Industrial Wastewater Samples Research Articles

Nickel oxide/nickel ferrite/layered double hydroxide nanocomposite as a novel magnetic adsorbent for chromium speciation

A facile hydrothermal method was used to prepare a magnetic nanocomposite (MNC) based on nickel oxide/nickel ferrite/Ni-Al layered double hydroxide (NiO/NiFe2O4/LDH). The synthesized NiO/NiFe2O4/LDH MNC was characterized using various techniques, including X-ray diffraction, field emission scanning electron microscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, and vibrating sample magnetometry. After evaluation of its capability to selective extraction of Cr(VI) ions, an efficient magnetic solid-phase extraction method was developed for the pre-concentration and speciation of chromium species (Cr(III) and Cr(VI)) using the as-prepared NiO/NiFe2O4/LDH MNC as an adsorbent and flame atomic absorption spectrometry. Due to owning positively charged surface, the LDH can establish selective electrostatic interaction with Cr(VI) species in the form of CrO42- or HCrO4-. Numerous important parameters influencing the extraction efficiency were studied and optimized. Based on the method validation applying the optimized extraction conditions, the calibration curve was linear in the range of 0.5 to 120 ng mL−1 with a correlation coefficient of 0.9983. The limit of detection was estimated to be 0.14 ng mL−1, and the method intera- and inter-day precisions were 1.47% and 3.19%, respectively. The presented method was validated by the analysis of the certified reference material NIST SRM 1643e, and applied for the speciation of Cr(VI) and Cr(III) species in various water and industrial wastewater samples.

Intramolecularly hydrogen-bonded cavity containing macrocyclic/acyclic aromatic pyridone foldarands as modularly tunable ionophores for selective potentiometric sensing of metal ions

Abstract Three kinds of intramolecularly hydrogen-bonded cavity containing macrocyclic and crescent-shaped aromatic pyridone foldarands were evaluated as ionophores for polymeric membrane metal ions selective electrodes. Highly selective potentiometric alkali metal ion (such as K+) and heavy metal ions (for example, Cu2+ and Hg2+) determination could be achieved over their environmentally significant interfering cations, owing to the comfortable cavity surrounded by convergently aligned O atoms whose electron density is significantly higher than that of the O/S atoms in crown/thio-crown ethers, which have been traditionally used as metal ions ionophores. To disclose their comprehensive ion-differentiating profiles provide pragmatic guiding principles for designing other potential ion-selective foldarands, the cation-ionophore complex constants in membrane phase were determined and inspected carefully. Optimizing the membrane composition such as lipophilic additives and plasticizers yielded ISEs displaying superior response to K+, Cu2+ and Hg2+ in a wide pH range with good reversibility and long on-shelf time. The analytical results from the proposed ISEs for target ions detection in artificial groundwater, industrial waste water and bottle water samples demonstrate their potential for real-life applications. These results provide pragmatic guiding principles and shed new light on how new ionophores could be designed to broad the scope of potentiometric sensing.

Target-induced mimic enzyme deactivation based on mixed-node metal-organic frameworks for colorimetric assay of hydrogen sulfide

Accurate detection of hydrogen sulfide (H2S) is of great significance for environmental monitoring and protection. We propose a colorimetric method for the detection of H2S by the use of mixed-node Cu-Fe metal organic frameworks (Cu-Fe MOFs) as highly efficient mimic enzymes for target-induced deactivation. The Cu-Fe MOFs were synthesized by a simple solvothermal method and could catalyze the H2O2 mediated oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to oxTMB with a blue color. The presence of dissolved H2S would deactivate the mimic enzymes, and then the blue color disappeared. The mechanism of the sensor was discussed by steady-state kinetic analysis. The designed assay was highly sensitive for H2S detection with a linear range of 0−80 μmol/L and a detection limit of 1.6 μmol/L. Moreover, some potential substances in the water samples had no interference. This method with the advantages of low cost, high sensitivity, selectivity, and visual readout with the naked eye was successfully applied to the determination of H2S in industrial wastewater samples.

Magnetic nanobiosorbent (MG-Chi/Fe3 O4 ) for dispersive solid-phase extraction of Cu(II), Pb(II), and Cd(II) followed by flame atomic absorption spectrometry determination.

Trace amounts of Cu (II), Pb (II), and Cd (II) in a wastewater sample were preconcentrated with a novel cross‐linked magnetic chitosan modified with a new synthesised methionine‐glutaraldehyde Schiff's base (MG‐Chi/Fe3O4) as a dispersive solid‐phase extraction (DSPE) adsorbent. The adsorbed metal ions were then eluted with a specific volume of suitable solution and determined by flame atomic absorption spectrometry (FAAS). Various parameters affecting the extraction efficiency of the metal ions were investigated and optimised, including pH, amount of adsorbent, extraction time, type and volume rate of eluent, elution time, sample volume, and effect of interfering ions. The adsorption kinetics are more consistent with the pseudo‐second order model. The results were statistically interpreted and the analytical performance of the proposed method was found to have preconcentration factors of 55, 60, and 50 μg L−1 for Cu(II), Pb(II), and Cd(II), respectively, limits of detection were 0.22, 0.24, and 0.10 μg L−1 for Cu(II), Pb(II), and Cd(II), respectively, with a relative standard deviation (1.5%‐2.8 %), and the liner range was 5–1000 for Cu(II) and Pb(II) and 2.5–1000 for Cd(II). It was concluded that this method was suitable for successful simultaneous determination of Cu(II), Pb(II), and Cd(II) in industrial wastewater samples.

Treatment of complex multi-sourced industrial wastewater — New opportunities for nanofiltration membranes

Restrictions on the volume of organics discharged from industrial wastewater (IWW) treatment plants has created an impetus to implement nanofiltration (NF) membrane technology at these facilities. However, NF membranes are rated based on simple performance metrics (i.e. permeability and salt rejection), not their capacity to reject organic content. In this study, three IWW samples with varying concentrations (measured via COD) and compositions (analyzed via gas chromatography-mass spectrometry) were filtered using four commercial NF membranes (NF90, TS80, NFS and NFX). The NF90 membrane demonstrated the best COD removal, however compositional differences between samples significantly influenced the magnitude of COD reduction, the permeate flux performance during filtration, and the change in the measured hydraulic permeability and salt rejection after wastewater filtration. To investigate this further, separate solutions of commonly occurring chemical compounds (benzyl alcohol, 2-phenyl ethanol, pentanoic acid) were made with equivalent COD concentrations and filtered using the NF90 and NFX membranes. The NF90 membrane demonstrated significantly better COD removal for all three solutions. It was found that the NFX membrane achieved an increase in permeate flux during constant pressure filtration which was attributed to a “solvent activation” phenomena. These results serve as “proof-of-concept” that commercial NF membranes can significantly reduce the COD concentration of IWW, however, performance metrics that encompass both bulk and compositional properties must be adopted and standardized.

Removal of Cr (III) from industrial wastewater using coconut shell carbon and limestone as adsorbent

Agricultural waste materials gained attention among researchers to study the effectiveness of adsorbent media in heavy metal treatment. In this study, application of coconut shell carbon and limestone as modified adsorbent was used to remove Cr (III) from industrial wastewater. Synthetic industrial wastewater sample containing 2 mg/L of Cr (III) was prepared using distilled water and standard solution of Cr (III). Batch adsorption study was conducted to determine the effect of varied contact time (0 to 120 minutes) and pH (pH3 to pH7). The result shows that at 60 minutes of contact hour, the removal of Cr (III) from the synthetic industrial wastewater is about 98% with optimum adsorption capacity is 0.000019 mg/g at 250 rpm of agitation speed in pH5 as optimum pH. The kinetic data obtained specified that the data follow closely the pseudo-second-order. Thus, this indicates that mixing coconut shell carbon and limestone as a modified adsorbent has a potential in reducing Cr (III) concentration in industrial wastewater.

Analisis Kandungan Logam Berat Cu dan Zn dalam Air Limbah Industri

Industrial wastewater is water from the processing of an industrial process. This type of water is classified as having poor quality because of the contaminants it contains. The contaminants contained in industrial water vary depending on the related processes that produced the water. This study aims to determine the concentrations of heavy metals Cu and Zn in industrial wastewater at three locations in Batam City. Wastewater testing was carried out using the ICP-AES. The results obtained indicate that the levels of Cu and Zn in the industrial wastewater samples at the three locations are still below the maximum concentration limit permitted by the Environmental Quality Standards and are in accordance with the Regulation of the Minister of Environment of the Republic of Indonesia No. 5 of 2014 Annex 47 About Wastewater Quality Standards.

Heavy Metal Chemistry of Waste Water of Textile Dyeing Industries, Tongi, Gazipur, Bangladesh

The present research work shows the dominance of iron in the industrial waste water and river water samples of the investigated area of Gazipur district. The mean iron concentrations for both types of water samples are higher than the maximum permissible limits of WHO and NEQS. The excess amount of iron in water can cause health hazards of the human beings and ecosystem. Attempts should be taken to remove the excess amount of iron from the waters of the study area. On the basis of median concentration values of the heavy metals, they can be arranged as Fe>Zn>Ni>Cr>Pb. The factor analysis reveals the dominance of first two factors which comprise 83.298% of the total variance. The factor-1 is characterized by the contamination of Fe, Ni and Zn whereas factor-2 is dominated by the presence of Cu and Pb.Â

Preparation of nanocellulose modified with dithizone for separation, extraction and determination of trace amounts of manganese ions in industrial wastewater samples

In order to preconcentrate and clarify the trace amounts of Mn (II) ions, a very efficient natural adsorbent was prepared by cellulose nanofiber and its modification of the surface. Cellulose nanofibers were made by wood pulp hydrolysis using a concentrated acid under sonicating and reflux conditions and modification by dithizone immobilization. The influential elements like pH of extraction, the quantity of nanocomposite, time of extraction, the ionic power and typical volume were made better for numerical clarification of Mn (II) ions. According to findings, there is a linear range for the optimized technique between 1.0 and 15 ng mL−1 by the detection limit of 0.29 ng mL−1. As shown by statistical analysis of the results, there are small intra- and inter-day precision values from 0.8 to 2.7% and 1.6–5.4%, respectively, high pre-concentration factor and enrichment factor. It was found that the maximum adsorption capacity of the nanosorbent is 137 mg g−1. High selectivity and sensitivity were observed in the nanocomposite in terms of detection of low Mn (II) ions concentration at the ng mL−1 level with high precision for the samples.

Effective Enrichment and Quantitative Determination of Trace Hg2+ Ions Using CdS-Decorated Cellulose Nanofibrils.

Water pollution caused by metal contamination is of serious concern. Direct determination of trace metal ions in real water samples remains challenging. A sample preparation technique is a prerequisite before analysis. Herein, we report the facile water-based hydrothermal synthesis of cadmium sulfide nanoparticles on a cellulose nanofiber surface to prepare a new adsorbent material. Field emission scanning electron microscopy, high-resolution tunneling electron microscopy, elemental mapping and X-ray photoelectron microscopy were used to characterize the surface morphology, structural determination, elemental composition and nature of bonding. The nanoadsorbent (cadmium-sulfide-decorated cellulose nanofibrils (CNFs@CdS)) was employed for the solid-phase extraction and determination of trace Hg(II) from aqueous media. The experimental conditions were optimized systematically and the data show a good Hg(II) adsorption capacity of 126.0 mg g−1. The CNFs@CdS adsorbent shows the selective removal of Hg(II) accordingly to the hard and soft acid–base theory of metal–ligand interaction. A high preconcentration limit of 0.36 µg L−1 was obtained with a preconcentration factor of 580. The lowest level of trace Hg(II) concentration, which was quantitatively analyzed by the proposed method, was found to be 0.06 µg L−1. No significant interferences from the sample matrix were observed in the extraction of Hg(II). Analysis of the standard reference material (SRM 1641d) was carried out to validate the proposed methodology. Good agreement between the certified and observed values indicates the applicability of the developed methodology for the analysis of Hg(II) in tap water, river water and industrial wastewater samples.

Occurrence, Fate and Adverse Effects of Residual Levels of Preservatives and Active Whitening Agents from Wasterwater of Personal Care Products Industries

The present study was carried out to estimate the residual level of preservatives and active whitening agents from personal care products (PCPs) wastewater by using high performance liquid chromatography (HPLC) along with characterization of wastewater. Diverse types of pollutants are being detected in aqueous environment with PCPs and related compounds containing large variety of groups, including parent molecules and their respective metabolites. Intensive research is required on this subject to gain reliable information about their occurrence, fate and adverse effects on health. For this purpose, development of extremely sensitive analytical methods of determination in industrial wastewater samples are not only need of the hour but also a challenge. Liquid chromatography is an advanced analytical method for such pollutants. In this study, samples were collected from industrial sites located at distant points of Lahore and characterization was done through different parameters to illustrate wastewater quality. It has been found that values were within limits of National Environmental Quality Standard (NEQS) except for turbidity and total suspended solids (TSS) in some samples. Six preservatives including methylparaben, benzoic acid, salicylic acid, sodium benzoate, propylene glycol and formic acid along with five whitening agents like kojic acid, arbutin, ascorbic acid, nicotinamide and hydroquinone were quantified. It was interpreted that residues are present in almost all collected PCPs wastewater samples. The concentration of selected preservatives and active whitening agents in wastewater was ranged between 0.91–4.17 and 1.13–15.65 mg/L respectively. The most quantified concentrations were of methylparaben and sodium benzoate among preservative residues. In whitening agents, kojic acid and ascorbic acid were quantified in the highest concentrations.

Development of an innovative nitrite sensing platform based on the construction of carbon-layer-coated In2O3 porous tubes

Excessive uptake of nitrite has been proven to be harmful for human health and ecological systems, so it is vital to develop a reliable methodology for nitrite analysis. In this work, we have synthesized innovative carbon-layer-coated In2O3 porous tubes (C@In2O3 PTs) to electrochemically detect nitrite in industrial wastewater samples. C@In2O3 PTs were prepared through the thermal decomposition of metal organic frameworks (MOFs, MIL-68-In) based on the two-step synthetic processes. The obtained C@In2O3 PTs displayed obviously increased catalytic activity to the electrochemical oxidation of nitrite, which benefited from the enhanced surface area and electron transfer based on the porous and hollow structure, and the maximized synergistic effect due to the intimate contact between In2O3 core and carbon layer. Thus, the sensitive determination of nitrite with a detection limit of 0.08 μM was realized, which was promising for sensitive determination of nitrite in the environmental analysis and food industry.

Selective Fluorometric Analysis of Hg(II) in Industrial Waste Water Samples.

The highly selective and sensitive fluorometric method has been developed for trace level determination of Hg(II) is based on photo-induced electron transfer between rhodamine-6G dye and metal complex. Quenching in fluorescence intensity by fluorescence resonance energy transfer (FRET) is due to interaction between metal ion complex and dye. The fluorescence emitted was measured at 510 and 550nm, for excitation and emission wavelengths respectively. Possible interferences present in water samples, which could affect the analytical response are studied and determined. The calibration graph was dynamically linear from 0.002 to 0.05mgL-1 of Hg(II) with limit of detection 7 × 10-4mgL-1 and limit of quantitation 1.9 × 10-3mgL-1. The Stern-Volmer constant (KSV) calculated for the quenching of R-6G with Hg (II) was 8.47 Lmg-1s-1 at optimized reaction conditions. The proposed FRET based fluorometric method was applied successfully in different industrial wastewater samples with satisfactory outcome.

A New Strategy for the Analysis of Steroid Hormones in Industrial Wastewaters by Paper Spray Ionization Mass Spectrometry.

A new approach using paper spray ionization mass spectrometry (PSI-MS) for the analysis of steroid hormones in wastewater samples has been demonstrated. Triangular papers containing paraffin barriers as microfluidic channels were used to direct the sample solution to the paper tip, preventing the sample from spreading over the corners of the paper. The method was used to analyze the hormones levonorgestrel and algestone acetophenide in industrial wastewaters. Analytical curves presented a correlation coefficient (R2) above 0.99. Limits of quantification were below 2.3 ppm and limits of detection below 0.7 ppm. Values of precision (coefficient of variation) and accuracy (relative error) were less than 15% for all analyses. Recovery results ranged from 82% to 102%. Levonorgestrel was also analyzed by high-performance liquid chromatography coupled to mass spectrometry in order to compare the analytical performance with PSI-MS. No statistically significant differences were found between both methods. This study demonstrates the usefulness of PSI-MS for rapid analysis of hormones in industrial wastewater samples and also indicates its potential to be employed as a simple and reliable analytical method in environmental sciences.

A strategy for the implementation of water-quality-based discharge limits for the regulation of hazardous substances.

Many developing countries apply technology-based discharge standards that set quantitative limits on pollutant discharges. These standards do not inherently consider ambient constraints and, therefore, cannot guarantee to protect aquatic life from hazardous pollutants. It is a challenge for developing countries to enforce water-quality-based limits for wastewater discharges and guarantee the intended use of water. This study aims to develop a strategy that suits the needs of developing countries for a transition from technology-based discharge standards to water-quality-based discharge limits. To this end, a pilot monitoring program was carried in the Gediz River Basin in Turkey. Surface water, industrial, and urban wastewater samples were collected and analyzed for 45 priority pollutants identified by the European Union and 250 national river basin specific pollutants. The monitoring results revealed that the environmental quality standards (EQSs) were exceeded for 8 priority, and 28 specific pollutants. This finding indicated that the existing technology-based discharge standards are not satisfactory to guarantee the intended water quality, and there is a need for adopting a new strategy for the implementation of water-quality-based discharge limits in Turkey. As a widely applied approach for determining water-quality-based discharge limits, firstly, conservative mass balance with and without consideration of mixing zone was evaluated. The results indicated that this approach was not applicable due to the receiving environment concentrations being higher than the EQSs. As an alternative approach, the dilution methodology, which considers the level of dilution occurring at the immediate discharge point, was tested. The results proved that the dilution methodology is the most appropriate strategy for developing countries with relatively poor surface water quality to improve the water quality to the level where the conservative mass balance approach can be applicable.

Selenium functionalized magnetic nanocomposite as an effective mercury (II) ion scavenger from environmental water and industrial wastewater samples

A novel core-shell magnetic-selenium nanocomposite (Fe3O4@SiO2@Se) was synthesized for fast and effective removal of Hg (II) ions from various industrial and environmental water samples. The composition, property, and structure of Fe3O4@SiO2@Se were characterized by spectral and microscopic techniques. The key parameters affecting the removal were evaluated and optimized. The concentration of residual Hg (II) ions in the solution was measured using a cold vapor atomic absorption spectrometer. At pH = 3.0, Fe3O4@SiO2@Se was capable to remove Hg (II) ions ranged from 100 μg L−1 to 10 mg L−1 within 20 min with the efficiency of approximately 99% in a way that residual concentration levels matched international standards. This level of removal efficiency was well maintained up to salinity of 25 g L−1. Kinetic investigations revealed compliance with a second-order kinetic model. The linear regression coefficient suggested the adsorption of Hg (II) ions by the adsorbent followed the Langmuir isotherm model (R2 > 0.997). The maximum capacity of the adsorbent obtained through investigating the isotherms was 70.42 mg g−1. The Fe3O4@SiO2@Se adsorbent effectively removed the Hg (II) ions spiked to different samples, including tap water, river water, seawater, and industrial wastewater. Therefore, this nano-adsorbent can be used as a good alternative for Hg (II) removal, in practical applications.

Effects of Several Physicochemical Factors on the Biodegradation of 1,4-Dioxane by Microbial Consortium CDIK-3 Enriched from Industrial Wastewater

Objective : With the ultimate aim of application for effluent treatment, the relationships between 1,4-dioxane degradation by microbial consortium CDIK-3 and several relevant physicochemical environmental parameters were investigated.Methods : Microbial consortium CDIK-3 enriched from an industrial wastewater sample developed to grow aerobically with 1,4-dioxane as the sole carbon substrate was used to evaluate the degradation of 1,4-dioxane depending on the various environmental parameters and HPLC methodology was used to measure residual 1,4-dioxane in the test consortium.Results and Discussion : The microbial consortium, designated CDIK-3, was originally enriched from industrial wastewater sample. Complete depletion of 1,000 mg/L 1,4-dioxane was achieved in this experiment within 168 h. Effective 1,4-dioxane degradation was observed in slightly alkaline conditions (pH 8) and 30℃. The effect of supplemented carbon and nitrogen (<i>e.g</i>., glucose, yeast extract, ethylene glycol, tetrahydrofuran) on the 1,4-dioxane degradation by the CDIK-3 test culture was evaluated. The results indicated that the addition of glucose, yeast extract, or tetrahydrofuran accelerated bacterial growth compared to growth in the absence of supplemented carbons. In contrast, the addition of low concentrations (≤100 mg/L) of ethylene glycol accelerated 1,4-dioxane degradation, but the degradation of 1,4-dioxane was delayed in the culture to which high concentrations (≥200 mg/L) of ethylene glycol were added.Conclusions : 1,4-Dioxane as a wastewater contaminant can be removed by the microbial consortium CDIK-3 enriched from industrial wastewater. Effective 1,4-dioxane removal was obtained by the control of various physicochemical parameters. These results provide clues for understanding improved 1,4-dioxane degradation by microbial consortium CDIK-3 with relevant environmental parameters and possible applications in the processing of industrial wastewater containing relatively high 1,4-dioxane concentrations.

Curcumin graphite pencil electrode modified with molybdenum disulfide nanosheets decorated gold foams for simultaneous quantification of nitrite and hydrazine in water samples

A non-enzymatic sensor based on a curcumin modified pencil graphite electrode, loaded with molybdenum disulfide nanosheets decorated gold foam, was constructed. Herein, the electrochemical deposition strategy was adopted throughout the sensing platform design stepwise. The electroactivity of the pencil electrode platform enables sensitive simultaneous quantification of hydrazine and nitrite where the respective working potentials typically are at + 0.2 V for hydrazine and + 0.75 V for nitrite (both vs. Ag/AgCl, saturated KCl). It is shown that the resulting sensor demonstrates excellent analytical performances in terms of limits of detection (18.3, 21.7 nM), sensitivities (0.051, 0.061 μA μM−1), and reproducibility standard deviations (RSD) of 3.1 and 2.7% for hydrazine and nitrite, respectively. Furthermore, long term stability studies showed that the electrodes exhibited an effectively unchanged response after some 30 days. The sensor was used to analyze spiked samples of river water and industrial wastewater.

Phosphorus-Doped Carbon Quantum Dots as Fluorometric Probes for Iron Detection.

Carbon quantum dots (CQDs), a novel fluorescent nanomaterial, have been extensively employed/explored in various applications, that is, biosensors, bioimaging, nanomedicine, therapeutics, photocatalysis, electrocatalysis, energy storage system, and so forth. In this study, we report the synthesis, characterization, and the application of phosphorus-doped CQDs (PCQDs), synthesized using trisodium citrate and phosphoric acid by the hydrothermal method. The effect of phosphorus doping on optical features and the formation of PCQDs have been explored elaborately by controlling the concentrations of precursors, reaction time, and the temperature. The fluorescent quantum yield for PCQDs was determined to be 16.1% at an excitation/emission wavelength of 310/440 nm. Also, the optical and structural properties of PCQDs were determined by using various spectroscopic and microscopic techniques. Static quenching of fluorescence was determined upon the addition of Fe3+ to PCQDs because of the formation of the fluorescent inactive complex (PCQDs–Fe3+). Hence, this chemistry leads to the development of a new fluorometric assay for the detection of Fe3+. The lower limit of Fe3+ detection is determined to be 9.5 nM (3σ/slope), with the linear fit from 20 nM to 3.0 μM (R2 = 0.99). We have validated this new assay in the raw, ejected, and purified water samples of the RO plant by the standard addition method. These results suggest the possibility of developing a new commercial assay for Fe3+ detection in blood, urine, and various industrial waste and sewage water samples. Furthermore, recycling the pollutant water into the freshwater using filters that consist of PCQDs offers a great deal.

Determination of fipronil and bixafen pesticides residues using gas chromatography mass spectroscopy with matrix matching calibration strategy after binary dispersive liquid-liquid microextraction

The objective of this study was to determine bixafen and fipronil residues in domestic and industrial wastewater, soil and mint samples by binary dispersive liquid-liquid microextraction method (BDLLME) prior to gas chromatography-mass spectrometry (GC-MS). Extraction efficiency for the selected analytes was improved by optimizing the parameters such as solvent type, ratio and volume, dispersive solvent type/volume, mixing type and duration to increase overall analytical performance. Under the optimum chromatographic and extraction conditions, limits of detection values for bixafen and fipronil were determined as 7.3 and 6.1 µg L−1, respectively. Spiking experiments were performed for domestic and industrial wastewater, soil and mint samples to evaluate applicability and accuracy of the proposed method. Recovery results for the samples were calculated in the range of 89.4%–112.6% via matrix matching calibration strategy. It was determined that the detection power of GC-MS system was improved 7.8 times for bixafen and 119 times for fipronil over LOD comparisons of conventional GC-MS and B-DLLME-GC-MS systems.