Phototransformation of fibrate drugs in aqueous media

The photochemical conversion of bezafibrate, gemfibrozil, fenofibrate and fenofibric acid has been examined in aqueous media. Irradiation with a solar simulator in distilled water caused about 10% degradation for the first three drugs after 200 hr, while fenofibric acid was completely degraded after 100 hr. Experiments have also been performed in the presence of nitrates or humic acids, considered as environmental photosensitizers, and only for gemfibrozil a reduction of degradation has been observed. Photoproducts have been characterized and the mechanistic pathways discussed on the basis of experimental and literature data.     

Analysis of polymeric quaternary ammonium salts as found in cosmetics by metachromatic polyelectrolyte titration

Metachromatic polyelectrolyte titration was investigated as a means of analyzing polymeric quaternary ammonium salts (polyquaterniums) of relatively low charge density used as ingredients in cosmetics. They are of possible toxicological concern, but little is known of their environmental fate and behavior. With o-toluidine blue as the indicator, determination of the concentration of a range of polyquaterniums of commercial importance and cosmetic origin was possible. Using a visual endpoint, normalities as low as 3 × 10^?5 N could be determined, while with a spectrophotometric endpoint, the technique was effective to approximately 3 × 10^?6 N. The concentrations (g L^?1) to which these normalities correspond depend on the charge density of the polymer. Polyquaterniums are frequently used in association with anionic surfactants in cosmetic formulations and the presence of an anionic surfactant even in excess did not affect results although the color change was less stable. Titration in the presence of prepared humic acid was also possible.     

Degradation of bisphenol A by photo-fenton processes

The photo-Fenton reactions, which could yield hydroxyl radicals via the catalytic degradation of H₂O₂ by Fe(II), were focused as one of the abiotic degradation processes of bisphenol A (BPA) in surface waters. At pH 6, in the presence of H₂O₂ only, 32% of BPA was degraded after 120?min of irradiation. However, 97% of BPA was degraded in the presence of both H₂O₂ and Fe(II). Without light irradiation, no BPA degradation was observed even in the presence of Fe(II) and H₂O₂. These results show that photo-Fenton processes are effective in the natural attenuation of BPA in surface water. In addition, the presence of humic acids (HAs), which were of more aliphatic nature, resulted in enhancing BPA degradation via the photo-Fenton processes. Therefore, HAs can be one of the important factors in enhancing the degradation of BPA in surface water via the photo-Fenton processes.     

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.     

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.     

Strong adsorption of DNA molecules on humic acids

Analysing soil microbial communities is often hampered by DNA adsorption on soil organic compounds such as humic acids. However the role of humic acids in DNA adsorption and stability in soils remains controversial. To characterize DNA–humic acid interactions, we studied DNA adsorption on two commercially available humic acids and a soil humic acid extracted from an Andosol. Desorption of the adsorbed DNA using 4 different solutions—distilled water, 0.1 M NaCl, 0.1 M sodium phosphate buffer (pH 6.0), and 1% sodium dodecyl sulfate solution—was also studied to understand the mechanism of DNA adsorption on humic acids. Here, we show that humic acids play an important role in DNA adsorption to soils. DNA molecules were adsorbed on the humic acids, with adsorption increasing proportionally with the DNA concentrations in the solution. The adsorption on all humic acid samples was fitted with Freundlich equation, and the parameters obtained from the equation indicated a high affinity between the humic acids and DNA molecules. The total amount of DNA desorbed by the 4 solutions was less than 2% of the total DNA adsorbed on all the humic acids. The results demonstrate that DNA molecules are able to bind strongly to humic acids by ligand binding, hydrophobic interaction, aggregation, or precipitation.     

辉光放电等离子体技术处理印染废水的研究

用辉光放电等离子体技术对茜素红降解进行了研究，藉助紫外光谱分析了其降解过程，结果表明，在pH=7时，茜素红于60min便可以被完全降解，且其排放液接近无色，降解过程中溶液pH值降低，说明反应过程中可能有羧酸类物质生成．两电极间的距离与催化剂对降解率有显著影响，COD先升高后降低，若在Fe^2 存在时，反应只需10min，且COD值不断减小．     

Effect of humic acids on the Fenton degradation of phenol

We show that the degradation of phenol by Fe(III) and hydrogen peroxide is faster in the presence of humic acids. This is most likely due to faster reduction of Fe(III)-humate complexes by H₂O₂/HO₂^·/O₂^–· when compared with Fe(III)-H₂O complexes. The fact that humic acids, a major class of naturally occurring compounds, favour the Fenton reaction has great relevance in the field of water and soil decontamination, where organic compounds usually have a negative effect. Furthermore, it adds insight into the self-depuration processes of natural aquifers.     

近地面O_3含量升高条件下土壤中腐殖质单体儿茶酚转化的放射性~（14）C示踪研究

近地面大气臭氧（O3）含量不断升高对生态环境的影响已引起人们的广泛关注,然而O3含量升高对土壤有机碳的矿化及转化影响却少有研究。土壤有机碳是全球碳循环的重要组成部分,土壤碳库的微小变化将引起大气CO2浓度的显著改变。文章以典型土壤腐殖质单体化合物儿茶酚为代表,利用14C示踪技术,研究了O3含量比当前背景升高约0.15μmol·mol-1时对土壤中腐殖质苯酚类前体化合物的矿化及转化的影响。结果表明,O3含量升高会对土壤中培育12d后儿茶酚的矿化及残留物分布具有显著的影响,而且这种影响程度和规律同土壤有关。O3含量升高促进了黄棕壤中儿茶酚的矿化,增加了儿茶酚残留物在黄棕壤腐殖酸（HA）中的总量,并使残留物在HA中偏向于同大分子结合。O3含量升高对灰潮土中儿茶酚的矿化有抑制作用,但对儿茶酚残留在HA内总量及分布没有显著影响。O3含量升高对儿茶酚在土壤中的稳定性及归趋的影响可能是O3对于微生物活性的抑制作用和O3的直接氧化作用的共同结果。后续工作中应研究土壤腐殖质中其它组份的稳定性及转化对近地面大气O3含量升高的响应,以全面考察O3含量升高对土壤碳库的影响。     

Diuron herbicide degradation catalyzed by low molecular weight humic acid-like compounds

Phenylureas such as diuron are major herbicides used worldwide to control undesirable weeds. The environmental fate of phenylureas is of great interest because massive amounts of those herbicides are used. It is known that abiotic degradation of phenylureas in soil–water systems is catalyzed by humic acids. However, due to the chemical heterogeneity and large molecular sizes of humic acids, the specific effects of functional groups during catalysis have not been elucidated. Therefore, we studied here for the first time the kinetics of diuron degradation in the presence of low molecular weight humic acid-like compounds such as benzoic acid derivatives. Experiments were carried out at various pH and temperature, and monitored by high-performance liquid chromatography. Results show that all benzoic acid derivatives efficiently catalyzed diuron hydrolysis. The catalytic efficiency decreased in the following order: 0.88 M^?1 day^?1 for 3,4-dihydroxybenzoic acid, 0.72 M^?1 day^?1 for 4-hydroxybenzoic acid, 0.23 M^?1 day^?1 for phthalic acid, 0.11 M^?1 day^?1 for 2-hydroxybenzoic acid, and 0.09 M^?1 day^?1 for 2,4-dihydroxybenzoic acid. These differences in the catalytic efficiency are explained by steric hindrance affecting the accessibility of reactive sites and hence influencing the rate of the overall process. Steric factors are therefore expected to control the catalytic activity of humic acids because of the chemical similarities between humic acids and low molecular weight humic acid-like compound. Our results should help predict more accurately the fate and abiotic degradation mechanism of phenylureas in the environment.     

Ozonation as an efficient pretreatment method to alleviate reverse osmosis membrane fouling caused by complexes of humic acid and calcium ion

Humic acids (HA) didn’t cause obvious reverse osmosis (RO) membrane fouling in 45 h. Osmotic pressure (NaCl) affected slightly the RO membrane fouling behavior of HA. Ca²⁺ promoted aggregation of HA molecules and thus aggravated RO membrane fouling. Ozonation eliminated the effect of Ca²⁺ on the RO membrane fouling behavior of HA. The change of the structure of HA was related to its membrane fouling behavior. Humic acid has been considered as one of the most significant sources in feed water causing organic fouling of reverse osmosis (RO) membranes, but the relationship between the fouling behavior of humic acid and the change of its molecular structure has not been well developed yet. In this study, the RO membrane fouling behavior of humic acid was studied systematically with ozonation as a pretreatment method to control RO membrane fouling. Furthermore, the effect of ozone on the structure of humic acid was also explored to reveal the mechanisms. Humic acid alone (10–90 mg/L, in deionized water) was found not to cause obvious RO membrane fouling in 45-h operation. However, the presence of Ca²⁺ aggravated significantly the RO membrane fouling caused by humic acid, with significant flux reduction and denser fouling layer on RO membrane, as it was observed by scanning electron microscope (SEM) and atomic force microscope (AFM). However, after the pretreatment by ozone, the influence of Ca²⁺ was almost eliminated. Further analysis revealed that the addition of Ca²⁺ increased the particle size of humic acid solution significantly, while ozonation reduced the SUVA₂₅₄, particle size and molecular weight of the complexes of humic acid and Ca²⁺ (HA-Ca²⁺ complexes). According to these results and literature, the bridge effect of Ca²⁺ aggregating humic acid molecules and the cleavage effect of ozone breaking HA-Ca²⁺ complexes were summarized. The change of the structure of humic acid under the effect of Ca²⁺ and ozone is closely related to the change of its membrane fouling behavior.     

微生物降解褐煤产生的腐植酸化学特性研究

本文对微生物降解褐煤产生的腐植酸的化学特性进行了分析.结果表明,褐煤经微生物降解后其腐植酸与降解前相比,氢和氧百分含量增加,碳百分含量减少,分子量减小 ,而絮凝极限明显增大,红外吸收光谱也发生明显变化.     

添加剂对绿色木霉JQF-04纤维素酶热稳定性的影响

如何提高酶蛋白的热稳定性是分子生物学、微生物学、生化工程学等学科长期所关注的重要研究课题之一.本文研究了多种添加剂对绿色木霉纤维素酶热稳定性的影响.在60℃的溶液中,多元醇(乙二醇、甘油、赤藓糖醇、木糖醇和山梨糖醇)能提高该酶的热稳定性,随着浓度的增加,赤藓糖醇、木糖醇和山梨糖醇促进酶的热稳定性呈线性增高;适当的多元醇分子长度对该酶的热稳定性有最优的保护效应;不同浓度和不同分子量的聚乙二醇对该酶的热稳定性具有明显的影响;在无机盐中,单价金属阳离子比二价金属阳离子更能显著地提高该酶的热稳定性;酶液溶剂的改变直接影响着该酶的热稳定性,该酶在D2O溶液中比在水溶液中稳定,其酶活半衰期延长了2.6倍.研究表明,热环境使酶蛋白分子的螺旋结构发生变化而失活,但某些溶质和溶剂的存在可能通过作用于蛋白质分子的三维结构而影响该酶的热稳定性.图7参15     

Plant Bioavailability of “natural” and “model” Humic acid‐bound [14c] Atrazine residues

The release of bound [14C] atrazine residues and their uptake by maize plants was investigated.

“Natural”; humic acids, extracted from a brown soil, and “model”; humic acids, prepared from catechol, both containing bound [14C] atrazine residues were incubated with plants in soil. After 21 days, the maize plants contained 0.7% (plants grown in soil mixed with “natural”; humic acids) to 1.7% (plants grown in soil mixed with “model”; humic acids) of the radioactivity originally introduced.

The roots contained 55 to 70% of the [14C] residues whereas the remainder was present in the shoots. A significant amount of the total [14C] residues (29 to 53%) became again bound in plant tissues, whereas the, majority of extractable [14C] residues was present in the form of conjugates.

The behaviour of “model”; humic acid‐bound residues was comparable to that of “natural”; humic acid‐bound residues or soil‐bound residues.     

Release of Cd immobilized by soil constituents and its bioavailability

Release of Cd immobilized by soil constituents (clay, humic acids, bacterial cells) in vitro and under soil conditions and its bioavailability to lettuce were studied. The most resistant to extraction with 0.02 M EDTA in vitro as well as under soil conditions was cadmium immobilized by humic acids during decomposition of contaminated plant residues but Cd‐dead cells when 0.1 M NaNO₃ was the extractant.

Cadmium addition (3 mg kg^‐1) to soil and its form were without effect on plant growth and amount of metal accumulated in roots. Tops of plants grown in soil supplemented with Cd‐resting cells contained significantly less metal then other ones.     

涕灭威及其复合物对茎线虫DNA的影响

选择了一种毒性很高的氨基甲酸酯农药涕灭威、一种最常见的阴离子表面活性剂十二烷基苯磺酸钠(SDBS)及一种土壤中普遍存在的天然物质腐殖酸,组成两种复合污染体系;研究了它们对茎线虫的生态毒理效应和对DNA的影响.结果发现,涕灭威-SDBS复合体系在4 d内对茎线虫的DNA造成了明显的损伤,而涕灭威-SDBS-腐殖酸复合体系在8 d内对茎线虫DNA造成的损伤却远远低于未加入腐殖酸的复合体系.关于涕灭威及其复合污染物对茎线虫的生态毒理效应和对DNA损伤的研究尚未见文献报道.     

Thermal defluorination behaviors of PFOS,PFOA and PFBS during regeneration of activated carbon by molten salt

• New method of mineralizing PFCs was proposed. • Activated carbon was regenerated while mineralizing PFCs. • Molten NaOH has good mineralization effect on PFOS and PFBS. Current study proposes a green regeneration method of activated carbon (AC) laden with Perfluorochemicals (PFCs) from the perspective of environmental safety and resource regeneration. The defluorination efficiencies of AC adsorbed perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonate (PFBS) using three molten sodium salts and one molten alkali were compared. Results showed that defluorination efficiencies of molten NaOH for the three PFCs were higher than the other three molten sodium salts at lower temperature. At 700°C, the defluorination efficiencies of PFOS and PFBS using molten NaOH reached to 84.2% and 79.2%, respectively, while the defluorination efficiency of PFOA was 35.3%. In addition, the temperature of molten salt, the holding time and the ratio of salt to carbon were directly proportional to the defluorination efficiency. The low defluorination efficiency of PFOA was due to the low thermal stability of PFOA, which made it difficult to be captured by molten salt.The weight loss range of PFOA was 75°C–125°C, which was much lower than PFOS and PFBS (400°C–500°C). From the perspective of gas production, fluorine-containing gases produced from molten NaOH-treated AC were significantly reduced, which means that environmental risks were significantly reduced. After molten NaOH treatment, the regenerated AC had higher adsorption capacity than that of pre-treated AC.     

Scanning Electron Microscopy of Humic Substances Produced During Cellulose Decomposition

Humic substances (HS) produced during the aerobic decomposition of polysaccharides still need to be recognized as such and characterized. Humic (HA) and fulvic (FA) acids extracted at different time intervals during composting of cotton residues from carding, where no decomposition of lignin occurred, were investigated by scanning electron microscopy (SEM) size exclusion chromatography and infrared spectroscopy. Throughout the experiment, fulvic acids possessed a larger number of carboxyl groups but a lower number of weak acidic groups (negatively charged acid groups at pH 11) than humic acids. the number of carboxyl groups increased with time in both fulvic and humic acids, while that of phenolic groups decreased. Infrared spectra showed that the ratio between carboxyl and methyl groups decreased from 8.5 to 4 in FA after 18 days. This change corresponded with the disappearance of flat sheet structures observed by SEM at pH 6. Our results suggest that the shape of humic molecules as observed by SEM reflects the strength of hydrophilic/hydrophobic interactions with the solvent molecules. About 80% of FA molecules had a molecular weight lower than 3500 as deduced from column calibration with HS standards obtained by ultrafiltration. About 40% of humic acids were composed of small molecules; only 20% HA had a molecular weight larger than 45000. Polysaccharide-derived HS may not be limited to the high molecular weight poorly transformed fraction containing bonded polysaccharide structures, but may also consist of low molecular weight components with no structural similarity to the original material.     

Chromium (VI) tolerance in two halotolerant strains of Nostoc

The present study reports on chromium (VI) tolerance of two cyanobacterial strains Nostoc linckia and Nostoc spongiaeforme isolated from salt affected soils using uni-algal and bi-algal systems. Besides distinct halophilism, the two strains exhibited remarkable tolerance to chromium (VI) and revealed 1.2 to 2.8 times more chlorophyll in the presence of the metal. While phycobilins and carotenoids also increased in Nostoc linckia with total dissolved salts (TDS) as well as metal, a decline was observed in Nostoc spongiaeforme in the presence of Cr (VI). Relative algal biomass (as % of control) showed significantly higher values (123-239) in Nostoc linckia in the presence of salt, metal and combination of the two. In Nostoc spongiaeforme it declined in the presence of metal (72-81) but increased in the presence of salts (143-249) and also in the binary systems (121-440). The bi-algal consortium showed relatively less tolerance to salt and metal stress. Nostoc linckia (20 day culture) showed upto 40% chromium removal whereas Nostoc spongiaeforme showed up to 12% removal, indicating greater suitability of the former for use in bioremediation studies.     

Effect of cyanobacterial exopolysaccharides on salt stress alleviation and seed germination

Effectof exopolysaccharides (EPS) produced by a consortium of cyanobacteria on germination of three crops wheat, maize and rice was studied at different salt concentrations. Production of EPS was found to be stimulated by salts, which in turn had a significant Na+ removal capability from aqueous solution. Seed germination, vigor index and mobilization efficiency in all the three crops remarkably improved when cyanobacterial EPS was applied. While germination improved significantly by 13 to 30%, mobilization efficiency increased marginally by 1.03 to 1.1 times and vigor index increased by 1.15 to 2.4 times in these crops in response to EPS under non-saline conditions. Salinity had an inhibitory effect on seed germination of all the species showing 18 to 54% reduction. However, in the presence of EPS, the salt induced inhibition diminished to 13 to 18%. Inhibitory effect of salt on chlorophyll concentration, vigor index and mobilization efficiency of the seedlings was much less in these crops in the presence of EPS, indicating the latter's role in salt stress alleviation.