Application of Passive Sampling Technique for Organic Pollutant and its Comparison with Convention Sampling Technique

Status:

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Abstract

Figures

Introduction

Experimental Setup

Results

Declarations

Acknowledgement:

References

Additional Declarations

Status:

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