Selective effects of fenitrothion on murine splenic T-lymphocyte populations and cytokine/granzyme production

The aim of this study was to investigate in vitro effects of fenitrothion (FNT) on mouse splenic lymphocytes. Here, naïve mice had their spleens harvested and splenocytes isolated. After exposure to FNT for 48 hr: splenocyte viability was measured using a tetrazolium dye assay; cell phenotypes, i.e., B-cells (CD19⁺), T-cells (CD3⁺), and T-cell subsets (CD4⁺ and CD8⁺), were quantified by flow cytometry; and, production of cytokines/granzyme-B was assessed via enzyme-linked immunosorbent assay. The ability for FNT to induce oxidative stress in the cells was evaluated by measuring hydroxyl radical (·OH) and malondialdehyde (MDA) production and changes in glutathione peroxidase (GSH-Px) and superoxide dismutase (SOD) activity. The results showed that FNT significantly inhibited splenocyte proliferation, and decreased production of interleukin (IL)-2, interferon gamma, IL-4, and granzyme B, but had no impact on IL-6 production. FNT also selectively decreased splenic T-cell levels but did not induce changes in CD19⁺ B-cells. Further, within the T-cell populations, percentages of CD3⁺, CD4⁺, and CD8⁺ T-cells (particularly CD8⁺ T-cells) were reduced. Lastly, FNT selectively increased MDA and ·OH production and inhibited SOD and GSH-Px activities in the splenic lymphocytes. These findings suggest that, due to oxidative damage, FNT selectively inhibits splenic T-lymphocyte survival and cytokine/granzyme production in vitro.     

Persistence characteristics of operationally sprayed fenitrothion in nearby unsprayed areas of a conifer forest ecosystem in New Brunswick

Abstract

Persistence characteristics of operationally sprayed fenitrothion were investigated in various substrates sampled from neighbouring unsprayed areas in New Brunswick. Air, water, sediment, aquatic plants, fish, balsam fir [Abies balsamea (L.) Mill] foliage, forest soil and litter samples were collected from random sampling locations selected within 200 m from the operational spray blocks. The same substrates were resampled from the same plots and from the same locations about a year later just prior to the commencement of the operational spraying. Control samples were collected from an unsprayed site, near Sault Ste. Marie, Ontario. All samples were analysed for fenitrothion, by gas‐liquid chromatography. Except the fish samples all the substrates collected during the time of operational spraying contained low but detectable levels of fenitrothion. When collected a year later prior to the operational spray program, only balsam fir showed any detectable levels (detection limit, 0.01 ppm) of the chemical. All other samples showed no fenitrothion residues (detection limit for air, 10 ng/m³; for water, 0.01 ppb; and for other samples, 0.01 ppm). The findings confirmed that fenitrothion does not persist for an extended period of time in the aquatic substrates. The conifer foliage, however, showed persistent residues at a level of about 0.55 ppm even after the winter months, although there was no indication of accumulation of the chemical as a result of repeated exposure. The study demonstrated that the conifer needles acted as a micro sink for the chemical which showed a tendency to persist in the leaf tissues for a considerable length of time.     

Simultaneous determination of fenitrothion and aminocarb in blueberry foliage and fruits: Application to the analysis of residues in field samples

Abstract

Samples of blueberry foliage and fruits were collected from spray blocks in Ontario after aerial application of fenitrothion and aminocarb at dosage rates of 210 g active ingredient (AI)/ha and 70 g AI/ha respectively. Residues were extracted from the samples by homogenizing with ethyl acetate, cleaned up by microcolumn chromatography using alumina as adsorbent, and analyzed by GLC‐AFID with a glass column packed with 1.5% OV‐17 and 1.95% OV‐210 on 80–100 mesh Chromosorb W‐HP. Average recoveries for fenitrothion and aminocarb from foliage at three fortification levels (1.0, 0.10 and 0.01 ppm) were respectively 99 and 96%. The corresponding values for the fruits were 99 and 95%. Foliage samples collected 1 h post‐spray contained on average 1.13 ppm of fe‐nitrothion and 1.14 ppm of aminocarb. However, residue levels reached below the detection limit (<0.01 ppm) in foliage collected 15 d after treatment. In addition, the fruit samples collected after 15 d post‐spray contained extremely low levels (0.03 ppm for fenitrothion and 0.02 ppm for aminocarb) of residues, and were barely above the detection limit.     

Foliar and ground deposits of fenitrothion following aerial application over a plantation forest

Abstract

Spray deposits were measured on spruce foliage at tree canopy level and on glass plates at ground level, after aerial application of an emulsion formulation of fenitrothion at the rate of 0.21 kg AI in 1.46 L per ha over a 16 ha plot in a plantation forest. Fenitrothion deposits were quantified by gas‐liquid chromatography. A wide variation was observed in deposits on foliage and at the forest floor. Deposits were relatively higher on foliar samples collected from the upwind side of a tree canopy than those on the downwind side. Similarly, the glass plate placed under a tree on the upwind side received relatively higher deposit than the one on the downwind side. However, the glass plates placed in the adjacent forest openings collected markedly higher deposits. Results clearly indicate filtration of the spray droplets by canopy foliage. Assessment of the average deposit of fenitrothion at ground level (mean deposit from all sampling locations) indicated that ca. 19.4% of the applied material reached the forest floor. Within a sampling station, correlation was poor between foliar depsits and those on glass plates under the same trees or in nearby clearings. Analysis of fenitrothion deposits on foliage collected at 1 and 2 h after application indicated that the droplets took, more than 1 h for deposition on the tree canopy. On the other hand, deposition on the glass plates at ground level appeared to be practically complete within 1 h post‐treatment. This was attributed to the higher sedimentation velocities of the larger droplets which tend to travel faster to the floor level than the smaller droplets which float for a longer period near the tree canopy.     

A simplified clean-up procedure for the rapid determination of PCDDs and PCDFs based on retention on activated carbon AX-21

Different 2,3,7,8-substituted polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) were investigated for their retention behaviour on a disposable minicolumn containing activated carbon AX-21. Elution behaviour and recovery were examined, using native and radiolabelled PCDD and PCDF isomers.

A comparison of the total mass chromatograms of PCDDs and PCDFs in an extract from animal adipose tissue, before and after activated carbon treatment, demonstrates the efficiency of this cleanup step with respect to the elimination of interfering compounds.     

Cyp35a2 gene expression is involved in toxicity of fenitrothion in the soil nematode Caenorhabditis elegans

In this study, the effect of organophosphorous (OP) pesticide, fenitrothion (FT), on the non-target organism was investigated using the soil nematode, Caenorhabditis elegans. Toxicity was investigated on multiple biological levels, from organism to molecular levels, such as, immoblity, growth, fertility, development, acetyl cholinesterase (AChE) activity and stress-response gene expressions. FT may provoke serious consequences on the C. elegans population, as it induced significant developmental disturbance. As expected, FT exposure inhibits AChE activity of C. elegans. The increased expression of the cytochrome p450 family protein 35A2 (cyp35a2) gene was also observed in FT exposed worms. To experimentally demonstrate the relationships between organism-level effects and the cyp35a2 gene expression in FT-exposed C. elegans, the integration of the gene expression with biochemical-, and organism level endpoints were attempted using a C. eleganscyp35a2 RNA interference (RNAi) and cyp35a2 mutant (gk317). The 24 h-EC50s of C. elegans on FT exposure were in the order of cyp35a2 RNAi in cyp35a2 mutant (gk317) > cyp35a2 mutant (gk317) > cyp35a2 RNAi in wildtype (N2) > wildtype (N2). The higher EC50 values of cyp35a2 RNAi and cyp35a2 mutant (gk317) compared to that of wildtypeC. elegans strongly supported that cyp35a2 gene plays an important role in the toxicity of FT towards C. elegans. The experiments with cyp35a2 RNAi also indicated that the development disturbance and decreased AChE activity, which were observed in FT exposed wildtype C. elegans were significantly rescued in the cyp35a2 RNAi C. elegans. Overall results suggest that the cyp35a2 may be an important gene for exerting FT toxicity in C. elegans.     

A modified clean-up procedure for the determination of PCDDs in soil samples

PCDDs can be determined in soil samples in the presence of high amounts of hexachlorocyclohexanes with a modified method, including a clean-up procedure with a column containing carbon. To reach low detection limits use is made of a column switching system in the GC-MS analysis.     

A simple effective procedure for the determination of adenosine triphosphate in soils

A simple method for the extraction and determination of adenosine 5′-triphosphate (ATP) in soil is described. ATP was extracted by stirring with dimethyl sulphoxide (DMSO), followed by adding 0.01 M trisodium phosphate (Na₃PO₄) buffer solution for a further dispersion. The ATP content was quantitatively measured by luciferin-luciferase system employing a standard addition technique. The method was most efficient in comparison with 7 other extraction procedures. The recoveries of ATP in spiked soil were found to be approximately 100 %. ATP contents in 16 selected soils were in ranges of 0.76±0.05 – 7.79±0.83 μg/g (dry weight). A significant correlation between ATP amounts and biomasses in these soils was also observed.     

A rapid method for determination of Aroclor 1260 in cattle adipose tissue

Abstract

A simple analytical procedure for the determination of Aroclor 1260 in cattle adipose tissue is described. The polychlorinated biphenyls residues are extracted from the tissue using a soxhlet extractor and the extracts are cleaned up using a florisil SEP‐PAK cartridge. The residues are detected using a gas chromatograph equipped with an electron capture detector. The effect of extraction time of the Aroclor 1260 residues from the tissue has been investigated and a period of four hours is found to give satisfactory percent recoveries. Greater than 85 percent recoveries were obtained from adipose tissue spiked with Aroclor 1260. The method can be used to detect Aroclor 1260 residue levels as low as 0.10 parts per million.

The method was used to analyze thirty‐one cattle adipose tissue samples out of which twenty‐six samples were taken from cattle suspected of exposure to a pasture containing electrical transformers and capacitors containing Aroclor 1260. Five control samples were collected from cattle with no known exposure. All twenty‐six samples were found to contain non‐detectable Aroclor 1260 residues.     

A rapid spectrophotometric determination of persulfate anion in ISCO

Due to a gradual increase in the use of persulfate as an in situ chemical oxidation (ISCO) oxidant, a simple measurement of persulfate concentration is desirable to analyze persulfate distribution at designated time intervals on/off a site. Such a distribution helps evaluate efficacy of ISCO treatment at a site. This work proposes a spectrophotometric determination of persulfate based on modification of the iodometric titration method. The analysis of absorption spectra of a yellow color solution resulting from the reaction of persulfate and iodide in the presence of sodium bicarbonate reveals an absorbance at 352 nm, without significant interferences from the reagent matrix. The calibration graph was linear in the range of persulfate solution concentration of 0-70 mM at 352 nm. The proposed method is validated by the iodometric titration method. The solution pH was at near neutral and the presence of iron activator does not interfere with the absorption measurement. Also, analysis of persulfate in a groundwater sample using the proposed method indicates a good agreement with measurements by the titration method. This proposed spectrophotometric quantification of persulfate provides a simple and rapid method for evaluation of ISCO effectiveness at a remediation site.     

A new bioseed for determination of wastewater biodegradability: analysis of the experimental procedure

A new bioassay proposed in the patent P201300029 was applied to a pre-treated wastewater containing a mixture of commercial pesticides to simulate a recalcitrant industrial wastewater in order to determine its biodegradability. The test uses a mixture of standardized inoculum of the lyophilized bacteria Pseudomonas putida with the proper proportion of salts and minerals. The results highlight that biodegradation efficiency can be calculated using a gross parameter (chemical oxygen demand (COD)) which facilitates the biodegradability determination for routine water biodegradability analysis. The same trend was observed throughout the assay with the dehydrated and fresh inoculums, and only a difference of 5 % in biodegradation efficiency (E _f) was observed. The obtained results showed that the P. putida biodegradability assay can be used as a commercial test with a lyophilized inoculum in order to monitor the ready biodegradability of an organic pollutant or a WWTP influent. Moreover, a combination of the BOD₅/COD ratio and the P. putida biodegradability test is an attractive alternative in order to evaluate the biodegradability enhancement in water pre-treated with advanced oxidation processes (AOPs).     

A new method for the rapid determination of volatile organic compound breakthrough times for a sorbent at concentrations relevant to indoor air quality

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25%) relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

土壤中苯并[a]芘和二苯并[a，h]蒽的快速测定及其降解特性研究

建立了加速溶剂萃取-高效液相色谱-二极管阵列检测(ASE-HPLC-PAD)快速测定土壤中苯并[a]芘(BaP)和二苯并[a.h]葸(DBA)的方法.通过提取剂、提取方法的优化,检测波长(BaP、DBA的λmax分别为294.6、295.8 nm)的选择,减少了干扰物的影响,提高了检测灵敏度.土壤中添加BaP、DBA的质量浓度均为0.02～0.50 mg/kg时,其平均回收率均为77.26%～109.56%,相对标准偏差为0.60%～2.74%;土壤中BaP、DBA的最小检测质量浓度分别为2.15、1.10μg/kg.将ASE-HPLC-PAD方法应用于污染场地土壤中BaP与DBA的测定及其降解特性研究表明,BaP与DBA的降解半衰期分别达210、693 d.     

A rapid, sensitive screening test for polycyclic aromatic hydrocarbons applied to Antarctic water

We describe a rapid, sensitive, fluorescence screening test for polycyclic aromatic hydrocarbons in water samples that avoids more costly time-consuming methods. The screening test works by detecting benzo[a]pyrene. It runs without the need for any pre-concentration step, thus rendering it suitable for routine use in water-quality-control laboratories. The test recognizes contaminated samples rapidly (150 s) and inexpensively with a cut-off level of 10 ng l(-1), which is the value that the European Union and World Health Organization (WHO) have laid down in its assessment of the quality of water for human consumption. This was first ascertained by analysing tap and waste-water samples before studying environmental water samples from the Antarctic region. The reliability of the screening test was 2% false positives and 4% false negatives in 200 samples of tap and waste-water. The applicability was confirmed by the fact that the predictions of the screening test coincided exactly with results obtained with gas chromatography-mass spectrometry assays. We also discuss the polluted Antarctic samples and the possible sources of the contamination involved.     

A simple procedure for correcting loading effects of aethalometer data

A simple method for correcting for the loading effects of aethalometer data is presented. The formula BC(CORRECTED) = (1 + k x ATN) x BC(NONCORRECTED), where ATN is the attenuation and BC is black carbon, was used for correcting aethalometer data obtained from measurements at three different sites: a subway station in Helsinki, an urban background measurement station in Helsinki, and a rural station in Hyyti?l? in central Finland. The BC data were compared with simultaneously measured aerosol volume concentrations (V). After the correction algorithm, the BC-to-V ratio remained relatively stable between consequent filter spots, which can be regarded as indirect evidence that the correction algorithm works. The k value calculated from the outdoor sites had a clear seasonal cycle that could be explained by darker aerosol in winter than in summer. When the contribution of BC to the total aerosol volume was high, the k factor was high and vice versa. In winter, the k values at all wavelengths were very close to that obtained from the subway station data. In summer, the k value was wavelength dependent and often negative. When the k value is negative, the noncorrected BC concentrations overestimated the true concentrations.     

Photolytic degradation of methyl-parathion and fenitrothion in ice and water: Implications for cold environments

Here we investigate the photodegradation of structurally similar organophosphorus pesticides; methyl-parathion and fenitrothion in water (20 °C) and ice (−15 °C) under environmentally-relevant conditions with the aim of comparing these laboratory findings to limited field observations. Both compounds were found to be photolyzed more efficiently in ice than in aqueous solutions, with quantum yields of degradation being higher in ice than in water (fenitrothion > methyl-parathion). This rather surprising observation was attributed to the concentration effect caused by freezing the aqueous solutions. The major phototransformation products included the corresponding oxons (methyl-paraoxon and fenitroxon) and the nitrophenols (3-methyl-nitrophenol and nitrophenol) in both irradiated water and ice samples. The presence of oxons in ice following irradiation, demonstrates an additional formation mechanism of these toxicologically relevant compounds in cold environments, although further photodegradation of oxons in ice indicates that photochemistry of OPs might be an environmentally important sink in cold environments.     

A rapid and efficient determination of natural estrogens in soils by pressurised liquid extraction and gas chromatography-mass spectrometry

We present a new analytical procedure for the extraction and determination of natural estrogens in soils based on pressurised liquid extraction and GC-MS determination. After testing twelve solvents, acetone proved to be the most efficient extractant. The optimum extraction temperature is 60 degrees C. Soil extracts have to be purified and concentrated by C-18 solid phase extraction. The dried extracts are derivatised by N-methyl-N-(trimethylsilyl)trifluoro-acetamide before measurement by GC-MS. Recoveries of 79-103% with relative standard deviations 相似文献   

Extraction procedure optimization for perfluorooctane sulfonate and perfluorooctanoic acid in food packaging determination by LC-MS/MS

This research aimed to optimize the extraction method parameters for sample pretreatment and determine the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in food packaging made of paper. Techniques used were pressurized liquid extraction (PLE) followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Influence parameters of PLE were carefully evaluated for extracted concentration of samples in low level (ng g^?1). The study found that the optimal conditions for PLE were 30 min static extraction time with a flush volume of 100% cell volume and one extraction cycle at 80°C and 1,000 psi. The extraction technique validated the absolute recovery from PFOS and PFOA fortified control samples at three different levels (5, 50, and 200 ng g^?1), with seven repeats at each fortification level. The average recoveries were 79% or higher, with relative standard deviation (RSD) less than 11%. Optimization of the PLE method was established based on recovery data, accuracy, precision, and repeatability of the method. Using optimal PLE technique, PFOS and PFOA were extracted from 34 food-packaging samples collected in Thailand. PFOS and PFOA were detected in all kinds of collected samples, with average concentrations of 4.89 and 2.87 ng g^?1, respectively. The concentrations of PFOS and PFOA were highest in fast-food container samples: 36.99 and 9.99 ng g^?1, respectively.     

Residue levels of fenitrothion and aminocarb in the air samples collected from experimental spray blocks in New Brunswick in 1982

Abstract

Fenitrothion and aminocarb formulations were aerially sprayed over mixed coniferous forests near Fredericton and Bathurst, New Brunswick, Canada. Insecticide concentrations inside the spray blocks were measured at intervals of time by trapping the airborne toxicants in a fritted‐glass bubbler containing dimethylformamide (DMF). The residues in DMF were analysed by gas chromatography. Concentrations of the insecticides in the air sampled decreased rapidly with time from peak levels of 1997 ng/m³ (fenitrothion) and 1201 ng/m³ (aminocarb). Concentrations of the two insecticides in the air samplers were dependent upon the nature of the chemicals, type of formulation used, spray timings and other environmental factors.     

Application of a purge and trap TDS-GC/MS procedure for the determination of emissions from flame retarded polymers

Emissions of volatile organic compounds (VOCs) from different thermoplastic polymers used in electrotechnical applications were investigated using a purge and trap procedure that involved adsorption on Tenax GR. Results were compared to those for an operating TV set monitored in a test chamber. The analyses were in both cases carried out using thermodesorption gas chromatography with mass spectrometric detection (TDS-GC/MS). Substances identified were monomers, volatile additives, or related compounds. Special attention was given to the detection of halogenated compounds. Their origin was studied using reference samples and synthetic standards.