Chlorothalonil binding to aquatic humic substances assessed from gas purge studies

Abstract

Fate of the fungicide chlorothalonil (TCIN) binding to dissolved organic acid fractions was quantified using gas‐purge desorption studies. Binding studies were conducted to measure the dissolved organic carbon partition constant (K_DOC) with aquatic fulvic and humic acid fractions purified from cranberry bog water. Desorption studies at DOC concentrations up to 50 mg L^‐1 resulted in mean log K_DOC values of 4.63 (s.d.=0.5, n=8) and 4.81 (s.d.=0.7, n=7) for fulvic and humic acids, respectively. These values deviated from reported K_OC (organic carbon) values by 0.5 to 1.5 orders of magnitude. The relationship between K_OC and K_DOC did not conform to accepted ratios of 10: 1 to 3: 1, although these studies were conducted with the strong hydrophobic fraction of DOC. Binding was rapid suggesting hydrophobic partitioning or weak Van Der Waals forces as binding mechanisms. The strong binding potential for TCIN to aquatic humic substances corresponds to increased solubility in the aqueous system. Sorption to DOC suggests a possible transport mechanism which may result in elevated concentrations of TCIN in cranberry bog systems.     

Natural resistance of rose petals to microbial attack

Petals of red, yellow and white roses (Rosa damascene Mill.) of the family Rosaceae were extracted with (1:1) methylene chloride/methanol and tested for their antimicrobial activities against four species of Gram-positive bacteria (Bacillus cereus, Bacillus subtilis, Micrococcus luteus and Staphylococcus aureus), five species of Gram-negative bacteria (Enterobacter aerogenes, Escherichia coli, Klebsiella pneumonia, Pseudomonas aeruginosa and Serratia marcescens) and five species of fungi (Penicillium notatum, Aspergillus niger, Rhizopus stolonifer, Saccharomyces cerevisiae and Fusarium oxysporum). All of the crude extracts showed a wide range of antimicrobial activities according to the tested organism and rose's type. Micrococcus luteus was found to be the most susceptible bacteria to all crude extracts. Red and yellow petal extracts showed much higher antibacterial activity than the white petals extract. Bacillus subtilis was found to be the least susceptible to all extracts. The fungus, Penicillium notatum was found to be the most susceptible with white petal extract being the most effective. Saccharomyces cerevisiae and Fusarium oxysporum were the least susceptible to all extracts. White roses extract showed much higher antifungal activities against Penicillium notatum than red or yellow roses, therefore, it was subjected to several bioassay guided chromatographic fractionations and purification to isolate the active chemical(s) responsible for the antifungal activity. Chemical structure of the isolated antifungal compounds were identified by spectroscopy techniques and found to be a γ-sitosterol and (Z,Z)-9,12-octadecadienoic acid. Antibacterial activity of the various types of rose extracts were due to complex mixtures of organic compounds which are still under chemical investigation and will be published later.     

Determination of dithiocarbamate fungicide propineb and its main metabolite propylenethiourea in airborne samples

A simple, rapid and sensitive GC–MS method for the determination of dithiocarbamate fungicide propineb [polymeric zinc propylenebis (dithiocarbamate)] and an improved HPLC procedure for the simultaneous determination of its main metabolite, propylenethiourea, and ethylenethiourea, the main metabolite of all ethylenedithiocarbamates, in airborne samples are described. The method for the analysis of propineb involves the evolution of carbon disulfide (CS₂), under acidic conditions in the presence of stannous chloride, extraction of the generated CS₂ into a layer of isooctane which is then analyzed for CS₂ content by GC–MS in SIM mode. Under the optimum conditions, the retention time of CS₂ was 1.89 min and the total time of chromatographic analysis was 5 min. Recoveries from spiking glass microfibre filters (GF/A) and silica gel filters were 86 ± 7 (n = 9) and 89 ± 4 (n = 9), respectively. The limit of detection is 0.7 ng per filter, which is equivalent to about 0.8–1.0 ng m⁻³ in air. In parallel, an HPLC method with ultraviolet detection is presented for the simultaneous analysis of the metabolites. Separation of the two metabolites was attained in less than 5 min. Recoveries from spiking GF/A and silica gel filters for ethylenethiourea were 100 ± 1 (n = 3) and 98 ± 2 (n = 3), respectively, while for propylenethiourea were 102 ± 1 (n = 3) and 98 ± 1 (n = 3), respectively. The detection limits are about 36–43 and 40–49 ng m⁻³ in air for ethylenethiourea and propylenethiourea, respectively. All the analytes spiked in the filters are proven to be stable for more than one month, at −4 °C.     

Octachlorinated dioxin in pulps and effluents: Where does it come from?

Studies on the formation/destruction of dioxins associated with the pulping of wood artificially impregnated with an industrial grade of pentachlorophenol lend support to an earlier observation that ambient dioxins deposition may not necessarily be a unique source of the higher chlorinated dioxins occasionally found in pulps and final effluent discharges. These dioxins, which seemingly occur in products from a wide range of pulping technologies including recycle operations, may also originate from pentachlorophenol-based fungicides.     

Toxicity of metalaxyl,azoxystrobin, dimethomorph,cymoxanil, zoxamide and mancozeb to Phytophthora infestans isolates from Serbia

A study of the in vitro sensitivity of 12 isolates of Phytophthora infestans to metalaxyl, azoxystrobin, dimethomorph, cymoxanil, zoxamide and mancozeb, was conducted. The isolates derived from infected potato leaves collected at eight different localities in Serbia during 2005–2007. The widest range of EC₅₀ values for mycelial growth of the isolates was recorded for metalaxyl. They varied from 0.3 to 3.9 μg mL^?1 and were higher than those expected in a susceptible population of P. infestans. The EC₅₀ values of the isolates were 0.16–0.30 μg mL^?1 for dimethomorph, 0.27–0.57 μg mL^?1 for cymoxanil, 0.0026–0.0049 μg mL^?1 for zoxamide and 2.9–5.0 μg mL^?1 for mancozeb. The results indicated that according to effective concentration (EC₅₀) the 12 isolates of P. infestans were sensitive to azoxystrobin (0.019–0.074 μg mL^?1), and intermediate resistant to metalaxyl, dimethomorph and cymoxanil. According to resistance factor, all P. infestans isolates were sensitive to dimethomorph, cymoxanil, mancozeb and zoxamide, 58.3% of isolates were sensitive to azoxystrobin and 50% to metalaxyl. Gout's scale indicated that 41.7% isolates were moderately sensitive to azoxystrobin and 50% to metalaxyl.     

Fungicidal Impact on Chickpea–Mesorhizobium Symbiosis

Abstract

The effects of carbendazim, captan, thiram, and mancozeb, on plant vitality, chlorophyll content, N uptake, protein content, nodulation, and seed yield in chickpea (Cicer arietinum) were assessed in a controlled environment. Seeds treated with fungicides at 1 and 1.5 g. a.i./kg seed had no significant adverse effect on plant vigor, seed yield, and N and protein contents. In contrast, fungicides applied at 2 g. a.i./kg of captan, thiram and mancozeb, significantly reduced the measured parameters. In general, the toxicity of fungicides in terms of seed yield increased in the following order: Control = carbendazim > thiram > captan > mancozeb. Total chlorophyll content in foliage declined consistently with fungicides dose rates and application days. Seeds treated with lower rates of fungicides significantly increased nodulation (nodule number per plant and its dry mass) and were compatible with chickpea inoculum used in this study. Although carbendazim at 2 g a.i./kg seed had no phytotoxic effect assessed under greenhouse conditions, it significantly reduced the chlorophyll content, nodulation (60 d) and N content in shoots.     

The biochemical activity of soil contaminated with fungicides

Excess fungicides can pose a serious threat to the soil environment. Fungicides can lower the microbiological and biochemical activity of soil and lead to yield declines. Soils contaminated with fungicides have to be remediated to maintain the optimal function of soil ecosystems. This study evaluates the effect of neutralizing substances on soil enzymatic activity and the yield of Triticum aestivum L. in soil contaminated with fungicides. Sandy loam (Eutric Cambisols) with pH_KCl 7.0 was contaminated with an aqueous solution of Amistar 250 SC and Falcon 460 EC in the following doses: 0 (soil without fungicide – treated as a control), RD (dose recommended by the manufacturer) and 300?×?RD (dose 300-fold higher than the recommended dose). Soil was supplemented with bentonite and basalt meal at a dose of 10?g kg^?1 DM of soil (dry mass of soil). The fungicide dose recommended by the manufacturer did not induce changes in soil enzymatic activity or the yield of T. aestivum L. Our findings indicate that the tested fungicides can be safely applied to protect crops against fungal pathogens. However, when applied at the dose of 300?×?RD, the tested fungicides strongly inhibited soil enzymatic activity and disrupted the growth and development of spring wheat. Soil supplementation with bentonite and basalt meal improved the yield of T. aestivum L., and bentonite was more effective in reducing fungicide stress. The analyzed substances were not highly effective in restoring biochemical homeostasis in soil.     

Organochlorinated pesticides in sediments from the Lake Albufera of Valencia (Spain)

Bottom sediment samples from 121 sites of the Lake Albufera of Valencia were analyzed. Dieldrin, endrin, heptachlor and op′-DDT were not detected (<0.01 ng g⁻¹) in 88–93% of the sites. Aldrin and HCB concentration ranges were between <0.01 and 0.1 ng g⁻¹ in 86% and 94% of the sites, respectively. Heptachlor-epoxide and lindane 95% confidence intervals were 0.2–0.5 and 0.06–0.12, respectively. The greatest average concentration corresponds to pp′-DDE, pp′-DDD and pp′-DDT. The sum of six isomers and derivatives of the DDT average concentration reaches 2.1 ng g⁻¹, as opposed to 2.7 ng g⁻¹ for the sum of 13 pesticides considered. In the site with a major contamination, 27.0 ng g⁻¹ of pp′-DDD and 12.8 ng g⁻¹ of pp′-DDT were accumulated. The DDE:DDT proportion average was 0.37, indicating an aged DDT contamination. Concentrations of pesticides in sediments were compared to three sediment quality guidelines, and indicated that a low biological effects level can be expected in either sediments or aquatic organisms.     

Effect of processing on the disappearance of pesticide residues in fresh-cut lettuce: Bioavailability and dietary risk

The aim of this research is to establish the processing factors of six pesticides durong the preparation of fresh-cut lettuce and to assess the risk of ingestion of pesticide residues associated with the consumption of the same. A field study was carried out on the dissipation of three insecticides (imidacloprid, tebufenozide, cypermethrin) and three fungicides (metalaxyl, tebuconazole, azoxystrobin) during treatment conditions simulating those used for commercial fresh-cut lettuce. A simultaneous residue analysis method is validated using QuEChERS extraction with acetonitrile and CG-MS and LC-MS/MS analysis. The residues detected after field application never exceed the established Maximum Residue Limits. The processing factors were generally less than 1 (between 0.34 for tebufenozide and 0.53 for imidacloprid), indicating that the process, as a whole, considerably reduces residue levels in processed lettuce compared to fresh lettuce. It is confirmed that cutting, followed by washing and drying, considerably reduces the residues. A matrix effect in the dialyzation of the pesticides is observed and the in vitro study of bioavailability establishes a low percentage of stomach absorption capacity (<15%). The EDI/ADI ratios found in all cases were well below their ADI values, and the dietary exposure assessed (EDI) in fresh-cut lettuce showed no concerns for consumer health.     

Pollutant toxicology with respect to microalgae and cyanobacteria

Microalgae and cyanobacteria are fundamental components of aquatic ecosystems. Pollution in aquatic environment is a worldwide problem. Toxicological research on microalgae and cyanobacteria can help to establish a solid foundation for aquatic ecotoxicological assessments. Algae and cyanobacteria occupy a large proportion of the biomass in aquatic environments; thus, their toxicological responses have been investigated extensively. However, the depth of toxic mechanisms and breadth of toxicological investigations need to be improved. While existing pollutants are being discharged into the environment daily, new ones are also being produced continuously. As a result, the phenomenon of water pollution has become unprecedentedly complex. In this review, we summarize the latest findings on five kinds of aquatic pollutants, namely, metals, nanomaterials, pesticides, pharmaceutical and personal care products (PPCPs), and persistent organic pollutants (POPs). Further, we present information on emerging pollutants such as graphene, microplastics, and ionic liquids. Efforts in studying the toxicological effects of pollutants on microalgae and cyanobacteria must be increased in order to better predict the potential risks posed by these materials to aquatic ecosystems as well as human health.