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.     

Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions

The mobility of phenanthrene (PHE) in soils depends on its sorption and is influenced by either the existing soil humus or exogenous humic substances. Exogenous humic acids (HAs) were added to soil to enhance the amount of soil organic carbon (SOC) by 2.5, 5.0, and 10.0 g kg⁻¹. PHE desorption of the treated soils was determined at two pH levels (3.0 and 6.0) and temperatures (15 and 25 °C). Soil PHE adsorption was related to pH and the type and quantity of added HAs. Humic acid (HA) and fulvic acid (FA) derived from peat had different effects on adsorption of PHE. Adsorption increased at first and then decreased with increasing quantity of exogenous FA. When the soil solution pH (in 0.005 M CaCl₂) was 4.5 or 3.0, the turning points were 2.5 g FA kg⁻¹ at pH 3.0 and 5 g FA kg⁻¹ at pH 4.5. When soil solution pH was 6, the amount of adsorbed PHE was enhanced with increasing exogenous HAs (HA or FA) and amount of adsorption by soil treated with FA was higher than with HA. Adsorption of PHE in the FA treatment at 10.0 g kg⁻¹ was lower than the controls (untreated soil or treatment with HAs at 0 g kg⁻¹) when the soil solution pH was 3.0. This suggests that FA adsorbed by soil was desorbed at low pH and would then increase PHE solubility, and PHE then combined with FA. PHE adsorption was usually higher under lower pH and/or lower temperature conditions. PHE sorption fitted the Freundlich isotherm, indicating that exogenous humic substances influenced adsorption of phenanthrene, which in turn was affected by environmental conditions such as pH and temperature. Thus, exogenous humic substances can be used to control the mobility of soil PAHs under appropriate conditions to decrease PAH contamination.     

2种水稻土中Cu(Ⅱ)和Pb(Ⅱ)的解吸动力学

用一次平衡法研究了2种水稻土表面吸附态Cu(Ⅱ)和Pb(Ⅱ)的解吸动力学行为及柠檬酸和酒石酸对2种重金属离子解吸的影响。结果表明,虽然2种土壤对Pb(Ⅱ)的吸附量比Cu(Ⅱ)高得多,但无论在单一重金属体系还是Cu(Ⅱ)和Pb(Ⅱ)共存体系中,Cu(Ⅱ)的解吸量均大于Pb(Ⅱ),湖州水稻土Cu(Ⅱ)的解吸量大于嘉兴水稻土,说明土壤对重金属离子的吸附亲和力越大,吸附的重金属离子越不易解吸。用E lovich方程拟合动力学数据可以获得比较满意的结果。解吸速率与时间的关系曲线表明,Cu(Ⅱ)和Pb(Ⅱ)的解吸速率随时间的增加迅速减小。Cu(Ⅱ)的解吸速率大于Pb(Ⅱ),柠檬酸和酒石酸不仅使重金属的解吸量增加,而且使Cu(Ⅱ)和Pb(Ⅱ)的解吸速率大大提高。2种有机酸对Cu(Ⅱ)解吸的促进作用大于Pb(Ⅱ),柠檬酸的促进作用大于酒石酸。     

Effect of Ca(II), Fe(II), and Fe(III) on Cu(II) adsorption by a polyvinylidene fluoride-based chelating membrane from Cu(II)–EDTA complex solution

A polyvinylidene fluoride-based membrane bearing the diethylenetriaminepentaacetic acid chelating group was employed to recover Cu(II) from the Cu(II)-ethylenediaminetetraacetic acid complex aqueous solution. Effects of Ca(II), Fe(II), and Fe(III) on Cu(II) uptake were investigated by static batch adsorption tests and dynamic adsorption filtration. Isotherms, kinetics, and breakthrough curves of Cu(II) uptakes in the presence of the three cations at concentrations of 1 mmol L^?1 were elucidated. The three cations showed a positive effect on the Cu(II) uptake; the stimulative roles were in the order of Fe(III) > Fe(II) > Ca(II). They did not alter the adsorption behavior of the membrane; adsorption isotherms and kinetics could be described by Langmuir and Lagergren second-order models, and Cu(II) adsorption was a spontaneous and exothermic process. The presence of Ca(II), Fe(II), and Fe(III) increased the sorption capacity of the membrane stack by 1.3, 1.9, and 3 times. Breakthrough time and the exhaustion time of membrane stacks were also extended.     

Effect of low molecular weight organic acids on adsorption and desorption of fluoride on variable charge soils

The effect of four low molecular weight organic acids on F⁻ adsorption by two variable charge soils was investigated using a batch method. The organic acids reduced F⁻ adsorption through competition by the acids with F⁻ for sorption sites. Oxalic and malonic acids, both of which have simpler chemical structures, were more effective than citric or malic acid. The effect of organic acids on F⁻ adsorption was more prominent at higher pH values and with larger amounts of the organic acids. The desorption study showed that the organic acids enhanced the desorption of F⁻ adsorbed by the soils. In the control and malic acid systems, desorption increased sharply with decreasing pH, while in the oxalic acid system, desorption rose slightly with decreasing pH. Desorption also increased with increasing amount of organic acid added. There are two possible mechanisms for the effect of the organic acids on F⁻ adsorption and desorption: (1)␣competition of the organic acids with F⁻ for adsorption sites and (2) dissolution of the adsorbents, especially dissolution of soil Al.     

土壤胶体表面吸附态铜的解吸动力学特征

供试土壤胶体吸附态Cu的解吸过程分为两个阶段,0~60min时间段为快速反应阶段,对应于静电吸附态Cu的解吸;60min以后为慢速反应阶段,对应于专性吸附态Cu的解吸.解吸遵循两点位一级反应方程;在3种介质下,两点位解吸速率常数及吸附量大小为k1＞k2,C2＞C1;各土壤胶体的解吸速率大小次序与表面电荷密度的大小相反.草酸、柠檬酸可以增加吸附态Cu的解吸;在NaNO3介质中,第二点位吸附态Cu量与总吸附量的比值(C2/C0)可作为专性吸附的特征值.     

Suitability of various chemically prepared activated carbons for the removal of copper(II) ions

Studies on the suitability of various chemically prepared activated carbons (CPACs) like straw carbon (SC), sawdust carbon (SDC), dates nut carbon (DNC) and commercial activated carbon (CAC) for the removal of copper(II) ions by adsorption from simulated wastewater have been carried out under batch mode at 30?±?1°C and the results are compared. The percentage removal of Cu(II) ions increased with a decrease in initial concentration, particle size and added electrolytes (ionic strength) and increased with an increase in contact time, dose of adsorbent and initial pH of the solution. The adsorption data were fitted with the Langmuir isotherm. The applicability of the first order kinetic equation viz. Lagergren equation was tested by correlation analysis. The adsorption process is concluded to be a spontaneous, first order reaction, occurring with increased randomness at the solid–liquid interface. Studies on the desorption of Cu²⁺-loaded activated carbons (ACs) were carried out with nitric acid (0.2–1?N). The possibility of reuse of the regenerated ACs in cycle (in cue-one after another) was tested. SC was found to be a suitable adsorbent alternative to CAC among CPACs for the removal of metal ions, in general, and Cu²⁺ ions, in particular.     

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb(II) and Cu(II) ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 mol·L^-1 CaCl₂ as background electrolyte. The desorption isotherms of Pb(II) and Cu(II) were similar to the adsorption isotherms, which can be fitted well by Freundlich equation (R₂>0.96). The soil in the three sites had greater sorption capacities for Pb(II) than Cu(II), which was affected strongly by the soil characteristics. In the binary metal solution containing 1∶1 molar ratio of Pb(II) and Cu(II), the total amount of Pb(II) and Cu(II) adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared (FT-IR) spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.     

Effect of metallic cations on the sorption of pesticides on soil

We studied the adsorption and desorption of two pesticides, namely isoproturon and dimetomorph, onto a model soil sample. We first show that the adsorption of isoproturon depends on pH, from 1 mg g⁻¹ at pH 4 to 2 mg g⁻¹ at pH 10, contrary to the adsorption of dimetomorph (5.8 mg g⁻¹). We also studied the influence of metallic cations, copper(II), iron(III), manganese(II), and chromium(III), on the sorption of isoproturon and dimetomorph. We found that in the case of isoproturon, the presence of metallic cations does influence the retention capacity of the soil sample. The sorption becomes very weak in the presence of copper and chromium, whereas in the case of iron and manganese the sorption properties are slightly modified.     

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.     

A sandy loam soil as a natural control for Pb contamination

The Pb (II) adsorption/desorption mechanism onto a natural sandy loam soil was studied by batch experiments at different pHs (3.0, 4.5, 6.0), at different ionic strength (0, 0.02 and 0.1 M) and with different electrolytes solutions of NaCl, NaAcO and NaNO₃. Pb was strongly adsorbed onto the soil due to the formation of a mix of inner-sphere and outer-sphere complexes. Experimental adsorption data fitted Freundlich and Langmuir isotherms. The desorption results with 0.1 M Mg (NO₃)₂ and 0.1 M NaAcO solutions corroborated the mechanisms proposed. The strong binding of Pb (II) to high affinity sites on soil minerals seems to be responsible for the extent of hysteresis. The sandy loam soil under study thus constitutes a natural control for Pb contamination.     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^?1) on ¹³⁷Cs adsorption–desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26–99.97%) of added ¹³⁷Cs (3.7?×?10³?7.03?×?10⁵ Bq l^?1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K _ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄ ⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K _ads and soil pH was observed. The ¹³⁷Cs adsorption–desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09–0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

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.

     

风沙土不同有机组分对氨氮的解吸特征影响

采用平衡解吸法研究了风沙土不同有机组分对氨氮的解吸特征影响。结果表明,去除腐殖质后的风沙土氨氮解吸比例增加（由0.58增加到0.68）,同时,解吸迟滞性指数显著降低（由0.067降低到0.021）,说明腐殖质是影响风沙土氨氮解吸特征的重要因素;氨氮在轻组有机组分上的表面分配作用吸附是导致解吸比例增大,解吸迟滞性指数减小的原因;重组有机组分中的紧结态腐殖质（胡敏素）对氨氮的解吸起关键作用,它不但解吸比例较低（Dr=0.23）,而且解吸迟滞性指数较大（TⅡ=0.458）;氨氮在紧结态和稳结态腐殖质所形成的团聚体颗粒微孔隙中的不可逆吸附是导致解吸比例降低、解吸迟滞性指数增大的根本原因;考查土壤对氨氮的解吸特征不但要考虑有机质的含量,更要考虑有机质的存在形态,它也是影响土壤氨氮解吸特征的重要因素,轻组有机组分、重组有机组分及重组有机组分中的稳结态加紧结态腐殖质（HⅡ＋HⅢ组）和紧结态腐殖质（HⅢ组）携载的吸附态氨氮进入水体后,对上覆水体的扩散通量可分别按其饱和吸附量的0.94、0.58、0.33和0.23倍估算。     

环丙氨嗪在Aldrich胡敏酸中吸附-解吸特征的研究

采用批平衡法,研究了不同温度下环丙氨嗪在Aldrich胡敏酸中的吸附与解吸特征。结果表明：环丙氨嗪吸附和解吸过程都包含极快速、快速和缓慢阶段。伪二级动力学方程能较好地描述不同温度下环丙氨嗪的吸附动力学特性,表明吸附速率决定于胡敏酸表面吸附位点的可用度,而不是溶液中环丙氨嗪的浓度。环丙氨嗪在极快速吸附阶段的吸附速率随温度的升高而增大,但平衡时的吸附量却随温度的增加而降低。吸附等温线和解吸曲线符合Langmuir方程和Freundlich方程。环丙氨嗪在胡敏酸上的解吸速率小于吸附速率,表明存在滞后效应。吸附焓变、熵变和自由能都为负值,表明环丙氨嗪在胡敏酸上的吸附是一个自发、熵减小的放热过程。-Go〈40 kJ.mol^-1表明环丙氨嗪在胡敏酸表面以物理吸附为主。     

菜园土壤铜吸附--解吸特性的研究

研究了菜园土壤铜的吸附—解吸特性。结果表明 ,3种菜园土壤吸附 Cu2 的量均随平衡液中Cu2 浓度的增加而增大 ,可用 L angmuir方程和 Freundlich方程来描述。由 Langmuir方程求得的菜园土壤对 Cu2 的最大吸附量和最大缓冲容量的大小顺序为 :黄松土 >江涂土 >粉泥土 ,菜园土壤对 Cu2 的解吸量和解吸率均随其吸附量的增加而增加 ,吸附量与解吸量之间呈显著或极显著线性正相关。     

碱性条件下胡敏酸吸附镉的特征研究

为了探讨胡敏酸在碱性条件下的吸附镉机理,了解碱性盐化土壤中镉污染机理和生态环境之间的关系,实验研究了胡敏酸在碱性条件吸附镉的特征。采用批吸附试验方法,研究不同Cd初始浓度、反应时间、不同pH和离子强度对胡敏酸吸附镉的影响,结果表明：胡敏酸具有较强吸附镉的能力,可以用Langmuir吸附模型和Temkin吸附模型很好地拟合其等温吸附过程（r分别为0.9809和0.9816）;在60 min内的快速反应阶段和60 min至6 h间的慢速反应阶段,胡敏酸对镉的吸附量分别为2.895 mg·g-1和3.342 mg·g-1,吸附反应平衡前6 h的动力学过程可以用Elovich方程进行很好的拟合（r为0.9285）;随着pH增加,吸附率表现出逐步增加趋势,并以pH为4.5和8.5为界,呈现两端增加速度快,中间增加慢的规律性;在较低浓度离子强度下,离子强度的增加促进胡敏酸吸附镉;而在高离子强度下,表现出相反的规律性;在相同的条件下,不同离子强度对胡敏酸吸附镉的影响大小为：氯化钙〉氯化镁〉氯化钾〉氯化钠。土壤在盐化的过程中,由于无机盐浓度的增加,增加了重金属离子的生物可利用性,加大了重金属离子的生态风险。     

Adsorption‐desorption hysteresis of α‐endosulfan in tropical soils using isotopic techniques

This study was designed to evaluate the adsorption‐desorption hysteresis of endosulfan (1,2,3,4, 7,7‐hexachlorobicyclo[2,2,1]‐2‐heptene‐5,6‐bisoxymethylene sulfite) in selected tropical soils. Two major tropical soils from Thailand were selected, Rangsit lowland soils (Rangsit series) and Phrabat upland soils (Pakchong series). The soil types were sub‐divided into plow soils, 0–20cm depth from the surface, and subsoils, 20–40cm depth. Adsorption was determined in 24h batch equilibrium, with five different concentrations of ¹⁴C endosulfan ranging from 1.04 to 16.64 ng/mg soils. Four successive desorption studies were performed continuously after three adsorption concentrations, 24h for each successive. Adsorption coefficient values (K _ads) as determined by Freundlich model ranged from 0.02 to 0.14 and found to be higher in Rangsit soils as expected when compared with Phrabat soils. Desorption was hysteresis in every desorption study. Desorption coefficient values (K _des) were higher than adsorption (K _des).     

Uptake of Ni2+ and rhodamine B by nano-hydroxyapatite/alginate composite beads: batch and continuous-flow systems

Alginate encapsulated nano-hydroxyapatite beads were synthesized and characterized by Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface analysis, and X-ray diffraction. Their adsorptive potential for Ni²⁺ and rhodamine B was explored in batch mode and by fixed-bed column passage. In the batch system, maximum uptake capacity for Ni²⁺ was 360 mg g^?1 and 480 mg g^?1 for rhodamine B. In the presence of humic acid, sorption was enhanced. For the continuous-flow system, adsorption was effective at low flow rate. For both pollutants, mass transport resistance increased during adsorption. The overall rates of rhodamine B and Ni²⁺ uptake were found to be controlled by external mass transfer.     

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.