A modified quick-easy-cheap-effective-rugged-and-safe method involving carbon nano-onions-based dispersive solid-phase extraction and dispersive liquid-liquid microextraction for pesticides from grapes.

A combination of modified quick easy cheap effective rugged and safe extraction approach with carbon nano-onions-based dispersive solid-phase extraction and dispersive liquid-liquid microextraction was developed for the extraction of several pesticides (diazinon, chlorpyrifos, tebuconazole, deltamethrin, permethrin, haloxyfop-methyl, penconazole, and cyhalothrin) from grape before their analysis by gas chromatography-flame ionization detection. In the extraction approach, an aliquot of grape sample is chopped and after separating its juice, the pesticides that remained in the refuse are extracted by the quick, easy, cheap, effective, rugged, and safe extraction method. The obtained acetonitrile phase is mixed with juice and the analytes are extracted by the carbon nano-onions-based dispersive solid-phase extraction. The analytes are concentrated using the microextraction procedure to obtain high enrichment factors. The results showed low limits of detection (0.5-1.6 ng/g) and quantification (1.8-5.4 ng/g) with satisfactory linearity of the calibration curves (determination coefficient, r2 ≥ 0.994). The precision of the developed method expressed as relative standard deviations was good (≤7.2%). The method provided high enrichment factors (350-410) and extraction recoveries (70-82%). Finally, seven grape samples were analyzed successfully.

Extraction of permethrin from impregnated fabrics for determination by ultra-high performance liquid chromatography with diode array detection.

Permethrin is a synthetic pyrethroid insecticide that is largely used in the impregnation of fabrics employed for different purposes. This paper reports a detailed study on the conditions for its extraction from fabrics and for its determination by ultra-high performance liquid chromatography with diode array detection (UHPLC-DAD). Several parameters that could affect the extraction efficiency of permethrin were evaluated, such as the extraction time, agitating mode (mechanical or ultrasound-assisted), solvent type (methanol or acetonitrile), concentration, and volume. Under optimized conditions, the extraction was performed for 10 min using a 2 × 2 cm piece of impregnated fabric and 5 mL of pure methanol. The flask containing the sample and the solvent was shaken mechanically using a horizontal roller mixer. The accuracy of the method was assessed by a recovery test, which presented satisfactory results ranging from 86.8% to 95.2%. The method was employed in the analysis of nine samples of commercial fabrics of different colors and grammages that were impregnated with permethrin. The concentration of permethrin found in these samples varied between 25.6 ± 4.2 and 934 ± 119 mg m-2.

A Comparison of Different Statistical Methods for Addressing Censored Left Data in Temporal Trends Analysis of Pyrethroids in a California Stream.

This study compared four different statistical methods, involving six estimation procedures, for addressing censored left data in measuring temporal trends of eight different pyrethroids measured in sediment from a 10-year data set in a residential California stream (Pleasant Grove Creek). The statistical methods used were: the Kaplan-Meier (km) method; the robust regression on order statistics (ros using normal and log normal distributions rosln); the maximum likelihood estimation (mlen using normal and log normal distributions mleln); and a substitution method (sub) using ½ the detection limit. For five of the eight pyrethroids (bifenthrin, cyfluthrin, cypermethrin, lambda-cyhalothrin, and permethrin), the six statistical methods generally agree, with one exception, that the data set exhibit significant declining trends. In the case of bifenthrin, the slight disagreement among statistical methods only occurred for the mleln estimate that did not show a significant declining trend, whereas the other five methods did. For deltamethrin, esfenvalerate, and fenpropathrin, all six statistical methods were in agreement showing no significant trends. Possible reasons for declining sediment concentrations of pyrethroids in Pleasant Grove Creek are urban label changes effective in 2012-2015 that reduced residential use, variable annual rainfall, and more responsible homeowner use based on outreach/education programs.

Comparing the un-comparable: Olyset Plus and Olyset, different malaria impact.

BACKGROUND: In a recent article in The Lancet, Protopopoff et al. stated that insecticide resistance must be tackled and concluded that adding the insecticide synergist piperonyl butoxide (PBO) to a bed net with a pyrethroid as principal insecticide might be a part of the response. MAIN TEXT: The study in Tanzania compares malaria prevalence between users of two different nets with the principal insecticide permethrin: Olyset and Olyset Plus (Olyset+), the latter also holding the synergist molecule PBO, the first not. The article is based on randomized cluster trial of very high quality, but Olyset+ exposes much more permethrin at the surface so the higher efficacy may not be because of the added PBO. CONCLUSION: Data published by the World Health Organization (WHO) when evaluating Olyset+ as well of the study of Protopopoff et al. showed that much more permethrin is available on the surface of Olyset+ than on the surface of Olyset and the relatively small and rapidly dwindling dosage of PBO may have nothing to do with the superior effect of Olyset+. The WHO should not change politics for "PBO nets" based on this study alone.

A review on test methods for insecticidal fabrics and the need for standardisation.

Insecticidal fabrics are effective personal protective measures against disease vectors and unlike bed nets, these fabrics can provide protection from day-biting mosquitoes and in outdoor environments. The rapid geographical expansion of day-biting mosquitoes and their role in disease transmission necessitate technological interventions, which can be effectively used during the daytime. There is a renewed interest in insecticidal fabrics mainly due to the recent outbreaks and geographical spread of dengue and chikungunya and with the emerging threat of Zika virus infection. Insecticidal fabrics are useful for protection from night-biting mosquitoes and also in situations were sleeping under a bed net is not possible. They are also effective against other biting arthropods like ticks, mites, tsetse flies, sand flies and body lice. Although long-lasting insecticidal fabrics factory-treated with permethrin are now commercially available for military and civilian use, there are no international guidelines for testing their efficacy. The different methods employed so far for testing bioefficacy, washing and quantification of permethrin are compiled in this review. The future prospects and challenges ahead for long-lasting insecticidal fabrics are discussed in the context of the increased threat from day-biting mosquitoes and the diseases transmitted by them. The review focuses on the need for standardisation of the test methods for ensuring adequate bioefficacy and safety to the user. The differences between long-lasting insecticidal nets and long-lasting insecticidal fabrics are elaborated, and the need for a separate registration and licencing procedure for long-lasting insecticidal fabrics is highlighted. A test procedure for insecticidal fabrics is described, which could be used until internationally accepted guidelines are available.

Optimization of a methodology for the simultaneous determination of deltamethrin, permethrin and malathion in stored wheat samples using dispersive liquid-liquid microextraction with solidification of floating organic drop and HPLC-UV.

The purpose of this study was to investigate common pesticides in stored wheat at Kermanshah province's silos in Iran. A simple, inexpensive, reliable and environmentally friendly method based on dispersive liquid-liquid microextraction with solidification of floating organic drop was developed. The analytical characteristics of the method were determined. Also, various parameters such as the materials of the silos, types of ownerships of the silos, geographic orientation of silo locations and climatic conditions of silo locations on pesticide residues in studied wheat samples were investigated. Among all the studied parameters, the climatic conditions of silo locations showed the highest influence on pesticide residues in wheat samples. Generally, 61.2% of the samples had pesticide levels below the method detection limits and 38.8% of the total samples had at least one of the understudied pesticides. Also, 13.9% of the samples had deltamethrin residues, 16.7% of the samples had permethrin, 22.2% of the samples had malathion, 11.1% of the samples had both permethrin and malathion and 2.8% of the samples had both deltamethrin and malathion. The results revealed that the residues of deltamethrin and malathion were lower than the standard level announced by European Union regulation and only three samples contained permethrin higher than Europe standard level.

Durability of Olyset campaign nets distributed between 2009 and 2011 in eight districts of Tanzania.

BACKGROUND: Long-lasting insecticidal nets (LLINs) are the first line choice for malaria vector control in sub-Saharan Africa, with most countries adopting universal coverage campaigns. However, there is only limited information on LLIN durability under user conditions. Therefore, this study aimed to assess the durability of Olyset(®) LLINs distributed during campaigns between 2009 and 2011 in Tanzania. METHODS: A retrospective field survey was conducted in eight districts in Tanzania mainland to assess the durability of Olyset campaign nets. Household questionnaires were used to assess attrition, i.e. net loss. All nets remaining in households were collected. A sub-sample of 198 Olyset campaign nets was examined for bio-efficacy against Anopheles gambiae s.s. mosquitoes, permethrin content and physical integrity following standard World Health Organization (WHO) methods. RESULTS: Of 6067 campaign nets reported to have been received between 2009 and 2011, 35% (2145 nets) were no longer present. Most of those nets had been discarded (84%) mainly because they were too torn (94%). Of the 198 sub-sampled Olyset LLINs, 61% were still in serviceable physical condition sufficient to provide personal protection while 39% were in unserviceable physical condition according to WHO proportionate Hole Index (pHI). More than 96% (116/120) of nets in serviceable condition passed WHO bioefficacy criteria while all nets in unserviceable condition passed WHO bioefficacy criteria. Overall mean permethrin content was 16.5 g/kg (95% CI 16.2-16.9) with 78% of the sub-sampled nets retaining recommended permethrin content regardless of their age or physical condition. Nets aged 4 years and above had a mean permethrin content of 14 g/kg (95% CI 12.0-16.0). The only statistically significant predictor of reduced physical net integrity was rats in the house. CONCLUSIONS: Two-to-four years after a mass campaign, only 39% of distributed nets remain both present and in serviceable physical condition, a functional survival considerably below WHO assumptions of 50% survival of a 'three-year' net. However, the majority of nets still retained substantial levels of permethrin and could still be bio-chemically useful against mosquitoes if their holes were repaired, adding evidence to the value of net care and repair campaigns.

Bioactivity and laundering resistance of five commercially available, factory-treated permethrin-impregnated fabrics for the prevention of mosquito-borne diseases: the need for a standardized testing and licensing procedure.

Personal protective measures against hematophagous vectors constitute the first line of defense against arthropod-borne diseases. In this regard, a major advance has been the development of residual insecticides that can be impregnated into clothing. Currently, however, information on specific treatment procedures, initial insecticide concentrations, arthropod toxicity, residual activity, and laundering resistance is either fragmentary or non-existent, and no World Health Organization Pesticides Evaluation Scheme or other guidelines exist for the standardized testing and licensing of insecticide-treated clothing. The aim of this study was to analyze the insecticide content, contact toxicity, laundering resistance, and residual activity of five commercially available and commonly used permethrin-treated fabrics-Insect Shield, ExOfficio, Sol's Monarch T-shirts, battle dress uniforms (BDUs), and Labonal socks-against vector-competent Aedes aegypti, Anopheles stephensi, and Culex pipiens mosquitoes under laboratory conditions. Prior to laundering, permethrin concentrations ranged from 4300 to 870 mg/m(2) whereas, after 100 defined machine launderings, the remaining permethrin content fell to between 1800 and 20 mg/m(2), a percentage permethrin loss of 58.1 to 98.5 %. The highest 99 % knockdown (KD99) efficacy of permethrin was detected in Ae. aegypti, followed by An. stephensi and Cx. pipiens demonstrating that Ae. aegypti is the most sensitive species and Cx. pipiens the least sensitive. After 100 launderings, the remaining biocidal efficacy differed markedly among the five brands, with KD99 times varying from 38.8 ± 2.9 to >360 min for Ae. aegypti, from 44 ± 3.5 to >360 min for An. stephensi, and from 98 ± 10.6 to >360 min for Cx. pipiens. Overall, the ranking of the residual biocidal efficacies within the five brands tested was as follows: BDU ≈ Labonal > Sol's Monarch > ExOfficio > Insect Shield. When applying German Armed Forces licensing conditions, none of the four products available in the civilian market would completely meet all the necessary efficacy and safety requirements fulfilled by BDUs. Therefore, we strongly recommend standardized testing and licensing procedures for insecticide-treated clothing, with defined cutoff values for initial maximum and post-laundering minimum concentrations of permethrin as well as figures for permethrin migration rates, arthropod toxicity, homogeneity on fabrics, residual activity, and laundering resistance.

Spatiotemporal Trends Analysis of Pyrethroid Sediment Concentrations Spanning 10 Years in a Residential Creek in California.

The objective of this study was to assess temporal and spatial trends for eight pyrethroids monitored in sediment spanning 10 years from 2006 to 2015 in a residential stream in California (Pleasant Grove Creek). The timeframe for this study included sampling 3 years during a somewhat normal non-drought period (2006-2008) and 3 years during a severe drought period (2013-2015). Regression analysis of pyrethroid concentrations in Pleasant Grove Creek for 2006, 2007, 2008, 2012, 2013, 2014, and 2015 using ½ the detection limit for nondetected concentrations showed statistically significant declining trends for cyfluthrin, cypermethrin, deltamethrin, permethrin, and total pyrethoids. Additional trends analysis of the Pleasant Grove Creek pyrethroid data using only measured concentrations, without nondetected values, showed similar statistically significant declining trends for cyfluthrin, cypermethrin, deltamethrin, esfenvalerate, fenpropathrin, permethrin, and total pyrethroids. Spatial trends analysis for the specific creek sites showed that six of the eight pyrethroids had a greater number of sites with statistically significant declining concentrations. Possible reasons for reduced pyrethroid concentrations in the stream bed in Pleasant Grove Creek during this 10-year period are label changes in 2012 that reduced residential use and lack of precipitation during the later severe drought years of 2013-2015.

Comparison of pollutant concentrations from weekly discrete versus composite samples for residential dry-weather runoff.

As urbanization has increased, so has degradation of urban streams. Urban water quality monitoring has focused on storm runoff sampling, but in arid climates, dry-weather runoff is a significant contributor of pollutants to aquatic systems. The majority of dry-weather runoff studies sample a small window of the entire dry-season. For this study constituent concentrations were compared using two sampling protocols. The first protocol repeatedly collected samples on the same day of the week at the same time of day. The second protocol collected samples during two week-long intensive sampling events consisting of sample collection every hour for 24 h for seven consecutive days. The two protocols were compared to determine if sampling at the same time of the week was representative of the entire week. For nitrate, total phosphorous, fipronil, permethrin, total organic carbon, and total suspended solids, sampling at the same time was not representative of the weekly mean; however, variability was observed between sites and constituents. For those constituent concentrations with significant differences seen between the two protocols, load adjustment factors (LAF) were determined, using a ratio of treatment means, and employed to adjust dry-season load estimates. Future work should include determining if LAF values can be used at similar sites excluded from the study or for similar constituents from the current sampling sites.

Analysis of Pesticides and Toxic Heavy Metals Contained in Mosquito Coils.

In this study, 10 mosquito coils manufactured in China were obtained in Suriname, South America, where they are used extensively. The coils were analyzed for organics (allethrin, permethrin, and butylated hydroxytoluene) and heavy metals (Cr, Co, As, Cd, and Pb) by GC-MS and ICP-MS, respectively. Allethrin was the only target organic compound detected in all mosquito coils with concentrations ranging from ~1900 to ~4500 µg/g. The concentrations of heavy metals varied as follows (in µg/g): Cr: 2.9-9.4, Co: 0.1-1.2, Cu: 0.7-16.1, Se: 0.10-0.4, Ni: 2.1-5.8, As: 0.10-2.2, Cd: 0.10-0.2, and Pb: 1.1-3.6.

Urinary pyrethroid and chlorpyrifos metabolite concentrations in Northern California families and their relationship to indoor residential insecticide levels, part of the Study of Use of Products and Exposure Related Behavior (SUPERB).

Since the 2001 U.S. federally mandated phase-out of residential uses of organophosphates (OPs), use of and potential for human exposure to pyrethroids in the indoor residential environment has increased. We report concentrations of common pyrethroids, pyrethroid metabolites, and chlorpyrifos in floor wipes, and urinary concentrations of pyrethroid metabolites and 3,5,6-trichloro-2-pyridinol (TCPy) in samples collected in 2007-2009 from 90 northern California families as part of the Study of Use of Products and Exposure Related Behavior (SUPERB). Correlation and regression analyses examined associations between floor wipe and urine sample concentrations. The most frequently detected urinary metabolites were TCPy (64.7%, median concentration of 1.47 ng/mL) and 3-phenoxybenzoic acid (3PBA) (62.4%, 0.79 ng/mL). Compared to the National Health and Nutrition Examination Survey (NHANES) 2001-2002 general U.S. population, this population had substantially higher pyrethroid metabolite and lower TCPy urinary concentrations. This may be related to the increased residential use of pyrethroids after the phase-out of OPs. Chlorpyrifos (98.7%), cis- and trans-permethrin (97.5%), bifenthrin (59.3%), and 3PBA (98.7%) were frequently detected in the floor wipes. Floor wipe concentrations for pyrethroid insecticides were found to be significant predictors of child creatinine-adjusted urinary metabolite concentrations (log-log regression coefficients ranging from 0.26 to 0.29; p < 0.05) suggesting that indoor residential exposure to pyrethroid insecticides is an important exposure route for children.

A test house study of pesticides and pesticide degradation products following an indoor application.

UNLABELLED: Preexisting pesticide degradates are a concern for pesticide biomonitoring studies as exposure to them may result in overestimation of pesticide exposure. The purpose of this research was to determine whether there was significant formation and movement, of pesticide degradates over a 5-week period in a controlled indoor setting after insecticide application. Movement of the pesticides during the study was also evaluated. In a simulated crack and crevice application, commercially available formulations of fipronil, propoxur, cis/trans-permethrin, and cypermethrin were applied to a series of wooden slats affixed to the wall in one room of an unoccupied test house. Floor surface samples were collected through 35 days post-application. Concentrations of the pesticides and the following degradates were determined: 2-iso-propoxyphenol, cis/trans 3-(2,2-dichlorovinyl)-3-3-dimethyl-(1-cyclopropane) carboxylic acid, 3-phenoxybenzoic acid, fipronil sulfone, fipronil sulfide, and fipronil desulfinyl. Deltamethrin, which had never been applied, and chlorpyrifos, which had been applied several years earlier, and their degradation products, cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid, and, 3,5,6-trichloro-2-pyridinol, respectively, were also measured. Propoxur was the only insecticide with mass movement away from the application site. There was no measurable formation or movement of the degradates. However, all degradates were present at low levels in the formulated product. These results indicate longitudinal repetitive sampling of indoor degradate levels during short-term studies, is unnecessary. PRACTICAL IMPLICATIONS: Exposure to preexisting pesticide degradates may inflate estimates of exposure in biomonitoring studies where these compounds are used as biomarkers. To date, there is no published information on formation of pesticide degradates following an indoor application. We found that the study pesticides have low rates of degradation and are unlikely to be a significant factor affecting results of short-term (weeks) biomonitoring studies. Therefore, relatively few indoor samples are needed to estimate background levels of degradation products resulting from a recent pesticide application.

Simultaneous Determination of Fipronil, Permethrin, and Their Key Related Substances in a Topical Drug Product by a Single Stability-Indicating High-Performance Liquid Chromatography Method.

BACKGROUND: The topical veterinary drug product containing fipronil and permethrin provides an effective repellent protection and high insecticidal efficacy for dogs. OBJECTIVE: The objective of this study was to develop a stability-indicating high-performance liquid chromatography (HPLC) method for simultaneous detection and quantification of fipronil, permethrin, their key degradation products, and butylated hydroxytoluene (BHT) in a topical drug product. METHOD: The two active ingredients, their degradation products, and the antioxidant (BHT) were separated by a gradient elution on a Phenomenex Kinetex C18 column (150 × 3 mm, 2.6 µm particle size) maintained at 37°C with H2O acetonitrile isopropyl alcohol 85% H3PO4 (65.5 + 32.5 + 4/0.0053, v/v/v/v) as mobile phase A and acetonitrile (100%) as mobile phase B. The flow rate was 0.9 mL/min, and analytes were detected and quantified at 235 nm. RESULTS: The specificity of the method was demonstrated by adequate separation of fipronil, permethrin, their degradation products, and BHT in the forced degraded finished product. The linearity of the method was demonstrated in the range of 0.2% to 150% of target analytical concentration of both active ingredients and 50% to 150% for BHT. Excellent recoveries of fipronil, permethrin, and BHT in placebo spiked active ingredient solutions in the linearity range showed sufficient accuracy of the method. The LOQ and LOD of the method were determined to be 0.2% and 0.07% of the analytical concentration. A robustness study did not identify any critical parameter that adversely affected the separation and quantification. CONCLUSIONS: Here, we report the development and validation of a robust, stability-indicating HPLC method for identification and assay of fipronil, permethrin, and BHT, including estimation of fipronil's and permethrin's degradation products in a topical drug product for dogs. HIGHLIGHTS: The new HPLC method permits the acquisition of data for all analytes of interest for a topical finished drug product containing fipronil, permethrin, and BHT.

Development and validation of a 'universal' HPLC method for pyrethroid quantification in long-lasting insecticidal mosquito nets for malaria control and prevention.

OBJECTIVES: To outline the development and validation of a universal method for quantifying deltamethrin, permethrin and alpha-cypermethrin levels in a variety of long-lasting insecticidal mosquito nets. METHODS: Using the HPLC conditions found in the CIPAC method for deltamethrin quantification, the method is based on a simple extraction technique for sample preparation (heating in isooctane at approximately 100 °C for 15 min). The method was validated for linearity, specificity, accuracy, precision, insecticide stability to extraction conditions and required extraction time for insecticide removal. RESULTS: The method was found valid for insecticide quantifications for various types of nets, namely for deltamethrin coated on polyester nets, deltamethrin incorporated into polyethylene nets, permethrin incorporated into polyethylene nets, alpha-cypermethrin coated on polyester nets and alpha-cypermethrin incorporated into polyethylene nets. CONCLUSIONS: This method will provide a more simplified approach to testing a variety of nets (different types of fibre) containing deltamethrin, permethrin or alpha-cypermethrin.

Avoidance behavior of Hyalella azteca in response to three common-use insecticides.

Non-target organisms in aquatic environments may experience lethal or sublethal effects following exposure to contaminants. Most protocols and regulations, however, are designed to provide protection from lethal effects and are thus based on conventional estimates of population lethality. The relative lack of reliable behavioral endpoints makes it challenging to implement regulations that are similarly protective against sublethal toxicity. The objective of this study was to quantify the avoidance behavior of Hyalella azteca when exposed to three insecticides-bifenthrin (B), chlorpyrifos (C), and permethrin (P)-at a range of estimated lethal concentrations. A two-choice behavioral arena was used for each chemical to quantify H. azteca activity and time spent in either uncontaminated sediment or sediment spiked at concentrations reflecting estimated 48-h lethal concentrations (LC50, LC25, and LC10). For all three insecticides, naïve H. azteca demonstrated a preference for the uncontaminated sediment over the contaminated sediment at the LC50 (B: 312 ng/gOC; C: 1265 ng/gOC; P: 5042 ng/gOC) and LC25 (B: 230 ng/gOC; C: 859 ng/gOC; P: 3817 ng/gOC), spending significantly more time in the uncontaminated side of the arena. H. azteca did not avoid sediment at LC10 (B: 204 ng/gOC; C: 609 ng/gOC; P: 1515 ng/gOC) levels, indicating the existence of a potential threshold of detection. Despite the lack of substrate preference at this exposure level, H. azteca were nevertheless more active (i.e., increased zone-switching) when exposed to bifenthrin at the LC10, suggesting a possible irritation response (e.g., movement after exposure) to this chemical. Our results provide evidence that H. azteca exhibit innate avoidance responses to sediments contaminated with common insecticides at concentrations below those represented by traditional toxicological endpoints (e.g., LC50). The sensitivity and ease with which this behavioral endpoint can be assayed demonstrates the potential utility of behavioral endpoints in toxicological assessments using model organisms.

Carcinogenic and non-carcinogenic risk assessment induced by pesticide residues in fresh pistachio in Iran based on Monte Carlo simulation.

This research is aimed at the analysis of 87 pesticides in 30 fresh pistachio samples prepared from stores in Iran by QuEChERS-ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The results showed at least one pesticide was in 67% of fresh pistachio samples. Kresoxim methyl residue was detected in 20 samples with average of 0.11 mg kg-1; this average is 2.2 times more than maximum residue limit (MRL). Buprofezin was recognized in five samples with average of 0.17 mg kg-1 was observed with 3.4 times more than MRL; hexaconazole and permethrin were recognized in three samples lower than MRL with an average residue of 0.030 and 0.028 mg kg-1, respectively. In addition, potential non-carcinogenic and carcinogenic health risk assessments were evaluated using probabilistic methods performed with the Monte Carlo simulation algorithm. The order of pesticide ranking based on hazard quotient (HQ) was hexaconazole > buprofezin > permethrin > kresoxim methyl. Total HQ (HI) was 2.0E-4 and for children, 9.0E-4. Hence, it means fresh pistachio consuming maybe not have significant short-term health risks for consumer. Ranking based on cancer risk (CR) was hexaconazole > kresoxim methyl > metalaxyl > permethrin > buprofezin. However, total CR due to pesticide residues was not higher than 1E-6 value (1.09E-9); therefore, consumers were not at significant risk of carcinogenicity in this product.

Assessment of Dermal and Inhalation Exposure to Permethrin During Field Treatment of Military Uniforms.

INTRODUCTION: Permethrin is a common pesticide spray-applied to civilian clothing and military uniforms for protection against biting arthropods in an effort to reduce risks to arthropod-borne diseases. During mass clothing spray events, exposure is possible through the dermal, inhalation, and ingestion routes. The potentially exposed population during a spray event includes the pesticide applicator(s) and working party (personnel who handle clothing/uniforms by positioning on the ground, flipping, and removing after spraying is complete). Previous investigation is limited regarding permethrin exposure via multiple routes of entry. Additionally, most exposure assessments are limited to pesticide applicators rather than working party that support applicator personnel. The purpose of this investigation was to conduct a multi-route exposure assessment for all personnel normally participating in mass permethrin military uniform treatments. MATERIALS AND METHODS: The protocol and Informed Consent Document were approved by the Uniformed Services University of the Health Sciences (USUHS) Institutional Review Board (IRB) before fieldwork initiation (IRB number: USUHS.2019-032). Sampling occurred during routine spray events performed by 14 U.S. Navy personnel (3 applicators and 11 working party) over 2 days. Personal exposures were measured with dermal sampling, and airborne concentrations were measured with area air sampling. Permethrin area air sampling and analysis were conducted using OSHA Versatile Sampler-2 sampling media (n = 36). Dermal exposure was measured using dosimeter gloves (n = 26) and a dermal patch (n = 26) worn by study participants. RESULTS: All air samples were reported below the 0.4 µg limit of quantification. Glove sample results ranged from 45 to 120,000 µg and patch results ranged from 0.57 to 45 µg. A repeated-measures ANOVA showed non-statistically significant differences in dermal concentrations (P-value = .8340) between the applicators and working party in patches and gloves. CONCLUSIONS: Results suggest dermal contact is the primary route of exposure compared to inhalation when mass spraying clothing with permethrin. Similar dermal exposures between these two occupations may necessitate reconsidering risk assessment procedures, training and personal protective equipment (PPE) requirements for mass spray uniform treatments. Specifically, while PPE requirements for applicators are highly regulated by the Armed Forces Pest Management Board and include items such as Tyvek suits, chemical protective gloves, and air-purifying respirators, PPE was not regulated for working party personnel before this investigation.

Pyrethroid-induced oxidative stress and biochemical changes in the primary mussel cell cultures.

Pyrethroids are among the most widely used insecticides. Permethrin and tetramethrin, which are synthetic pyrethroids, are generally used to control insects in agricultural areas and household applications. Due to broad use areas, they contaminate aquatic ecosystems and cause adverse effects to the non-target aquatic organisms. Even though permethrin and tetramethrin are known to alter the oxidative stress parameters of in vivo aquatic animal model organisms, there are limited studies in vitro. This study aims to determine the adverse effects of permethrin and tetramethrin in the in vitro models of freshwater mussels exposed to 1 mg/L, 10 µg/L, 100 ng/L and 1 ng/L concentrations of chemicals for 24 h. For this purpose, reduced glutathione activities were evaluated as biomarkers of the primary gill and digestive gland cell cultures. In both cell cultures, reduced glutathione values increased in the exposed groups, compared to the control group. Even though the results showed that reduced glutathione activities had not significantly changed concentration-dependently (p > 0.05), significant differences were observed in the reduced glutathione activities of both cell cultures (p < 0.05). This study showed that permethrin and tetramethrin had highly toxic effects in the in vitro models of mussels even at low concentrations.

Importance of fine particles in pesticide runoff from concrete surfaces and its prediction.

Pesticides such as pyrethroids have been frequently found in runoff water from urban areas and the offsite movement is a significant cause for aquatic toxicities in urban streams and estuaries. To better understand the origination of pesticide residues in urban runoff, we investigated the association of pyrethroid residues with loose particles in runoff water from concrete surfaces after treatment with commercial products of bifenthrin and permethrin. In runoff water generated from simulated precipitations after 1 to 89 d exposure under dry outdoor conditions, over 80% of the pesticides was found on particles >0.7 µm for most treatments. The solid-water partitioning coefficient (K(d)) on day 1 was estimated to be 2.4 × 10(3) to 1.1 × 10(5) L/kg for permethrin and bifenthrin on these solids. Except for solid formulations, the pesticide-laden particles likely originated from dust particles preexisting on the concrete before treatment and the disintegration of the surficial concrete matter through weathering. We consequently tested a simple sponge-wipe method to collect and analyze the loose particles on concrete. Concurrent analyses (n = 30) showed an excellent linear correlation between the amount of pesticides transferrable to runoff water and that on the wipe (R(2) = 0.78, slope = 1.13 ± 0.11, P < 0.0001). The fact that the linear relationship has a slope close to 1.0 suggests that this method may be used to predict pesticide residues available for contaminating runoff water before runoff actually occurs. The importance of loose particles should be considered when developing practices to mitigate pesticide runoff contamination from urban residential areas.