Simultaneous analysis of thiabendazole,carbendazim and 2-aminobenzimidazole in concentrated fruit juices by liquid chromatography after a single mix-mode solid-phase extraction cleanup

A method using liquid chromatography and a single mix-mode solid-phase extraction cleanup for the simultaneous analysis of thiabendazole [2-(1,3-thiazol-4-yl)-1H-benzoimidazole], carbendazim [(methyl N-(1H-benzoimidazol-2-yl)-carbamate)] and 2-aminobenzimidazole (1H-benzimidazol-2-amine) in concentrated fruit juices is described. The three fungicides were isolated from the samples and concentrated by solid-phase extraction on Oasis MCX cartridges. The determination was performed by liquid chromatography with a diode array, detecting at 288 nm. In this method, the average recoveries from blank control juice samples spiked in a concentration range of 0.01–0.10 mg/kg were in the range of 81–95%, with relative standard deviations below 8%. Detection limits and limits of quantification were 4 μ g/kg and 10 μ g/kg, respectively, for each fungicide. Real juice samples were analyzed by the proposed method. The results were compared to those from liquid chromatography-tandem mass spectrometry.     

Occurrence and fate of alkylphenols and alkylphenol ethoxylates in sewage treatment plants and impact on receiving waters along the Ter River (Catalonia, NE Spain)

The partitioning of alkylphenols in the dissolved and particulate matter of influents, effluents, accumulation onto sludge and the impact of sewage treatment plant upon receiving waters was studied along the Ter River basin (Catalonia, NE Spain). A solid-phase extraction or pressurized liquid extraction followed by liquid chromatography-mass spectrometry was developed and permitted to determine target compounds with high efficiency in waters, particulate material and sludge. Nonylphenol mono- and diethoxylate, nonylphenol and octylphenol partitioned preferably upon particulate matter and sludge, whereas long chain NPE(3-15)O prevailed in the dissolved phase and was released by effluents. Within the treatment process, a net accumulation of alkylphenols in sludge was found, producing up to 148g/t/month. The removal efficiency of alkylphenols was of 37-90% and depended on the treatment. Assessment on the fate of these contaminants within STPs is discussed in terms of flow rates, biological oxygen demand and tons of sludge produced.     

Characteristics and removal mechanism of the precursors of N-chloro-2,2-dichloroacetamide in a drinking water treatment process at Taihu Lake

• N-Cl-DCAM, an emerging N-DBP in drinking water was investigated. • A new BAC has a better removal efficiency for N-Cl-DCAM precursors than an old BAC. • N-Cl-DCAM precursors are more of low molecular weight and non-polar. • Adsorption of GAC plays a major role in removal of N-Cl-DCAM precursors by an O₃-BAC. N-chloro-2,2-dichloroacetamide (N-Cl-DCAM) is an emerging nitrogenous disinfection by-product (N-DBP) which can occur in drinking water. In this study, an analytical method based on liquid chromatography with tandem mass spectrometry (LC-MS/MS) was developed to validate the concentration of N-Cl-DCAM, which was found to be 1.5 mg/L in the effluent of a waterworks receiving raw water from Taihu Lake, China. The changes of N-Cl-DCAM formation potential (N-Cl-DCAMFP) in the drinking water treatment process and the removal efficiency of its precursors in each unit were evaluated. Non-polar organics accounted for the majority of N-Cl-DCAM precursors, accounting for 70% of the N-Cl-DCAM FP. The effect of conventional water treatment processes on the removal of N-Cl-DCAM precursors was found to be unsatisfactory due to their poor performance in the removal of low molecular weight (MW) or non-polar organics. In the ozonation integrated with biological activated carbon (O₃-BAC) process, the ozonation had little influence on the decrease of N-Cl-DCAM FP. The removal efficiency of precursors by a new BAC filter, in which the granular activated carbon (GAC) had only been used for four months was higher than that achieved by an old BAC filter in which the GAC had been used for two years. The different removal efficiencies of precursors were mainly due to the different adsorption capacities of GAC for individual precursors. Low MW or non-polar organics were predominantly removed by GAC, rather than biodegradation by microorganisms attached to GAC particles.     

Self-ignition in stone wool insulation contaminated with fatty acid (fundamentals,case study,analysis methodology)

A combination of a residual film of flammable organic substance, air and porous structures like insulation material (e.g. stone wool) may result in a fire. The initiating self-heating process depends on the substance (reactivity, volatility), amount of accumulated liquid, volume and temperature. Specific information is given for application and extension of the Thomas criterion with a 2nd order reaction. The experimental part includes new experimental techniques to determine heat transfer and formal reaction kinetic data. The applied self-ignition temperature (SIT) simulation model relies on liquid film volume and not on liquid film surface reaction. As a further result of the studies detailed working procedure of three simplified methodologies for estimation of SITs in technical scale are presented. New techniques to determine parameters necessary for SIT prediction, especially in combination with Methodology III, have the power to reduce the costs for estimating the SIT up to 80%.     

The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene

Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.     

Scaled-up bioconversion of fish waste to liquid fertilizer using a 5 L ribbon-type reactor

A scaled-up conversion process of fish waste to liquid fertilizer was performed in a 5 L ribbon-type reactor. Biodegradation was performed by inoculation of autoclaved fish waste with 5.84 × 10(5) CFU mL(-1) of mixed microorganisms for 96 h. As a result, the pH changed from 6.92 to 5.72, the cell number reached 7.28 × 10(5) CFU mL(-1), and approximately 430 g (28.3%) of fish waste was degraded. Analyses indicated that the 96 h culture of inoculated fish waste possessed comparable fertilizing ability to commercial fertilizers in hydroponic culture with amino acid contents of 6.91 g 100 g(-1). Therefore, the scaled-up production achieved a more satisfactory fish waste degradation rate (3.61 g h(-1)) than the flask-scale production (0.24 g h(-1)). The biodegraded broth of fish waste at room temperature did not undergo putrefaction for 6 months due to the addition of 1% lactate.     

Effects of oxidizing environment on digestate humification and identification of substances governing the dissolved organic matter (DOM) transformation process

• Liquid digestate humification was investigated under different oxidizing environment. • Tryptophan-like substances dominated the transformation of the liquid digestate DOM. • The humification sequence of the liquid digestate DOM was identified. • UV₃₂₅ was first identified as a pre-humus intermediate during humification reaction. The formation of humic-like acids (HLAs) is an essential process for converting liquid digestate into organic soil amendments to enhance agricultural sustainability. The aim of this study was to investigate the impact of oxygen and/or MnO₂ on the production of HLAs. Herein, abiotic humification performance of the digestate dissolved organic matter (DOM) is investigated with fluxes of air and N₂ in the absence and presence of MnO₂. Our results demonstrated that the fate of digestate DOM greatly depends on the oxidizing environment, the MnO₂ enhanced nitrogen involved in the formation of HLAs. The synergistic effects of MnO₂ and oxygen effectively improved the production of HLAs, and the corresponding component evolution was analyzed using spectroscopic evidence. The two-dimensional correlation spectroscopy results demonstrated that the reaction sequence of digestate DOM followed the order of protein-like substances, substances with an absorbance at 325 nm, substances with UV absorbance at 254 nm and HLAs. Additionally, excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) showed that tryptophan-like C3 was more prone to transformation than tyrosine-like C2 and was responsible for the humification process. The substance with an absorbance at 325 nm was a reaction intermediate in the transformation process of protein-like substances to HLAs. The above findings can be used to promote the production of liquid fertilizer associated with carbon sequestration as well as the sustainable development of biogas production.     

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.