Electrochemical oxidation of herbicide bifenox acid in aqueous medium using diamond thin film electrode

The electrochemical oxidation of bifenox acid was studied at a boron-doped diamond thin film by cyclic voltammetry and galvanostatic electrolysis. The course of the electrolysis was monitored by measurement of chemical oxygen demand (COD) and by gas chromatography/mass spectrometry (GC / MS) analysis. It was found that exhaustive electrolysis leads to degradation and, ultimately, to mineralization of the starting herbicide. The degradation intermediates were identified showing that the oxidation process begins with the fragmentation of the molecule followed by reactions involving the hydroxyl radical, which is generated by the discharge of water. The study of the effect of current density and concentration showed that the degradation efficiency increases with decreasing current densities and increasing concentrations. The whole results were interpreted in a mechanistic scheme involving two oxidation pathways, the first is a direct oxidation at the electrode and the second uses hydroxyl radical as mediator of the oxidation. Finally, a kinetic study based on spectrophotometric measurements showed that the degradation process is pseudo first order.     

Growth,photosynthesis and removal responses of the cyanobacteria Chroococcus sp. to malathion and malaoxon

Abstract

Malathion is an organophosphorus pesticide widely used in agricultural crops, despite its toxicity. In addition, malaoxon occurs by oxidation of malathion being more toxic. The toxic effects of malathion and malaoxon in humans include hepatoxicity, breast cancer, genetic damage and endocrine disruption. The aim of this study involved assessing the effect of malathion commercial grade on Chroococcus sp., and its potential as an alternative to the removal of this pesticide and its transformation product such as malaoxon. We evaluated the effect of malathion at different concentrations (1, 25, 50, 75 and 100?ppm) on the biomass of the cyanobacteria Chroococcus sp. grown in medium BG-11; also, we analyse its ability to degrade both malathion and malaoxon into a temperature of 28?±?2?°C and at pH 6. The results showed that 50?ppm of malathion the cyanobacteria Chroococcus sp. reached the highest removal efficiency of malathion and malaoxon (69 and 65%, respectively); also, the growth rate of Chroococcus sp. increased without inhibiting the production of chlorophyll “a”, this can be explained by the hormesis phenomenon. Therefore, we consider that the cyanobacteria Chroococcus sp. may be a good candidate for bioremediation of aquatic systems contaminated with organophosphorus pesticides such as malathion and its transformation product such as malaoxon.     

江汉平原农村食品中农药残留研究

研究了湖北省潜江市农村６类食品中农药的残留情况,采样测定结果表明,在被检食品中有机氯农药污染普遍存在,但残留量均低于最大残留限量（ＭＲＬ）,以植物油残留量为最大;有机磷农药残留只在蔬菜中检出,检出率以根菜类为最大,叶菜类次之,果菜类和花菜类最小;菊酯类农药残留较少;杀菌剂多菌灵残留未检出。     

北方泥炭地泥炭土矿化速率、温度敏感性及其影响因素研究

北方泥炭地是全球重要的碳汇,也是全球变暖最为敏感的区域之一.然而,由于泥炭地表层和亚表层泥炭土碳排放过程对全球变暖的响应过程及机制仍存在一定争议,目前对全球变暖背景下泥炭地碳排放的认识仍存在一定不足.本研究于2019年8月在大兴安岭满归泥炭地采集表层(0～10 cm)和亚表层(15～30 cm)泥炭土进行室内增温模拟有氧培养,测定其矿化速率、有机质性质和水解酶活性.结果表明,表层泥炭土矿化速率在5、15、25℃下培养时((142.8±66.9)～(545.3±30.6)、(575.0±62.1)～(1843.0±547.4)、(888.4±123.9)～(3646.7±167.9)μg·g^-1·d^-1)均高于亚表层((113.0±41.5)～(367.1±64.1)、(357.4±52.3)～(1122.1±218.8)、(697.1±38.1)～(2336.4±150.6)μg·g^-1·d^-1),但表层和亚表层矿化作用的温度敏感性不具有显著差异;培养过程中,表层与亚表层泥炭土β-1,4-N-乙酰葡...     

Modeling the carbon dynamics of the La Grande hydroelectric complex in northern Quebec

A mechanistic semi-empirical carbon cycle model of the La Grande reservoir complex in northern Quebec, Canada was conceived in order to investigate the climate impact of such a large alteration of the continental water cycle. The model includes inputs from the drainage basin, organic matter release from flooded soils, CO₂ emissions across the water-atmosphere interface and sedimentation. Most input data stems from previous research by our group on those ecosystems. The model includes the seven reservoirs of the La Grande complex and was run for periods of 50 and 100 years. Terrigeneous dissolved, particulate and suspended soil carbon fluxes and concentrations were computed. Over 100 years, 31.3 × 10¹² g C are released from flooded soils, equivalent to 28-29% of inputs from the drainage basin. 40-74% of dissolved organic carbon is mineralized. CO₂ fluxes over 100 years are 50.5-79.8 × 10¹² g C, 46.4-67.9 × 10¹² g C more than in the absence of reservoirs. The increase in mineralization of organic matter and in CO₂ emissions is a result of the increase in cumulated water residence time due to the creation of the reservoirs. Changes in other carbon sinks and sources likely offset a part of this additional carbon flux to the atmosphere. In the first years following flooding of the reservoir, organic carbon release from flooded soils exceeds CO₂ emissions, implying the downstream export of large quantities of eroded soil organic carbon. After this initial period, CO₂ emissions are fuelled by organic carbon originating from the drainage basin.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Distribution,fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, ¹⁴C- and ¹³C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied ¹⁴C was mineralized. The bioavailable, water extractable portion was low (9 % of applied ¹⁴C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied ¹⁴C was incorporated into organo-clay complexes as NER, whereas 9 % of applied ¹⁴C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Ozone-driven photocatalyzed degradation and mineralization of pesticide,Triclopyr by Au/TiO2

Triclopyr is a widely used pesticide which is non-biodegradable and enters aquatic systems. The ozone facilitated photocatalyzed degradation and mineralization of Triclopyr using Au-loaded titania as heterogeneous catalyst is reported. The oxidative degradation activity of the hazardous pesticide was investigated at pH 7.8 under varied reaction conditions, including in presence and absence of ozone, titania alone, in presence and absence of light and with different loadings of Au on support. Photocatalysis with 2% Au/TiO₂ in the presence of ozone yielded 100% degradation of Triclopyr in 2 h. The extent of degradation of pesticide and its mineralization were confirmed by GC-MS. For 10 mg/L of Triclopyr, 0.1 g/L of catalyst was found to be the optimum for mineralization. Results show that photocatalyzed ozonation with Au/TiO₂ as catalyst is a very effective for its removal. No leaching of Au was observed in triplicate runs. Catalyst was fully recoverable and reusable with no loss of activity.     

Nitrogen Budget of a Spruce Forest Ecosystem After Six-year Addition of Ammonium Sulphate in Southwest Sweden

A nitrogen (N) budget was constructed for a period of 6 years (1988–1993) in a Norway spruce stand with current deposition of 19 kg N and 22 kg S ha⁻¹ year⁻¹. The stand was fertilized annually by addition of 100 kg N and 114 kg S ha⁻¹ (NS). Above and below ground biomass, litterfall, fine- root litter production, soil solution and net mineralization were measured to estimate pools, fluxes and accumulation of nitrogen. The average needle litterfall in control (C) and NS plots in 1993 was 2.2 and 2.5 ton ha⁻¹ year⁻¹, respectively. The fine root litter production prior to treatment (1987) was 4.4 ton ha⁻¹ year⁻¹ and after treatment (1993) it was 4.5 and 3.9 ton ha⁻¹ year⁻¹ in C and NS plots, respectively. Net N mineralization in the soil profile down to 50 cm was estimated to be 86 and 115 kg ha⁻¹ year⁻¹ in C and NS plots, respectively in 1992. During the treatment period the uptake of N in the needle biomass in C and NS plots was 29 and 77 kg ha⁻¹ year⁻¹, respectively. No N was accumulated in needles of C plot where the NS plots accumulated 34 kg ha⁻¹ year⁻¹. Of the annually added inorganic N to NS plots 47% was accumulated in the above and below ground biomass and 37% in the soil. N fluxes via fine-root litter production in the C plots were much higher (54 kg ha⁻¹ year⁻¹) than that via litterfall (29 kg ha⁻¹ year⁻¹). The corresponding values in the NS plots were 65 and 43 kg ha⁻¹ year⁻¹, respectively. Most of the net N mineralization occurred in the FH layer and upper mineral soil. It is concluded that fine root litter and litterfall play an important role in the cycling of N. Despite a high N uptake the losses of N in litterfall and fine root litter resulted in an incorporation of N in soil organic matter.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).