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.

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.

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.

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.

[Modified QuEChERS method based on multi-walled carbon nanotubes coupled with gas chromatography-tandem mass spectrometry for the detection of 10 pyrethroid pesticide residues in tea].

A modified QuEChERS method, based on multi-walled carbon nanotubes (MWCNTs), was established for the detection of 10 pyrethroid pesticides (cyfluthrin, flucythrinate, fenpropathrin, bifenthrin, cyhalothrin, permethrin, cypermethrin, etofenprox, fenvalerate, deltamethrin) in tea, in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS). The purification effects and dosages of four carbon nanomaterials, viz. single-walled carbon nanotubes (SWCNTs), MWCNTs, amino-modified MWCNTs, and graphene, were compared. An orthogonal experimental design was used to determine the optimal experimental conditions for sample pretreatment. The experimental factors governing the process were analyzed using variance. The results showed that the optimized sample pretreatment parameters were as follows. Acetonitrile was used as the extraction solvent with ultrasonic extraction for 35 min, while 60 mg MWCNTs, 200 mg PSA, and 200 mg C18, were used as purifiers. The effects of the extraction solvent and the carbon nanomaterials used on the recoveries of the 10 pyrethroid pesticides were significantly different (p<0.001), and the effect of extraction time on the recoveries was statistically different (p<0.05). The dosage of carbon nanomaterials had no significant effect on the recoveries (p>0.05). Good linearities were observed for the 10 pyrethroid pesticides in the concentration range of 0.01-2 mg/L. The limits of detection (LODs) and limits of quantification (LOQs) were in the ranges of 0.001-0.01 mg/kg and 0.005-0.04 mg/kg, respectively. The average recoveries of the pyrethroid pesticides spiked into blank samples of green tea were 91.4%-109.7%, and the relative standard deviations were 0.12%-9.80% (n=6). Furthermore, the matrix effects (MEs) of scented green tea, green tea, and black tea were evaluated. It was found that the addition of MWCNTs to the purifier can effectively reduce the matrix effect in green tea and black tea matrices. The developed method and the national standard method were used to detect the residues of the 10 pyrethroid pesticides in 120 tea samples available in the market. The results showed that cyfluthrin, deltamethrin, fenvalerate, permethrin, fenpropathrin, cypermethrin, bifenthrin and cyhalothrin were detected, and the contents obtained with the two methods were similar. Although pyrethroids were detected in most tea samples, the contents of all pesticide residues were below the maximum residue limits (MRLs). Therefore, the developed method is suitable for the rapid quantitative analysis of pesticide residues in tea.

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.

Remediating Indoor Pesticide Contamination from Improper Pest Control Treatments: Persistence and Decontamination Studies.

The improper and excessive use of pesticides in indoor environments can result in adverse human health effects, sometimes necessitating decontamination of residential or commercial buildings. A lack of information on effective approaches to remediate pesticide residues prompted the decontamination and persistence studies described in this study. Decontamination studies evaluated the effectiveness of liquid-based surface decontaminants against pesticides on indoor surfaces. Building materials were contaminated with 25-2,400 µg/100cm2 of the pesticides malathion, carbaryl, fipronil, deltamethrin, and permethrin. Decontaminants included both off-the-shelf and specialized solutions representing various chemistries. Pesticides included in this study were found to be highly persistent in a dark indoor environment with surface concentrations virtually unchanged after 140 days. Indoor light conditions degraded some of the pesticides, but estimated half-lives exceeded the study period. Decontamination efficacy results indicated that the application of household bleach or a hydrogen peroxide-based decontaminant offered the highest efficacy, reducing malathion, fipronil, and deltamethrin by >94-99% on some surfaces. Bleach effectively degraded permethrin (>94%), but not carbaryl (<70%) while the hydrogen peroxide containing products degraded carbaryl (>71-99%) but not permethrin (<54%). These results will inform responders, the general public and public health officials on potential decontamination solutions to remediate indoor surfaces.

Imaging and quantitative analysis of insecticide in mosquito net fibers using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS).

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis was used to qualitatively and quantitatively assess the distribution of permethrin insecticide on the surfaces and interiors of Olyset long-lasting insecticidal net (LLIN) fibers. Total insecticide content in LLINs has been established using many analytical methods. However, it is important to quantify the bioavailable portion residing on the fiber surfaces for incorporated LLINs. ToF-SIMS is a very surface sensitive technique and can directly image the spatial distribution of permethrin insecticide on the surface of Olyset fibers. Surface permethrin appeared as patchy deposits which were easily removed by acetone and reappeared after several days as interior permethrin migrated (bloomed) from the fiber interior. After a wash/incubation cycle, permethrin deposits were more diffuse and less concentrated than those on the as-received fibers. ToF-SIMS is particularly sensitive to detect the Cl- ion, which is the characteristic ion of permethrin. Ion implantation and quantification of dopants using SIMS is well established in the semiconductor industry. In this study, quantitative depth profiling was carried out using 35Cl- ion implantation to correlate secondary ion yield with permethrin concentration, yielding a limit of detection of 0.051 wt% for permethrin. In some cases, surface concentration differed greatly from the fiber interior (>1 µm below the surface). Two- and three-dimensional mapping of Cl at sub-micrometer resolution showed permethrin to be dissolved throughout the fiber, with about 2 vol% residing in disperse, high-concentration domains. This suggests that these fibers fall into the class of monolithic sustained-release devices. It is expected that ToF-SIMS can be a valuable tool to provide insight into the insecticide release behavior of other LLIN products, both current and future.

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.

Pyrethroid pesticide residues in the global environment: An overview.

Pyrethroids are synthetic organic insecticides with low mammalian toxicity that are widely used in both rural and urban areas worldwide. After entering the natural environment, pyrethroids circulate among the three phases of solid, liquid, and gas and enter organisms through food chains, resulting in substantial health risks. This review summarized the available studies on pyrethroid residues since 1986 in different media at the global scale and indicated that pyrethroids have been widely detected in a range of environments (including soils, water, sediments, and indoors) and in organisms. The concentrations and detection rates of agricultural pyrethroids, which always contain α-cyanogroup (α-CN), such as cypermethrin and fenvalerate, decline in the order of crops > sediments > soils > water. Urban pyrethroids (not contain α-CN), such as permethrin, have been detected at high levels in the indoor environment, and 3-phenoxybenzoic acid, a common pyrethroid metabolite in human urine, is frequently detected in the human body. Pyrethroid pesticides accumulate in sediments, which are a source of pyrethroid residues in aquatic products.

First report of a fish kill episode caused by pyrethroids in Italian freshwater.

INTRODUCTION: Fish kills are events of strong emotional impact on the population because of the frequent suspicion that they can be the result of serious pollution accidents. As a matter of fact, they are often due to natural occurrences, such as low levels of dissolved oxygen in the water, but in many cases the causes remain unknown. Fish are particularly sensitive to pesticides and pyrethroids are reported to be the most ecotoxicologically active in the aquatic environment. Nevertheless, the reported cases of massive wild fish mortalities due to these toxicants are very few. This paper describes a fish kill episode occurred in the Padua Province (Veneto Region - North Eastern Italy) which involved several fish species and for which it was possible to identify the cause in the presence of pyrethroids in the water. CASE PRESENTATION: When a whitish liquid coming from the rainwater drain of an industrial area was seen to be spilling into a drainage channel, a fish massive mortality was noticed and investigated. The collected water samples showed the presence of relevant concentrations of cypermethrin, permethrin, deltamethrin and tetramethrin. Analyses on the fish tissues revealed the presence of cypermethrin and permethrin at a concentration range of 476-2834µg/kg and 346-2826µg/kg on a lipid basis, respectively. DISCUSSION: According to the results of the performed analyses, we can reasonably state that the described episode had been caused by the exposure of biota to high concentrations of pyrethroids. The present case report significantly contributes to the limited literature available on pesticides-related fish kills. Moreover, it highlights the importance of sharing protocols for fish kill management at a national level, as this would help to better define the roles of the different institutions involved and to improve the investigation and the reporting of these events.

Pyrethroids in chicken eggs from commercial farms and home production in Rio de Janeiro: Estimated daily intake and diastereomeric selectivity.

In this study, pyrethroids were determined in chicken eggs from commercial farm (n = 60) and home egg production (n = 30). These pyrethroids were investigated: bifenthrin, phenothrin, permethrin, cyfluthrin, cypermethrin and fenvalerate, including most diastereomers. Quantification was done using GC-MS in a negative chemical ionization mode. Pyrethroids residues were found in 79% of the analyzed samples. Cypermethrin presented the highest occurrence, being quantified in 62 samples (69%) in concentrations (lipid weight - l w.) varying between 0.29 and 6408 ng g-1, followed by phenothrin (24%), 21-3910 ng g-1, permethrin (14%), 2.96-328 ng g-1, and bifenthrin (11%), 3.77-16.7 ng g-1. Cyfluthrin and fenvalerate were not detected. Home-produced eggs had a higher occurrence of pyrethroids (97%), with a greater predominance of phenothrin. In commercial production, 70% of the samples presented pyrethroid residues (predominantly cypermethrin). This is the first report about the presence of pyrethroids in home-produced eggs and the first description of a selectivity pattern with the predominance of cis diastereomers in chicken eggs. In general, estimated daily intake does not present a risk to human consumption, according to Brazilian and international standards (FAO/WHO). However, one third of the samples (30 eggs) had concentrations above the maximum residue limits (MRLs). The maximum cypermethrin concentration was 66 times the MRL, while the maximum phenothrin concentration was 11 times the limit. Further studies about transfer dynamics, bioaccumulation and metabolic degradation of stereoisomers are required, as well as determining if this selectivity pattern in food can increase consumer's health risk.

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.

Treated wastewater effluent as a source of pyrethroids and fipronil at todos santos bay, Mexico: Its impact on sediments and organisms.

Pyrethroids are insecticides widely used to control pests and disease vectors in residential areas and agricultural lands. Pyrethroids are emerging pollutants, and their use is a growing concern because of their toxicity potential to aquatic organisms. Todos Santos Bay and the Punta Banda estuary, 2 coastal bodies located to the south of the Southern California Bight, were studied to establish a baseline of the current conditions of pollution by pyrethroids and fipronil. Eight pyrethroids, along with fipronil and its 2 metabolites, were determined in effluents from wastewater-treatment plants (n = 3), surface sediments (n = 32), and 3 locations with mussels (Mytilus californianus, n = 9). Bifenthrin, permethrin, and cypermethrin were the most common pyrethroids found in the study areas and were widespread in sediments, mussels, and wastewater-treated effluents. Fipronil and its metabolites were detected in mussels and wastewater-treated effluents only. Total pyrethroid concentrations in sediments ranged from 0.04 to 1.95 ng/g dry weight in the Punta Banda estuary (n = 13) and from 0.07 to 6.62 ng/g dry weight in Todos Santos Bay (n = 19). Moreover, total pyrethroids in mussels ranged from 1.19 to 6.15 ng/g wet weight. Based on the toxic unit data calculated for pyrethroids and fipronil for Eohaustorius estuarius and Hyalella azteca, little to no impact is expected to the benthic population structure. Environ Toxicol Chem 2017;36:3057-3064. © 2017 SETAC.

Simultaneous determination of cis-permethrin and trans-permethrin in rat plasma and brain tissue using gas chromatography-negative chemical ionization mass spectrometry.

A sensitive method for the simultaneous determination of cis-permethrin (cis-PERM) and trans-permethrin (trans-PERM) in small volumes (100µL) of rat plasma and brain homogenate was developed, using a liquid-liquid extraction for sample preparation and gas chromatography-negative chemical ionization mass spectrometry (GCNCI-MS) for detection. Quantitation of trace levels of the insecticide in small volumes of biological samples is essential to support toxicokinetic studies in small animals. There are currently no validated methods in the literature for determining cis-PERM and trans- PERM in volumes as low as 100µL of rat plasma or brain homogenate. The method provided a linear range of 0.2-150.0ng/mL for analytes in both matrices. The intra- and inter-batch precision (as% relative standard deviation, RSD) and accuracy (as relative error, RE) of the method were better than 20% at the limit of quantitation and better than 15% across the remaining linear range. The validated method was applied in a toxicokinetic study in adult rats with oral dosing of 10mg/kg (cis-PERM) and 100mg/kg (trans-PERM) in corn oil. cis-PERM and trans- PERM were monitored in rat plasma and brain tissue samples for 6h following dosing, and both analytes were detected in all plasma and brain samples.

Do pyrethroid-resistant Hyalella azteca have greater bioaccumulation potential compared to non-resistant populations? Implications for bioaccumulation in fish.

The recent discovery of pyrethroid-resistant Hyalella azteca populations in California, USA suggests there has been significant exposure of aquatic organisms to these terrestrially-applied insecticides. Since resistant organisms are able to survive in relatively contaminated habitats they may experience greater pyrethroid bioaccumulation, subsequently increasing the risk of those compounds transferring to predators. These issues were evaluated in the current study following toxicity tests in water with permethrin which showed the 96-h LC50 of resistant H. azteca (1670 ng L-1) was 53 times higher than that of non-resistant H. azteca (31.2 ng L-1). Bioaccumulation was compared between resistant and non-resistant H. azteca by exposing both populations to permethrin in water and then measuring the tissue concentrations attained. Our results indicate that resistant and non-resistant H. azteca have similar potential to bioaccumulate pyrethroids at the same exposure concentration. However, significantly greater bioaccumulation occurs in resistant H. azteca at exposure concentrations non-resistant organisms cannot survive. To assess the risk of pyrethroid trophic transfer, permethrin-dosed resistant H. azteca were fed to fathead minnows (Pimephales promelas) for four days, after which bioaccumulation of permethrin and its biotransformation products in fish tissues were measured. There were detectable concentrations of permethrin in fish tissues after they consumed dosed resistant H. azteca. These results show that bioaccumulation potential is greater in organisms with pyrethroid resistance and this increases the risk of trophic transfer when consumed by a predator. The implications of this study extend to individual fitness, populations and food webs.

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.