土壤性质对土壤中汞赋存形态的影响

土壤是一个复杂的生态系统,典型相关分析表明,土壤的组成性状对土壤中汞的形态分布影响较大,影响因子主要有ＦＡ,ＨＡ,有机质和碳酸盐含量,土壤粘粒作用较小,土壤有机质表现出很强的表面络合能力。     

Species of Trace Metals, Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^-1, dry weight in fulvic acid and 820μg g^-1 in humic acid) and lead (821μg g^-1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Photoreactivity of humic substances: relationship between fluorescence and singlet oxygen production

Humic substances are natural compounds abundantly present in the environment. They play a significant role in the natural attenuation of pollution in surface water due to their capacity to generate reactive species upon solar light excitation. Finding physico chemical parameters related to this property would be of a great help in the prediction studies of the organic pollutants fate. In this work, we investigated relationships between the ability of the humic substances to produce singlet oxygen and their fluorescence properties. For this, a series of sixteen humic acids, fulvic acids, and water-extractable organic matter from soils were studied. The steady-state singlet oxygen concentrations in the irradiated humic substances solutions were measured by monitoring the loss of furfuryl alcohol added as a singlet oxygen scavenger. The emission spectra of the sixteen samples were also recorded. Values of the steady-state singlet oxygen concentrations and the emission intensities showed significant variations among the humic samples and a parallel increase. Thus, here we demonstrate that the rate of singlet oxygen production and the emission intensity of the humic samples are correlated, the best correlation being obtained for emission wavelengths between 500 and 580 nm. This correlation which was never reported until now can be used to estimate the singlet oxygen-production capacity of the humic substances based on their fluorescent properties.     

Light-induced variation in environmentally persistent free radicals and the generation of reactive radical species in humic substances

• Light irradiation increased the concentration of free radicals on HS. • The increased spin densities on HS readily returned back to the original value. • The “unstable” free radicals induced the formation of reactive radical species. • Reactive radicals’ concentration correlated strongly with EPFRs’ concentration. Environmentally persistent free radicals (EPFRs) in humic substances play an essential role in soil geochemical processes. Light is known to induce EPFRs formation for dissolved organic matter in aquatic environments; however, the impacts of light irradiation on the variation of EPFRs in soil humic substances remain unclear. In this study, humic acid, fulvic acid, and humin were extracted from peat soil and then in situ irradiated using simulated sunlight. Electron paramagnetic resonance spectroscopy results showed that with the increasing irradiation time, the spin densities and g-factors of humic substances rapidly increased during the initial 20 min and then gradually reached a plateau. After irradiation for 2h, the maximum spin density levels were up to 1.63 × 10¹⁷, 2.06 × 10¹⁷, and 1.77 × 10¹⁷ spins/g for the humic acid, fulvic acid, and humin, respectively. And the superoxide radicals increased to 1.05 × 10¹⁴–1.46 × 10¹⁴ spins/g while the alkyl radicals increased to 0.47 × 10¹⁴–1.76 × 10¹⁴ spins/g. The light-induced EPFRs were relatively unstable and readily returned back to their original state under dark and oxic conditions. Significant positive correlations were observed between the concentrations of EPFRs and reactive radical species (R² = 0.65–0.98, p<0.05), which suggested that the newly produced EPFRs contributed to the formation of reactive radical species. Our findings indicate that under the irradiation humic substances are likely to be more toxic and reactive in soil due to the formation of EPFRs.     

Species of Trace Metals,Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Abstract

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^?1, dry weight in fulvic acid and 820μg g^?1 in humic acid) and lead (821μg g^?1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Soil organic matter chemistry. Part 1. Characterization of several humic preparations by proton and carbon‐13 nuclear magnetic resonance spectroscopy

Both laboratory and commercial preparations of humic substances (HSs) such as fulvic acids and humic acids along with HC1‐HF preparation of Manitoba peat soil organic matter were characterized using Fourier Transformation (FT) proton (¹H) and carbon‐13 (¹³C) nuclear magnetic resonance (NMR) spectroscopy. All the samples were dissolved in a solution of 0.4 N NaOD in D₂O. In the case of ‘H‐NMR spectroscopy, all the investigated humic samples displayed resonance absorption peaks in the region of 1–4 ppm indicating the likely presence of aliphatic protons in the preparations. However, with the exception of one fulvic acid preparation (extracted from Manitoba Carrol clay‐loam soil with 0.5 N NaOH), ¹H‐NMR spectra of all other samples provided evidence for strong aromatic character. The aliphatic and aromatic characteristics of such samples of HSs were further confirmed with the aid of ¹³C‐NMR spectra.     

不同时期添加蘑菇渣对落叶堆肥过程的影响

研究不同时期添加蘑菇渣对落叶堆肥过程的影响.结果表明:堆肥降温期添加蘑菇渣有利于提高有机质的降解率,堆肥末期各处理有机质降解率分别为15.85%,10.17%,12.90%和15.16%;有利于吸收固定堆肥中的氨,减少氨的挥发,降低堆肥的pH值.在堆肥初始一次性添加蘑菇渣,有利于堆肥总氮的积累,提高堆肥产品中胡敏酸和腐殖质含量,降低堆肥总氮损失率.在堆肥初始和降温期分次添加蘑菇渣有利于堆肥硝态氮的合成,富里酸的分解以及HA/FA的增加.在整个堆肥过程中,各处理HA和HA/FA均呈增加趋势,FA呈降低趋势,较好地反映了落叶堆肥的腐熟程度.在堆肥不同阶段添加蘑菇渣各有其优点,综合后认为在堆肥初始添加蘑菇渣的效果最为理想.     

Monitoring trihalomethanes in water by differential ultraviolet spectroscopy

Ultraviolet (UV) spectroscopy is a valid surrogate for monitoring the formation of disinfection by-products (DBPs). Sodium thiosulphate is commonly used to remove disinfectant residual. However, it produces interferences with absorbance in the UV region. Relationship between trihalomethane (THM) formation and differential UV absorbance (−ΔA _λ ) was explored in the presence of sodium thiosulphate. Chlorination of two synthetic and five natural waters was carried out. Sodium thiosulphate showed high UV absorption at 254 nm. This effect can be overcome selecting a higher wavelength. Optimum wavelength varied being about 290 nm for fulvic acid and 300 nm for humic acid type natural organic matter. Correlation between THMs formation and −ΔA _λ was linear for all the analysed samples. Regression curves do not pass through zero indicating the existence of a threshold absorbance decreasment. Once it is surpassed THM release begins. Chlorination of surface waters showed that the presence of bromide significantly increases THMs vs. −ΔA _λ slope. Furthermore, slope decreased with the aromaticity–hydrophobicity of organic matter.     

氯化消毒饮用水中强致突变物MX[3-氯-4-(二氯甲基)-5-羟基-2(5H)-呋喃酮]的形成

利用一系列XAD吸附树脂及大孔阴、阳离子交换树脂,将太湖水中溶解态有机物分离为溶解态富里酸类、腐殖酸类、憎水弱酸类、憎水碱类、憎水中性物类、亲水酸类、亲水碱类七种组分,分别对不同组分的有机物进行氯化处理后,用GC/MS选择离子峰面积法测定了产物中的MX[3-氯-4-（二氯甲基）-5-羟基-2（5H）-呋喃酮]。结果表明,太湖水体中的溶解态腐殖酸类可能是生成MX的重要前驱物。     

Experimental study of chromium adsorption on minerals in the presence of phthalic and humic acids

The effect of phthalic acid (benzene 1,2 dicarboxylic acid), a surrogate compound for natural organic matter, and of humic acid, on the adsorption of chromium to the surface of minerals was observed. In ternary systems involving phthalic acid, chromium(III) adsorption decreases on clays, probably because of aqueous Cr(III)-phthalate complexation, preventing ionic-exchange. Phthalic acid was also found to reduce chromium(VI) adsorption onto alumina, because of a competitive effect. In ternary systems involving humic acid, Cr(III) adsorption is increased in the low pH range because of the formation of surface ternary complex S-L-Cr(III) and is decreased in the high pH range because of aqueous Cr(III)-humate complexation.     

Characterization of dissolved organic carbon and Humic substances in the well water of the Blackfoot disease area in Taiwan

Since the early 1960s, many investigators have reported that blackfoot disease, a peripheral vascular disease, observed in southwestern Taiwan is due to drinking the higher arsenic concentration in well water. However, recent studies indicated that the relationship with blackfoot disease is not only with arsenic but also humic substances. This paper presents some results concerning the characterization (such as fluorescence, elemental composition, molecular weight and carbon distribution) of humic substances isolated from the Fuhsing well water of the blackfoot disease area. For comparison, the dissolved organic carbon (DOC) and humic substances in the normal well water from Chiuying and the Nanwan coastal water were also analyzed. In general, in the well water of the blackfoot disease area, extremely high concentrations of DOC (18.5mg/L) and fulvic acid (7.54mg/L) with high fluorescence intensity (59.1, equivalent to 0.0282uM quinine sulfate solution) and high percentages (over 50%) of low molecular weights of less than 1,000 were obtained compared with those of normal waters. C‐13 Nuclear magnetic resonance spectroscopy showed a high content (37.2%) of aromatic carbon. These higher concentrations of DOC and fulvic acid with the higher content of aromatic carbon in well water might be one of the key factors causing the blackfoot disease in Taiwan.     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.     

褐煤风化过程中化学特性的变化

本文测定了６种不同风化程度褐煤的化学性状。结果表明，随着在自然界堆积风化时间的延长，褐煤的总碳，总氮含量及碳氮比都下降，灰分含量则增大，可提取的腐植酸及黄腐酸量明显增大，且紫外吸光值呈系统变化，尤其是黄腐酸中聚乙烯吡咯烷酮树脂可吸附部分（黄腐酸中腐植部分）随风化加深而降低，各种不同风化程度褐煤中腐植酸的红外吸收光谱变化不是很明显，且与土壤腐植吸收光谱相似。     

Characterization of humic substances in bio-treated municipal solid waste landfill leachate

Considerable organic matter remains in municipal solid waste landfill leachate after biological treatments. Humic substances (HSs) dominate the organic matter in bio-treated landfill leachate. In this study, the HSs from landfill leachate treated by membrane bioreactor (MBR-HSs) were analyzed via elemental analysis, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, and charge polarized magic-angle spinning-¹³C-nuclear magnetic resonance. The characteristic absorption in the UV wavelength range indicated the presence of high C=C and C=O double bonds within the MBR-HSs. Compared with commercial HSs, MBR-HSs had lower carbon content [48.14% for fulvic acids (FA) and 49.52% for humic acids (HA)], higher nitrogen content (4.31% for FA and 6.16% for HA), lower aromatic structure content, and higher carbohydrate and carboxylic atoms of carbon content. FA predominantly had an aliphatic structure, and HA had less condensed or substituted aromatic ring structures than natural HA. The aromatic carbon content of MBR-HSs was lower than that of humus-derived HSs but higher than that of waste-derived HSs, indicating that MBR-HSs appeared to be more similar to humus-derived HSs than waste-derived HA.     

Effects of organic matter on the specific adsorption of heavy metals by soil

The adsorption of heavy metals on soil from the Neihu Landfill Site in Taipei City was investigated in order to assess the groundwater pollution problems. The effects of soil organic matter and the behaviors of organic complexing ligands like EDTA and humic acid to the overall adsorption process were studied and discussed. For explaining the results, the pH value of soil system and the properties of the soil/aqueous interface were chosen as two significant and interacted factors for discussion. The concept of the specific adsorption mechanism was also demonstrated and discussed. The results showed that the complexing ligands existing in soil liquid phase have more influences than natural organic matter does. The competitive sequences of different organic matter contents indicated that organic functional sites preferentially bind with Cu and Cd. The presence of EDTA and humic acid which formed ligandlike complexes will reduce Cd adsorption efficiency. These effects will induce mobility and the fate of heavy metals in soils, such as bioavailability.     

Comparative study of humic acids of the mound of a wood-feeding termite and of the litter directly below in the Amazon river delta

In order to determine the role of termites in the recycling of organic matter and in humification processes, organic matter from the mound of a wood-feeding termite (Nasutitermes sp.) and from the litter directly below has been studied in secondary forest on the campus of Belem University, in Brazil. The carbon content was slightly lower in the litter (just beneath the mound) than in the mound, but nitrogen was much more abundant in the mound. As a consequence, the C/N ratio of fragmented litter total organic matter is very high, which shows that the humification process is not complete. Therefore, plant debris seemed to be more degraded in the mound than in the litter, indicating a humification gradient from mound to litter. Humic acid extracted from the mound and from the litter was compared by using elemental, E4/E6 ratio, spectroscopic (FTIR) analyses, and Sephadex gel chromatography. First, humic acids were more abundant in the mound than in the litter, showing that humification processes were more advanced in the mound than in the litter. Gel-permeation chromatography showed that the humic acids of the mound contained more low-molecular-weight fractions than those of the litter. In addition, the results of infrared spectra, E4/E6 ratio and elemental composition can confirm the fulvic character of mound material and the humic character of litter material. Therefore, the plant debris seems to follow two different humification pathways in the two environments, as long as the mound is alive.     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

Comparative study of humic acids of the mound of a wood-feeding termite and of the litter directly below in the Amazon river delta

In order to determine the role of termites in the recycling of organic matter and in humification processes, organic matter from the mound of a wood-feeding termite (Nasutitermes sp.) and from the litter directly below has been studied in secondary forest on the campus of Belem University, in Brazil. The carbon content was slightly lower in the litter (just beneath the mound) than in the mound, but nitrogen was much more abundant in the mound. As a consequence, the C/N ratio of fragmented litter total organic matter is very high, which shows that the humification process is not complete. Therefore, plant debris seemed to be more degraded in the mound than in the litter, indicating a humification gradient from mound to litter. Humic acid extracted from the mound and from the litter was compared by using elemental, E4/E6 ratio, spectroscopic (FTIR) analyses, and Sephadex gel chromatography. First, humic acids were more abundant in the mound than in the litter, showing that humification processes were more advanced in the mound than in the litter. Gel-permeation chromatography showed that the humic acids of the mound contained more low-molecular-weight fractions than those of the litter. In addition, the results of infrared spectra, E4/E6 ratio and elemental composition can confirm the fulvic character of mound material and the humic character of litter material. Therefore, the plant debris seems to follow two different humification pathways in the two environments, as long as the mound is alive.     

Identification of Anthropogenic Organic Contamination Associated with the Sediments of a Hypereutropic Tropical Lake, Venezuela

The concentrations of organic carbon (Corg), inorganic carbon (Cinorg), organic nitrogen (Norg) and total aromatic (Arom_T) were determined in 25 samples of bottom sediments from the Lake Valencia, Venezuela, as a contribution to the knowledge about pollution by organic compounds in tropical lakes. Results demonstrate that the Corg and Norg concentrations do not show the pollution indexes by themselves. This is a consequence of the masking effect of naturally derived organic matter from the decay of algae and organisms in the water column and terrestrial plants, which are transported to the lake. Nevertheless, the Arom_T concentrations and the normalised Arom_T (normalized to organic carbon) make it possible to detect organic matter of anthropogenic origin, in the Arom_T levels are about nine times higher than those natural. The variation in the band intensity of the IRFT spectra for some functional groups present in the saturate and aromatic hydrocarbon fractions gives an indication of anthropogenic contribution for some zones of the lake. With the ¹H NMR spectra it was not possible to differentiate a natural source from an anthropogenic one in the lake. Naturally occurring organic compounds (eicosane, pentacosane, and hexacosane) were detected with GC technique in the saturated hydrocarbon fraction. The presence of an unresolved complex mixture (UCM) in the GC chromatograms indicates pollution by branched and cyclic hydrocarbons. These compounds are probably produced by the incomplete combustion of oil products. Potentially toxic organic compounds such as anthracene, phenanthrene and chrysene were found in the aromatic hydrocarbon fraction, which despite presenting low concentrations (ppb order) accumulate in the lake sediments along with the natural source organic matter. The main access paths of organic pollutants to the lake are the rivers which cross the two urban and industrial areas (Maracay and Valencia cities). The mixture of polluted sediments with bottom natural sediments and the autochthonous contribution of organic matter mitigate the pollution levels progressively towards the center of the lake.     

Bio-mediated silver nanoparticle synthesis: mechanism and microbial inactivation

Even though plenty of literature is available on the biosynthesis of metal nanoparticles, there are serious lacunae on the mechanisms of their formation. In the present study, the mechanism of formation of mono-crystalline silver nanoparticles using a fruit extract of the ornamental tree Thevetia peruviana is emphasized, i.e. how the pH of the reaction mixture affected reaction kinetics and size of the nanoparticles. The facilitation of formation of Ag₂O at higher pH resulted in a faster rate of particle formation. The diameter of the bare particles at neutral pH determined by field emission scanning electron microscopy and the hydrodynamic diameter determined by dynamic light scattering were 53 and 104 nm, respectively. The silver nanoparticles exhibited good inactivation of Escherichia coli due to participation of free radicals as evidenced by electron spin resonance spectroscopy.