Retention and rainfastness of mancozeb as affected by physicochemical characteristics of adaxial apple leaf surface after enhanced UV-B radiation

It is not clear so far whether alteration of leaf micromorphology and surface wax chemistry due to the impact of environmental factors, such as UV-B radiation, affects retention and rainfastness of applied pesticide solutions. In this study; UV-B treated and untreated adaxial leaf surfaces of apple seedlings (Malus domestica Borkh.) were characterized in terms of chemical composition, micromorphological fine structure, hydrophobicity, and wettability. Furthermore, the retention and rainfastness of applied fungicide mancozeb were studied. The samples were examined 0, 24 and 48 h after ultraviolet (UV)-B radiation (0.022 kW m(-2) for 150 min) The total wax mass, recovered from the adaxial leaf surface, amounted from 0.38 microg cm(-2) (control) up to 0.49 microg cm(-2) (24 h). Chemical composition of surface wax altered, whereas the contact angle of applied water droplets on leaf surface of UV-B treated plants did not change significantly compared to the control. The alteration of surface wax quantity and quality significantly affected retention of a.i.; it increased at a sampling time of 24 h after UV-B irradiation, whereas rainfastness of the fungicide spray solution was not significantly influenced.     

Enzymological mechanism for the regulation of lanthanum chloride on flavonoid synthesis of soybean seedlings under enhanced ultraviolet-B radiation

In order to probe into the enzymological mechanism for the regulation of lanthanum chloride (LaCl₃) on flavonoid synthesis in plants under enhanced ultraviolet-B (UV-B) radiation, the effects of LaCl₃ (20 and 60 mg l^?1) on the content of flavonoids as well as the activities of phenylalanine ammonia-lyase (PAL), cinnamate-4-hydroxylase (C4H), 4-coumarate?:?coenzyme A ligase (4CL), and chalcone synthase (CHS) in soybean seedlings under enhanced UV-B radiation (2.6 and 6.2 kJ m^?2 day^?1) were investigated. Enhanced UV-B radiation (2.6 and 6.2 kJ m^?2 day^?1) caused the increase in the content of flavonoids as well as the activities of PAL, C4H, 4CL, and CHS in soybean seedlings. The treatment of 20 mg l^?1 LaCl₃ also efficiently increased these indices, which promoted the flavonoid synthesis and provided protective effects for resisting enhanced UV-B radiation. On the contrary, the treatment of 60 mg l^?1 LaCl₃ decreased the content of flavonoids as well as the activities of C4H, 4CL, and CHS in soybean seedlings except increasing the activity of PAL, which were not beneficial to the flavonoid synthesis and provided negative effects for resisting enhanced UV-B radiation. In conclusion, enhanced UV-B radiation caused the increase in the flavonoid synthesis by promoting the activities of PAL, C4H, 4CL, and CHS in soybean seedlings. The treatment of LaCl₃ could change flavonoid synthesis in soybean seedlings under enhanced UV-B radiation by regulating the activities of PAL, C4H, 4CL, and CHS, which is an enzymological mechanism for the regulation of LaCl₃ on flavonoid synthesis in plants under enhanced UV-B radiation.     

Effect of triazole pesticide formulation on bovine culture cells

To date, most data about the possible genotoxic effect of triazole pesticides are focused on laboratory animals resulting in limited information on further non-target organisms such as cattle. The objective of the present study was to investigate the effect of triazole (tebuconazole/prothioconazole) fungicide formulation on the induction of chromosomal aberrations (CAs), sister chromatid exchanges (SCEs) and DNA fragmentation in bovine cultured lymphocytes. Our results showed that the fungicide formulation did not induce significant number of CAs in bovine cells after 24 h treatment. Nevertheless, the dose-dependent reduction of mitotic division was observed, with the strongest effect at 30.0 μg mL^?1 in both donors (P < 0.01 and P < 0.001, respectively). Prolonged 48 h exposure caused the increased level of breaks in treated cultures (3.0?15.0 μg mL^?1; P < 0.05) and significant decrease in mitotic index (MI). The tested fungicide failed to produce any statistical changes in the SCE frequency neither after 24 h nor 48 h treatment. However, the significant decline of the proliferation index (PI) was observed after 24 h indicating the fungicide influence on cell cycle kinetics. Prolonged 48 h exposure caused cytotoxicity reflecting in lower PI value relative to control mainly at the highest fungicide concentrations (30.0 μg mL^?1, P < 0.001). Using painting probes for bovine chromosomes 1, 5 and 7 (BTA1, BTA5 and BTA7) only low levels of aneuploidies were detected. Significant increase of polyploidy cells (P < 0.05) was induced by a 3.0 μg mL^?1 dose of the fungicide after 48 h. DNA fragmentation assay didn't reveal the presence of DNA nucleosome ladder in cell cultures at any time (24 h and 48 h) and fungicide concentration.     

Evaluation of potential genotoxic/cytotoxic effects induced by epoxiconazole and fenpropimorph-based fungicide in bovine lymphocytes in vitro

Potential genotoxic/cytotoxic effects of the epoxiconazole/fenpropimorph-based fungicide were investigated using single cell gel electrophoresis and cytogenetic assays: chromosomal aberrations, sister chromatid exchanges, micronuclei and fluorescence in situ hybridization in cultured bovine lymphocytes. No statistically significant elevations of DNA damage and increases in cytogenetic endpoints were seen. However, evident cytotoxic effect presented as a decrease in mitotic and proliferation indices were recorded after exposure of bovine lymphocytes to the fungicide for 24 and 48 h at concentrations ranging from 3 to 15 µg mL^?1 (P < 0.05, P < 0.01, P < 0.001). Similarly, for 24 h an inhibition in the cytokinesis block proliferation index (CBPI) was obtained after exposure to the fungicide at concentrations ranging from 1.5 to 15 µg mL^?1 (P < 0.01, P < 0.001) in each donor.     

Potential exposure of children and adults to cypermethrin following use of indoor insecticide foggers

The magnitude and distribution of cypermethrin from total release, over-the-counter foggers was studied in a test room and in residences to facilitate evaluation of regulatory exposure algorithms and new human exposure assessments based upon urine biomonitoring. Surface residue (SR) was evenly distributed in a small test room (3.6 μ g cypermethrin/cm²) where thorough mixing of the aerosol occurred. In a residence SR was significantly affected by room size and distance from the fogger. Air levels in the residence were as high as 30 μ g cypermethrin/cm³ after 4.5 h. The availability of surface residues was measured with an automated surface cotton cloth wipe and ethyl acetate extraction. Only 5% of the SR was available from nylon carpet. Tile, wood and linoleum resulted in 30, 10, and 10% of SR being available, respectively. These data are used to estimate cypermethrin exposure of children and adults for comparison with existing regulatory reference dosages and exposure assessments based upon biomonitoring.     

Wild tomato leaf extracts for spider mite and cowpea aphid control

Glandular trichomes on the leaves of wild tomato, L. hirsutum f. hirsutum Mull, also known as Solanum habrochaites (Solanaceae), synthesize and accumulate high levels of methyl ketones (MKs). L. hirsutum accession LA 407, having high concentration of MKs, was grown from seeds under greenhouse conditions. Four MKs (2-undecanone, 2-dodecanone, 2-tridecanone, and 2-pentadecanone) were screened for their toxicity to spider mites, Tetranychus urticae Koch and cowpea aphids, Aphis craccivora Koch. The objectives of this investigation were to: (1) develop a bioassay for testing MKs on spider mite and cowpea aphid mortality and (2) compare the efficacies of wild tomato leaf crude extracts and pure standard materials of MKs against spider mite and cowpea aphid mortality. Our results revealed that spider mites are most sensitive to 2-tridecanone (LC₅₀ = 0.08 μmole cm^?2 of treated leaf surface) and least sensitive to 2-undecanone (LC₅₀ = 1.5 μmole cm^?2 of treated leaf surface) 4 h after treatment. Similarly, 2-tridecanone caused greatest mortality (LC₅₀ = 0.2 μmole cm^?2 of treated leaf surface), whereas 2-undecanone caused the lowest morality (LC₅₀ = 0.48 μmole cm^?2 of treated surface) of cowpea aphid. We concluded that all MKs tested in this investigation are toxic to spider mites and aphids. 2-Tridecanone is more effective in killing mites and aphids compared to other MKs. Toxicity of crude extracts, prepared from the leaves of L. hirsutum accession LA 407, to spider mites and cowpea aphids revealed greater mortality compared to a combined mixture of MKs standard material (used at the same concentration as found on LA 407 leaves). This indicates that in addition to MKs, other unidentified compounds in LA 407 leaf extract also have pesticidal properties. Accordingly, leaf extracts of LA 407 could be explored in crop protection, and they might open a new area of MK formulations and discovery of biorational alternatives for pest control in agricultural fields.     

Commercial trials evaluating the novel use of ethyl formate for in-transit fumigation of shipping containers

Sediment samples from 25 sites in 17 rivers of the Pantanal (Brazil) were analyzed with the objective of evaluating pesticide contamination in sediments. Samples were extracted with an acetone, ethylacetate, and water mixture 2:2:1 (v/v/v). The extract was purified by flash chromatography with aluminum oxide and florisil. A multiresidue gas chromatography-mass spectrometry method was applied to monitor 23 pesticides of different chemical classes (organochlorine, organophosphorus, triazines, anilides and pyrethroids) with some of their degradation products. Compounds identified in sediment samples included λ -cyhalothrin (1.0 to 5.0 μ g kg^{? 1}), p,p′-DDT (3.6 μ g kg^{? 1}), deltamethrin (20.0 μ g kg^{? 1}) and permethrin (1.0 to 7.0 μ g kg^{? 1}).     

Reactive uptake of ozone at simulated leaf surfaces: Implications for ‘non-stomatal’ ozone flux

The reaction of ozone (O₃) with α-pinene has been studied as a function of temperature and relative humidity and in the presence of wax surfaces that simulate a leaf surface. The objective was to determine whether the presence of a wax surface, in which α-pinene could dissolve and form a high surface concentration, would lead to enhanced reaction with O₃. The reaction of O₃ itself with the empty stainless steel reactor and with aluminium and wax surfaces demonstrated an apparent activation energy of around 30 kJ mol^?1 for all the surfaces, similar to that observed in long-term field measurements of O₃ fluxes to vegetation. However, the absolute reaction rate was 14 times greater for aluminium foil and saturated hydrocarbon wax surfaces than for stainless steel, and a further 5 times greater for beeswax than hydrocarbon wax. There was no systematic dependence on either relative or absolute humidity for these surface reactions over the range studied (20–100% RH). Reaction of O₃ with α-pinene occurred at rates close to those predicted for the homogeneous gas-phase reaction, and was similar for both the empty reactor and in the presence of wax surfaces. The hypothesis of enhanced reaction at leaf surfaces caused by enhanced surface concentrations of α-pinene was therefore rejected. Comparison of surface decomposition reactions on different surfaces as reported in the literature with the results obtained here demonstrates that the loss of ozone at the earth's surface by decomposition to molecular oxygen (i.e. without oxidative reaction with a substrate) can account for measured ‘non-stomatal’ deposition velocities of a few mm s^?1. In order to quantify such removal, the effective molecular surface area of the vegetation/soil canopy must be known. Such knowledge, combined with the observed temperature-dependence, provides necessary input to global-scale models of O₃ removal from the troposphere at the earth's surface.     

Deposition and Leaching of Tebuthiuron on Sugar Cane Straw Applied with and Without Alkyl Polyglycoside Adjuvant

Abstract

A laboratory experiment was carried out aiming to study the effects of an alkyl polyglycoside adjuvant (APG) on deposition and leaching of the herbicide tebuthiuron applied on sugar cane straw. Tebuthiuron, at concentration of 1200 mg L^?1, was applied separately and in tank mix with the APG adjuvant, at concentrations of 0.07 and 0.09% (wt v^?1), using a spraying volume of 204 L ha^?1. A precipitation equivalent to 20 mm of rain was simulated, 24 h after the applications, to evaluate the herbicide leaching. The quantification of tebuthiuron was carried out by the high performance liquid chromatography (HPLC). It was observed that the addition of APG adjuvant at 0.07% (wt v^?1) provided an increase of 11.5% in the deposition of tebuthiuron on straw, reduction of 50.4% in the drift of the herbicide and it did not affect significantly the leached amount (68.5%), when compared with the treatment where tebuthiuron was applied alone (70.8%). At the concentration of 0.09% (wt v^?1), the APG adjuvant caused an increase of 22.7% in the deposition; it reduced the drift of the herbicide by 99.9% and reduced the leached amount by 7.6% thereby increasing the retention of the herbicide by straw.     

Measurements of nitrogen oxides from Hudson Bay: Implications for NOx release from snow and ice covered surfaces

Measurements of NO and NO₂ were made at a surface site (55.28 °N, 77.77 °W) near Kuujjuarapik, Canada during February and March 2008. NO_x mixing ratios ranged from near zero to 350 pptv with emission from snow believed to be the dominant source. The amount of NO_x was observed to be dependent on the terrain over which the airmass has passed before reaching the measurement site. The 24 h average NO_x emission rates necessary to reproduce observations were calculated using a zero-dimensional box model giving rates ranging from 6.9 × 10⁸ molecule cm^?2 s^?1 to 1.2 × 10⁹ molecule cm^?2 s^?1 for trajectories over land and from 3.8 × 10⁸ molecule cm^?2 s^?1 to 6.6 × 10⁸ molecule cm^?2 s^?1 for trajectories over sea ice. These emissions are higher than those suggested by previous studies and indicate the importance of lower latitude snowpack emissions. The difference in emission rate for the two types of snow cover shows the importance of snow depth and underlying surface type for the emission potential of snow-covered areas.     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 μ g g^{? 1} dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 μ g g^{? 1} and 150 μ g g^{? 1} dry weight, respectively. Aluminum concentrations were (in μ g g^{? 1} dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 μ g g^{? 1}) and aluminum (> 360 μ g g^{? 1}), while leaves had less than 200 μ g g^{? 1} of iron and 165 μ g g^{? 1} of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 μ g g^{? 1}), Zn (50 μ g g^{? 1}) and Cu (3.6 μ g g^{? 1}). Some presence of lead in leaves (2.0 μ g g^{? 1}) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

In vitro toxicity of fungicides with different modes of action to alfalfa anthracnose fungus,Colletotrichum destructivum

Abstract

Sensitivity of 24 isolates of Colletotrichum destructivum O’Gara, collected from alfalfa plants in Serbia, to eight selected fungicides, was investigated in this study. Molecular identification and pathogenicity test of isolates tested were also performed. Fungicide sensitivity was evaluated in vitro, using mycelial growth assay method. All isolates exhibited significant pathogenicity, causing necrosis at the alfalfa seedling root tips two days after inoculation. Using the primer pair GSF1-SR1 and by comparing the amplified fragments of the tested isolates with the marker (M), the presence of the amplicon of the expected size of about 900?bp was determined for all isolates. The isolates tested in this study showed different sensitivity towards fungicides in vitro. Mycelial growth was highly inhibited by QoI (quinone outside inhibitors) fungicide pyraclostrobin (mean EC₅₀=0.39?µg mL^?1) and by DMI (demethylation-inhibiting) fungicide tebuconazole (mean EC₅₀=0.61?µg mL^?1), followed by azoxystrobin (mean EC₅₀=2.83?µg mL^?1) and flutriafol (mean EC₅₀=2.11?µg mL^?1). Multi-site fungicide chlorothalonil and MBC (methyl benzimidazole carbamate) fungicide thiophanate-methyl evinced moderate inhibition with mean EC₅₀=35.31 and 62.83?µg mL^?1, respectively. Thirteen isolates were sensitive to SDHI (succinate dehydrogenase inhibitors) fungicide boscalid and fluxapyroxad, (mean EC₅₀=0.49 and 0.19?µg mL^?1, respectively), while the rest of isolates were highly resistant.     

The effect of pesticides and metals on acetylcholinesterase (AChE) in various tissues of blue mussel (Mytilus trossulus L.) in short-term in vivo exposures at different temperatures

The purpose of the study was to assess the impact of short-term exposure to selected toxicants as well as metal accumulation upon acetylcholinesterase (AChE) in the blue mussel, Mytilus trossulus L., in laboratory in vivo experiments. Mussels were exposed for up to 48 hours to a mixture of copper (Cu^{2 +}, 400 μ g L^?1) and cadmium (Cd^{2 +}, 200 μ g L^?1), to dichlorvos (DDVP, 100 μ g L^?1), and to carbaryl (100 μ g L^?1) at two temperatures: 5°C and 20°C. Samples were collected after 0, 6, 12, 24, and 48 hours of exposure, and AChE activity and metal concentration (where applicable) were analysed in gills, digestive gland, mantle+muscles, and the whole soft tissue. Very strong AChE inhibition was observed in response to the dichlorvos treatment, mainly in gills. Carbaryl and the metals caused a short-term inhibition effect. Considerable differences in AChE activity between the two temperatures were noticed. In particular, the metals were accumulated much faster at 20°C than at 5°C, especially in gills. No correlation between AChE activity and metal concentration was found. Gills turned out to be the optimal tissue for AChE activity analysis in short-term studies.     

Effect of adjuvants on rainfastness and herbicidal activity of glyphosate deposits on trembling aspen foliage

Abstract

Radiolabelled end‐use mixtures of glyphosate with and without a cationic surfactant (Ethomeen® T/25) and an organosilicone surfactant (Silwet® L‐77) were applied onto trembling aspen (Populus tremuloids Michx.) leaves at the rate of 1.0 kg of AE (acid equivalent) in 35 L/ha area of foliage. A 5‐mm rainfall with an intensity of 10 mm/h was applied at intervals of 0.5, 8, 24, 36, 48, 72, and 96 h after treatment. Glyphosate washoff was determined by liquid scintillation counting of radioactivity in the rain‐washing. At 36 h post‐treatment, both the adjuvants significantly reduced glyphosate washoff (Ethomeen by 69.6% and Silwet by 59.7%) from foliage, compared to the washoff (82.6%) when Vision alone was applied without the adjuvants. Results on the rate of plant growth indicated that with a rain‐free period of 8 h or more, the growth of most seedlings was stunted within 1 or 2 d. Percentage of foliar browning 20 d after treatment with rain‐free period of 8 to 48 h ranged from 8 to 80% for Vision alone, 75 to 100% for Vision with Ethomeen, and 85 to 100% for Vision with Silwet, respectively. Physical properties of the end‐use mixtures were measured with and without the two adjuvants to examine droplet spreading and drying rates in relation glyphosate rainfastness. The Silwet adjuvant lowered the surface tension of the end‐use mixture, but Ethomeen did not. Droplets containing Silwet were spread more than those containing Ethomeen. However, the greater area of contact caused by Silwet did not contribute to a significant increase in the translocation rate of glyphosate into untreated parts of the seedlings, and showed no relationship with rainfastness of glyphosate deposits on trembling aspen.     

Trace level determination of selected sulfonylurea herbicides in wetland sediment by liquid chromatography electrospray tandem mass spectrometry

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg^{? 1}. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg^{? 1}). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg^{? 1}.     

Mixture Toxicity of the Antifouling Compound Irgarol to the Marine Phytoplankton Species Dunaliella tertiolecta

This study examined the toxicity of irgarol, individually and in binary mixtures with three other pesticides (the fungicide chlorothalonil, and the herbicides atrazine and 2,4-D), to the marine phytoplankton species Dunaliella tertiolecta. Standard 96-h static algal bioassays were used to determine pesticide effects on population growth rate. Irgarol significantly inhibited D. tertiolecta growth rate at concentrations ≥ 0.27 μ g/L. Irgarol was significantly more toxic to D. tertiolecta than the other pesticides tested (irgarol 96 h EC₅₀ = 0.7 μ g/L; chlorothalonil 96 h EC₅₀ = 64 μ g/L; atrazine 96 h EC₅₀ = 69 μ g/L; 2,4-D 96 h EC₅₀ = 45,000 μ g/L). Irgarol in mixture with chlorothalonil exhibited synergistic toxicity to D. tertiolecta, with the mixture being approximately 1.5 times more toxic than the individual compounds. Irgarol and atrazine, both triazine herbicides, were additive in mixture. The toxicity threshold of 2,4-D was much greater than typical environmental levels and would not be expected to influence irgarol toxicity. Based on these interactions, overlap of certain pesticide applications in the coastal zone may increase the toxicological risk to resident phytoplankton populations.     

Free Fatty Acids and Sterols in Swine Manure

Free fatty acids and sterols were assessed in fresh manure and anaerobic lagoon sludge from swine production facilities in North Carolina. Eight free fatty acids and five sterols were identified and quantified in both manure and sludge samples. Compound identification was performed by gas chromatography/mass spectroscopy (GC-MS), and compound quantities were determined by gas chromatography after solid phase extraction with a 50:50 mixture of diethyl ether and hexane. The free fatty acids occurring in greatest abundance in both fresh manure and lagoon sludge were palmitic, oleic, and stearic. Free fatty acid content in fresh manure ranged from approximately 3 μ g g^?1 dry weight (dw) to over 45 μ g g^?1 dw. In lagoon sludge, free fatty acid content ranged from about 0.8 μ g g^?1 dw to nearly 4 μ g g^?1 dw. Coprostanol and epicoprostanol were the sterols in largest concentrations in fresh manure and lagoon sludge samples. Total sterol content ranged from approximately 0.5 μ g g^?1 dw to around 11 μ g g^?1 dw in fresh manure and from 3.5 μ g g^?1 dw to almost 9 μ g g^?1 dw in lagoon sludge. Fresh manure and lagoon sludge both had high levels of inorganic cations (e.g., Ca, Mg, Fe) capable of binding free fatty acids and forming insoluble complexes, thereby potentially reducing fatty acid biodegradation. In anaerobic lagoons, sterols are an organic fraction of sludge that are resistant to bacterial degradation. In the case of fresh manure, fatty acids could represent a potential source of energy via the manufacture of biodiesel fuel, if efficient means for their extraction and transesterification can be devised.     

Headspace solid phase microextraction method for determination of triazine and organophosphorus pesticides in soil

A headspace solid phase microextraction method (HS-SPME) for simultaneous determination of five pesticides belonging to triazine and organophosphorus pesticide groups in soil samples was developed. Microextraction conditions, such as temperature, extraction time and sodium chloride (NaCl) content were investigated and optimized using 100 μ m polydimethyl-siloxane (PDMS) fiber. Detection and quantification were done by gas chromatography-mass spectrometry (GC-MS). Relative standard deviation (RSD) and recovery values for multiple analysis of soil samples fortified at 30 μ g kg^{? 1} of each pesticide were below 13 % and higher than 70 %, respectively. Limits of detection (LOD) for all the compounds studied were less than 3.2 μ g kg^{? 1}. The proposed method was applied in the analysis of some agricultural soil samples.     

Differential aggregation of polystyrene and titanium dioxide nanoparticles under various salinity conditions and against multiple proteins types

The interaction of nanoplastics (NPls) and engineered nanoparticles (ENPs) with organic matter and environmental pollutants is particularly important. Therefore, their behavior should be investigated under the different salinity conditions, mimicking rivers and coastal environments, to understand this phenomenon in those areas. In this work, we analyzed the elementary characteristics of polystyrene-PS (unmodified surface and modified with amino or carboxyl groups) and titanium dioxide-TiO2 nanoparticles. The effect of salinity on their colloidal properties was studied too. Also, the interaction with different types of proteins (bovine serum albumin-BSA and tilapia proteins), as well as the formation of the BSA corona and its effect on the colloidal stability of nanoparticles, were evaluated. The morphology and dispersion of sizes were more uniform in unmodified-surface PS-NPs (70.5?±?13.7 nm) than in TiO2-NPs (131.2?±?125.6 nm). Likewise, Rama spectroscopy allowed recognizing peaks associated with the PS phenyl group aromatic ring in unmodified-surface PS-NPs (621, 1002, 1582, and 1602 cm^?1). For TiO2-NPs, the data suggest belonging to the tetragonal form, also known as rutile (445, 610 cm^?1). The elevation of salinity dose-dependently decreased NP colloid stability, with more significant variation in the PS-NPs compared to TiO2-NPs. The organic matter is also involved in this phenomenon, differentially as a function of time compared to its absence (unmodified-surface PS-NPs 30 psu/TOC 5 mgL^?1/24 h: 2876.6?±?378.03 nm; unmodified-surface PS-NPs 30 psu/24 h: 2133?±?49.57 nm). In general, the TiO2-NPs demonstrated greater affinity with all proteins tested (0.066 g/L). It was observed that morphology, size, and surface chemical modification intervene in a relevant way in the interaction of the nanoparticles with bovine serum albumin (unmodified-surface PS-NPs 298 K: 6.08E⁺⁰²; 310 K: 6.63E⁺⁰²; TiO2-NPs 298 K: 8.76E⁺⁰²; 310 K: 1.05E⁺⁰³ L mol^?1) and tilapia tissues proteins (from blood, gills, liver, and brain). Their morphology and size also determined the protein corona formation and the NPs’ agglomeration. These findings can provide references during knowledge transfer between NPls and ENPs.

     

Evaluation of substrate removal kinetics for UASB reactors treating chlorinated ethanes

Purpose

Lack of focus on the treatment of wastewaters bearing potentially hazardous pollutants like 1,1,2 trichloroethane and 1,1,2,2 tetrachloroethane in anaerobic reactors has provided an impetus to undertake this study. The objective of this exercise was to quantify the behavior of upflow anaerobic sludge blanket reactors and predict their performance based on the overall organic substrate removal.

Methods

The reactors (wastewater-bearing TCA (R2), and wastewater-bearing TeCA (R3)) were operated at different hydraulic retention times (HRTs), i.e., 36, 30, 24, 18, and 12?h corresponding to food-to-mass ratios varying in the range of 0.2?C0.7?mg chemical oxygen demand (COD) mg^?1 volatile suspended solids day^?1. The process kinetics of substrate utilization was evaluated on the basis of experimental results, by applying three mathematical models namely first order, Grau second order, and Michaelis-Menten type kinetics.

Results

The results showed that the lowering of HRT below 24?h resulted in reduced COD removal efficiencies and higher effluent pollutant concentrations in the reactors. The Grau second-order model was successfully applied to obtain the substrate utilization kinetics with high value of R ² (>0.95). The Grau second-order substrate removal constant (K ₂) was calculated as 1.12 and 7.53?day^?1 for reactors R2 and R3, respectively.

Conclusion

This study demonstrated the suitability of Grau second-order kinetic model over other models, for predicting the performance of reactors R2 and R3, in treating wastewaters containing chlorinated ethanes under different organic and hydraulic loading conditions.