Solubility of organic acids in various methanol and salt concentrations: the implication on organic acid sorption in a cosolvent system

The well-known cosolvency-induced sorption model is not applicable to predict the sorption of carboxylic acids in cosolvent system. To investigate the phenomenon, sorption and solubility of chlorinated phenols (2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP)) and carboxylic acids (benzoic acid and 2,4-dichlorophenoxyacetic acid (2,4-D)) were measured in soil-methanol mixture with various ionic strengths. The sorption (K_m) of chlorinated phenols was explained by a cosolvency-induced sorption model; the inverse log-linear relationship between the K_m and methanol volume fraction (f_c). However, the K_m of carboxylic acids increased with increasing f_c. This discrepancy was attributed to the effect of the carboxylic moiety. To explain the effect, solubility was measured for benzoic acid and 2,4,6-TCP from various liquid conditions. For both solutes, the cosolvency power (σ) increased with CaCl₂ concentrations and the salting constant (K^s) became smaller as f_c increased. However, the σ value at a given salt concentration and the K^s value at a given f_c were greater for 2,4,6-TCP than for benzoic acid, both of which were due to the greater hydrophobicity of the former. Overall, the solubility profiles of the both solutes on combination of f_c and CaCl₂ concentration evidenced no specific role of the carboxylic moiety. Therefore, it can be reasonably concluded that the positive relationship between K_m and f_c for carboxylic organic acid can be attributed to the modification of the activity coefficient occurred in the solid phase, which cannot be traceable by cosolvency-based model.     

超声处理与碱性调节的组合强化低挥发分城市污泥水解酸化

为提高低挥发分城市污泥水解酸化的效率,采用超声处理与碱性调节组合的手段强化水解酸化过程,探讨组合的方式、条件及其作用效果。通过先进行碱性调节再超声处理与先超声处理再进行碱性调节2种组合方式下的6种组合条件,分析水解酸化过程SCOD、VFAs、氮、磷的变化情况。实验结果表明,2种组合方式的各条件均可促进污泥水解酸化;超声处理后即调pH为9.5的组合条件较其他组合条件更有利于有机质的转化和VFAs的产生,SCOD的转化率达到20.46%,VSS可降低约40%,在5 d水解酸化过程中污泥水解酸化液HAc/VFAs均高于50%,VFAs最高达1 072.51 mg/L;而各组合条件对水解酸化过程中氮磷的释放影响不大。研究指出,超声处理后即进行碱性调节的组合条件能显著强化低挥发分城市污泥的水解酸化效果。     

Effect of humic acids on photodegradation of chloroacetanilide herbicides under UV irradiation

The effects of two humic acids (HAs) of different origins on the photodegradation of the chloroacetanilide herbicides acetochlor, propisochlor and butachlor were investigated in this study. One of the tested HAs was a standard sample that was purchased from a commercial source, and the other was isolated from the black soil of Northeast China. The photolysis of all three herbicides followed pseudo-first-order kinetics under ultraviolet (UV) irradiation conditions, regardless of whether HAs were present or not. Both HAs improved the photolysis rates of acetochlor in a dose-reversed way, whereas they inhibited butachlor degradation under all experimental concentrations. The two HAs differed in their effects on propisochlor photolysis, changing from enhancement to inhibition, depending on the origin and concentration of HAs. Element and Fourier Transform Infrared spectroscopy analyses showed that the isolated HAs had more polysaccharides and less aliphatic groups than the commercial HAs, and it was indicated that some characteristic radicals (C═O, O─H and phenolic hydroxyls) in HAs were involved in the photolysis of the herbicides. Gas chromatography/mass spectrometry (GC/MS) analyses indicated that the presence of HAs had no effects on the photolysis pathway and photoproduct species of the three herbicides.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'_W) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb_T) in pure water. Experimental breakthrough volumes (Vb_E) were first determined using purified and deionized water as the matrix for selected compounds having Vb_T < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4–5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb_E curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5–6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb_E in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

The use of naturally generated volatile fatty acids for herbicide removal via denitrification

This research focuses on the removal of 2, 4-D via denitrification, with a particular emphasis on the effect of adding naturally generated volatile fatty acids (VFAs) as a carbon source. These VFAs had been produced from an acid-phase anaerobic digester (mean VFA concentration of 3153 ± 801 mg/L [as acetic acid]). The first step involved developing 2, 4-D degrading bacteria in a sequencing batch reactor (SBR) fed with both sewage and 2, 4-D (30–100 mg/L). Subsequent denitrification batch tests demonstrated that the specific denitrification rate increased from 0.0119 ± 0.0039 to 0.0192 ± 0.0079 g NO₃-N/g volatile suspended solids (VSS) per day, when using 2, 4-D alone versus 2, 4-D plus natural VFAs from the digester as a carbon source. Similarly, the specific 2, 4-D consumption rate increased from 0.0016 ± 0.0009 to 0.0055 ± 0.0021 g 2,4-D/g VSS per day, when using 2, 4-D alone as compared to using 2, 4-D plus natural VFAs. Finally, a parallel increase in the percent 2, 4-D removal was observed, rising from 28.33 ± 11.88 using 2, 4-D alone to 54.17 ± 21.89 using 2, 4-D plus natural VFAs.     

Fatty acid profile and elemental content of avocado (Persea americana Mill.) oil –effect of extraction methods

Interest in vegetable oil extracted from idioblast cells of avocado fruit is growing. In this study, five extraction methods to produce avocado oil have been compared: traditional solvent extraction using a Soxhlet or ultrasound, Soxhlet extraction combined with microwave or ultra-turrax treatment and supercritical fluid extraction (SFE). Traditional Soxhlet extraction produced the most reproducible results, 64.76 ± 0.24 g oil/100 g dry weight (DW) and 63.67 ± 0.20 g oil/100 g DW for Hass and Fuerte varieties, respectively. Microwave extraction gave the highest yield of oil (69.94%) from the Hass variety. Oils from microwave extraction had the highest fatty acid content; oils from SFE had wider range of fatty acids. Oils from Fuerte variety had a higher monounsaturated: saturated FA ratio (3.45–3.70). SFE and microwave extraction produced the best quality oil, better than traditional Soxhlet extraction, with the least amount of oxidizing metals present.     

Metabolism of nC11 fatty acid fed to Trichoderma koningii and Penicillium janthinellum II: Production of intracellular and extracellular lipids

Abstract

Little is known about the fungal metabolism of nC₁₀ and nC₁₁ fatty acids and their conversion into lipids. A mixed batch culture of soil fungi, T. koningii and P. janthinellum, was grown on undecanoic acid (UDA), a mixture of UDA and potato dextrose broth (UDA+PDB), and PDB alone to examine their metabolic conversion during growth. We quantified seven intracellular and extracellular lipid classes using Iatroscan thin-layer chromatography with flame ionization detection (TLC-FID). Gas chromatography with flame ionization detection (GC-FID) was used to quantify 42 individual fatty acids. Per 150 mL culture, the mixed fungal culture grown on UDA+PDB produced the highest amount of intracellular (531 mg) and extracellular (14.7 mg) lipids during the exponential phase. The content of total intracellular lipids represented 25% of the total biomass-carbon, or 10% of the total biomass dry weight produced. Fatty acids made up the largest class of intracellular lipids (457 mg/150 mL culture) and they were synthesized at a rate of 2.4 mg/h during the exponential phase, and decomposed at a rate of 1.8 mg/h during the stationary phase, when UDA+PDB was the carbon source. Palmitic acid (C_16:0), stearic acid (C_18:0), oleic acid (C_18:1), linoleic acid (C_18:2) and vaccenic acid (C_18:1) accounted for >80% of the total intracellular fatty acids. During exponential growth on UDA+PDB, hydrocarbons were the largest pool of all extracellular lipids (6.5 mg), and intracellularly they were synthesized at a rate of 64 μg/h. The mixed fungal species culture of T. koningii and P. janthinellum produced many lipids for potential use as industrial feedstocks or bioproducts in biorefineries.     

Effects of pollution on humic substances

Abstract

To assess effects of industrial and environmental pollution on analytical characteristics of humic substances, we isolated humic acids (HA's) and fulvic acids (FA's) from unpolluted and polluted soils and sediments. Following purification, the HA's and FA's were characterized by elemental (C, H, O, N, S) and functional group (CO₂H, phenolic OH, total acidity) analyses, infrared (IR) spectrophotometry, differential thermal analysis (DTA) and by metal (Fe, Al, Cu, Mn, Pb, Ni, Co, Zn, Cr, Cd, Hg, Ca and Mg) analyses. Si was also determined in all samples.

Polluted HA's and FA's contained more N and S but less 0 and were richer in all metals and Si than were unpolluted ones. IR spectra showed that polluted humic materials were enriched in COO^‐ groups, secondary non‐cyclic amides and possible also in SO₃H groups. DTA curves indicated that polluted HA's and FA's were more thermostable than unpolluted HA's and FA's. Unusually high N, S, Cu, Cr, Zn and Hg contents of humic materials appear to be useful indicators of soil and sediment pollution.     

Effect of manganese on the concentration of amino acids in different regions of the rat brain

Abstract

The present study was designed to determine if chronic exposure of weanlings and adult rats to Mn produces significant alterations in amino acid concentrations in different regions of the rat brain. Weanling (30 day old) and adult (90 day old) male rats were exposed to 10 and 20 mg Mn/kg body weight per day, by gavage, for 30 days. Forty‐ eight hours after the last dose, animals were sacrificed by decapitation and brains were dissected into different regions to determine the concentration of amino acids by HPLC/EC. A dose dependent decrease in body weight gain was found in the adult, but not in the weanling rats. Significant increases occurred in concentrations of aspartate, glutamate, glutamine, taurine and y‐aminobutyric acid (GABA) in the cerebellum of the adult rats dosed with 20 mg/kg per day, Mn. A significant decrease in the concentration of glutamine was observed in caudate nucleus and hippocampus of weanling rats dosed with 10 mg/kg, Mn. These data suggest that chronic Mn exposure can produce a decrease in body weight gain in adult rats and alterations in amino acids in different regions of weanling and adult rat brains.     

稻秆负荷与pH对稻秆厌氧发酵产酸系统启动过程的影响

为探讨稻秆负荷（即稻秆VS/污泥VSS）与发酵pH对稻秆厌氧发酵产酸系统启动过程产挥发性脂肪酸（VFAs）效果的影响,利用厌氧搅拌罐反应系统考察在不同的稻秆负荷（0.556、0.945、1.334和1.724 g/g）和不同的发酵pH（8.0、9.0和10.0）启动运行条件下的产酸性能,并分析了系统启动过程产酸与稻秆主要成分降解之间的关系。实验结果表明,VFAs浓度随稻秆负荷提高而增大,随发酵pH的升高而降低;发酵18 d时,发酵pH为9.0时,稻秆负荷1.334 g/g的产酸效果最好,VFAs浓度与稻秆产酸量分别为4 385.10 mg/L和2.19 gVFAs/g稻秆,此时半纤维素、纤维素和酸性洗涤木质素降解率分别为32.69%、22.53%和6.40%;稻秆负荷为0.945 g/g条件下,VFAs浓度在pH为8.0时达到最高值4 409.51 mg/L,此时稻秆降解量也最多,半纤维素、纤维素和酸性洗涤木质素降解率分别为28.60%、47.32%和22.69%。研究表明,稻秆负荷与发酵pH通过影响稻秆半纤维素、纤维素和木质素的降解影响稻秆厌氧发酵产酸的进程和效果。