Au-Ag OHCs-based SERS sensor coupled with deep learning CNN algorithm to quantify thiram and pymetrozine in tea.

Pesticide residue detection in food has become increasingly important. Herein, surface-enhanced Raman scattering (SERS) coupled with an intelligent algorithm was developed for the rapid and sensitive detection of pesticide residues in tea. By employing octahedral Cu2O templates, Au-Ag octahedral hollow cages (Au-Ag OHCs) were developed, which improved the surface plasma effect via rough edges and hollow inner structure, amplifying the Raman signals of pesticide molecules. Afterward, convolutional neural network (CNN), partial least squares (PLS), and extreme learning machine (ELM) algorithms were applied for the quantitative prediction of thiram and pymetrozine. CNN algorithms performed optimally for thiram and pymetrozine, with correlation values of 0.995 and 0.977 and detection limits (LOD) of 0.286 and 29 ppb, respectively. Accordingly, no significant difference (P greater than 0.05) was observed between the developed approach and HPLC in detecting tea samples. Hence, the proposed Au-Ag OHCs-based SERS technique could be utilized for quantifying thiram and pymetrozine in tea.

Highly sensitive SERS detection in a non-volatile liquid-phase system with nanocluster-patterned optical fiber SERS probes.

The use of surface-enhanced Raman scattering (SERS) spectroscopy for the detection of substances in non-volatile systems, such as edible oil and biological cells, is an important issue in the fields of food safety and biomedicine. However, traditional dry-state SERS detection with planar SERS substrates is not suitable for highly sensitive and rapid SERS detection in non-volatile liquid-phase systems. In this paper, we take contaminant in edible oil as an example and propose an in situ SERS detection method for non-volatile complex liquid-phase systems with high-performance optical fiber SERS probes. Au-nanorod clusters are successfully prepared on optical fiber facet by a laboratory-developed laser-induced dynamic dip-coating method, and relatively high detection sensitivity (LOD of 2.4 × 10-6 mol/L for Sudan red and 3.6 × 10-7 mol/L for thiram in sunflower oil) and good reproducibility (RSD less than 10%) are achieved with a portable Raman spectrometer and short spectral integration time of 10 s even in complex edible oil systems. Additionally, the recovery rate experiment indicates the reliability and capability of this method for quantitative detection applications. This work provides a new insight for highly sensitive and rapid SERS detection in non-volatile liquid-phase systems with optical fiber SERS probes and may find important practical applications in food safety and biomedicine.

Chlorogenic acid suppresses miR-460a in the regulation of Bcl-2, causing interleukin-1ß reduction in thiram exposed chondrocytes via caspase-3/caspase-7 pathway.

BACKGROUND: Apoptosis is thought to be involved in all processes, including normal cell cycle, immune system, atrophy, embryonic development, and chemical-induced cellular damage. However, if the normal apoptotic process fails, the results might be disastrous, e.g., chondrocytes damage in tibial dyschondroplasia (TD). TD is a worldwide issue in the poultry sector due to thiram toxicity. Thiram (Tetramethyl thiuram disulfide) is a dithiocarbamate pesticide and fungicide commonly used in horticulture to treat grains meant for seed protection and preservation. PURPOSE: According to prior studies, chlorogenic acid (CGA) is becoming essential for regulating apoptosis. But still, the specific role of CGA in chondrocyte cells remains unclear. The present study explored the molecular mechanism of CGA on chondrocytes' apoptosis with B-cell lymphoma 2 signaling under the effect of miR-460a. METHODS: An in vivo and in vitro study was performed according to our previously developed methodology. Flow cytometry, western blotting, reverse transcription-quantitative polymerase chain reaction, and immunofluorescence assay were used to investigate the involvement of apoptosis and inflammasome related pathways. RESULTS: The CGA decreased the apoptosis rate with the deactivation of miR-460a, accompanied by the activation of Bcl-2. The high expression of miR-460a reduced the cell viability of chondrocytes in vitro and in vivo, that led to the interleukin-1ß production. While the apoptotic executioners (caspase-3 and caspase-7) acted upstream in miR-460a overexpressing cells, and its depletion downgraded these executioners. The CGA administrated cells negatively regulated miR-460a expression and thus indicating the deactivation of the apoptotic and inflammasome related pathways. CONCLUSION: Chlorogenic acid had a negative effect on miR-460a, setting off specific feedback to regulate apoptotic and inflammasome pathways, which might be a key feature for chondrocytes' survival.

Chlorogenic acid suppresses mitochondrial apoptotic effectors Bax/Bak to counteract Nod-like receptor pyrin domain 3 (NLRP3) inflammasome in thiram exposed chondrocytes.

BACKGROUND: Tibial dyschondroplasia (TD) is a common disease characterized by proliferation and the deterioration of growth plate's chondrocytes due to widespread utilization of thiram in the agriculture and industrial sector. PURPOSE: In recent years, Nod-like receptor pyrin domain 3 (NLRP3) inflammasome has become a dilemma in the occurrence of many diseases. According to many research investigations, NLRP3 inflammasome has been linked to various diseases caused by pesticides and environmental toxins. Its involvement in such conditions opens up new treatment approaches. However, the role of the NLRP3 inflammasome in the development of TD is not fully understood under the impact of chlorogenic acid (CGA). METHODS: Chondrocytes were cultured with our previously developed methodology from growth plates. After morphological and molecular identification, chondrocytes were split into different groups to investigate the efficacy of chlorogenic acid. Cell apoptosis was determined through flow cytometry and Tunnel assay. Furthermore, RT-qPCR, immunofluorescence, and western blotting techniques were used to check marker genes and proteins expression. RESULTS: In thiram-induced TD, Bax/Bak activation persuade a parallel pathway, mediated by the NLRP3 base inflammasome. It is worth mentioning that the apoptotic executioners (caspase-3 and caspase-7) act upstream for inflammasome. Furthermore, chondrocytes' ability to undergo mitochondrial apoptosis was governed by anti-apoptotic members, e.g., Bcl-2 and Bcl-xl. Equilibrium of these anti-apoptotic proteins ensured appropriate regulation of apoptosis during the development and survival of chondrocytes. CONCLUSION: Chondrocytes have ability to undergo Bax/Bak-mediated apoptosis and generate pro-inflammatory signals, e.g., NLRP3 in thiram-induced TD. So, the Nod-like receptor pyrin domain 3 is the potential target to eliminate TD at all stages of pathology, while drugs, e.g., CGA, can significantly improve chondrocytes' survival by targeting these pro-inflammatory signals.

Hysteresis of heavy metals uptake induced in Taraxacum officinale by thiuram.

Dandelion (Taraxacum officinale) yields active substances frequently used in herbal medicinal preparations. Its plantations are exposed to fungal plagues which pose a threat to herbal crops. The aim of this study was to evaluate the long time effects of a fungicide thiuram on dandelion growth and photosynthesis. Additionally, the manganese, iron, copper, zinc, cadmium, and lead uptake and transport were also investigated. Plants were cultivated under greenhouse conditions by the pot method in a universal flowering soil. The elements content in soil and plants were determined by the HR-CS FAAS spectrometer. Thiuram concentrations were established by the HPLC. Those analyses showed that almost 80% of thiuram decomposed within two weeks of its application. The photosynthesis indicators suggested, that plants were in good conditions and the fungicide supplementation facilitated plant growth. The latter could be prompted by thiuram acting as a sulfur rich chemical micro fertilizer. The hypothesis, that thiuram significantly affects heavy metals interactions in dandelion was proved by the one-way analysis of variance. Notable, metals uptake did not completely recover after fungicide decomposition for all investigated elements except iron We suggest to define this chemically induced, time-dependent heavy metals migrations in the soil-plant system as hysteresis of heavy metals uptake.

Controlled bacteriostasis of tea polyphenol loaded ultrahigh molecular weight polyethylene with high crosslink density and oxidation resistance for total joint replacement.

To avoid catastrophic bacterial infection in prosthesis failure, ultrahigh molecular weight polyethylene (UHMWPE), a common bearing material of artificial joints, has been formulated with antibiotics to eliminate bacteria locally at the implant site. However, the pressing issues regarding cytotoxic effects and evolution of drug resistant bacteria necessitates the development of bio-friendly bacteriostat with long bacteriostatic efficacy. Herein, tea polyphenol extracted from nature source was introduced in UHMWPE as a biogenic antimicrobial. Controlled antimicrobial activity was achieved by chemical crosslinking to regulate the release of the tea polyphenol. In addition, the crosslinking efficiency of UHMWPE blends with high loaded tea polyphenol was significantly improved in comparison to radiation crosslinking. The immobilized tea polyphenols also enhanced the oxidation stability of the UHMWPE, which is essential to prolong the service life in vivo and the storage time in vitro. The blends presented good biocompatibility, despite cell repellent on the highly crosslinked surface. Chemically crosslinked tea polyphenol/UHMWPE exhibited feasible properties for total joint implants, which is promising for clinical application.

Core size optimized silver coated gold nanoparticles for rapid screening of tricyclazole and thiram residues in pear extracts using SERS.

Silver-coated gold nanoparticles (Au@AgNPs) were optimized with different gold (Au) core sizes and modified surface with mercaptooctane (MCO) to determine fungicide residues in pear fruit extracts. The developed MCO/Au@AgNPs with a gold core size of 28 nm and silver shell thickness of 6 nm exhibited high sensitivity and significant enhancement of Raman scattering in detecting tricyclazole (TCZ) and thiram fungicides in standard and pear fruit samples. The detection limits for TCZ and thiram in the pear fruit extracts were 0.005 and 0.003 ppm with coefficients of determination of (R2) of 0.9984 and 0.9971, percent recovery ranging from 82.7 to 107.4% and 80.7 to 109.8%, and relative standard deviation (RSD) of 1.5 to 7.9% and 3.7 to 9.5%, respectively. Results showed that this easily prepared method could be employed as SERS active platforms for the rapid assessment of trace contaminants of agrochemicals in agriculture production.

Lactobacillus rhamnosus JYLR-005 Prevents Thiram-Induced Tibial Dyschondroplasia by Enhancing Bone-Related Growth Performance in Chickens.

Tibial dyschondroplasia (TD) is a leg disorder caused by the abnormal development of the tibia in fast-growing poultry. Lactobacillus rhamnosus (L. rhamnosus) strains have been reported to have effects on increasing bone growth and improving osteoporosis in animals. However, whether L. rhamnosus JYLR-005 can improve bone growth in TD chickens remains unclear. In this study, we noted that L. rhamnosus JYLR-005 could not reduce the suppression of the production performance of TD broilers (p > 0.05) but had a slight protective effect on the broiler survival rate (χ2 = 5.571, p = 0.062). However, for thiram-induced TD broiler chickens, L. rhamnosus JYLR-005 could promote tibia growth by increasing tibia-related parameters, including the tibia weight (day 11, p = 0.040), tibia length (day 15, p = 0.013), and tibia mean diameter (day 15, p = 0.035). Moreover, L. rhamnosus JYLR-005 supplementation improved the normal growth and development of the tibial growth plate by maintaining the morphological structure of the chondrocytes and restored the balance of calcium and phosphorus. Taken together, these findings provide a proof of principle that L. rhamnosus JYLR-005 may represent a therapeutic strategy to treat leg disease in chickens.

Ameliorative effect of naringin against thiram-induced tibial dyschondroplasia in broiler chicken.

Tetramethyl thiuram disulfide (thiram) is widely used in agricultural production as an insecticide and fungicide, which can also lead to tibial dyschondroplasia (TD) in poultry. TD is characterized by leg disorders and growth performance retardation, and no targeted drugs have been found to treat TD until now. Therefore, the objective of the present study was to explore the ameliorative effect of traditional Chinese medicine naringin on thiram-induced TD chickens. A total of 180 one-day-old Arbor Acres (AA) broiler chickens were randomly divided into three equal groups (n = 60): control group (standard diet), thiram-induced group (thiram 50 mg/kg from day 3 to day 7), and naringin-treated group (naringin 30 mg/kg from day 8 to day 18). During the 18-day experiment, the growth performance, tibial bone parameters, antioxidant property of liver, serum biochemical changes and clinical symptoms were recorded to evaluate the protective effect of naringin in thiram-induced TD broiler chickens. Additionally, mRNA expressions and protein levels of Ihh and PTHrP genes were determined via quantitative real-time polymerase chain reaction and western blot. Administration of naringin showed significant results by alleviating lameness, increased growth performance, recuperated growth plate (GP) width, and improved functions and antioxidant enzyme level of liver in broilers affected by TD. Moreover, naringin treatment restored the development of damaged tibia bone via downregulating Ihh and upregulating PTHrP mRNA and protein expressions. In conclusion, our study determines naringin could be used as an effective medicine to treat TD.

Plastrum Testudinis Extract Mitigates Thiram Toxicity in Broilers via Regulating PI3K/AKT Signaling.

Tibial dyschondroplasia (TD) negatively affects broilers all over the world, in which the accretion of the growth plate (GP) develops into tibial proximal metaphysis. Plastrum testudinis extract (PTE) is renowned as a powerful antioxidant, anti-inflammatory, and bone healing agent. The current study was conducted to evaluate the efficacy of PTE for the treatment of thiram-induced TD chickens. Broilers (day old; n = 300) were raised for 3 days with normal feed. On the 4th day, three groups (n = 100 each) were sorted, namely, the control (normal diet), TD, and PTE groups (normal diet+ thiram 50 mg/kg). On the 7th day, thiram was stopped in the TD and PTE group, and the PTE group received a normal diet and PTE (30 mg/kg/day). Plastrum testudinis extract significantly restored (p < 0.05) the liver antioxidant enzymes, inflammatory cytokines, serum biochemicals, GP width, and tibia weight as compared to the TD group. The PTE administration significantly increased (p < 0.05) growth performance, vascularization, AKT (serine/threonine-protein kinase), and PI3K expressions and the number of hepatocytes and chondrocytes with intact nuclei were enhanced. In conclusion, PTE has the potential to heal TD lesions and act as an antioxidant and anti-inflammatory drug in chickens exposed to thiram via the upregulation of AKT and PI3K expressions.

Chlorogenic Acid Alleviates Thiram-Induced Tibial Dyschondroplasia by Modulating Caspases, BECN1 Expression and ECM Degradation.

Chlorogenic acid (CGA) is a widely applied traditional Chinese medicine ingredient which can be used for the treatment of osteoporosis. In this experiment, we investigated the potential therapeutic effect of chlorogenic acid on thiram-induced tibial dyschondroplasia (TD) and explored the underlying mechanisms that have been rarely mentioned by others yet. Performance indicator analysis and tibial parameter analysis showed that CGA exhibited a definite positive effect on thiram-induced TD chickens. In order to further explore the mechanisms underlying the positive actions of CGA, apoptotic, autophagic genes and MMPs involved in matrix mineralization of growth plate were evaluated in this study. The results showed that CGA decreased the expression of pro-apoptotic genes caspases-3 and caspases-9, leading to the reduction of apoptotic cells accumulated in growth plate. In addition, CGA also increased the level of BECN1, an important gene involved in autophagy, which benefits the survival of abnormal cells. Furthermore, CGA also increased the expression of MMP-9, MMP-10, and MMP-13, which can directly affect the ossification of bones. Altogether, these results demonstrate that CGA possesses a positive therapeutic effect on thiram-induced TD via modulating the expression of caspases and BECN1 and regulating the degradation of ECM (extracellular matrix).

Clinical efficiency and safety of Hsp90 inhibitor Novobiocin in avian tibial dyschondroplasia.

Tibial dyschondroplasia (TD) is a bone defect of broilers and other poultry birds that disturbs growth plate and it causes lameness. Previously we evaluated differential expression of multiple genes involved in growth plate angiogenesis and reported the safety and efficacious of medicinal plant root extracted for controlling TD. In this study, clinical and protective effect of an antibiotic Novobiocin (Hsp90 inhibitor) and expression of Hsp90 and proteoglycan aggrecan was examined. The chicks were divided into three groups; Control, thiram-induced TD, and Novobiocin injected TD. After the induction of TD, the Novobiocin was administered through intraperitoneal route to TD-affected birds until the end of the experiment. The expressions and localization of Hsp90 were evaluated by qRT-PCR, immunohistochemistry (IHC) and western blot, respectively. Morphological, histological examinations, and serum biomarker levels were evaluated to assess specificity and protective effects of Novobiocin. The results showed that TD causing retarded growth, enlarged growth plate, distended chondrocytes, irregular columns of cells, decreased antioxidant capacity, reduced protein levels of proteoglycan aggrecan, and upregulated in Hsp90 expression (p < 0.05) in dyschondroplastic birds as compared with control. Novobiocin treatment restored growth plate morphology, reducing width, stimulated chondrocyte differentiation, sprouting blood vessels, corrected oxidative imbalance, decreased Hsp90 expressions and increased aggrecan level. Novobiocin treatment controlled lameness and improved growth in broiler chicken induced by thiram. In conclusion, the accumulation of the cartilage and up-regulated Hsp90 are associated with TD pathogenesis and irregular chondrocyte morphology in TD is along with reduced aggrecan levels in the growth plate. Our results indicate that Novobiocin treatment has potential to reduce TD by controlling the expression of Hsp90 in addition to improve growth and hepatic toxicity in broiler chicken.

Evaluation of the Persistence and Leaching Behaviour of Thiram Fungicide in Soil, Water and Oil Palm Leaves.

The residual levels and persistence of thiram in the soil, water and oil palm seedling leaves were investigated under field conditions. The experimental plots were carried out on a clay loam soil and applied with three treatments namely; manufacturer's recommended dosage (25.6 g a.i. plot-1), manufacturer's double recommended dosage (51.2 g a.i. plot-1), and control (water) were applied. Thiram residues were detected in the soil from day 0 to day 3 in the range of 0.22-27.04 mg kg-1. Low concentrations of thiram were observed in the water and leave samples in the range of 0.27-2.52 mg L-1 and 1.34-12.28 mg kg-1, respectively. Results have shown that thiram has a rapid degradation and has less persistence due to climatic factors. These findings suggest that thiram is safe when applied at manufacturer's recommended dosage on oil palm seedlings due to low residual levels observed in soil and water bodies.

Photo-patch and patch tests in patients with dermatitis over the photo-exposed areas: A study of 101 cases from a tertiary care centre in India.

BACKGROUND: Many patients with dermatitis over photo-exposed body areas are positive to many contact allergens and have a pre-existing allergic contact dermatitis. METHODS: This study included patients who presented to a tertiary centre in India with dermatitis on photo-exposed body areas suspected of chronic actinic dermatitis. Their detailed histories were recorded and cutaneous and systemic examinations were performed. Patch testing was done in all the patients and photo-patch testing was carried out in 86 patients. RESULTS: Altogether 101 patients were included (69 males, 32 females). The most common presentation was lichenified hyperpigmented plaques on the photo-exposed sites. Photosensitivity was recorded in 64 (63%) patients and summer exacerbation in 52 (52%). Exposure to the Parthenium hysterophorus weed was recorded in 70 (69%) patients, 27 (26.7%) had a history of hair dye application and 20 (20%) had a history of atopy. Photo-patch test was positive in 11 (12.8%) patients and patch testing was positive in 71 (70%). Parthenium hysterophorus was the most common allergen implicated and was positive in three (4%) photo-patch and 52 (52%) patch tests. Other positive photo-patch test allergens were perfume mix, balsam of Peru, thiuram mix, Compositae mix and promethazine hydrochloride. Other common patch test allergens were parthenolide, colophony, fragrance mix and p-phenylenediamine (PPD) base. CONCLUSION: In the Indian population parthenium and perfume mix are the most common photoallergens in patients with dermatitis over photo-exposed areas, while parthenium, colophony, fragrance mix and PPD are the common positive allergens.

Comparative study of antifungal effect of green and chemically synthesised silver nanoparticles in combination with carbendazim, mancozeb, and thiram.

This study reports synthesis and characterisation of silver nanoparticles and their effect on antifungal efficacy of common agricultural fungicides. Silver nanoparticles were synthesised using biological and chemical reduction methods employing Elettaria cardamomum leaf extract and sodium citrate, respectively. Nanoparticles were then characterised using UV-Visible spectroscopy, X-ray diffraction (XRD), transmission electron microscopy, and dynamic light scattering (DLS). While XRD assigned particles size of 31.86 nm for green and 41.91 nm for chemical silver nanoparticles with the help of the Debye-Scherrer formula, DLS specified monodisperse nature of both suspensions. Nanoparticles were tested individually and in combination with fungicides (carbendazim, mancozeb, and thiram) against fungal phytopathogens. Silver nanoparticles exhibited good antifungal activity and minimum inhibitory concentration (MIC) was observed in the range of 8-64 µg/ml. Also, they positively influenced the efficacy of fungicides. The mean MIC value (mean ± SD) for combination of all three fungicides with green AgNPs was 1.37 ± 0.6 µg/ml and for chemical AgNPs was 1.73 ± 1.0 µg/ml. Hence, it could be concluded that green AgNPs performed better than chemical AgNPs. Synergy was observed between green AgNPs and fungicides against Fusarium oxysporum. In conclusion, this study reports synthesis of monodisperse silver nanoparticles which serve as efficient antifungal agents and also enhance the fungicidal action of reported agricultural fungicides in combination studies.

In Vitro Effect of Apigenin and Danshen in Tibial Dyschondroplasia Through Inhibition of Heat-Shock Protein 90 and Vascular Endothelial Growth Factor Expressions in Avian Growth Plate Cells.

Tibial dyschondroplasia (TD) is one of the common skeletal abnormalities in fast-growing birds, and it is characterized by nonvascularized, unmineralized, and nonviable cartilage in the tibial growth plate that fails to form bone. The aim of this study was to check the in vitro effect of apigenin and danshen on heat-shock protein 90 (Hsp90) and vascular endothelial growth factor (VEGF) expressions in avian growth plate cells treated with sublethal concentration of thiram. Initially, chondrocytes from chicken growth plates were isolated on culturx ed medium with and without various concentration of thiram to determine the sublethal dose. Then, to check the effect of apigenin and danshen, the chondrocytes were treated first with a sublethal (2.5 µM) concentration of thiram and then with different doses (10, 20, 40, and 80 µM) of apigenin and danshen. The mRNA expression levels of Hsp90 and VEGF genes were evaluated by quantitative reverse transcription polymerase chain reaction (RT-qPCR). The results showed that the expression levels of Hsp90 and VEGF mRNA transcripts were increased significantly (P < 0.05) in thiram-treated chondrocytes culture medium up to 1.5-fold, whereas apigenin and danshen therapy to chondrocytes in culture medium significantly (P < 0.05) reduced the Hsp90 and VEGF expression levels. In conclusion, up-regulation of both (Hsp90 and VEGF) genes and damage to chondrocytes in culture medium caused by thiram can be restored by using apigenin and danshen. Therefore, apigenin and danshen therapies are suggested and encouraged as a promising approach to control TD in broiler chickens.

Hsp90 inhibitor celastrol reinstates growth plate angiogenesis in thiram-induced tibial dyschondroplasia.

Tibial dyschondroplasia (TD) is an important long bone defect of broiler chickens that disturbs the proximal growth plate and is characterized by non-vascularized cartilage, a distended growth plate and lameness. Celastrol, a medicinal root extract from the plant Tripterygium wilfordii, is reported widely as a well-known heat-shock protein 90 (Hsp90) inhibitor. Recently, Hsp90 inhibition in chondrocyte differentiation and growth-plate vascularization were effective in restoring the morphology of the growth plate. The present study was aimed at investigating Hsp90 inhibition in TD using celastrol. The broiler chicks were divided into three groups; Control; TD induced (40 mg/kg thiram) and celastrol treatment. Hsp90, vascular endothelial growth factor and Flk-1 expressions were evaluated by quantitative real-time polymerase chain reaction and the protein levels of Hsp90 were measured by Western blot analysis. Antioxidant enzymes were determined to assess the liver damage caused by thiram and the protective effects of the medicine were evaluated by levels of serum biomarkers. The expression levels of Hsp90 and vascular endothelial growth factor mRNA transcripts were increased while Flk-1 receptor was decreased in TD-affected chicks. Celastrol therapy inhibited Hsp90 mRNA and protein levels and up-regulated the expressions of receptor Flk-1 in TD-affected tibial growth plates significantly (P < 0.05) in addition to rectifying the damaging effects of thiram on the liver by decreasing the levels of aspartate aminotransferase, alanine aminotransferase and malondialdehyde and correcting the oxidative imbalance. In conclusion, administering celastrol to dyschondroplastic chicks prevented un-vascularized growth plate, lameness and reinstated angiogenesis. Celastrol may be efficacious for the treatment of TD through the inhibition of Hsp90 expression and limiting the liver damage caused by thiram in broiler chickens.

Secondary production of freshwater zooplankton communities exposed to a fungicide and to a petroleum distillate in outdoor pond mesocosms.

Ecological risk assessment of chemicals in mesocosms requires measurement of a large number of parameters at the community level. Studies on invertebrate communities usually focus on taxonomic approaches, which only provide insights into taxonomic structure changes induced by chemicals. In the present study, abundance, biomass (B), theoretical production (P), and instantaneous P/B ratio were used as endpoints to assess the effects of the commercial form of the dithiocarbamate fungicide thiram (35 µg/L and 170 µg/L nominal concentrations) and of the hydrocarbon water accommodated fraction (HWAF) of a petroleum distillate (0.01 mg/L, 0.4 mg/L, 2 mg/L, and 20 mg/L loadings) on the zooplankton community in freshwater pond mesocosms. Endpoints were measured during a 4-wk treatment period (1 pulse/wk) followed by a 5-mo posttreatment period to evaluate zooplankton population recovery. The chlorophyll a concentration in water was significantly increased after treatment with HWAF, whereas it was not affected by thiram treatment. Zooplankton abundance-based analysis showed effects on a limited number of taxa, whereas other endpoints (mainly the P/B ratio) revealed that more taxa were impacted, with recovery depending on the chemical and concentration. Exposure to HWAF mainly had a negative impact on cladocerans, which resulted in top-down effects (between cladocerans and phytoplankton). Thiram negatively affected rotifers and copepods, suggesting more direct toxic effects. The results show that the use of secondary production as an endpoint provides a more comprehensive assessment of potential direct and indirect effects of chemicals on a community, and they also support evidence of alteration in functional processes.

Colorimetric determination of thiram based on formation of gold nanoparticles using ascorbic acid.

A novel optical method for the determination of thiram has been developed using surface plasmon resonance peak of gold nanoparticles (AuNPs). The stable and dispersed AuNPs were directly synthesized by reduction of HAuCl4 with ascorbic acid in micellar media according to a simple approach. The presence of thiram during formation of AuNPs results in the decrease of the intensity of plasmon resonance peak. The variation in the plasmon absorbance allows the colorimetric determination of thiram. The effect of different variables such as pH, ascorbic acid and CTAB concentrations was studied and optimized. The proposed method is capable of determining thiram over a range of 2.0×10(-7)-1.0×10(-5) mol L(-1) with a limit of detection 1.7×10(-7) mol L(-1). The relative standard deviation of the method was <3.7%. The method was successfully applied to the determination of thiram in water and plant seed samples.

Comparison of neem or oregano with thiram on organic matter decomposition of a sand loam soil amended with compost, and on soil biological activity.

BACKGROUND: Oregano essential oil and neem have been reported to be effective against soil-borne pathogens and nematodes. The possibility of having an effect on soil properties was the aim of this investigation. Moreover, thiram, a common widely used chemical pesticide, was used for comparison. RESULTS: The effects of all three above-mentioned substances were investigated during an incubation experiment, for 15 weeks. Crushed neem pellets were added at 1.0, 2.0 or 3.0 g per 50 g of soil. Oregano dry matter was applied at 0.2, 0.4 or 0.6 g per 50 g of soil. Finally, thiram was applied at 0.1, 0.2 and 0.3 g per 50 g of soil. The addition of neem resulted in a decrease in organic carbon mineralisation, higher than that of oregano, but not as prominently as thiram. The addition of neem resulted in an increase in the content of nitrate, organic P, bioavailable P, bioavailable K and bioavailable Mn. Oregano had a slight negative effect on organic matter biodegradation, but caused an increase of nutritional mineral elements. Microbe colonies in soil were increased by the addition of neem cake granules, whereas oregano and thiram treatments caused a decrease. The addition of thiram reduced nitrate and available Mn contents, but at the lowest dose increased organic P and available K. Thiram reduced prominently available Cu at the upper rates, but it increased these forms at the lowest rate, while available Zn content was increased in two lowest rates. CONCLUSION: The results of this study indicated that neem or oregano could be applied to the soil without any extremely negative effect on the available forms of nutritional mineral elements, as thiram does.