Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

Dissolved Organic Carbon Fractions Formed during Composting of Municipal Solid Waste: Properties and Significance

The properties and transformation of dissolved organic matter (DOM) extracted (10 L water per kilogram compost) from municipal solid waste (MSW) compost at five stages (days 47, 77, 105, 126, and 187) of composting were investigated. The DOM was fractionated into hydrophobic or hydrophilic neutrals, acids, and bases. The unfractionated DOM, the hydrophobic acids and neutrals (HoA and HoN, respectively), and the hydrophilic neutrals (HiN) fractions were studied using solid-state ¹³C-NMR, FTIR, and DRIFT spectroscopy. The HoA fraction was found to be the dominant (percentage of total DOM) hydrophobic fraction, exhibiting a moderate increase during composting. The HoN fraction increased sharply from less than 1% to 18% of the total DOM during 187 days of composting, while the hydrophobic bases (HoB) exhibited the opposite trend. The HiN represented the major fraction of the hydrophiles up to 120 days of composting, decreasing thereafter by 38%. The relative concentration of the hydrophilic acids and bases (HiA and HiB, respectively) exhibited no consistent trend during composting. DRIFT spectra of the unfractionated DOM taken from the composting MSW revealed a decreasing level of polysaccharide structures with time. The ¹³C-NMR and FTIR spectra of the HoA fraction exhibited a polyphenol-humic structure, whereas the HoN spectra exhibited strong aliphatic features. The spectra of the HiN fraction confirmed its polysaccharide nature. During the final stage of composting, the DOM concentration was steady, while a relative decrease of HiN concomitant with an increase of HoA and HoN fractions was observed. These indicate that the DOM contained a low concentration of biodegradable organic matter and a higher content of macromolecules related to humic substances. The biological significance and heavy metal binding of these fractions are being studied based on earlier observations showing enhanced plant growth in the presence of DOM extracted from mature as opposed to immature compost.     

Evaluation of Composts from Agricultural Wastes with Fish Pond Sediment as Bulking Agent to Improve Compost Quality

Composts with five different ratios of agricultural wastes, viz. rice straw (RS), wheat straw (WS), potato plant (PP), and mustard stover (MS) were prepared with or without fish pond bottom sediment to investigate the compost maturity and their suitability for field application. The composting process was monitored through the changes in physico‐chemical parameters and germination index (GI) at every 7 days interval of the composting process. All the composts were dark brown and smelled like forest soil within 56 days of composting, which reflected its matured status. On the basis of the physico‐chemical parameters (bulk density: 0.84 g/cm³; pH 7.05; electrical conductivity: 3.52 mS/cm; cation exchange capacity:82.4 cmol/kg; total carbon:321.4 g/kg; total nitrogen: 16.9 g/kg; As: 6.8 mg/kg; Cd: 2.96 mg/kg; Cr: 29.6 mg/kg, Cu: 243.6 mg/kg; Hg: 0.019 mg/kg; Ni: 24.3 mg/kg; Pb: 62.1 mg/kg and Zn: 812 mg/kg) and GI (89–96%), it could be concluded that RS/WS/PP/MS, 1:1:2:1 v/v/v/v with fish pond sediment produced better compost in accordance with the Indian compost standard. Application of a combined randomized block design analysis revealed that there is a significant difference in the responses of the five composts, in relation to the time of composting. Hierarchical clustering algorithm was applied with a view to form homogeneous groups of five different composts on the basis of different physico‐chemical parameters. Therefore, the ratio of waste incorporation is an important decision for composting and addition of pond sediment can improve the quality of compost.     

Spectroscopic Characterization of Compost at Different Maturity Stages

We studied the physicochemical and molecular changes of compost during its maturation within 60, 90, and 150 days after the composting process. Moreover, the changes were also studied in compost residues after sequential removal of lipidic compounds. Infrared DRIFT spectrometry and ¹³C‐CPMAS‐NMR spectroscopy indicate that the molecular composition of compost changes dramatically during the stabilization period. The most decomposable components, mainly represented by bioavailable lipidic and peptidic structures, were progressively mineralized passing from 60 days to longer periods of compost stabilization. At increasing maturity stages, the composition of organic matter underwent a progressive enrichment in stable hydrophobic and ligno‐cellulosic material. The sequential extraction of lipidic compounds allowed an improved characterization of substrates and confirmed the outlined progressive transformation of compost. Compost may well be chosen on the basis of selected characteristics for environmental applications.     

Preparation,Characterization and Adsorption Mechanism of Cu(II) onto Protonated Rubber Leaf Powder

The adsorption of Cu(II) onto HCl treated rubber leaf powder (HHBL) was investigated in batch and column studies. The adsorbent was characterized by spectroscopic and quantitative analyses in order to understand the mechanism of copper adsorption. HHBL is mesoporous in nature as indicated by Bruneuer, Emmett and Teller (BET) analysis, and has various kinds of functional groups such as Si‐OH, ROH, RCOOH, RCOO^–, RNH₂, C‐O‐C and aromatic rings as detected by Fourier transform infrared (FTIR) spectroscopy. Copper adsorption was confirmed by scanning electron microscopy (SEM) and energy dispersive X‐ray spectroscopy (EDS). The equilibrium process was described well by the Langmuir isotherm model, and a maximum adsorption capacity of 8.39 mg/g was recorded for the smallest adsorbent size (<180 μm). The two main adsorption mechanisms involved were ion exchange and complexation. The fixed bed column study demonstrated satisfactory applicability of HHBL in removing Cu(II) from aqueous solutions.     

Comparison of marine and river water humic substances in a Patagonian environment (Argentina)

Structural aspects of humic substances (HSs) in marine waters of Engaño Bay (Atlantic Ocean) and water from the Chubut River (Patagonia, Argentina) were compared. The HSs were isolated, purified, and analyzed using a multiple-method approach for structural characterization: elemental analysis, nuclear magnetic resonance (¹³C and ¹H NMR), infrared spectroscopy (FTIR), UV-visible absorption and fluorescence. Similarities between the marine and freshwater components were evaluated on the basis of N and O contents, H/C and C/N atomic ratios, infrared bands from nitrogen-containing and carboxylic groups, percentage of functional groups obtained from NMR spectra, spectral slope coefficient of absorption spectra, absorbance ratios at 250 and 365 nm (E ₂/E ₃), aromaticity, excitation–emission matrices and fluorescence quantum yield. Both the Engaño Bay and Chubut River waters have HSs that are mainly composed of fulvic acids (FAs); although they are very similar, they may be distinguished from one another. Similarities include the predominance of aliphatic carbon content (low aromatic content); however, the water bodies differed in their content of proteins and carboxylic acids. The Engaño Bay FAs have mainly an aquatic origin; although the Chubut River FAs suggest a similar aquagenic origin, there is also evidence of contributions from pedogenic FAs.     

Influence of the pore structure and surface chemical properties of activated carbon on the adsorption of mercury from aqueous solutions

Reactivation and chemical modification were used to obtain modified activated carbons with different pore structure and surface chemical properties. The samples were characterized by nitrogen absorption–desorption, Fourier transform infrared spectroscopy and the Bothem method. Using mercury chloride as the target pollutant, the Hg²⁺ adsorption ability of samples was investigated. The results show that the Hg²⁺ adsorption capacity of samples increased significantly with increases in micropores and acidic functional groups and that the adsorption process was exothermic. Different models and thermodynamic parameters were evaluated to establish the mechanisms. It was concluded that the adsorption occurred through a monolayer mechanism by a two-speed process involving both rapid adsorption and slow adsorption. The adsorption rate was determined by chemical reaction.     

Base Treated Cogon Grass (Imperata cylindrica) as an Adsorbent for the Removal of Ni(II): Kinetic,Isothermal and Fixed‐bed Column Studies

The adsorption of Ni(II) from aqueous solutions using base treated cogon grass or Imperata cylindrica (NHIC) was performed under batch and column modes. Batch experiments were conducted to determine the factors affecting adsorption such as pH, adsorbent dosage, initial nickel concentration, contact time and temperature. The fixed‐bed column experiment was performed to determine the practical applicability of NHIC and to obtain the breakthrough curve. Adsorption was fast as equilibrium was achieved within 60 min, and was best described by the pseudo second order model. According to the Langmuir model, a maximum adsorption capacity of 6.96 mg/g was observed at pH 5 and at a temperature of 313 K. Thermodynamic parameters such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated, and indicated that adsorption was a spontaneous and endothermic process. The mechanistic pathway of Ni(II) uptake was examined by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) spectroscopy. The Thomas and Yoon‐Nelson models were used to analyze the fixed‐bed column data.     

Influence of IHSS Standard and Reference Materials on Copper and Mercury Toxicity to Vibrio fischeri

The reduction in light emission of the marine bacterium Vibrio fischeri used in the standard Microtox^® bioassay was measured for the metals copper and mercury. The concentration at which the light emission was reduced by 50% (EC₅₀) was determined to be (3.43 ± 0.83) μmol/L for Cu²⁺ and (0.66 ± 0.01) μmol/L for Hg²⁺. The reduction of the toxicity of these metals by humic and fulvic acids were studied using IHSS Standard and Reference Materials. Copper toxicity was reduced 17...20% by the soil and peat fulvic acids and 9...20% by the aquatic fulvic acids. While there appeared to be little difference in the reduction of Cu toxicity by fulvic acids from soils, peats, or aquatic systems, Hg toxicity was reduced 3.6...7.3% by the soils and peats, while aquatic fulvic acids reduced Hg toxicity 14...16%. Soil fulvic acids appear to have significantly less capacity to reduce Hg toxicity than Cu toxicity. Humic acids had much higher reductions of Cu toxicity (44...124%) compared to the fulvic acids, with little difference between aquatic and soil or peat humic acids, 44...124% and 67...100%, respectively. However, humic and fulvic acids, regardless of origin, had approximately the same effect on Hg toxicity with 3.5...16% reduction by fulvic acids and 8...20% reduction by humic acids. Unlike the fulvic acids, no clear trend was observed relative to origin of the humic acids. There was no correlation between percent reduction of Cu or Hg toxicity by the organic compounds and copper binding capacity (CuBC), C/N ratio, or carboxyl content of the materials. Examination of natural organic matter (NOM) isolated by reverse osmosis techniques from three water sources had reductions of both Cu and Hg toxicity that were most similar to the Suwannee River and Nordic fulvic acids.     

针铁矿对湖泊草、藻来源可溶有机质的非均质吸附

为探究富营养化湖泊中自生源可溶有机质(DOM)在泥水界面的吸附行为,以马来眼子菜(Potamogeton malaianus)和铜绿微囊藻(Microcystis aeruginosa)释放的DOM为代表,考察针铁矿对草、藻源DOM中不同组分的吸附特征.三维荧光平行因子分析表明类富里酸组分C1和类胡敏酸组分C4的含量很低,而类蛋白物质(类酪氨酸组分C2和类色氨酸组分C3)分别占草、藻源DOM荧光组成的70%和93%. 2种DOM均可被针铁矿吸附,吸附过程符合伪一级动力学.通过等温线拟合发现针铁矿吸附藻源DOM的非线性更强,饱和吸附量(23.77 mg/g)高于草源DOM(19.10 mg/g).特别地,类蛋白组分呈现非线性吸附,而类腐殖物质的吸附近似线性,且针铁矿对于DOM各荧光组分的吸附量顺序为:C3C2 C4 C1,此非均质吸附特征与DOM组分的初始含量、分子大小、芳香性及有效吸附位点有关.红外光谱证实氨基、羧基和羟基是吸附过程中的重要官能团.因此,草、藻源DOM显著改变了针铁矿表面的有机物质组成,影响湖泊沉积物的生物地球化学行为.     

Adsorption of Cationic Dyes from Aqueous Solution by Termite Feces,a Non‐Conventional Adsorbent

The adsorption of three cationic dyes (rhodamine B, RB; crystal violet, CV; and malachite green, MG) onto termite feces, a low‐cost adsorbent, was investigated. The adsorbent was characterized by IR spectroscopy, point of zero charge measurement, and the Boehm titration method. The adsorption follows the pseudo‐second‐order kinetic model and the Langmuir–Freundlich isotherm with maximum adsorption capacities of 95.53 mg g^?1 (RB), 75.71 mg g^?1 (CV), and 44.78 mg g^?1 (MG). The study of thermodynamics showed that the adsorption is a spontaneous and endothermic process. This works suggest that termite feces can be used as a new low‐cost adsorbent for cationic dye removal.     

Präzipitation von Aluminium und Phosphat in Gewässern unter dem Einfluss von Versauerung

Precipitation of Aluminium and Phosphate Affected by Acidification Acidified waters often show elevated concentrations of Al (with up to 6 mg L^–1 being not unusual). A pH increase resulting e.g. from mixing with non‐acidified water or from biological activities may be linked with Al precipitation. Up to now, this phenomenon was described for acid mine drainages. This investigation focuses on a whitish precipitate naturally formed in a brook of an atmospherically acidified catchment in the Ore Mountains, Germany. Based on infrared spectra the precipitate was identified as an Al‐hydroxosulfate with crystal water. A simulation of natural conditions in the laboratory showed that Al precipitated only if sulfate or phosphate ions were added to the solution. In the case of sulfate being added, the infrared spectrum of the precipitate was similar to the natural precipitate. ²⁷Al NMR spectroscopy revealed tetrahedrally coordinated Al in some precipitates which evidences the participation of the tridecameric [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺ cation beside other polymeric Al cations. Precipitation experiments subjected to the given conditions showed that the phosphate elimination from solution with Al was much higher than with Fe. With Al and Fe added together, the P elimination rate was likewise high, and phosphate was bound onto Al in the precipitate. This was demonstrated by SEM‐EDX spectroscopy. Based on these results we present a possible reaction mechanism. The precipitation of Al together with P allows a significant retention of both elements in sediments because in contrast to Fe, Al immobilizes phosphate even under anoxic conditions.     

Removal of Nitro Aromatic Compounds from 2,4,6‐Trinitrotoluene Red Water Using 1,2‐Ethanediamine Modified Macroporous Polystyrene Microspheres

To remove nitro aromatic compounds (NACs) from 2,4,6‐trinitrotoluene (TNT) red water, large‐pore‐size (pore size = 200 nm) polystyrene (PSt) microspheres were activated with chloroacetyl chloride followed by reaction with 1,2‐ethanediamine (EDA). Fourier transform IR analyses showed that the amino group was introduced onto PSt microspheres. Determination of the total amino group and primary amino densities suggested that the imino group was the functional group of EDA–PSt. Scanning electron microscope images and mercury porosimetry measurements indicated that the pore structure was well maintained during the reaction. After adsorption with EDA–PSt, 98.5% chemical oxygen demand and 99% acute toxicity of TNT red water was removed. As shown by HPLC and GC–MS, all the neutral and acid NACs in TNT red water were removed by EDA–PSt, while the basic NACs were not. The results showed that hydrogen bonding and electrostatic attraction were involved in adsorption. The adsorbed neutral and acid NACs were eluted using methanol and 0.1 mol L^?1 NaOH, respectively.     

Differences between Humic Substances from Riverine,Estuarine, and Marine Environments Observed by Fluorescence Spectroscopy

Sixteen samples of fulvic acids and XAD‐4 fractions of riverine, estuarine, coastal, and open ocean origin have been studied by emission and synchronous molecular fluorescence spectroscopy. Certain features of the molecular fluorescence are related to the nature, the content, and the origin of those aquatic humic substances (HS). Riverine HS appear several times richer in fluorophores than marine HS, which can be well observed by emission fluorescence spectroscopy. Synchronous‐scan spectra of fulvic acids and of XAD‐4 fractions from the aquatic environments studied, emphasized the quality differences of their fluorophores. These features are useful as tracers of humic substances related with their natural environment source or even with their anthropogenic origin.     

Adsorption of cobalt by using inorganic components of sediment samples from water bodies

The adsorption of cobalt ions was evaluated using sediment samples from water bodies to investigate the adsorption properties of sediment and the behavior of these natural materials in the presence of nuclear and industrial waste.The two sediments(S1 and S2)were treated to eliminate humic and fulvic acids and then they were characterized by several techniques.The minerals found in both the sediments(X-ray diffraction)were quartz and albite;plus,goethite and muscovite in S1,and kaolinite and montmorillonite in S2.Point of zero charge(PZC)of S1 and S2 was 6.00 and 5.22,respectively.The specific area of S1(63.3 m²/g)is higher than S2(1.5 m²/g).Adsorption kinetics data for S1 and S2 were best fitted to the pseudo second-order model.The removal efficiency of S1 for cobalt was 96%with an adsorption capacity(qe)of 0.93 mg/g,and for S2 was 45%with a qeof 0.40 mg/g.The experimental data of the adsorption isotherms were adjusted to Langmuir and Freundlich models for S1 and S2,respectively.The thermodynamic parameters(enthalpy,entropy,and Gibb’s free energy)indicated that the adsorption processes were endothermic,spontaneous,and chemisorption mechanism.The results show that the adsorption capacities of the sediments depend on their composition.These water sediments have important adsorption properties for cobalt,and they can be used in the treatment of nuclear and industrial aqueous wastes.     

Removal of Organic Dyes in Environmental Water onto Magnetic‐Sulfonic Graphene Nanocomposite

A magnetic‐sulfonic graphene nanocomposite (G‐SO₃H/Fe₃O₄) was synthesized and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray diffraction. It was used for removal of three cationic dyes: safranine T (ST), neutral red (NR), victoria blue (VB), and three anionic dyes: methyl orange, brilliant yellow, and alizarin red, from environmental water. The experimental conditions were optimized, including pH, amount of adsorbent, adsorption kinetics, adsorption isotherms, ionic strength, etc. The results show that G‐SO₃H/Fe₃O₄ can adsorb cationic dyes more efficiently and selectively than anionic dyes at pH 6.0. In the first 10 min of adsorption time, more than 93% of the cationic dyes were removed by the sorbent. Adsorption kinetics follow the pseudo‐second‐order kinetic model well. The adsorption isotherm coincided with Langmuir and Freundlich adsorption models. The maximum adsorption capacities of G‐SO₃H/Fe₃O₄ for ST, NR, and VB dyes were 199.3, 216.8, and 200.6 mg g^?1. The adsorbed cationic dyes were eluted by using different pH values of ethanol as the solvent. The established method was simple, sensitive, and rapid, and was suitable for the adsorption of cationic dyes in environmental water.     

Removal of Ni(II) from Aqueous Solutions by Nanoscale Magnetite

Magnetite nanoparticles were applied to remove Ni(II) from aqueous solutions as a function of pH, contact time, supporting electrolyte concentration, and analytical initial Ni(II) concentration. The highly crystalline nature of the magnetite structure with diameter of around 10 nm was characterized with transmission electron microscopy (TEM) and X‐ray diffractometry (XRD). The surface area was determined to be 115.3 m²/g. Surface chemical properties of magnetite at 25°C in aqueous suspensions were investigated. The point of zero charge (pHzpc) was found to be 7.33 and the intrinsic acidity constants (${\rm p}K_{{\rm a}1}^{{\rm s}} $ and ${\rm p}K_{{\rm a}2}^{{\rm s}} $ ) were found to be 9.3 and 5.9, respectively. The surface functional groups were investigated with Fourier transform‐infrared spectroscopy (FTIR) as well. Batch experiments were carried out to determine the adsorption kinetics and mechanism of Ni(II) by these magnetite nanoparticles. The adsorption process was found to be pH dependent. In NaCl solutions, Ni(II) adsorption increased with increasing ionic strength while in NaClO₄ solutions, Ni(II) adsorption exhibited little dependence on the ionic strength of the solution. The adsorption process better followed the pseudo‐second order equation and Freundlich isotherm.     

Reduction of Ammonia,Hydrogen Sulfide,and Short‐Chain Fatty Acids Emission during the Sewage Sludge Composting

The effect of mature compost (MC) used as a bulking agent on ammonia, hydrogen sulfide, and short‐chain fatty acids emission reduction during sewage sludge (SS) composting process was studied in this paper. Three types of mixtures, single SS, SS + wood chips (SS + WC), and SS + MC, were composted in a laboratory reactor. Among the different treatments, decrement rates of NH₃ emission (based on initial TN) from SS to SS + MC and SS + WC to SS + MC were 63 and 59%, respectively. The H₂S concentration ranged from 0.759 to 1.140 mg m^?3 for SS, from 0.075 to 0.455 mg m^?3 for SS + WC, and from 0.075 to 0.425 mg m^?3 for SS + MC and the short‐chain fatty acids (C₂–C₅) concentration ranged from 0.10 to 1.00 ppm for SS, from 0.10 to 1.50 ppm for SS + WC, and from 0.10 to 0.80 ppm for SS + MC. In addition, the temperature apparently, as well as the thermophilic stage, was also elevated by bulking agent addition, especially by the MC addition. The denaturing gradient gel electrophoresis analysis indicated that there was more diversity of the bacterial community during the SS + MC process. According to these results, MC was a suitable bulking agent for reduction ammonia, hydrogen sulfide, and short‐chain fatty acids emission during the SS composting.     

Using DNA‐Stable Isotope Probing to Identify MTBE‐ and TBA‐Degrading Microorganisms in Contaminated Groundwater

Although the anaerobic biodegradation of methyl tert‐butyl ether (MTBE) and tert‐butyl alcohol (TBA) has been documented in the laboratory and the field, knowledge of the microorganisms and mechanisms involved is still lacking. In this study, DNA‐stable isotope probing (SIP) was used to identify microorganisms involved in anaerobic fuel oxygenate biodegradation in a sulfate‐reducing MTBE and TBA plume. Microorganisms were collected in the field using Bio‐Sep® beads amended with ¹³C₅‐MTBE, ¹³C₁‐MTBE (only methoxy carbon labeled), or ¹³C₄‐TBA. ¹³C‐DNA and ¹²C‐DNA extracted from the Bio‐Sep beads were cloned and 16S rRNA gene sequences were used to identify the indigenous microorganisms involved in degrading the methoxy group of MTBE and the tert‐butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading ¹³C‐labeled MTBE and TBA in situ and the ¹³C was incorporated into their DNA. Several sequences related to known MTBE‐ and TBA‐degraders in the Burkholderiales and the Sphingomonadales orders were detected in all three ¹³C clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate‐reducing bacteria and iron‐reducers, such as Geobacter and Geothrix, were only detected in the clone libraries where MTBE and TBA were fully labeled with ¹³C, suggesting that they were involved in processing carbon from the tert‐butyl group. Sequences similar to the Pseudomonas genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with ¹³C. It is likely that members of this genus were secondary degraders cross‐feeding on ¹³C‐labeled metabolites such as acetate.