Occurrence of Carbaryl, DDT and Deltamethrin Residues in Bovine Milk in Chhattisgarh, India and Risk Assessment to Human Health

The aim of this study was to determine the occurrence of pesticide residues in bovine milk and associated health risks in human. To assess the pesticide residues, a total of 200 milk samples were analyzed using High Performance Liquid Chromatography (HPLC) with Photo Diode Array Detector (PDA).The residues of carbaryl, 4’4’ DDT and deltamethrin pesticides were found in the 27.5%, 11% and 5% milk samples, respectively. The spatial distribution of pesticide residues in milk samples indicated that carbaryl was wide spread over the entire study area. The non-significance differences in mean residual concentrations of all three pesticides in cow and buffalo milk samples were recorded. The human health risk assessment in terms of non-carcinogenic and carcinogenic health hazard was calculated based on both lower bound [LB (mean residue levels)] and upper bound [UB (95th percentile level)] limits at current levels of pesticides in bovine milk samples. The estimated average daily dietary intake (EADDI) of studied pesticides was found below the acceptable dietary intake (ADI) for both adult and children, at mean as well as 95th percentile upper bound (UB) levels. The values suggesting lower carcinogenic and non-carcinogenic health risk to adult however children are at greater health risk.Keywords: Bovine milk, carbaryl, deltamethrin

Synergists action of piperonyl butoxide and S,S,S-tributyl phosphorotrithioate on toxicity of carbamate insecticides against Blattella germanica

Objective To determine the synergists action of piperonyl butoxide (PBO) and S,S,S-tributyl phosphorotrithioate (DEF) on toxicity of carbamate insecticides against Blattella germanica in Tehran city. Methods In the current study, German cockroach strains were collected from several hospitals and dormitories in Tehran. At the beginning, different concentrations of bendiocarb and carbaryl (insecticides belong to carbamate group) were determined by surface contact on a susceptible strain. Then, the level of susceptibility and type of resistance mechanisms in the collected strains from contaminated sites to the aforementioned insecticides were studied by using PBO and DEF synergists with different insecticide ratios to synergist (1:0, 1:1, 1:2, 1:3). Results The DEF synergist along with bendiocarb and carbaryl completely eliminated the resistance in all strains but PBO did not completely eliminate the resistance in the strains of Mofid, Alvand, Valiasr hospitals and Shariati dormitory. Generally, the impact of DEF was observed in the removing resistance more than PBO. Conclusions In most of these strains, resistance to bendiocarb and carbaryl is completely eliminated by DEF, showing a very high role of estraze enzymes in resistance to bendiocarb and carbaryl. But in most strains PBO does not remove the resistance because other mechanisms, such as reduced cuticle penetration and insensitivity to the acetylcholine esterase enzyme, may be involved.

Synergists action of piperonyl butoxide and S,S,S-tributyl phosphorotrithioate on toxicity of carbamate insecticides against Blattella germanica

OBJECTIVE@#To determine the synergists action of piperonyl butoxide (PBO) and S,S,S-tributyl phosphorotrithioate (DEF) on toxicity of carbamate insecticides against Blattella germanica in Tehran city.@*METHODS@#In the current study, German cockroach strains were collected from several hospitals and dormitories in Tehran. At the beginning, different concentrations of bendiocarb and carbaryl (insecticides belong to carbamate group) were determined by surface contact on a susceptible strain. Then, the level of susceptibility and type of resistance mechanisms in the collected strains from contaminated sites to the aforementioned insecticides were studied by using PBO and DEF synergists with different insecticide ratios to synergist (1:0, 1:1, 1:2, 1:3).@*RESULTS@#The DEF synergist along with bendiocarb and carbaryl completely eliminated the resistance in all strains but PBO did not completely eliminate the resistance in the strains of Mofid, Alvand, Valiasr hospitals and Shariati dormitory. Generally, the impact of DEF was observed in the removing resistance more than PBO.@*CONCLUSIONS@#In most of these strains, resistance to bendiocarb and carbaryl is completely eliminated by DEF, showing a very high role of estraze enzymes in resistance to bendiocarb and carbaryl. But in most strains PBO does not remove the resistance because other mechanisms, such as reduced cuticle penetration and insensitivity to the acetylcholine esterase enzyme, may be involved.

Carbaryl degradation by bacterial isolates from a soil ecosystem of the Gaza Strip

Abstract Carbaryl is an important and widely used insecticide that pollutes soil and water systems. Bacteria from the local soil ecosystem of the Gaza Strip capable of utilizing carbaryl as the sole source of carbon and nitrogen were isolated and identified as belonging to Bacillus, Morganella, Pseudomonas, Aeromonas and Corynebacterium genera. Carbaryl biodegradation by Bacillus, Morganella and Corynebacterium isolates was analyzed in minimal liquid media supplemented with carbaryl as the only source of carbon and nitrogen. Bacillus and Morganella exhibited 94.6% and 87.3% carbaryl degradation, respectively, while Corynebacterium showed only moderate carbaryl degradation at 48.8%. These results indicate that bacterial isolates from a local soil ecosystem in the Gaza Strip are able to degrade carbaryl and can be used to decrease the risk of environmental contamination by this insecticide.

Determination of Trace Carbaryl in Water by Europium-Diallyl Phthalate Fluorescent Probe / 分析化学

A rapid and sensitive method for the determination of trace carbaryl in water by using diallyl phthalate-europium ( Eu3+) as fluorescent probes was developed. The interaction between Eu3+ and diallyl phthalate and carbaryl was studied by high resolution mass spectrum, and the fluorescence spectra change of complexes before/after binding with carbaryl was also investigated. The influence factors of fluorescence intensity including solution pH and interferent were studied. The results showed that two diallyl phthalate molecules were complexed with one Eu3+to form stable complexes. Carbaryl could also interact with the probe to form multiple complexes, which significantly increased the fluorescent efficiency of the probe. At pH 9. 0 of solution and by using 245/615 nm as excitation/emission wavelength, the fluorescence intensity showed good linear relationship with the carbaryl concentration ranged from 6. 25í10-8 mol/L to 2. 50í10-6 mol/L, and the linear correlation coefficient was 0. 9968. The detection limit of the method was 9. 6í10-9 mol/L. Water samples were extracted by acetonitrile, and then detected by europium ( Eu3+)-diallyl phthalate fluorescent probe. The recovery of the method was 91. 8%-94. 5%, while RSD was within 6. 1%. The method is suitable for the rapid determination of carbaryl in water samples.

Avaliação de melanócitos humanos expostos ao inseticida carbaril e à radiação solar em cultura / Evaluation of cultured human melanocytes exposed to carbaryl insecticide and solar radiation

O carbaril (metilcarbamato de naftila), um inseticida de amplo espectro, foi recentemente associado ao desenvolvimento de melanoma cutâneo em estudo epidemiológico de coorte com trabalhadores agrícolas norte-americanos, expostos também à radiação solar, o principal fator etiológico para o desenvolvimento de tumores cutâneos. Apesar de abrangente e bem planejado, aquele estudo epidemiológico não é suficiente para caracterizar a contribuição direta do inseticida e da radiação solar na melanomagênese. Diversos estudos têm explorado o efeito sinérgico de determinadas substâncias químicas à radiação UV, potencializando seus efeitos deletérios sobre a pele, e possivelmente contribuindo para o desenvolvimento de tumores. A hipótese deste trabalho é de que a exposição ao carbaril associada à radiação solar possa estimular a transformação de melanócitos. Esse estudo visou caracterizar melanócitos humanos após exposição individual ou combinada ao carbaril (100uM) e à radiação solar (375 mJ/ cm2). Em ensaio de microarray, o carbaril, mas não a radiação solar, induziu uma importante resposta a estresse oxidativo, evidenciada pelo aumento da expressão de genes antioxidantes, como o Hemeoxigenase-1 (HMOX1), e pela diminuição da expressão do gene MiTF, regulador da atividade melanocítica; os resultados foram confirmados por qRT-PCR. Além disso, tanto o carbaril quanto a radiação solar induziram respostas que sugerem dano ao DNA e alteração de ciclo celular. A expressão dos genes nestas categorias, como p21 e BRCA1/2, foi notavelmente mais intensa no grupo de tratamento combinado e de fato, ensaios por citometria de fluxo demonstraram parada de ciclo celular na fase S, redução do número de células em apoptose e indução mais rápida de lesões do tipo CPD neste grupo experimental. Nossos dados sugerem que o carbaril é genotóxico para melanócitos humanos, especialmente quando associado à radiação solar

Carbaryl (1-naphthyl-methylcarbamate), a broad spectrum insecticide, has recently been associated with the development of cutaneous melanoma in an epidemiological cohort study with U.S. farm workers also exposed to ultraviolet radiation, which is known to be the main etiologic factor for skin carcinogenesis. Although comprehensive and well designed, the epidemiological study is not sufficient to characterize the direct contribution of the insecticide and solar radiation in melanomagenesis. Several studies have explored the synergistic effect of certain chemicals with UV radiation, increasing its deleterious effects on the skin, possibly contributing to tumor development. We hypothesized that Carbaryl exposure associated with UV solar radiation may induce melanocyte transformation. This study aims to characterize human melanocytes after individual or combined exposure to Carbaryl (100uM) and solar radiation (375 mJ/ cm2). In a microarray analysis, Carbaryl, but not solar radiation, induced an important oxidative stress response, evidenced by the upregulation of antioxidant genes, such as Hemeoxygenase-1 (HMOX1), and downregulation of MiTF, the main regulator of melanocytic activity; results were confirmed by qRT-PCR. Moreover, both Carbaryl and solar UV induced a gene response that suggests DNA damage and cell cycle alteration. The expression of genes in these categories, such as p21 and BRCA1/2, was notably more intense in the combined treatment group in an additive manner and in fact, flow cytometry assays demonstrated cell cycle arrest in S phase, reduced apoptosis induction and faster induction of CPD lesions in this experimental group. Our data suggests that carbaryl is genotoxic to human melanocytes, especially when associated with solar radiation

Effect of carbaryl on biochemical contents in Escherichia coli and soil isolate Pseudomonas aeruginosa.

The wide use of carbamate pesticides in agriculture has persuaded the rapid evolution and dissemination of specific degradative pathways for the compound in soil bacteria. Carbamate insecticide, carbaryl (1-naphthyl-Nmethylcarbamate), is highly toxic with a wide range of activity and known to be metabolized by microorganisms belonging to a variety of bacterial genera by interacting with different components, thereby impairing the physiological and metabolic activities of the cell. To evaluate its toxicity, the present study was undertaken by using increasing concentrations of carbaryl (10-8 to 10-2M) and evaluated for its toxicity to Escherichia coli with emphasis on biochemical contents such as DNA, RNA, protein, glucose utilization, growth and was further compared to the soil isolate- Pseudomonas aeruginosa at a given periods of 24 -72 hrs respectively. The results indicated that carbaryl treated groups exhibited a significant (P ≤ 0.05) decrease in the levels of biochemical contents and increase in the % inhibition in these parameters was observed with an increase in dose and durational exposure to carbaryl when compared to the controls. While, in assessment with its free corresponding, the activity was less in immobilized Escherichia coli cells enlightening that immobilized system is less responsive to carbaryl. Present study suggested that carbaryl is a toxicant affecting the synthesis of biochemical contents and growth in a dose and dependent manner and alterations in the parameters of Escherichia coli and Pseudomonas aeruginosa on exposure to carbaryl are can be due to carbaryl intoxication.

Effects of granulated baits on meso and macrofauna in soybean soil system.

Studies were done to see the effects of five toxic baits based on metaldehyde and/or carbaryl on the taxonomic composition of soil meso and macrofauna, and determined the density of beneficial organisms in soybean under no tillage. Six treatments were tested and soil monoliths were taken before application and at 45 and 75 days after application (DAA). Before application, 1601 individuals were recorded, belonging 1086 to mesofauna and 515 to macrofauna. In soil mesofauna such as Annelida: Enchytraeidae (44%), Nematoda (33%) and Arthropoda (23%) were found. In the macrofauna Arthropoda 93% and Annelida: Oligochaeta, Megadrilli 7% were observed. No differences were observed among the treatments (p>0.05) in the total mesofauna density, at 45 and 75 DAA. The density of enchytraeids, mites, collembolans and symphylids showed no differences at 45 and 75 DAA (p>0.05). The total macrofauna density showed differences (p<0.05) at 45 and 75 DAA. The highest density was obtained with 4 kg ha-1 MataBibos Acay at 45 and 75 DAA. Earthworm and diplopod densities at 45 and 75 DAA showed no differences (p>0.05). The diversity of meso and macrofauna was not affected at 45 and 75 DAA. Bait application did not affect either the abundance or the diversity of soil beneficial invertebrates.

Sub-lethal impact of carbaryl on food utilization in the freshwater prawn Macrobrachium malcolmsonii.

This study determines the toxic effect of carbaryl (Sevin® 50% W.P) on the food utilization parameters in intermoult juveniles of the prawn, Macrobrachium malcolmsonii. The prawns (4.5-5.0 cm in length and 1.0- 1.25 g wet wt.) were exposed to three sub-lethal concentrations of carbaryl (5.15, 7.73 and 15.47 μg l-1) for duration of 40 days. The toxic medium was renewed daily. The prawns were fed ad libitum with known energy quantity of boiled goat liver on daily basis. The overall wet weight gain was calculated. The energy lost through unconsumed food (15-60%), faeces (15-109%), ammonia excretion (9-27%) and moults (13-26%) of the prawns were calculated. The feeding rate, the rate and efficiency of absorption, the metabolic and food conversion rates and the gross and net food conversions efficiencies were found to be significantly declined (p<0.05) in test prawns when compared to that of the control. The energy lost through faeces, ammonia excretion and exuvia was found to be significantly elevated (p<0.05) in test prawns than that of the control. The effect of carbaryl on the bioenergetics parameters was severe in the highest sub-lethal concentration, less in the intermediate concentration and least in the lowest sub-lethal concentration. The results indicated that decrease in feeding, absorption, metabolism and food conversion are interdependent and toxicity of carbaryl diverting energy from production to maintenance pathways, which ultimately resulting in declined growth of M. malcolmsonii.

Evaluation of carbamate insecticides as chemotherapeutic agents for cancer.

Background: Cancer chemotherapy has already been in practice by the use of toxins and some of the specific poisonous compounds of cyanide derivatives. Carbamate insecticides inhibit cellular metabolism including energy, protein, and nucleic acid metabolism, thereby, causing cell regression and death. Aim: Preliminary evaluation of three carbamate insecticides, namely, baygon, carbaryl, and carbofuran as chemotherapeutic agents for cancer is undertaken in the present study. Materials and Methods: The toxicity of carbamates on squamous cell carcinoma was assessed in-vitro using dye binding tests. Cells were grown in microtitration ELISA plates, as adherent cultures, for six hours, and then exposed to the drugs for 2, 4, 8, and 12 hours, and finally stained with neutral red, to assess the viable cell number, and with methylene blue for the determination of protein in the monolayer. Optical density was read in an ELISA reader. Statistical Analysis: The data obtained during the experiment was subjected to statistical analysis by using the student 't' test. Results: The results indicated that the percentage of the viable cell number reduced with an increase in the time of exposure of the drugs. Exposure of the tumor cells to the drugs for 12 hours detached them completely from the wells, and hence, all the cells were washed out. Exposure of the drugs prior to the establishment of the culture in-vitro resulted in the non-formation of the monolayer in the wells. Conclusions: Among the three drugs studied, the survival percent was least with carbaryl treatment followed by baygon, and with carbofuran treatment it was almost near to control group.

Manifestation of carbaryl toxicity on soluble protein and histopathology in the hepatopancreas and gills of the prawn, Macrobrachium malcolmsonii.

The present study examined alterations in the protein pattern and histopathology of the hepatopancreas and gills of Macrobrachium malcolmsonii following exposure to Sevin®, the commercial grade of carbaryl (1-Naphthylmethyl carbamate) pesticide. Juvenile prawns were exposed to sub-lethal concentrations 5.15 'g l-1, 7.73 'g l -1and 15.47 'g l -1of carbaryl for 21 days. Samples were obtained from the hepatopancreas and gills of prawns. The concentration of buffer soluble protein in tissues of test prawns was significantly (p<2.5%) lower than the control. This suggests that proteins were utilized to generate energy in order to withstand carbaryl induced toxic stress. Polypeptide bands of different molecular mass (150 - 10 kDa) in tissues of test prawns stained less intensely than those in control. This indicates that carbaryl toxicity caused protein degradation in tissues of test prawns. The histology of the hepatopancreas and gills showed few marked pathological changes in prawns exposed to carbaryl. These include rupture of the basal laminae, abnormal infiltration / aggregation of hemocytes in the interstitial sinus of the hepatopancreas and in the hemocoelic space of gill lamellae, fused gill lamellae and necrosis like appearance both in the tubules of the hepatopancreas and gill lamellae. The structural alterations observed in the hepatopancreas and gills of the prawns suggest that carbaryl caused tissue damage in M. malcolmsonii. Protein degradation is a phenomenon in damaging tissues, and thus, under such condition the hepatopancreas and gills of test prawns would not perform their vital functions, which in turn ultimately affect the survival and growth of M. malcolmsonii. The changes noted in protein and histology of test prawns can be taken as biomarkers for monitoring pesticide pollution in aquatic environments. Since this species of prawn is a nutritious delicacy to human being, monitoring aquatic pollution by carbaryl is warranted.

Evaluación de riesgo por plaguicidas sobre aguas superficiales de la región norpatagónica argentina / Assessing pesticide hazards on surface water from the northern patagonian region argentina

Aunque el manejo integrado de plagas se aplica en forma creciente en la Región Norpatagónica, todavía una amplia gama de plaguicidas es utilizada con el fin de controlar apropiadamente las principales plagas agrícolas. Otros agroquímicos también son aplicados en las actividades industriales asociadas. El objetivo del presente trabajo es evaluar el impacto potencial causado por estos plaguicidas sobre los organismos acuáticos y para ello se utilizan datos bibliográficos de toxicidad aguda y resultados analíticos locales. Se utilizó un procedimiento escalonado, permitiendo la selección de aquellos xenobióticos ambientales que justificarían un estudio de ecotoxicidad posterior. Los residuos máximos de metil azinfos (S-(3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazin-3-ylmethyl)O,O-dimethyl phosphordithioate), indican la probabilidad de efectos agudos en el 37% de las especies estudiadas en el río, principalmente peces y zooplancton. Este valor se incrementa en los drenajes hasta un 42%. En el caso del carbaril (1-napthylmethylcarbamate) los residuos encontrados en drenajes afectarían al 14% de las especies estudiadas, mientras que en el río el impacto es despreciable.

Although the Integrated Pest Management (IPM) is increasingly being applied in the Northern Patagonia Region, different pesticides are still used in order to properly control agricultural pests. Other agrochemicals are also applied in the agriculture associated activities like conservation and packaging industries. The potential impact caused by these pesticides on aquatic organisms is assessed in the present study by means of acute toxicity data available in the literature and local analytical results. A tiered procedure was used allowing the selection of those environmental xenobiotics that need further ecotoxicity studies. The observed maximum residues of azinphos-methyl, (S-(3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazin-3-ylmethyl) O,O-dimethyl phosphordithioate), indicate the probability of acute effects in 37 % of the studied species in the river, mainly fish and zooplankton.This value increased in drainage channels samples up to 42 %. Additionally, carbaryl (1-napthylmethylcarbamate) residues foundin drainage channels affect 14 % of the studied species, while in the river samples the impact was negligible.

Gene expression of acetylcholinesterase in hybrid catfish (Clarias gariepinus X Clarias macrocephalus) exposed to chlorpyrifos and carbaryl.

After serving as a neurotransmitter, acetylcholine is hydrolyzed by acetylcholinesterase (AChE). Inhibition of AChE is considered to be a specific biomarker for exposure to organophosphate and carbamate insecticides. In this study, the AChE gene was isolated from hybrid catfish brain by RT-PCR methods using degenerate primers. The amplified fragment of 966 nucleotides generated by PCR was cloned, and sequence analysis showed 82% nucleotide identity with AChE of the Electrophorus electricus. Specific primers of the hybrid catfish AChE gene were then synthesized and used in the examination of AChE gene expression in brain tissue of hybrid catfish exposed to sublethal concentrations of chlorpyrifos (0.43, 4.3 and 43 2M) and carbaryl (1.19, 11.9 and 119 2M) for 24 hr. Real-time PCR was used to compare with the amplified 28S rRNA gene. AChE gene expression was significantly elevated 12.4 times in catfish exposed to 43 2M chlorpyrifos in comparison to the control group (p<0.05). Carbaryl did not produce any significant change. These results indicate that AChE is more sensitive to administration of chlorpyrifos than carbaryl. The induction of the AChE gene indicates the possibility of using this gene as biomarker for detecting effects of organophosphate insecticides in hybrid catfish.

Validation of an electrometric blood cholinesterase measurement in goats

A modified electrometric method was described and validated for measurement of plasma and erythrocyte cholinesterase activities in 6~18 months old goats. The enzymatic reaction mixture contained 3 ml distilled water, 3 ml barbital-phosphate buffer (pH 8.1), 0.2 ml plasma or erythrocytes and 0.1 ml acetylthiocholine iodide (7.5%) as a substrate. The mixture was incubated at 37 degrees C for 40 minutes. The pH of the reaction mixture was determined by a pH meter before and after the incubation. The initial pH was measured before the substrate addition. The enzyme activity was expressed as deltapH/40 min. The coefficients of variation of the described method in measuring plasma and erythrocyte cholinesterase activities were 4 and 2%, respectively. Preliminary reference values (n = 14) of the mean cholinesterase activity (deltapH/40 min) and 95% confidence interval in the plasma were 0.194 and 0.184~ 0.204, respectively, and those of the erythrocytes were 0.416 and 0.396~0.436, respectively. The pseudocholinesterase activity of the plasma cholinesterase was 63.5% as determined by quinidine sulfate inhibition. The organophosphorus insecticides dichlorvos and diazinon at 0.5~4 micrometer and the carbamate insecticide carbaryl at 5~20 micrometer in the reaction mixture significantly inhibited plasma (13.7~85.5%) and erythrocyte (16.4~71.9%) cholinesterases in vitro in a concentration-dependent manner. The results suggest that the described electrometric method is simple, precise and efficient in measuring blood cholinesterase activity in goats.