Effect of humic acids,nitrate and oxygen on the photodegradation of the flubendiamide insecticide: identification of products

Flubendiamide is a ryanodine insecticide that shows a strong insecticidal activity and is relatively safe for non-target organisms. Actually only flubendiamide and its product desiodo-flubendiamide have been studied during catalytic degradation using TiO₂ and ZnO. Therefore, here we tested the photocatalytic removal of flubendiamide in the presence of nitrates or humic acids. Degradation kinetics were monitored using high-performance liquid chromatography ultraviolet–visible detector. Product identification was done using a high-resolution time-of-flight mass spectrometer coupled to a gas chromatograph (GC-HRMS). Results show that the addition of humic acids at 10 mg l^?1 increased the removal of flubendiamide more than five times. The addition of nitrate ions at 10 mg l^?1 had no influence. The removal of flubendiamide was more than ten times faster in experiments with oxygen purging. Fourteen degradation products were identified, which can be classified into three groups: phthalimide and related phthalic acid derivatives, fluorinated species related to the second amide moiety, and advanced transformation products.     

Isolation and characterisation of a carbofuran degrading Burkholderia sp. PCL3 from carbofuran-phytoremediated rhizosphere soil

A bacterial strain capable of degrading carbofuran as the sole carbon source was isolated from carbofuran-phytoremediated rhizosphere soil of rice. A 16S rRNA study identified the strain as Burkholderia sp. (isolate PCL3). Free cells of isolate PCL3 possessed inhibitory-type degradation kinetics with a q _max of 0.087 day^?1 and S _m of 248.76 mg·L^?1. Immobilised PCL3 on corncob and sugarcane bagasse possessed Monod-type degradation kinetics with a q _max of 0.124 and 0.098 day^?1, respectively. The optimal pH and temperature with the highest degradation rate coefficient of carbofuran were pH 7.5 and 35 °C, respectively.     

Population health risk via dietary exposure to trace elements (Cu,Zn, Pb,Cd, Hg,and As) in Qiqihar,Northeastern China

The estimated daily intakes (EDIs) of six trace elements (Cu, Zn, Pb, Cd, Hg, and As) in vegetables (leafy vegetable, i.e., bok choy, fruit vegetables, i.e., cucumber and tomato, and other categories, i.e., mushroom, kidney bean, and potato), cereals (rice and wheat flour), and meats (pork, mutton, and beef) most commonly consumed by adult inhabitants of Qiqihar, Northeastern China, were determined to assess the health status of local people. The average EDIs of Cu, Zn, Pb, Cd, Hg, and As were with 20.77 μg (kg bw)^?1 day^?1 of Cu, 288 μg (kg bw)^?1 day^?1 of Zn, 2.01 μg (kg bw)^?1 day^?1 of Pb, 0.41 μg (kg bw)^?1 day^?1 of Cd, 0.01 μg (kg bw)^?1 day^?1 of Hg, and 0.52 μg (kg bw)^?1 day^?1 of As, respectively, which are below the daily allowance recommended by FAO/WHO. However, the maximum EDIs of Pb and Cd were 4.56 μg (kg bw)^?1 day^?1 and 1.68 μg (kg bw)^?1 day^?1, respectively, which are above the recommended levels [i.e., 3.58 μg (kg bw)^?1 day^?1 for Pb and 1.0 μg (kg bw)^?1 day^?1 for Cd] by FAO/WHO. This finding indicates that the potential health risk induced by daily ingestion of Pb and Cd for the local residents should receive a significant concern. Similarly, we detected elevated Pb and Cd concentrations, i.e., with average of 13.58 and 0.60 mg kg^?1 dw, respectively, in the adult scalp hairs. Consumption of rice, potato, bok choy, and wheat flour contributed to 75 and 82% of Pb and Cd daily intake from foodstuffs. Nevertheless, human scalp hair is inappropriate biological material for determination of the nutritional status of trace elements in this region.     

Reactivity of sulfate radicals with natural organic matters

Advanced oxidation processes based on sulfate radicals (SO ₄ ^·? ) are capable of efficiently degrade organic pollutants from ground, surface and wastewaters. However, this degradation may be limited by aqueous natural organic matter (NOM). Here we measured the absolute rate constants of reaction of SO ₄ ^·? with four types of organic matter: two fulvic acids and two lake organic matter. We used laser flash photolysis technique to monitor the SO ₄ ^·? decay and the formation of the transients from organic matters. Reaction rate constants comprised between 1530 and 3500 s^?1 mgC^?1 L were obtained by numerical analysis of differential equations and the weighted average of the extinction coefficient of the generated organic matters radicals between 400 and 800 M^?1 cm^?1.     

Fast and complete removal of the 5-fluorouracil drug from water by electro-Fenton oxidation

Cytostatic drugs are a troublesome class of emerging pollutants in water owing to their potential effects on DNA. Here we studied the removal of 5-fluorouracil from water using the electro-Fenton process. Galvanostatic electrolyses were performed with an undivided laboratory-scale cell equipped with a boron-doped diamond anode and a carbon felt cathode. Results show that the fastest degradation and almost complete mineralization was obtained at a Fe²⁺ catalyst concentration of 0.2 mM. The absolute rate constant for oxidation of 5-fluorouracil by hydroxyl radicals was 1.52 × 10⁹ M^?1 s^?1. Oxalic and acetic acids were initially formed as main short-chain aliphatic by-products, then were completely degraded. After 6 h the final solution mainly contained inorganic ions (NH₄ ⁺, NO₃ ^? and F^?) and less than 10% of residual organic carbon. Hence, electro-Fenton constitutes an interesting alternative to degrade biorefractory drugs.     

Enhanced degradation of trichloroethylene using bentonite-supported nanoscale Fe/Ni and humic acids

Nanoscale zero-valent iron, named nano-Fe⁰, is a reagent used to degrade trichloroethylene in groundwater. However, the efficiency of nano-Fe⁰ is moderate due to issues of dispersion and reactivity. As an alternative we synthesized bentonite-supported nanoscale Fe/Ni bimetals, named bentonite-Fe/Ni, to test the degradation of trichloroethylene in the presence of Suwannee River humic acids, as a representative of natural organic matter. 0.1 mmol/L trichloroethylene was reacted with 0.5 g/L of nano-Fe⁰, bentonite-Fe, Fe/Ni, and bentonite-Fe/Ni nanoparticles. Results show first that without humic acids the reaction rate constants k _obs were 0.0036/h for nano-Fe⁰, 0.0101/h for bentonite-Fe, 0.0984/h for Fe/Ni, and 0.181/h for bentonite-Fe/Ni. These findings show that bentonite-Fe/Ni is the most efficient reagent. Second, the addition of humic acids increased the rate constant from 0.178/h for 10 mg/L humic acids to 0.652/h for 40 mg/L humic acids, using the bentonite-Fe/Ni catalyst. This finding is explained by accelerated dechlorination by faster electron transfer induced by humic quinone moieties. Indeed, the use of 9, 10-anthraquinone-2, 6-disulfonate as a humic analogue gave similar results.     

Environmental impact of CO<Subscript>2</Subscript>, Rn,Hg degassing from the rupture zones produced by Wenchuan <Emphasis Type="Italic">M</Emphasis><Subscript>s</Subscript> 8.0 earthquake in western Sichuan,China

The concentrations and flux of CO₂, ²²²Radon (Rn), and gaseous elemental mercury (Hg) in soil gas were investigated based on the field measurements in June 2010 at ten sites along the seismic rupture zones produced by the May 12, 2008, Wenchuan M _s 8.0 earthquake in order to assess the environmental impact of degassing of CO₂, Rn and Hg. Soil gas concentrations of 344 sampling points were obtained. Seventy measurements of CO₂, Rn and Hg flux by the static accumulation chamber method were performed. The results of risk assessment of CO₂, Rn and Hg concentration in soil gas showed that (1) the concentration of CO₂ in the epicenter of Wenchuan M _s 8.0 earthquake and north end of seismic ruptures had low risk of asphyxia; (2) the concentrations of Rn in the north segment of seismic ruptures had high levels of radon, Maximum was up to level 4, according to Chinese code (GB 50325-2001); (3) the average geoaccumulation index I _geo of soil Hg denoted the lack of soil contamination, and maximum values classified the soil gas as moderately to strongly polluted in the epicenter. The investigation of soil gas CO₂, Rn and Hg degassing rate indicated that (1) the CO₂ in soil gas was characterized by a mean \(\updelta^{13}C_{CO2}\) of ?20.4 ‰ and by a mean CO₂ flux of 88.1 g m^?2 day^?1, which were in the range of the typical values for biologic CO₂ degassing. The maximum of soil CO₂ flux reached values of 399 g m^?2 day^?1 in the epicenter; (2) the soil Rn had higher exhalation in the north segment of seismic ruptures, the maximum reached value of 1976 m Bq m^?2 s^?1; (3) the soil Hg flux was lower, ranging from ?2.5 to 18.7 n g m^?2 h^?1 and increased from south to north. The mean flux over the all profiles was 4.2 n g m^?2 h^?1. The total output of CO₂ and Hg degassing estimated along seismic ruptures for a survey area of 18.17 km² were approximately 0.57 Mt year^?1 and 688.19 g year^?1. It is recommended that land-use planners should incorporate soil gas and/or gas flux measurements in the environmental assessment of areas of possible risk. A survey of all houses along seismic ruptures is advised as structural measures to prevent the ingress of soil gases, including CO₂ and Rn, were needed in some houses.     

Primary production and phytoplankton community structure during a winter shelf-scale phytoplankton bloom off Western Australia

Regions of high primary production along the oligotrophic west coast of Australia between 34 and 22°S in May–June 2007 (midway through the annual phytoplankton bloom) were found around mesoscale features of the Leeuwin Current. At 31°S, an anticyclonic eddy-forming meander of the Leeuwin Current had a mixed layer depth of >160 m, a depth-integrated chlorophyll a (Chl a)-normalised primary production of 24 mg C mg Chl a ^?1 day^?1 compared to the surrounding values of <18 mg C mg Chl a ^?1 day^?1. In the north between 27 and 24°S, there were several stations in >1,000 m of water with a shallow (<100 m) and relatively thin layer of high nitrate below the mixed layer but within the euphotic zone. These stations had high primary production at depths of ~100 m (up to 7.5 mg C m^?3 day^?1) with very high rates of production per unit Chl a (up to 150 mg C mg Chl a ^?1 day^?1). At 27–24°S, the majority of the phytoplankton community was the ubiquitous tropical picoplankters, Synechococcus and Prochlorococcus. There was a decline in the dominance of the picoplankters and a shift towards a more diverse community with more diatoms, chlorophytes, prasinophytes and cryptophytes at stations with elevated production. Photosynthetic dinoflagellates were negligible, but heterotrophic dinoflagellate taxa were common. Haptophytes and pelagophytes were also common, but seemed to contribute little to the geographical variation in primary production. The mesoscale features in the Leeuwin Current may have enhanced horizontal exchange and vertical mixing, which introduced nitrate into the euphotic zone, increasing primary production and causing a shift in phytoplankton community composition in association with the annual winter bloom.     

Degradation of diuron by the electro-Fenton process

The degradation of the herbicide diuron has been undertaken by electrochemical advanced oxidation in aqueous solution. This process generates catalytically hydroxyl radicals that are strong oxidizing reagents for the oxidation of organic substances. Hydroxyl radicals degrade diuron in less than 10 min. Kinetic results evidence a pseudo-first-order degradation, with a rate constant of reaction between diuron and hydroxyl radicals of 4.8x10⁹ M^–1 s^–1. Several degradation products were identified by chromatography-mass spectrometry (LC-MS). The mineralization degree of a 1.7x10^–4 M diuron solution reached 93% at 1,000 coulombs.     

Thermal treatment of plasma-synthesized goethite improves Fenton-like degradation of orange II dye

Various iron oxides are used for Fenton reactions to degrade organic pollutants. The degradation efficiency may be improved by transforming an iron oxide phase to another. Here, we report on the transformation of goethite into hematite by thermal treatment at 400 °C. The products were analyzed by X-ray diffractometry, Raman spectroscopy, scanning electron microscopy and N₂-physisorption. The catalytic activities were measured for orange II bleaching at initial concentration of 25 mg L^?1, pH 3, catalyst concentration of 0.2 g L^?1; 5 mM H₂O₂, 30 °C. Results show that the synthesized goethite was successfully transformed into hematite, and the specific surface area of the material increased from 134 to 163 m² g^?1. The bleaching efficiency of the orange II dye reached 100 % for the hematite product, versus 78 % for goethite. Therefore, a moderate thermal treatment of a plasma-synthesized goethite improves the catalytic oxidation of organic pollutants.     

The effects of evening primrose oil on arsenic-induced oxidative stress in rats

Forty-eight male Wistar albino rats were allocated to the four groups such that each comprised 12 animals. The first group was maintained as the control. In group 2, evening primrose oil was administered at a dose of 0.1 mL rat^?1 day^?1 (～500 mg kg^?1 bw) into the stomach via gavage, whilst in group 3 sodium arsenide was administered at a concentration of 100 mg L^?1 in ad-libitum drinking water for 30 days. The fourth group was given 0.1 mL rat^?1 day^?1 evening primrose oil into the stomach via gavage plus 100 mg L^?1 of sodium arsenide in ad-libitum drinking water for 30 days. At the end of the 30th day, tissue (liver, lung, kidney, brain, heart, spleen, and testis) and blood samples were collected from each group. Malondialdehyde (MDA) and nitric oxide (NO) levels and superoxide dismutase, catalase and glutathione peroxidase activities were measured in the samples. Exposure to arsenic in rats causes oxidative stress by increasing lipid peroxidation (increase of MDA and NO levels) and altering the activity of antioxidant enzymes. Evening primrose oil did not have any adverse effects. Furthermore, it was ascertained that the administration of arsenic with evening primrose oil reduced the severity of oxidative stress.     

Evaluation of the toxicity of tetrabromobisphenol A and some of its oxidation products using a micro-scale algal growth inhibition test

A micro-scale algal growth inhibition (μ-AGI) test using a common micro-plate based fluorometric detection was used to demonstrate the effects of humic substances (HSs) on the toxicity of tetrabromobisphenol A (TBBPA) and its oxidative decomposition products 2,5-dibromo-1,4-benzoquinone (2,5-DBBQ), 2,5-dibromohydroquinone (2,5-DBHQ), 2,6-dibromobenzoquinone (2,6-DBBQ), and 2,6-dibromophenol (2,6-DBP) to Pseudokirchneriella subcapitata. The EC₅₀ values were: EC_50(TBBPA) = 7 mg L^?1, EC_50(2,5-DBHQ) = 7 mg L^?1, EC_50(2,5-DBBQ) = 19 mg L^?1, EC_50(2,6-DBP) = 49 mg L^?1, and EC_50(2,6-DBBQ) = 13 mg L^?1. The toxicity of the chemicals was slightly lower in the presence of HA. The toxicity of TBBPA decomposed by a biomimetic catalytic system consisting of iron (III) 5,10,15,20-tetrakis (p-sulfonatophenyl) porphyrin (Fe(III)-TPPS) and KHSO₅ was also evaluated using P. subcapitata and Chlamydomonas reinhardtii.     

Comparison of different probe molecules for the quantification of hydroxyl radicals in aqueous solution

We show that the transformation of benzene into phenol is a more selective probe for the hydroxyl radical than the transformation of nitrobenzene or the generation of 4-hydroxybenzoic acid from benzoic acid. The benzene to phenol system showed adequate performance as a probe upon irradiation of lake water samples and humic acids. We show that the use of nitrobenzene and benzoic acid as hydroxyl probes should be avoided because of poor selectivity. Moreover, all the tested probe molecules underwent important interference by irradiated antraquinone-2-sulphonate, and considerably overestimated the formation of the hydroxyl radicals.     

Seasonal and diel variation in movement rhythms of sand dollar, Peronella lesueuri (Valenciennes 1841), in Cockburn Sound, Western Australia

Rates and direction of movement in the sand dollar Peronella lesueuri were measured in summer and winter in Cockburn Sound, a large coastal embayment in south-western Australia. P. lesueuri was found to have a diurnal activity pattern throughout the year and had a greater movement rate in the summer (mean of 5.3 cm h^?1, day; 3.9 cm h^?1, night) than in the winter (mean of 2.7 cm h^?1, day; 2.0 cm h^?1, night). Seasonal change in temperature and physiological requirements by the sand dollar are the most likely reason for the seasonal differences. Reasons for diurnal variation were not clear. Direction of movement was found to be random at both times of the year. Based on these movement rates, one sand dollar can bioturbate an approximate area of 0.1 m² day^?1 and 36.4 m² year^?1. At a conservative density estimate of 0.5 sand dollars per m² it takes approximately 20 days for the sand dollars to rework the entire area of the sediments in the habitats they occupy.     

Seasonal changes in biomass,growth rates and production of subantarctic calanoid copepods in the Bay of Morbihan,Kerguelen Islands

The present study addresses the ecology of two dominant copepod species in the Bay of Morbihan, Kerguelen Archipelago. The biomass of the herbivore Drepanopus pectinatus (from 2 mg m^?3 in winter up to 500 mg m^?3 in summer) is tightly coupled to seasonal changes in chlorophyll a concentration in the region, whereas the biomass of the predatory euchaetiid Paraeuchaeta antarctica increases during two distinct periods over the year: 250 mg m^?3 in early summer, with the recruitment of the annual generation, and 100 mg m^?3 in autumn, with the deposition of lipids as energy reserves in C5 stages and adults. The juvenile growth rates predicted by temperature-dependent models (0.09 day^?1) closely approximate those observed in D. pectinatusin summer, but are much greater than those observed in P. antarctica (from 0.001 to 0.04 day^?1 depending on developmental stages). This difference can be explained by the reproductive strategies and trophic positions of the two species and may also result from the dependence of larval growth on energy reserves in P. antarctica. The production rates are five- and tenfold greater in juvenile stages than in adults, respectively, for D. pectinatus and P. antarctica. The secondary production by D. pectinatusis insufficient to support P. antarcticaduring winter, when the predatory species probably shifts to alternate prey. In summer the predation by P. antarctica accounts for only a minor part of the mortality estimated for D. pectinatus (from 20% to 60% depending on the examined station). At two of the three stations examined in the Bay of Morbihan, the production of P. antarctica could potentially support the dietary requirements of planktivorous seabirds in the region (~2,000 kg prey day^?1 for common diving petrels, Pelecanoides urinatrix, and ~90 kg prey day^?1 for rockhopper penguins, Eudyptes chysocome filholi).     

Investigation of the effects of humic acid and H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s^?1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Biodegradation of phenylurea herbicide diuron by microorganisms from long-term-treated sugarcane-cultivated soils in Kenya

The phenylurea herbicide diuron [N-(3,4-dichlorophenyl)-N,N-dimethylurea] is widely used alone or in a broad range of herbicide formulations. Its degradation in sugarcane-cultivated soils which have been impacted by the herbicide through repeated applications was studied. Liquid culture experiments with diuron as the only carbon source led to the isolation of different bacterial strains capable of degrading diuron. The bacterial species belonging to the genera Bacillus, Vagococcus, and Burkholderia, identified through biochemical and molecular characterization, degraded diuron to different extents. The isolated Bacillus cereus, Vagococcus fluvialis, Burkholderia ambifaria, and Bacillus spp1 degraded diuron by 21%, 25%, 22%, and 19% of the initially applied concentration of 40?mg?L^?1, respectively, after 35 days of incubation in liquid culture media. Small amounts of 3,4-dichloroaniline and the de-methylated metabolite N-(3,4-dichlorophenyl)-N-methylurea were detected in liquid culture media. The combination of V. fluvialis and B. ambifaria showed an enhanced degradation of up to 30% of the initially applied concentration of 40?mg?L^?1. Degradation by pure isolates was low (18–25%) compared to the capacities of diuron degradation shown by the bacterial communities (58–74%). This study showed the presence of diuron degraders in sugarcane-cultivated soils impacted by diuron due to repeated applications.     

Uptake of Ni2+ and rhodamine B by nano-hydroxyapatite/alginate composite beads: batch and continuous-flow systems

Alginate encapsulated nano-hydroxyapatite beads were synthesized and characterized by Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface analysis, and X-ray diffraction. Their adsorptive potential for Ni²⁺ and rhodamine B was explored in batch mode and by fixed-bed column passage. In the batch system, maximum uptake capacity for Ni²⁺ was 360 mg g^?1 and 480 mg g^?1 for rhodamine B. In the presence of humic acid, sorption was enhanced. For the continuous-flow system, adsorption was effective at low flow rate. For both pollutants, mass transport resistance increased during adsorption. The overall rates of rhodamine B and Ni²⁺ uptake were found to be controlled by external mass transfer.     

Extraction,isolation, and identification of various environment friendly components from cock's comb (Celosia argentea) leaves for allelopathic potential

In this study, the aqueous extract of leaves of the plant cock's comb (Celosia argentea) was fractioned into five batches using n-hexane, dichloromethane, ethyl acetate, and n-butanol, respectively. High performance liquid chromatography analysis of the methanol re-dissolved residues of 3 polar fractions, including dichloromethane, ethyl acetate, and n-butanol separately which exhibited altogether 12 compounds identified as 4-hydroxycinnamic acid (p-coumaric acid), 4-hydroxybenzoic acid, protocatechuic acid, caffeic acid, m-coumaric acid, gallic acid, 4-hydroxybenzaldehyde, m-hydroxybenzaldehyde, 2,4-dihydroxybenzoic acid, pyrogallol, 3,5-dihydroxybenzoic acid, and genetic acid was categorized by retention time using known compounds. Similarly, the mass confirmation of most of the identified compounds was achieved by injecting 20 µl of composite sample of these three polar fractions into liquid chromatography–mass spectrometry. Similarly, the physiochemical analysis of C. argentea aqueous extract showed the presence of various constituents such as phenols, flavonoids, tannins, and glycosides. All four organic fractions were examined for phytotoxicity against Lepidium sativum. Analysis of variance showed significant differences among these fractions against germination and growth of L. sativum. Further allelopathic effects appeared to be concentration dependent. Thus, C. argentea may prove effective as a substitute of herbicides to control the weeds like L. sativum from attacking crops and to protect the environment from the health hazard effects of herbicides.     

Rates of apical septal extension of Desmophyllum dianthus: effect of association with endolithic photo-autotrophs

It has been hypothesized that endolithic photo-autotrophs inside the skeleton of cold-water corals may have a mutualistic relationship with the coral host positively affecting coral calcification. This study investigated the effect of endolithic photo-autotrophs on the apical septal extension of the cold-water coral Desmophyllum dianthus at Fjord Comau, southern Chile (42.41°–42.15°S, 72.5°W). The fluorescent staining agent calcein was used to document the linear apical extension of septae for a period of one and a half years between 2006 and 2007. The results showed a severe reduction in extension rates associated with the presence of endolithic photo-autotrophs. Infested individuals grew about half as fast as non-infested polyps with a median value of 1.18 μm day^?1 compared to 2.76 μm day^?1. Contrary to the initial hypothesis, these results point toward a parasitic relationship between D. dianthus and its endolithic photo-autotrophs potentially impairing coral fitness. However, further data on physiological parameters and other aspects of the calcification process are necessary to confirm these findings.