Physico-chemical processes of humic acid-trace element interactions

Experiments were carried out under various pH conditions since this factor may strongly influence the equilibrium of various physico-chemical forms in which a certain trace element may occur in the aquatic environment. Pick-up processes were investigated for iron, cobalt, zinc, ruthenium and mercury under various experimental conditions. The rate and type of bonding or association of trace metals in humic acids was investigated by means of their replacement with other ions. For this reason the pick-up of a radionuclide of a certain trace metal by humic acid was performed, and when equilibrium was reached, the humic acids were transferred to another system where a known concentration of another ion was present. Replacement reactions took place and their yields were followed by radioactivity measurements in the liquid phase. The shape of each curve indicates the specific kinetics of the interaction of a particular trace element with humic acids under experimental conditions. Speed, total yield and time needed to reach equilibrium are specific for each particular case. The purpose of our work is to investigate the nature of trace-element interactions with humic acids. Having in mind the large variations that may occur in the constitution of humic acids, our attention focussed primarily on the search for the role these chemical variations and the different processes of their formation play on the ability of humic acids to bind trace elements. Our results demonstrated that charge-dependent processes, such as ion exchange and sorption-desorption, present a major interaction mechanism in humic acidtrace element interaction. Another important mechanism by which some trace elements are associated with humic acids seems to be chelation.     

Humic substances as surfactants

Humic substances from soils and sediments can be defined as surface active substances based on the surface tension measurements. Although there are several micellar structural models of humic substances currently available, few studies evaluating humic substances as surfactants have been conducted to date. Therefore, we evaluated the ability of humic substances and their derivatives to influence surface tension. We found that the ability of a humic substance to influence the surface tension of a solution depends on its origin. Many industrially produced humic materials exerted little or no impact on surface tension, whereas humic substances isolated from natural environments (water, soil, peat, sediments, sludge from wastewater treatment facilities) exerted a large impact on surface tension. These findings indicate that the modification of humic substances can enable their use as surfactants. In addition, these findings indicate that solutions of humic substances and their derivatives can be used to increase the solubility of organic compounds.     

Huminstoffe in Sedimentporenwässern ausgewählter Bundeswasserstraßen

Humic substances are an important component of organic carbon in natural waters. Their character and properties are determined by the sources and the processes of their origin. Humic substances are not exclusively refractory compounds, but they are involved in several transformation processes in the water. It is not possible to directly analyze humic substances, therefore several methods were applied for their characterization. The presented LC-OCD-technique is a size-exclusion-chromatography with online UV- and carbon detection. Carbon fractions, e.?g. humic substances were differentiated by their molecular size. The portion of humic substances in sediment porewaters of the rivers Elbe, Rhine, Danube, Oder, Müritz-Elde-Waterway was determined. With only a few exceptions it ranges from 50 to 67?% of the dissolved organic carbon. The high molecular weight fraction accounts for 10 to 34?%, and the fraction of the low molecular weight substances was from 7 to 37?%. The ratio between the spectral absorption coefficient (254?nm) and the organic carbon is called SUVA (L/mg × m) and is an inidicator of the proportion of unsaturated bonds in the humic substances. Both high molecular herbal components (e.?g. cellulose, lignin) and biological degradiation products (e.?g. amino acids, sugar) are involved in sediment porewater transformation and degradiation processes. This demonstrates the distribution of the dissolved organic carbon between the fractions.     

现代农业快速发展背景下的农业生产废弃物管理对策探析——政府与农户的动态博弈

随着农业集约化、规模化发展,农业生产废弃物的管理问题凸显。循环农业、低碳农业的发展,在一定程度上激励了农户对农业生产废弃物资源化管理,取得了一定的成绩,但是也存在一定的问题,严重制约了农业生产废弃物资源化管理。文章通过构建政府与农户的动态博弈模型,分析补贴政策对农户提高农业生产废弃物资源化管理效率的作用,并基于政府与农户的动态博弈分析提出了促进农业生产废弃物管理效率提升及其可持续发展的建议,即：（1）根据不同的资源化管理方式的差异制定并实施差别补贴政策;（2）实行区域差别补贴标准;（3）延长补贴期限,实行分年度对农户进行不同数量的补贴;（4）培养农户管理意识,加强农户技能培训。     

水体环境中天然有机质腐殖酸研究进展

腐殖酸作为一种资源广泛存在于自然界中,它是影响环境生态平衡的重要因素,也是潜在的、可大力开发和综合利用的有机资源。腐殖酸类物质具有多种活性官能团,具有酸性、亲水性、界面活性、阳离子交换能力、络合作用及吸附分散能力。腐殖酸概念、理论出现了重大突破,已从传统腐殖酸重点或仅研究腐殖酸自身发生中的物质流动、能量转化规律,同时着眼研究腐殖酸与土壤、水体和生物多界面的环境过程和机理。文章主要以水环境为例,天然有机质研究历史、化学结构,对环境污染物效应和去除技术等几个方面的研究进展进行了简要的总结;对现代腐殖酸的研究趋势进行了展望。     

The molecular composition of humic substances extracted from green composts and their potential for soil remediation

Humic substances play empirically several essential functions in biogeochemical cycles such as storage of carbon, pollutants, nutrients and water, yet the underlying mechanisms remain poorly known because their precise molecular structure is largely unknown so far. Here, we extracted humic substances from biomass waste of bell pepper, fennel, artichoke, coffee ground, coffee husks, and nursery residues. We analyzed humic extracts by ultra-high resolution Orbitrap Fusion Lumos Tribrid 1 M mass spectrometry, using both positive photoionization and negative electrospray ionization modes, and by ¹³C cross polarization/magic angle spinning nuclear magnetic resonance spectroscopy. We identified 5000–7000 unique organic compounds in humic substances by integrating photoionization with electrospray ionization. The chemical distribution of all components was depicted by nuclear magnetic resonance. Humic substances from green composts are composed by a wide variety of hydrophilic and hydrophobic moieties, thus providing the required biosurfactant properties for effective soil washing capacities, with carboxyl-rich alicyclic molecules, fatty acids, and phenolic acids as major constituents. Overall, our findings provide a major insight in the molecular structure of humic substances, thus opening research on mechanisms ruling the origin, fate and behavior of humic substances.

     

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.     

First determination of Cu adsorption on soil humin

Humic substances are heterogeneous mixtures of organic compounds occurring in huge amounts mainly in waters, soils, sediments and organic wastes. They are formed during the decay of living organisms. They play a very important role in many environmental processes including carbon sequestration, water cleaning and retention, soil erosion, fertility and pollutant retention. However, due to their complex nature, humic substances are still poorly characterized and much less known than living matter. Humin is the most insoluble and, in turn, the least understood fraction of humic substances. To our knowledge, no information is currently available on the adsorption and desorption behaviors of metal ions on soil humin. Here, we report the adsorption and desorption properties of Cu(II) on humin and humic acids isolated from a forest soil in northeast China using the batch equilibration method. Solid-state ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (¹³C CPMAS NMR) spectroscopy was used to characterize and compare the chemical structures of humin and humic acid. The batch experiments’ results show that humin has a lower adsorption capacity and higher adsorption reversibility for Cu(II) than humic acid. The adsorption isotherms well fitted both the Langmuir and Freundlich equations. Humin, therefore, plays an important role in controlling the fate, transport and bioavailability of Cu(II) in the environment. The ¹³C CPMAS NMR spectra showed that compared with humic acid, humin was higher in alkyl C, carbohydrate C and phenolic C and was lower in methoxyl C, aryl C and carbonyl C. These findings mean that humin was less alkylated, more aliphatic and more hydrophobic.     

The ecosystem of the bay of Mali Ston natural and anthropogenic influence

Chemical hydrography, nutrients and trace metals in water, sediments and marine organisms were studied in the Bay of Mali Ston and their role in terms of pollution discussed. Results show that the entire study area is very strongly affected by the adjacent land. The overall area is well aerated so that no dangerous accumulation of nutrients with oxygen content reduction was recorded.

Results of analyses of trace metals show that the water and sediments of the bay contain high levels of some metals significantly higher than those from the open sea. This may be attributed to the natural sedimentation processes and the Neretva River and submarine spring runoffs carrying constituents of ignous and limestone rocks.     

Trace metal distribution in different chemical fractions of marine sediments along the eastern Aegean shelf

The major objective of this study was to carry out sequential chemical extraction for the partitioning of particulate trace metals in sediment samples, collected along the eastern Aegean shelf during cruises July‐August 1994, in the framework of a National Marine Measurement and Monitoring Programme for the Aegean Sea.

Five metals, Cd, Pb, Cu, Zn and Cr were examined in each of sediment samples. Three chemical fractions of the sediments were separated and concentrations of the trace metals were determined by AAS techniques. The three different leaches used were hydroxylamine hydrochloride‐acetic acid, hydrogen peroxide and nitric‐perchloric acids.

Metals were concentrated mainly in the fraction extracted by nitric‐perchloric acids. Lead in the first fraction were found in the sediments of Northern part of Aegean, where the concentration of organic material was high.

The total concentrations of Cd, Cu, Zn, Cr were higher in Izmir Bay than the other sampling points. The distribution of Pb concentrations was the highest in Edremit Bay and Izmir Bay.     

Heavy Metals in the Bed and Suspended Sediments of Anyang River, Korea: Implications for Water Quality

The objective of this study is to compare Anyang River bed sediments with water chemical composition and to assess the anthropogenic chemical inputs into the river system. Eight sampling locations were chosen along the river channel. Bed and suspended river sediments and water samples were collected, and analyzed for their chemical and physical composition. Data revealed that trace element concentrations in the river water were generally below world average, except for As, Mn, Ni and Cr. Among the three phases: water, bed and suspended sediment, more than 99% of the trace elements was associated with the bed sediment. Concentrations of trace elements in the sediment were a function a particle size distribution and organic content. The calculated degrees of enrichment based on the least influenced sample (ASD 1) indicated the river sediments were enriched with respect to background. The enrichment factors for Pb, Zn and As were relatively lower than for Cr, Co, Ni and Zn. The difference in the enrichment seems to reflect the human activities influence in the basin, and specially for Cd. Speciation of the elements in the five different chemical forms in the sediment by sequential extraction indicated that the reducible fraction was predominant for Fe, Zinc and Cu showed an irregular variation among the different fractions; whereas, Cd and Pb were more regular. Zinc and Cu highly existed mostly in exchangeable forms. Acid soluble and reducible forms were also important for most metals. The speciation implies that the metals associated with the sediment are subject to release into water bodies as goechemical variables (pH and Eh) change. Currently, the introduced metals are deposited near the source area and are mostly associated with the sediment, implying that the river bed sediment acts mainly as a sink, rather than a pool. The accumulated and enriched toxic trace elements can pose a potential pollution of river water.     

A comparative study on arsenic and humic substances in alluvial aquifers of Bengal delta plain (NW Bangladesh), Chianan plain (SW Taiwan) and Lanyang plain (NE Taiwan): implication of arsenic mobilization mechanisms

Humic substances in groundwater and aquifer sediments from the arsenicosis and Blackfoot disease (BFD) affected areas in Bangladesh (Bengal delta plain) and Taiwan (Lanyang plain and Chianan plain) were characterized using fluorescence spectrophotometry and Fourier transform infrared (FT-IR) spectroscopy. The results demonstrate that the mean concentration of As and relative intensity of fluorescent humic substances are higher in the Chianan plain groundwater than those in the Lanyang plain and Bengal delta plain groundwater. The mean As concentrations in Bengal delta plain, Chianan plain, and Lanyang plain are 50.65 μg/l (2.8–170.8 μg/l, n = 20), 393 μg/l (9–704 μg/l, n = 5), and 104.5 μg/l (2.51–543 μg/l, n = 6), respectively. Average concentrations and relative fluorescent intensity of humic substances in groundwater are 25.381 QSU (quinine standard unit) and 17.78 in the Bengal delta plain, 184.032 QSU and 128.41 in the Chianan plain, and 77.56 QSU and 53.43 in the Lanyang plain. Moreover, FT-IR analysis shows that the humic substances extracted from the Chianan plain groundwater contain phenolic, alkanes, aromatic ring and amine groups, which tend to form metal carbon bonds with As and other trace elements. By contrast, the spectra show that humic substances are largely absent from sediments and groundwater in the Bengal delta plain and Lanyang plain. The data suggest that the reductive dissolution of As-adsorbed Mn oxyhydroxides is the most probable mechanism for mobilization of As in the Bengal delta plain. However, in the Chianan plain and Lanyang plain, microbially mediated reductive dissolution of As-adsorbed amorphous/crystalline Fe oxyhydroxides in organic-rich sediments is the primary mechanism for releasing As to groundwater. High levels of As and humic substances possibly play a critical role in causing the unique BFD in the Chianan plain of SW Taiwan.     

Veränderung von Biokonzentration und Wirkung vom PSM in Anwesenheit von Huminstoffen

Humic substances, in aqueous bodies primarily fulvic acids, may demonstrate an inhibitory as well as an activating influence on organisms. We present evidence with bacteria-containing algal cultures and with cultures of the nematodeCaenorhabditis elegans. Structural elements of the fulvic acids which may be responsible for such effects are not yet known. Furthermore, the presence of fulvic acids may lead to increases in bioconcentration of xenobiotics. Increase in the toxicity of xenobiotics in the presence of humic substances have also been described. We present studies applying lethal as well as sublethal toxicity endpoints.     

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.     

14C and 125I Labelling of Humic Material for Use in Environmental Studies

Humic and fulvic acids are present in nearly all natural waters. These acids are known to affect the transport of environmental contaminants such as metals and hydrophobic organics through the terrestrial environment. an understanding of their role in the transport of contaminants is therefore essential and is facilitated if the acid is labelled with a suitable radioactive label. This paper reports the use of ¹⁴C-methylamine and ¹²⁵I to label humic acid with either ¹⁴C or ¹²⁵I and investigates factors which affect the yield of these reactions. the stability and mobility of the labelled humic material through sand is also reported.     

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.     

The common mussel Mytilus edulis as an indicator of pollution by zinc,cadmium, lead and copper. II. Relationship of metals in the mussel to those discharged by industry

Concentrations of zinc, cadmium, lead and copper were determined in whole soft parts of the common mussel Mytilus edulis (L.) sampled in Port Phillip Bay and Western Port Bay, both in Victoria, Australia. The mussels were sampled according to procedures suggested by previous studies in order to eliminate the effects of natural environmental variables. Results of the analytical studies were compared to data on the quantities of trace metals known to be discharged by industry into the catchments of each Bay. This allowed an evaluation of the indicator ability of the mussel without the need for multiple analyses of water samples. The results suggest that the mussel is capable of acting as an efficient time-integrated indicator of zinc, cadmium and lead over a wide variety of environmental conditions. Although additional variables may remain to be investigated, the mussel is recommended as an alternative to the analysis of water and sediments. With further development this organism may also be useful for monitoring industrial effluent characteristics at the discharge site, allowing rapid, reliable and inexpensive control of water quality. In contrast, the mussel is of doubtful use as an indicator of copper; other indicator types such as macroalgae may be better-suited to the study of this element.     

腐殖质的光化学降解及其对环境污染物环境行为的影响

腐殖质是地表环境中最重要的有机组分,也是生态环境中最主要的吸光物质之一,对环境污染物的形态、迁移、毒性和生物可利用性有着重要的影响。文章综述了腐殖质的结构特征和光化学降解反应过程和机理,指出腐殖质的光敏化和光化学降解过程对环境污染物的环境行为和归宿有重要的影响。通常,腐殖质的光敏化作用在低质量浓度下,尤其在一定铁离子的协同作用下可促进有机污染物的降解,但高质量浓度的腐殖质由于其本身的吸光作用以及参与自由基的竞争则抑制有机污染物的降解。腐殖质的光化学降解过程降低了环境体系的pH和腐殖质的分子量、破坏了腐殖质的芳环结构、改变了紫外和可见光区域的吸收等,导致其与重金属离子和有机污染物结合能力的下降,造成水体或颗粒态中游离的污染物质量浓度增加,对生态系统将造成更大的危害。目前对腐殖质和环境污染物本身的光化学降解机理已较为清晰,今后应加强对自然水体或土壤系统中腐殖质光化学降解的影响因素,腐殖质光化学降解过程中结构特性的变化机理,以及腐殖质的结构特性与环境污染物结合性质之间的构效关系等方面的研究。特别是随着平流层臭氧空洞的增加,增强了到达地球表面的紫外线强度,研究紫外线增强对腐殖质和有机污染物的降解以及对生态系统的影响可进一步深刻理解太阳光辐射对污染物环境行为和归宿的影响。     

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.     

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.