Evaluation of the potential of laser-induced breakdown spectroscopy for detection of trace element in liquid

The analytical figure of merit of the potential of laser-induced breakdown spectroscopy (LIBS) has been evaluated for detection of trace element in liquid. LIBS data of Mg, Cr, Mn, and Re were studied. Various optical geometries, which produce the laser spark in and at the liquid sample, were tested. The calibration curves for Mg, Cr, Mn, and Re were obtained at the optimized experimental conditions with bulk liquid and in liquid jet. It was found that measurements using a liquid jet provide better detection limits than bulk liquid measurements. The limits of detection (LOD) of Mg, Cr, Mn, and Re in the present liquid jet measurement are found to be 0.1, 0.4, 0.7, and 8 ppm, respectively. The LOD of Mg using Mg 279.55 nm was compared with the values found in other liquid work.     

Impact of soil quality on elemental uptake by,and distribution in,Colocasia esculenta (Amadumbe), an edible root

In this study the elemental distribution of selected essential (Ca, Mg, Al, Mn, Cu, Fe, Co, Cr, Zn, Ni and Se) and the non-essential (Pb, Hg and As) elements were determined in the bulb and peel of Amadumbe (Colocasia esculenta) samples from eight different sites in KwaZulu-Natal, South Africa. The concentration of Se and As in the soil and in the Amadumbe bulbs were below the detection limit of 0.09 μg g^?1. The total and bioavailable concentrations of the elements in conjunction with pH, soil organic matter (SOM) and cation exchange capacity (CEC) were determined in the soil samples from the eight sites. Statistical analysis was done to evaluate the impact of soil quality parameters on the chemical composition of the Amadumbe root. The results show accumulation or exclusion of certain elements by the bulb as evidenced by the noticeable increase or decrease of the concentrations of elements, respectively. Ca and Mg were found to be major elements in the range (2000–12000 μg g^?1), whilst Mn, Zn, Fe and Al were found to be minor elements in the range (20–400 μg g^?1). A general trend observed was that the plant favours the absorption of Zn over Cu. A positive correlation between Mg & Ca, Cu & Fe and Co & Ni was also observed. Statistical analysis revealed that the plant tended to accumulate Mg, Ca, Co, Cr and Pb whilst it excluded Hg and Fe, to a lesser extent.     

Evaluation of airborne particulate matter and metals data in personal,indoor and outdoor environments using ED-XRF and ICP-MS and co-located duplicate samples

Factors and sources affecting measurement uncertainty associated with monitoring metals in airborne particulate matter (PM) were investigated as part of the Windsor, Ontario Exposure Assessment Study (WOEAS). The assessment was made using co-located duplicate samples and a comparison of two analytical approaches: ED-XRF and ICP-MS. Sampling variability was estimated using relative percent difference (RPD) of co-located duplicate samples. The comparison of ICP-MS and ED-XRF results yields very good correlations (R² ≥ 0.7) for elements present at concentrations that pass both ICP-MS and ED-XRF detection limits (e.g. Fe, Mn, Zn, Pb and Cu). PM concentration ranges (median, sample number) of 24-h indoor PM₁₀ and personal PM₁₀ filters, and outdoor PM_2.5 filters were determined to be 2.2–40.7 (11.0, n = 48) μg m^?3, 8.0–48.3 (11.9, n = 48) μg m^?3, and 17.1–42.3 (21.6, n = 18) μg m^?3, respectively. The gravimetric analytical results reveal that the variations in PM mass measurements for same-day sampling are insignificant compared to temporal or spatial variations: 92%, 100% and 96% of indoor, outdoor and personal duplicate samples, respectively, pass the quality criteria (RPD ≤ 20%). Uncertainties associated with ED-XRF elemental measurements of S, Ca, Mn, Fe and Zn for 24-h filter samples are low: 78%–100% of the duplicate samples passed the quality criteria. In the case of 24-h filter samples using ICP-MS, more elements passed the quality criteria due to the lower detection limits. These were: Li, Na, K, Ca, Si, Al, V, Fe, Mn, Co, Cu, Mo, Ag, Zn, Pb, As, Mg, Sb, Sn, Sr, Th, Ti, Tl, and U. Low air concentrations of metals (near or below instrumental detection limits) and/or inadvertent introduction of metal contamination are the main causes for excluding elements based on the pass/fail criteria. Uncertainty associated with elemental measurements must be assessed on an element-by-element basis.     

Odor Threshold Measurement by Dynamic Olfactometry: Significant Operational Variables

Abstract

Combustion flue gases of three different industrial boilers firing miscellaneous fuels were monitored for a twoweek period. Nitric oxide (NO), sulfur dioxide (SO₂), carbon monoxide (CO), carbon dioxide (CO₂), and total hydrocarbons (CxHy) were continuously measured using single-component gas analyzers in parallel with a lowresolution Fourier Transform Infrared (FTIR) gas analyzer. Hydrogen chloride (HCl) was measured continuously using the FTIR analyzer and semi-continuously using a traditional liquid-absorption technique. Nitrous oxide (N₂O), nitrogen dioxide (NO₂), and water vapor (H₂O) were continuously measured using the FTIR analyzer only. Laboratory tests were conducted prior to the field measurements to assess the detection limits of the different measurement methods for each gas component. No significant differences were found between the results of the low-resolution FTIR analyzer and the single-component analyzers or the liquid absorption method.     

Impact of soil quality on elemental uptake by, and distribution in, Colocasia esculenta (Amadumbe), an edible root

In this study the elemental distribution of selected essential (Ca, Mg, Al, Mn, Cu, Fe, Co, Cr, Zn, Ni and Se) and the non-essential (Pb, Hg and As) elements were determined in the bulb and peel of Amadumbe (Colocasia esculenta) samples from eight different sites in KwaZulu-Natal, South Africa. The concentration of Se and As in the soil and in the Amadumbe bulbs were below the detection limit of 0.09 μg g?1. The total and bioavailable concentrations of the elements in conjunction with pH, soil organic matter (SOM) and cation exchange capacity (CEC) were determined in the soil samples from the eight sites. Statistical analysis was done to evaluate the impact of soil quality parameters on the chemical composition of the Amadumbe root. The results show accumulation or exclusion of certain elements by the bulb as evidenced by the noticeable increase or decrease of the concentrations of elements, respectively. Ca and Mg were found to be major elements in the range (2000-12000 μg g?1), whilst Mn, Zn, Fe and Al were found to be minor elements in the range (20-400 μg g?1). A general trend observed was that the plant favours the absorption of Zn over Cu. A positive correlation between Mg & Ca, Cu & Fe and Co & Ni was also observed. Statistical analysis revealed that the plant tended to accumulate Mg, Ca, Co, Cr and Pb whilst it excluded Hg and Fe, to a lesser extent.     

Performance evaluation of laser-induced breakdown spectrometry as a multimetal continuous emission monitor

Laser-induced breakdown spectroscopy (LIBS) has been evaluated as a multimetal continuous emissions monitor (CEM) at the U.S. Environmental Protection Agency (EPA) rotary kiln incinerator simulator (RKIS) facility in Raleigh, NC. Two detection systems with a bifurcated optical fiber bundle were used for simultaneously monitoring the concentrations of Be, Cd, Cr, and Hg in the test. Two calibration techniques were evaluated in the laboratory for the field measurements. On-line calibration of relative metal concentration was also performed in the simulated incinerator gas stream. Toxic metal concentrations measured with LIBS have been compared with the EPA reference method (RM) results.     

Air Pollution Damage to Exterior Household Paints

ABSTRACT

The present study focuses on the elemental characterization of fine and coarse particles collected at a coastal site of southwestern Italy, in a suburban area of the Calabria region. A chemical tracer analysis was carried out to identify the major emission sources influencing on the atmospheric aerosol levels. Size-resolved particulate samples were collected during three 2-week seasonal sampling campaigns: autumn (19 October to 2 November 2003), winter (19 January to 2 February 2004) and spring (26 April to 10 May 2004). Ambient concentrations of selected elements (Fe, Mn, Mg, Ca, V, Cu, Cr, Ni, Zn, Pb, and Cd) associated to fine and coarse size fractions were determined using atomic absorption spectrometry (AAS). The enrichment factor method was applied, suggesting a prevailing anthropogenic component for all the detected elements, with Fe, Mg, Mn, and Ca as exceptions. Trajectory sector analysis was used in order to discriminate the influence of different air mass origins and paths. Long-range transport from both the continental Europe and the Saharan region proved to be the main influencing factors. African dust outbreaks, whose occurrence frequency was greater during the autumn and spring seasonal monitoring periods, gave rise to a total of eight exceedances of the European Commission (EC) PM₁₀ daily limit value as well as an increase in values of the crustal-derived elements (Fe, Mg, and Ca). Long-range transport from the heavily industrialized area of Central/Eastern Europe contributed to the high levels of Zn, Cd, and Pb that were recorded during the winter sampling campaign. Seasonal trend and comparison with measurements previously performed across the Mediterranean basin were also presented and discussed.

IMPLICATIONS This paper, which investigates both natural and anthropogenic aerosol sources, contributes to the characterization of fine and coarse particles in a suburban area of the southern Italian region of Calabria whose air quality assessment is still being defined. The monitoring site involved in this study, located at the interface between continental Europe and the Mediterranean basin, offers an important platform to study the influence of seasonal meteorology and predominant circulation patterns on the aerosol concentration levels and their chemical composition.     

Multi-elemental analysis of Lentinula edodes mushrooms available in trade

ABSTRACT

The present study investigated the content of 62 elements in the fruiting bodies of Lentinula edodes (Shiitake mushroom) cultivated commercially in Poland on various substrates from 2007–2015. The general mean content (mg kg^?1 dry weight (DW)) of the studied elements ranked in the following order: K (26,335) > P (11,015) > Mg (2,284) > Ca (607) > Na (131) > Zn (112) > Fe (69) > Mn (33) > B (32) > Rb (17) > Cu (14.5) > Al (11.2) > Te (2.9) > As (1.80) > Cd (1.76) > Ag (1.73) > Nd (1.70) > Sr (1.46) > Se (1.41) > U (1.11) > Pt (0.90) > Ce (0.80) > Ba (0.61) > Co (0.59) > Tl (0.58) > Er (0.50) > Pb (0.42) > Li (0.40) > Pr (0.39) > Ir (0.37) > In (0.35) > Mo (0.31) > Cr (0.29) > Ni (0.28) > Sb (0.26) > Re (0.24) > Ti (0.19) > Bi (0.18) > Th (0.12) > La (0.10) = Pd (0.10) > Os (0.09) = Zr (0.09) > Rh (0.08) > Ho (0.07) > Ru (0.06) > Sm (0.04) = Eu (0.04) = Tm (0.04) > Gd (0.03) > Sc (0.02) = Y (0.02) > Lu (0.01) = Yb (0.01) = V (0.01). The contents of Au, Be, Dy, Ga, Ge, Hf, and Tb were below the limits of detection (0.02, 0.02, 0.01, 0.01, 0.01, 0.01, 0.02 mg kg^?1 respectively). The concentrations of Al, As, B, Ba, Ca, Cd, Cr, Er, Fe, In, Lu, Mn, Nd, Sr, Ti, Tm, and Zr were comparable over the period the mushrooms were cultivated. The study revealed that Lentinula edodes contained As and Cd at levels potentially adverse to human health. This highlights the need to monitor these elements in food products obtained from this mushroom species and ensure that only low levels of these elements are present in cultivation substrates.     

Laboratory and Field Evaluation of Measurement Methods for One-Hour Exposures to O3, PM25, and CO

ABSTRACT

While researchers have linked acute (less than 12-hr) ambient O₃, PM₂₅, and CO concentrations to a variety of adverse health effects, few studies have characterized short-term exposures to these air pollutants, in part due to the lack of sensitive, accurate, and precise sampling technologies. In this paper, we present results from the laboratory and field evaluation of several new (or modified) samplers used in the “roll-around” system (RAS), which was developed to measure 1-hr O₃, PM₂₅, and CO exposures simultaneously. All the field evaluation data were collected during two sampling seasons: the summer of 1998 and the winter of 1999.

To measure 1-hr O₃ exposures, a new active O₃ sampler was developed that uses two nitrite-coated filters to measure O₃ concentrations. Laboratory chamber tests found that the active O₃ sampler performed extremely well, with a collection efficiency of 0.96 that did not vary with temperature or relative humidity (RH). In field collocation comparisons with a reference UV photometric monitor, the active O₃ sampler had an effective collection efficiency ranging between 0.92 and 0.96 and a precision for 1-hr measurements ranging between 4 and 6 parts per billion (ppb). The limits of detection (LOD) of this method were 9 ppb-hr for the chamber tests and ~16 ppb-hr for the field comparison tests.

PM_2.5 and CO concentrations were measured using modified continuous monitors—the DustTrak and the Langan, respectively. A size-selective inlet and a Nafion dryer were placed upstream of the DustTrak inlet to remove particles with aerodynamic diameters greater than 2.5 um and to dry particles prior to the measurements, respectively. During the field validation tests, the DustTrak consistently reported higher PM_2.5 concentrations than those obtained by the collocated 12-hr PM_{2 5} PEM samples, by approximately a factor of 2. After the DustTrak response was corrected (correction factor of 2.07 in the summer and 2.02 in the winter), measurements obtained using these methods agreed well with R² values of 0.87 in the summer and 0.81 in the winter. The results showed that the DustTrak can be used along with integrated measurements to measure the temporal and spatial variation in PM_{2 5} exposures. Finally, during the field validation tests, CO concentrations measured using the Langan were strongly correlated with those obtained using the reference method when the CO levels were above the LOD of the instrument [~1 part per million (ppm)].     

The three-year monitoring of 18 elements in five edible mushroom species collected from an old orchard

Abstract

The content of Al, As, Be, Cd, Ca, Cr, Co, Cu, Fe, Pb, Li, Mg, Mn, Ni, Rb, Se, Sr, and Zn in fruiting bodies of edible mushrooms Calocybe gambosa, Entoloma clypeatum, Entoloma saepium, Xerocomellus chrysenteron, and Amanita rubescens growing in an orchard planted with fruit trees and situated close to a high-grown forest was studied during years 2016–2018. A. rubescens showed the highest potential of the element accumulation with bioconcentration factors of 48.5, 16.2, 7.80, 6.53, 1.75, and 1.68 obtained for Rb, Cd, Cu, Zn, Sr, and Mg, respectively. Both Entoloma species accumulated the elements similarly with bioconcentration factors >1.0 obtained for Rb, Cu, Cd, and Mg. Bioconcentration factors <0.05 were obtained for Al, Cr, Fe, and Pb in all studied species. The contents of beryllium (<0.1?mg/kg dry matter) were always the lowest among the studied elements. The contents of some elements of studied mushroom species significantly fluctuated over the years. Despite the fact that some studied elements (As, Be, Cd, Pb, Ni) are considerably toxic for humans, the pronounced effect on health is not expected if the studied mushroom species are consumed occasionally and do not represent the main component of the diet.     

Determination of glyphosate residue in maize and rice using a fast and easy method involving liquid chromatography–mass spectrometry (LC/MS/MS)

A fast and easy method was developed for the determination of glyphosate in maize and rice by using liquid chromatography triple quadrupole mass spectrometry with a Dionex Ion Pack column and phosphate buffer mobile phase. Samples were extracted with an acidified methanol solution. An isotope-labeled internal standard was added to the sample before extraction to ensure accurate tracking and quantification. The method’s performance was evaluated through a series of assessments to determine the accuracy, precision, linearity, matrix effect, limit of detection (LOD), and limit of quantification (LOQ). The mean recoveries for both matrices were within 70–105% at three fortification levels, including the LOQ. The precision for replicates was <20% (RSD%) for both matrices. Good linearity (R²=0.9982) was obtained over the concentration range of 0.01–1.5?mg kg^?1. The LOD was determined to be 0.002?mg kg^?1 for rice and 0.004?mg kg^?1 for maize. The LOQ was 0.01?mg kg^?1 for both maize and rice. Due to its versatility, the proposed method could be considered useful for the determination of glyphosate in cereals in routine analysis.     

Determination of T‐2 toxin in grain and grain products by HPLC and TLC

Abstract

The purpose of this study was to investigate the T‐2 toxin contaminated grain and grain products consumed especially by Turkish population. The T‐2 toxin was detected using the high performance liquid chromatography (HPLC) with UV detector at 208 nm and the identify of T‐2 was further confirmed by thin layer chromatography (TLC). The recovery was 91 ±4.24% for corn flour fortified with the known amount of T‐2 toxin (1 ppm). The detection limits of T‐2 toxin for the HPLC and the TLC were 25 ng and 50 ng, respectively. A total of 30 commercially available grain and grain product samples were analyzed. Two corn flour samples were found to contain detectable levels of T‐2 toxin at a level of 1.60 ppm and 4.08 ppm.     

Production of a monoclonal antibody and development of an immunoassay for detection of Cr(III) in water samples

In this study we report the production of a monoclonal antibody (Mab) specific for Cr(III)-chelate and the development of a competitive immunoassay for detection of Cr(III) in water samples. In the assay, the complete antigen (Cr(III)-ITCBE-BSA) was used as coating antigen, and Cr(III)-ITCBE as competitor competes with coating antigen to bind with Mab. Using this approach, the spiked water samples with Cr(III) were detected. The linear range of the detection was 0.7–12.4 ng mL⁻¹. The limit of the detection (LOD) was 0.51 ng mL⁻¹. The spiked results were also confirmed by ICP-MS, which showed a good correlation (R² = 0.997) between the two methods. The results indicated that the developed assay was reliable and suitable for the detection of Cr(III) in water samples.     

Overall elemental dry deposition velocities measured around Lake Michigan

Overall dry deposition velocities of several elements were determined by dividing measured fluxes by measured airborne concentrations in different particle size ranges. The dry deposition measurements were made with a smooth surrogate surface on an automated dry deposition sampler (Eagle II) and the ambient particle concentrations were measured with a dichotomous sampler. These long-term measurements were made in Chicago, IL, South Haven, MI, and Sleeping Bear Dunes, MI, from December 1993 through October 1995 as part of the Lake Michigan Mass Balance Study. In general, the dry deposition fluxes of elements were highly correlated with coarse particle concentrations, slightly less well correlated with total particle concentrations, and least well correlated with fine particle concentrations. The calculated overall dry deposition velocities obtained using coarse particle concentrations varied from approximately 12 cm s⁻¹ for Mg in Chicago to 0.2 cm s⁻¹ for some primarily anthropogenic metals at the more remote sites. The velocities calculated using total particle concentrations were slightly lower. The crustal elements (Mg, Al, and Mn) had higher deposition velocities than anthropogenic elements (V, Cr, Cu, Zn, Mo, Ba and Pb). For crustal elements, overall dry deposition velocities were higher in Chicago than at the other sites.     

Chronic toxicity of arsenic, cobalt, chromium and manganese to Hyalella azteca in relation to exposure and bioaccumulation

Chronic toxicity of As, Co, Cr and Mn to Hyalella azteca can be described using a saturation-based mortality model relative to total-body or water metal concentration. LBC25s (total-body metal concentrations resulting in 25% mortality in 4 weeks) were 125, 103, 152 and 57,900 nmol g-1 dry weight for As, Co, Cr and Mn respectively. LC50s (metal concentrations in water resulting in 25% mortality in 4 weeks) were 5600, 183, 731, and 197,000 nmol L-1, respectively. A hormesis growth response to As exposure was observed. Growth was a more variable endpoint than mortality for all four toxicants; however, confidence limits based on growth and mortality all overlapped, except Cr which had no effect on growth. Mn toxicity was greater in glass test containers compared to plastic. Bioaccumulation of As, Co, Cr, and Mn was strongly correlated with, and is useful for predicting, chronic mortality.     

The biological responses and metal phytoaccumulation of duckweed Spirodela polyrhiza to manganese and chromium

The phytoaccumulation ability of duckweed Spirodela polyrhiza on manganese (Mn) and chromium (Cr) was assessed by exposing the plant to various concentrations of single or dual metals (5–70 mg L^?1 Mn, 2–12 mg L^?1 Cr(VI)) under laboratory conditions. The results showed that S. polyrhiza can tolerate Mn at high concentrations of up to 70 mg L^?1, and its growth rate was barely affected by Mn. The effects of Cr on S. polyrhiza growth were dose-dependent, and the growth was completely inhibited in the presence of 12 mg L^?1 Cr. Analysis of metal content in the plant biomass revealed a high accumulation of Mn (up to 15.75 mg per g of duckweed dry weight). The Cr bioaccumulation (from below detection limit to 2.85 mg Cr (11.84 mg Cr₂O₇ ^2?) per g of duckweed dry weight) increased with cultivation time and metal concentration in the medium. Further study with the concurrence of Mn and Cr showed increased toxicity to plant growth and photosynthesis. The metal accumulations in the dual metal treatments were also significantly decreased as compared to the single metal treatments. Nevertheless, the phytoaccumulation of these two metals in S. polyrhiza in the dual metal treatments were still comparable to or higher than in previous reports. Thus, it was concluded that duckweed S. polyrhiza has the potential to be used as a phytoremediator in aquatic environments for Mn and Cr removal.

     

Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1microg l(-1) for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02microg g(-1), respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001-0.005microg g(-1).     

Near Surface Soil Vapor Clusters for Monitoring Emissions of Volatile Organic Compounds from Soils

ABSTRACT

The overall objective of this research was to develop and test a method of determining emission rates of volatile organic compounds (VOCs) and other gases from soil surfaces. Soil vapor clusters (SVCs) were designed as a low dead volume, robust sampling system to obtain vertically resolved profiles of soil gas contaminant concentrations in the near surface zone. The concentration profiles, when combined with a mathematical model of porous media mass transport, were used to calculate the contaminant flux from the soil surface. Initial experiments were conducted using a mesoscale soil remediation system under a range of experimental conditions. Helium was used as a tracer and trichloroethene was used as a model VOC. Flux estimations using the SVCs were within 25% of independent surface flux estimates and were comparable to measurements made using a surface isolation flux chamber (SIFC). In addition, method detection limits for the SVC were an order of magnitude lower than detection limits with the SIFC. Field trials, conducted with the SVCs at a bioventing site, indicated that the SVC method could be easily used in the field to estimate fugitive VOC emission rates. Major advantages of the SVC method were its low detection limits, lack of required auxiliary equipment, and ability to obtain realtime estimates of fugitive VOC emission rates.     

Presence of carbamazepine,naproxen, and ibuprofen in wastewater from northern Tunisia

We investigated the occurrence of three pharmaceutical residues in four wastewater treatment plants (WWTPs) from northern Tunisia. The selected compounds were carbamazepine, naproxen, and ibuprofen; they are among the most commonly prescribed and widely used pharmaceutical agents worldwide. Samples (200?mL) were pre-concentrated using the solid phase extraction (SPE) enrichment procedure and the analysis of the pharmaceuticals was performed with high-performance liquid chromatography (HPLC-UV). The overall procedure provided limits of detection (LOD) lower than 0.5 µg.L^?1and recoveries of 78–97%. For the carbamazepine compound, the mean concentrations were 60.58, 93.19, and 132 µg.L^?1 for the Bizerte, Jendouba, and Tunis WWTPs, respectively. This pharmaceutical was not detected in the Beja WWTPs. Naproxen and ibuprofens were not detected in the Jendouba WWTP but were found in the three other WWTPs with concentrations ranging from 2.94 to 36.17 µg.L^?1 and from 8.02 to 43.22 µg.L^?1, respectively. From the obtained data, it seems that these WWTPs are not able to eliminate this kind of micro-pollutants.     

Analysis of Organophosphorus Pesticides in Whole Milk by Solid Phase Microextraction Gas Chromatography Method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-μm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30°C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 μgL^?1 to 1.75 μgL^?1 for coumaphos and 0.69 μgL^?1 to 6.90 μgL^?1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 μgL^?1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 μgL^?1 for dichlorvos and 0.066 μgL^?1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.