Sorption interactions between imazaquin and a humic acid extracted from a typical Brazilian oxisol

Soil sorption of most hydrophobic organic compounds (e.g., nonpolar pesticides) is directly related to soil organic matter (SOM) content. Humic substances are the major SOM components, containing carboxylic, phenolic, amine, quinone, and other functional groups, and specific structural configurations. In this paper, sorption interactions between imazaquin (2-[4,5-dydro-4-methyl-4-(1-methylethyl)-5-oxo-1H- imidazol-2-yl]-3-quinoline-carboxylic acid) herbicide (IM) and a humic acid (HA) extracted from a typical Brazilian Oxisol were studied with electron paramagnetic resonance (EPR) and Fourier-transform infrared (FTIR) spectroscopic techniques. A polarographic technique was used to quantify sorption. The IM amount sorbed on the HA was much higher than that on the whole soil within the pH range studied, emphasizing the prominent role played by SOM on IM sorption. Moreover, IM sorption increased as the soil-solution pH decreased. This enhancement in sorption was attributed to the hydrophobic affinity of the herbicide by the HA and to the electrostatic interaction between the protonated quinoline group of IM and the negative sites of the HA. Hydrophobic regions in the HA's interior at low pH (< 5.0) were recently demonstrated by an EPR detectable spin-label molecule. The FTIR and EPR spectroscopy and polarography data indicated weak interaction between IM and the soil and its HA, involving hydrogen bonding, proton transfer, and cation exchange (at low pH), and mainly hydrophobic interactions. However, no strong reaction mechanism, such as charge transfer, was involved. In addition, this research suggested that soil amendment with organic material might increase magnitude of IM sorption, consequently avoiding leaching and carryover problems usually found for mobile and persistent herbicides such as imazaquin.     

Sorption of aromatic compounds to clay mineral and model humic substance-clay complex: effects of solute structure and exchangeable cation

Clay minerals and humic substance (HS)-clay complexes are widely distributed in soil environments. Improved predictions on the uptake of organic pollutants by soil require a better understanding of fundamental mechanisms that control the relative contribution from organic and inorganic constituents. Five selected aromatic compounds varying in electronic structure, including nonpolar phenanthrene (PHEN), 1,2,4,5-tetrachlorobenzene (TeCB), polar 1,3-dinitrobenzene (DNB), 2,6-dichlorobenzonitrile (dichlobenil [DNL]), and 1-naphthalenyl methylcarbamate (carbaryl [CBL]), were sorbed separately from aqueous solution to Na(+)-, K(+)-, Cs(+)-, and Ca(2+)-saturated montmorillonites with and without the presence of dissolved HS at pH about 6. Upon normalizing for hydrophobic effects by solute aqueous solubility, the overall trend of sorptive affinity to HS-free K(+)-clay is DNB > DNL, CBL > PHEN, TeCB, indicating preferential adsorption of the polar solutes. With the presence of HS, sorption of PHEN, TeCB, and CBL increases by several times compared with the pure clay, attributed to HS-facilitated hydrophobic partition (PHEN and TeCB) or H-bonding (CBL). The enhanced sorption of PHEN by HS is cation dependent, where Cs(+) shows the strongest facilitative effect. Coadsorption of HS does not affect sorption of DNB and DNL to clays except that of DNB to Ca(2+)-clay because cation-dipole interactions between the polar group (NO(2) or CN) of solute and weakly hydrated exchangeable cations dominate the overall sorption.     

Impact of methylene chloride on microorganisms and phenanthrene mineralization in soil

This study investigated the effects of the quantity of methylene chloride, used as a carrier solvent for phenanthrene when added to soil, on phenanthrene mineralization kinetics, soil phospholipid fatty add profiles (PLFA), and phenanthrene distribution. Methylene chloride dosages of 25 microL/g soil or more resulted in an enrichment of saturated PLFAs, suggesting soil microorganisms had adjusted their cell membranes in response to the solvent. A greater fraction of phenanthrene mineralized when spiked in 5 microL/g than in 25 microL/g methylene chloride suggesting that the methylene chloride became toxic to phenanthrene-degrading organisms in soil. Phenanthrene was more equally distributed among 0.1 g soil subsamples if spiked in 25 than 5 or 1 microL methylene chloride per gram soil. Thus the amount of methylene chloride used to spike phenanthrene in soil strongly impacted the mineralization kinetics, phenanthrene distribution, and microbial community in soil. Because a variety of spiking methods are used in biodegradation research, scientists should consider the quantity of solvents used when comparing results among different studies.     

Effect of surfactants on solubilization and degradation of phenanthrene under thermophilic conditions

The bioavailability and biodegradation of polycyclic aromatic hydrocarbons (PAHs) can be increased through the addition of surfactants. Previous studies of this nature have been conducted under mesophilic conditions. Hence, the aim of the present study was to investigate the effects of synthetic surfactants and biosurfactants on solubilization and degradation of phenanthrene (PHE) in a series of batch solution experiments under thermophilic conditions. Tween 80, Triton X-100, and biosurfactants produced from Pseudomonas aeruginosa strain P-CG3 (P-CG3) and Pseudomonas aeruginosa ATCC 9027 (P. 9027) were used in this study. Surfactants effectively enhanced the solubility of PHE at 50 degrees C and the biosurfactant from P-CG3 was most effective with a 28-fold increase in apparent solubility of PHE at a concentration of 10 x critical micelle concentration (CMC) compared with the controls. However, addition of synthetic surfactants or biosurfactants inhibited the biodegradation of PHE in mineral salts medium by an isolate Bacillus sp. B-UM. Degradation of PHE diminished with increasing surfactant concentrations, and PHE degradation was completely inhibited for all the surfactants tested when the concentrations were greater than their respective CMC. The growth test suggested that Tween 80 and biosurfactants were degradable, but preferential utilization of these surfactants as substrates was not the mechanism for explaining the inhibition of PHE biodegradation. Because of the hydrophobic property of B-UM, degradation inhibition of PHE by surfactants was probably due to the reduction of direct contact between bacterial cells and PHE.     

9,10-Phenanthrenequinone photoautocatalyzes its formation from phenanthrene, and inhibits biodegradation of naphthalene

Polycyclic aromatic hydrocarbons (PAHs) have earned considerable attention due to their widespread environmental distribution and toxicity. In the environment, PAHs decompose by a variety of biotic and abiotic pathways. In both polar and nonpolar environments, phenanthrene (Phe, a common, three-ring PAH) is converted by sunlight to more polar products such as 9,10-phenanthrenequinone (PheQ) and subsequent oxidation products such as the corresponding open-ring dicarboxylic acid product. Biodegradation of phenanthrene also usually leads to oxidative metabolites, and eventually ends in mineralization. Our experimental objective was to investigate the photodegradation of phenanthrene and determine the effect of reaction products such as PheQ on microbial biodegradation of two- and three-ring PAHs. Abiotic experiments were performed to examine the photolytic breakdown of Phe; Phe was converted to PheQ, which catalyzed its own formation. In biodegradation experiments PheQ (0.04-4 mg/L) caused marked inhibition of naphthalene (Nap) biodegradation by a Burkholderia species; Phe did not. Only 20% of the naphthalene was degraded in the presence of PheQ compared with 75% in the control culture with no PheQ added. No PAH-degrading cultures were able to use PheQ as sole carbon source; however, the Phe-degrading enrichment culture dominated by a Sphingomonas species was able to degrade PheQ cometabolically in the presence of Phe. These results may explain why photooxidized phenanthrene-containing mixtures can resist biodegradation.     

Effects of suspended sediment on the biodegradation and mineralization of phenanthrene in river water

High suspended sediment (SPS) concentration commonly exists in many Asian rivers. Furthermore, climate change can cause high floods and lead to the resuspension of sediments and soil erosion, resulting in high SPS concentration in many natural waters. This research studied the impact of the presence of SPS and organic C composition of SPS on the biodegradation and mineralization of phenanthrene (PHE). Three sediments, including original sediment (OS), 375 degrees C (S375), and 600 degrees C (S600) combusted sediment, were studied. A flask-based 14C-respirometer system was applied to study the mineralization of [14C]PHE by Agrobacterium sp. The mineralization rate of PHE in the absence of SPS was significantly lower than that with the presence of OS and S600 but higher than that with S375, suggesting that the effect of the presence of sediment on PHE mineralization depended on its organic C composition. The residual levels of PHE in the S375 and OS systems were about 1.5 times that of the S600 system after incubation for 2 d. After 26-d incubation, the mineralization rates of PHE were 34.64, 29.40, and 14.00% in the OS, S600, and S375 systems, respectively. The first-order rate constants of the OS and S600 systems were about three times that of the S375 system. The net influence of SPS on the biodegradation and mineralization rates of PHE was dependent on its effects on compound bioavailability and bacteria population. This study suggested that black C played a key role in reducing the mineralization rates of PHE in sediments-even without aging.     

Structural and sorption characteristics of adsorbed humic acid on clay minerals

Clay-humic complexes are commonly distributed in natural environments. They play very important roles in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study examined the structural changes of humic acid (HA) after adsorption by clay minerals and determined phenanthrene sorption by clay-humic complexes. Solid- and liquid-state 13C nuclear magnetic resonance (NMR), for the first time, provided direct evidence for HA fractionation during adsorption on mineral surfaces, that is, aliphatic fractions were preferentially adsorbed by clay minerals while aromatic fractions were left in the solution. The ratio of UV absorbance of HA at 465 and 665 nm (E4 to E6 ratio), which is related to aromaticity, corroborated with the NMR results. For both montmorillonite and kaolinite, adsorbed HA fractions had higher sorption linearity (N) and affinity (K(oc)) than the source HA. The K(oc) of adsorbed HA for the clay-humic complexes could be up to several times higher than that of the source HA. This large increase may be contributed by the low polarity of the bound HA. Moreover, for each mineral, the N values of adsorbed HA increased with increasing HA loading. It is believed that HA may develop a more condensed structure on mineral surface at lower HA loading level due to the stronger interactions between HA and mineral surface as a result of close contacts.     

On the interaction mechanisms of atrazine and hydroxyatrazine with humic substances

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) is retained against leaching losses in soils principally by sorption to organic matter, but the mechanism of sorption has been a matter of controversy. Conflicting evidence exists for proton transfer, electron transfer, and hydrophobic interactions between atrazine and soil humus, but no data are conclusive. In this paper we add to the database by investigating the role of (i) hydroxyatrazine (6-hydroxy-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and (ii) hydrophobicity in the sorption of atrazine by Brazilian soil humic substances. We demonstrate, apparently for the first time, that hydroxyatrazine readily forms electron-transfer complexes with humic substances. These complexes probably are the cause of the well-known strong adsorption by humic acids and they may be the undetected cause of apparent electron-transfer complexes between soil organic matter and atrazine, whose transformation to the hydroxy form is facile. We also present evidence that supports the important contribution of hydrophobic interactions to the pH-dependent sorption of atrazine by humic substances.     

Flocculant in wastewater affects dynamics of inorganic N and accelerates removal of phenanthrene and anthracene in soil

Recycling of municipal wastewater requires treatment with flocculants, such as polyacrylamide. It is unknown how polyacrylamide in sludge affects removal of polycyclic aromatic hydrocarbons (PAH) from soil. An alkaline-saline soil and an agricultural soil were contaminated with phenanthrene and anthracene. Sludge with or without polyacrylamide was added while emission of CO₂ and concentrations of NH₄⁺, NO₃⁻, NO₂⁻, phenanthrene and anthracene were monitored in an aerobic incubation experiment. Polyacrylamide in the sludge had no effect on the production of CO₂, but it reduced the concentration of NH₄⁺, increased the concentration of NO₃⁻ in the Acolman soil and NO₂⁻ in the Texcoco soil, and increased N mineralization compared to the soil amended with sludge without polyacrylamide. After 112 d, polyacrylamide accelerated the removal of anthracene from both soils and that of phenanthrene in the Acolman soil. It was found that polyacrylamide accelerated removal of phenanthrene and anthracene from soil.     

Sorption of polycyclic aromatic compounds to humic and fulvic acid HPLC column materials

Two different humic acids (HA) and a fulvic acid (FA) were chemically immobilized to a high performance liquid chromatography (HPLC) silica column material. The immobilization was performed by binding amino groups in HA/FA to the free aldehyde group in glutardialdehyde attached to the silica gel. The HPLC column materials were compared with a blank column material made by applying the same procedure but without immobilizing HA or FA. Also, a column was made by binding carbonyl groups in HA to amino groups attached to the silica gel. The humic substances were selected to secure appropriate variation of their structural features. The retention factors of 45 polycyclic aromatic compounds (PAC) to the four columns were determined by HPLC. The advantage of the technique is a large number of compounds can easily be studied. The binding procedure does not appear to cause a drastic selection between the HA molecules. The k' values obtained for the two Aldrich HA columns agree in general reasonably. The retention or sorption of the compounds increased with the size of the PAC and the number of lipophilic substituents, but decreased when polar substituents were present. The PAC retention was much stronger to the two HA columns than to the FA and blank column, both for hydrophobic polycyclic aromatic hydrocarbons (PAH) and the polar PAC. Other factors impacting the PAC binding may be specific interactions with HA and the ionic strength of the aqueous phase. The technique has been applied to do direct determinations of Koc.     

Sustainable recycling model: A comparative analysis between India and Tanzania

Higher economic growth in developing countries has caused higher amounts of wastes. Local government authorities in these countries usually fail to provide adequate services to dispose the increasing amounts of waste, resulting in threats for both the population and environment health. There is therefore an urgent need for recycling as a form of waste management in order to stop the devastating effects of solid waste in developing countries. Using a qualitative method of analysis, this study presents a model to measure and rank the sustainability of recycling programs in India and Tanzania. The model consists of six main constructs including “production, economic, governmental, social, technological, and international factors”. The results showed that India outperforms Tanzania in sustainable recycling programs: per capita waste generated per day in Delhi is higher than in Dar es Salaam; the government of India focuses more on developing recycling plans and techniques as compared to the government of Tanzania where the country is not actively involved in the recycling process; and the solid waste management planning in India is being performed better than Tanzania.     

Cadmium binding by fractions of dissolved organic matter and humic substances from municipal solid waste compost

The agricultural practice of amending soils with composted municipal solid waste (MSW) adds significant amounts of organic matter and trace metals, including Cd. Under these conditions, soluble organic complexes of Cd formed in the compost may be more significant than previously thought, due to Cd bioavailability and mobility in the soil environment. To study the relative importance of different types of organic ligands in MSW compost for the binding of Cd, six fractions of the dissolved organic matter (DOM) in addition to humic acid (HA) and fulvic acid (FA) were extracted and their complexation of Cd quantified at pH 7 using an ion-selective electrode (ISE). The highest complexing capacities (CC) for Cd were found for the most humified ligands: HA (2386 micromol Cd g(-1) C of ligand), predialyzed FA (2468 micromol Cd g(-1) C), and HoA, a fulvic-type, easily soluble fraction (1042 micromol Cd g(-1) C). The differences in CC for Cd of the various organic ligands were not directly related to total acid-titratable or carboxylic groups, indicating the importance of sterical issues and other functional groups. The strength of association between Cd and the organic ligands was characterized by calculating stability constants for binding at the strongest sites (pK(int)) and modeling the distribution of binding site strengths. The pK(int) values of the DOM fractions ranged between 6.93 (HiN: polysaccharides) and 8.11 (HiB: proteins and aminosugars), compared with 10.05 for HA and 7.98 for FA. Hence, the highly complex and only partially soluble organic molecules from compost such as HA and FA demonstrated the highest capacity to sequester Cd. However, strong Cd binding of organic ligands containing N-functional groups (HiB) in addition to a high CC of soluble, humified ligands like HoA indicated the relevance of these fractions for the organic complexation of Cd in solution.     

Enzymatic transformation and binding of labeled 2,4,6-trinitrotoluene to humic substances during an anaerobic/aerobic incubation

Organic pollutants are degraded in soil and simultaneously nonextractable residues are formed. However, proof is lacking that this fixation has a detoxifying effect. We investigated the transformation and binding of 2,4,6-trinitrotoluene (TNT) with catechol or soil humic acid as cosubstrates. Carbon-14-labeled TNT and its reaction products were quantified by radiocounting; extractable compounds were identified by high performance liquid chromatography (HPLC). Bound and extractable residues of 15N-labeled TNT and metabolites were studied by 15N nuclear magnetic resonance spectroscopy (15N NMR). Since TNT is not easily transformed under oxidizing conditions an anaerobic/aerobic treatment was used. Anaerobic microorganisms from cow manure were used to reduce TNT during the anaerobic phase and subsequently, a laccase from Trametes villosa was used in the aerobic phase to oxidatively couple the metabolites to humic matter. Seventy-four percent of TNT was immobilized with catechol as cosubstrate, but only 25% with humic acid. With catechol the main extractable component was TNT, while with humic acid it was mostly the metabolite 4-aminodinitrotoluene. For both co-substrates, the spectra of immobilized metabolites obtained by solid-state 15N-cross polarization magic angle spinning (CPMAS) NMR spectroscopy showed signals in the chemical shift region for protonated aromatic amino compounds. However, in the presence of catechol, an additional signal from nonextractable nitro groups was found, which could represent sequestered TNT. The partially reduced metabolites of TNT that formed nonextractable residues in humic acid are not likely to be remobilized easily and are thus regarded as detoxified.     

Comparative analysis of partial structures of a peat humic and fulvic acid using one- and two-dimensional nuclear magnetic resonance spectroscopy

Nuclear magnetic resonance (NMR) resonance integrals obtained from one-dimensional NMR spectra provide semiquantitative contents of humic constituents with limited resolution in structural detail. When supplemented by connectivity information available from homo- and heteronuclear two-dimensional NMR spectra a more reliable assignment of humic substructures becomes available. This is demonstrated with a comparative one- and two-dimensional NMR analysis of a fulvic and a humic acid obtained from Eriophorum peat. An example of a detailed analysis of the proton chemical shift region normally attributed to carbohydrates shows substantial contributions from amino acids, amino and desoxy sugars, and highly oxidized aliphatic chains of intermediate length. The very good resolution of structural detail by a combined analysis of all NMR spectra shows that the effect of the fractionation procedure on the composition and chemical structure of humic materials is very significant. The comparison of the partial structures comprising humic acid (HA) and fulvic acid (FA) of the peat humic materials studied indicates that FA is diagenetically downstream of HA, favoring the biopolymer degradation (BD) model of humification.     

Data model for the collaboration between land administration systems and agricultural land parcel identification systems

The Common Agricultural Policy (CAP) of the European Union (EU) has dramatically changed after 1992, and from then on the CAP focused on the management of direct income subsidies instead of production-based subsidies. For this focus, Member States (MS) are expected to establish Integrated Administration and Control System (IACS), including a Land Parcel Identification System (LPIS) as the spatial part of IACS. Different MS have chosen different solutions for their LPIS. Currently, some MS based their IACS/LPIS on data from their Land Administration Systems (LAS), and many others use purpose built special systems for their IACS/LPIS. The issue with these different IACS/LPIS is that they do not have standardized structures; rather, each represents a unique design in each MS, both in the case of LAS based or special systems. In this study, we aim at designing a core data model for those IACS/LPIS based on LAS. For this purpose, we make use of the ongoing standardization initiatives for LAS (Land Administration Domain Model: LADM) and IACS/LPIS (LPIS Core Model: LCM). The data model we propose in this study implies the collaboration between LADM and LCM and includes some extensions. Some basic issues with the collaboration model are discussed within this study: registration of farmers, land use rights and farming limitations, geometry/topology, temporal data management etc. For further explanation of the model structure, sample instance level diagrams illustrating some typical situations are also included.     

城市面源污染形成过程及其排放特征研究进展

随着城市的迅速发展,城市面源污染日益成为影响城市水体水质的重要因素。本文按照地表累积—降水—径流冲刷—输送这一城市面源污染的形成过程对次降雨径流平均浓度、初始冲刷效益等污染特征进行了研究,分析了不同下垫面及不同功能区的污染特性。     

气田气中汞的形成、危害及治理措施

针对近年来国内外因天然气汞中毒、汞腐蚀、汞污染等事故频发的现象,在阐述天然气中汞的形成、特性、分布及危害的基础上,参照国内外汞的控制指标,提出了固定床吸附脱汞、天然气冷却脱汞、使用防汞腐蚀涂层、定期检测和及时清除等治理措施,对气田企业含汞天然气污染防治有一定的指导作用。     

黄山自然景观成因及边际效应探讨

黄山是中国十大风景名胜之一，以奇特的自然景观著称于世，被誉为“天下第一奇山”，并已被联合国列为世界遗产保护区。黄山是以自然景观为特色的山岳风景区，呈现典型花岗岩峰林地貌，景观类型丰富多样，奇松、怪石、云海、温泉素称“黄山四绝”。以山石地貌为主体的自然景观成因是内、外力综合作用的结果，具有得大独厚的成景条件。自然景观的时空分布特征，反映了自然界普遍存在的边际效应规律，运用自然边际效应的启示，将有助于对旅游资源的发掘、开发和保护工作。     

湛江市区酸雨成因及防治对策

本文根据降水监测资料,分析了湛江市区酸雨的主要形成原因和影响因素,并提出了防治酸雨污染的对策。     

四川省“低荒”资源成因分析与开发对策

本文从分析评价四川省“低荒”资源入手，探讨了“低荒”资源的现状和分布特点，分析了其成因并提出了开发“低荒”资源的对策．