Combining spectroscopic and potentiometric approaches to characterize competitive binding to humic substances

In an area that contains high concentrations of natural organic matter, it is expected that it plays an important role on the behavior of rare earth elements (REE), like europium, and of trivalent actinides. Competitive interactions with H+, inorganic species, major cations, e.g. Ca(II) or Mg(II), could influence these metals transport and bioavailability. Competitive experiments between cations, which can bind differently to humic substances and Eu3+, will bring an improved understanding of the competitive mechanisms. The aim of this study is to acquire data for Eu(III)/Cu(II) and Eu(III)/Ca(II) competitive binding to a sedimentary originated humic acid (Gorleben, Germany). The NICA-Donnan parameters for Ca2+, Cu2+, and Eu3+ obtained from competitive binding experiments using Ca2+ or Cu2+ ion selective electrodes were used to model time-resolved laser fluorescence spectroscopy (TRLFS) measurements. Eu3+ and CU2+ are in direct competition for the same type of sites, whereas Ca2+ has an indirect influence through electrostatic binding.     

Colloidal α-Al2O3 Europium(III) and humic substances interactions: a macroscopic and spectroscopic study

Eu(III) sorption onto α-Al(2)O(3) in the presence of purified Aldrich humic acid (PAHA) is studied by batch experiments and time-resolved laser-induced luminescence spectroscopy of Eu(III). Experiments are conducted at varying pH, at 0.1 mol/L NaClO(4), 10(-6) mol/L Eu(III), 1 g/L α-Al(2)O(3) and 28 mg/L PAHA, which assured a complete Eu(III)-PAHA complexation. Adsorption of Eu(III) presents the expected pH-edge at 7, which is modified by addition of PAHA. Presence of Eu(III) slightly increases PAHA sorption throughout the pH range. The evolutions of luminescence spectra and decay times of the binary systems, that is, Eu(III)/α-Al(2)O(3) and Eu(III)/PAHA, indicate a progressive surface- and humic-complexation with increasing pH. The typical biexponential luminescence decay in Eu(III)/PAHA system is also recorded; the fastest deactivation depending barely on pH. In ternary Eu(III)/PAHA/α-Al(2)O(3) system, the existence of a luminescence biexponential decay for all pH means that Eu(III) is always in the direct neighborhood of the humic substance. Below pH 7, the spectra of the ternary system (Eu(III)/PAHA/α-Al(2)O(3)) are not different from the ones of Eu(III)/PAHA system, implying the same complex symmetry. Nevertheless, the increase of luminescence decay time points to a change in PAHA conformation onto the surface.     

用于夜光纤维的发光材料特性

使用荧光光谱仪、长余辉测试仪对发光材料的激发、发射光谱及余辉性能进行表征,并结合夜光纤维对发光材料粒径、光谱和余辉性能等方面的要求,对发光材料的特性进行研究与分析.结果表明:粒径为7～8 μm的发光材料余辉性能较好,并符合夜光纤维的制备要求,为夜光纤维用发光材料的首选;改变Eu2+和Dy3+的掺量不会使发光材料的光谱发...     

Effect of humic substance photoalteration on lead bioavailability to freshwater microalgae

The present study provides results on the influence of humic substance (HS) photoalteration on lead availability to the freshwater microalga Chlorella kesslerii . The evolution of the free lead-ion concentrations measured by the ion exchange technique [Pb](IET) and intracellular lead contents was explored in the presence of Suwannee River humic (SRHA) and fulvic (SRFA) acids, as well as Aldrich humic acid (AHA) exposed at increasing radiance doses under a solar simulator. Modifications of HS characteristics highly relevant to Pb complexation and accumulation of HS to algal surfaces, including Fourier transform infrared spectroscopy, were followed. It was demonstrated that simulated sunlight exposure of HS increased [Pb](IET) in the medium for SRFA and SRHA, but had no effect for AHA. No clear relationship was observed between the changes in free lead-ion concentrations and intracellular content in alga for all studied HS, suggesting that HS photodegradation products also exhibit Pb complexation properties, and that direct interactions between HS and alga are affected. Indeed, photoalteration of humic substances reduced the adsorption of HS to the algal surface; the effect was more pronounced for SRFA and AHA and less significant for SRHA. The bioavailability results were consistent with the characterization of the phototransformation of humic substances: Pb speciation changes followed the modification of the relative abundance of the carboxylic groups and their molecular environment, while the reduced HS adsorption to the alga correlated with losses of the double bond abundance and aromaticity.     

Binding of atrazine to humic substances from soil,peat and coal related to their structure

Partition coefficients for the binding affinities of atrazine to 16 different humic materials were determined by the ultrafiltration HPLC technique. Sources included humic acids (HA), fulvic acids (FA), and combined humic and fulvic fractions (HF) from soil, peat, and coal humic acid. Each of the humic materials was characterized by elemental composition, molecular weight, and composition of main structural fragments determined by 13C solution-state NMR. The magnitude of K(OC) values varied from 87 to 575 L/kg of C, demonstrating relatively low binding affinity of humic substances (HS) for atrazine. On the basis of the measured K(OC) values, the humic materials can be arranged in the following order: coal HA approximately = gray wooded soil HA > chernozemic soil HA and HF > sod-podzolic soil HA approximately = peat HF > sod-podzolic soil FA > peat dissolved organic matter. The magnitude of the K(OC) values correlated strongly with the percentage of aromatic carbon in HS samples (r = 0.91). The hydrophobic binding was hypothesized as the key interaction underlying the binding of atrazine to HS.     

Y2O3:Eu3+纳米纤维与纳米带的制备及其发光性能

以聚乙烯吡咯烷酮（PVP）、稀土硝酸盐为原料,分别以水和N,N二甲基甲酰胺（DMF）溶剂,通过静电纺丝与高温煅烧制备出两种不同形貌的一维结构纳米材料。通过热重分析（TG）、场发射扫描电镜（FE-SEM）、傅立叶红外光谱（FTIR）、X射线衍射仪（XRD）对材料的结构、形貌进行了表征,利用荧光光谱仪对样品的光致发光性能进行了评价。结果表明：以水为溶剂制备的Y2O3:Eu3+样品煅烧前后均为带状,并推测了纳米带的形成机理,而用DMF溶剂制备的样品煅烧前后则均为纤维状;800 °C煅烧后样品结晶良好且为立方相结构。此外,纳米纤维和纳米都显示出来良好的发光效果,而Y2O3:Eu3+纳米纤维的光致发光强度约为Y2O3:Eu3+纳米带的2倍。     

Antioxidant properties of humic substances

Humic substances (HS) are heterogeneous, redox-active organic macromolecules. While electron transfer to and from HS under reducing conditions is well investigated, comparatively little is known on the electron donating (i.e., antioxidant) properties of HS under oxic conditions. In this work, the electron donating capacities (EDCs) of terrestrial and aquatic HS were quantified by mediated electrochemical oxidation over a wide range of pH values and applied redox potentials (E(h)) using 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) as an electron transfer mediator. Electrochemical oxidation of three model humic acids (HAs) was largely irreversible, and the EDCs of these HAs increased with increasing E(h) and pH. These results suggest that HS contain a wide variety of moieties that are oxidized at different potentials and that, upon oxidation, release protons and undergo irreversible follow-up reactions. At a given pH and E(h), the EDCs of the HS correlated well with their titrated phenol contents suggesting phenolic moieties as major electron donating groups in HS. Comparing the EDCs of 15 HS with their electron accepting capacities (EACs), aquatic HS had higher EDCs and lower EACs than terrestrial HS of comparable aromaticities. These results indicate that oxidative transformation of HS in the environment results in a depletion of electron donating phenolic moieties with antioxidant properties relative to the electron accepting quinone moieties.     

静电纺稀土铝酸锶发光纳米短纤维的制备与表征

采用溶胶-凝胶/静电纺丝法制备了PVP/[Sr(NO3)2+Al(NO3)3+Eu(NO3)3+Dy(NO3)3]复合纳米纤维,讨论了硝酸盐含量对纺丝液性能及可纺性的影响;复合纳米纤维经1 100℃弱还原气氛煅烧4 h后获得Sr Al2O4:Eu2+,Dy3+发光纳米短纤维,利用XRD、SEM、FT-IR及荧光分光光度计等方法对发光纳米短纤维进行了表征,结果表明,所得样品为Sr Al2O4纯相,属单斜晶系,直径约为200 nm,尺寸均一;样品的激发光谱范围为250~450 nm,可日光或荧光激发,该样品在365 nm波长光激发下发射出Eu2+特征的510 nm绿色光,与微米级的粗晶粉体相比,其发射峰位置出现了蓝移,初始余辉强度为1.72 cd/m2。     

Study on the effects of humic and fulvic acids on quantum dot nanoparticles using capillary electrophoresis with laser-induced fluorescence detection

The increasing production and use of quantum dot (QD) nanoparticles have caused concerns on the possibility of contaminating the aquatic and terrestrial ecosystems with wastes that may contain QDs. Therefore, studies on the behavior of QDs upon interaction with components of the natural environment have become of interest. This study investigated the fluorescence and electrophoretic mobility of carboxylic or amine polyethylene glycol (PEG)-functionalized CdSe/ZnS QDs in the presence of two aquatic humic substances (HS), Suwannee River humic and fulvic acids, using capillary electrophoresis with laser-induced fluorescence detection. Results showed initial enhancement in fluorescence of QDs at the onset of the interaction with HS, followed by fluorescence quenching at longer exposure with HS (>30 min). It was also observed that the electrophoretic mobility of QDs increases with increasing concentration of HS, suggesting an increase in the ratio in charge to hydrodynamic size of the nanoparticles. To determine if the QDs degraded upon interaction with HS, the QD-HS mixtures were dialyzed to separate free Cd2+ from intact QDs, followed by analysis of the solutions using inductively coupled plasma-mass spectrometry. Results suggested that degradation of QDs in the presence of HS did not occur within the period of incubation.     

Effects of Humic Substances Obtained from Shives on Flax Yield Characteristics

The effects of humic substances (HS) extracted from flax shives on the fiber and seed yield of fiber flax were examined during 3 years field experiment. HS from shives consists of humic acids—5.3 gL^?1 and fulvic acids—0.7 gL^?1 were applied (6·10^–2 gL^?1 concentration, with 300 Lha^?1 of spraying liquid) in “herring-bone” stage (BBCH 13 growth stage). The HS action was evaluated in different climatic conditions and in three varieties. Application of HS on early stage of vegetation of flax plants increased fiber yield (exceeding control on 16.0–28.1%) and quality (5% of cellulose content), protein and oil content in seeds (up to 1.9–4.2% and 1.6–3.5%, respectively). Positive reply of flax plants on HS from flax shives in tested cultivars allows saying about prospects of this type of humic substances.     

不同改性聚丙烯腈纤维与Fe3+配位反应动力学

分别将低转化率和高转化率偕胺肟改性聚丙烯腈纤维（L-AO-PAN和H-AO-PAN）以及混合改性聚丙烯腈纤维（M-PAN）分别与Fe3+进行配位反应并生成改性PAN纤维铁配合物,重点研究了三种配体与Fe3+配位反应的动力学行为,求得和比较了相关的动力学参数。结果表明,三种不同改性聚丙烯腈纤维配体与Fe3+之间的配位反应属于一级反应,并能够使用Langmuir吸附模型进行描述。在相同条件下H-AO-PAN与Fe3+反应的饱和配合量、反应速率常数和活化能均高于L-AO-PAN和M-PAN与Fe3+反应的相应参数。反应温度的升高有利于三种纤维配体特别是H-AO-PAN与Fe3+配位反应的进行。     

Increased dietary vitamin D3 and calcium partially alleviate heat stress symptoms and inflammation in lactating Holstein cows independent of dietary concentrations of vitamin E and selenium

Twelve multiparous Holstein cows (42.2 ± 5.6 kg of milk/d; 83 ± 27 d in milk) were used in a split-plot design testing the effects of mineral and vitamin supplementation on the time course of animal performance, metabolism, and inflammation markers during heat stress. The main plot was the average concentrations of dietary vitamin E and Se (adequate: 11.1 IU/kg of vitamin E and 0.55 mg/kg of Se, and high: 223 IU/kg of vitamin E and 1.8 mg/kg of Se, respectively). Within each plot, cows were randomly assigned to (1) heat stress (HS) with adequate concentrations of vitamin D₃ and Ca (1,012 IU/kg and 0.73%, respectively), (2) HS with high concentrations of vitamin D₃ and Ca (HS+D₃/Ca; 3,764 IU/kg and 0.97%, respectively), or (3) pair-feeding (PF) in thermoneutrality with adequate concentrations of vitamin D₃ and Ca (1,012 IU/kg and 0.73% Ca) in a Latin square design with 14-d periods and 7-d washouts. The highest rectal temperature was recorded at 1700 h for HS (39.4°C; mean of d 1 to 14), being 1.2 and 0.8°C greater than for PF and HS+D₃/Ca, respectively. Respiratory rate and water intake were higher in HS (73 breaths/min and 115 L/d, respectively) relative to PF (28 breaths/min and 76 L/d). Heat stress decreased dry matter intake progressively, reaching a nadir on d 5 to 7 (33% reduction) and was not different between treatments. Milk yield decreased progressively in all treatments, but remained greater in PF relative to HS from d 3 to 14 (10%), whereas HS and HS+D₃/Ca were not different. Milk fat, protein, and lactose concentrations and yields were lower in HS relative to PF from d 3 to 14, but not different between HS and HS+D₃/Ca. Relative to PF, preprandial insulin concentrations were increased in HS, whereas plasma nonesterified fatty acids were decreased on d 7 and 14. Plasma lipopolysaccharide-binding protein concentrations increased in HS cows on d 7 and 14, respectively, relative to PF, whereas they were reduced in HS + D₃/Ca on d 14. Plasma C-reactive protein, tumor necrosis factor-α, and fecal calprotectin were increased in HS relative to both PF and HS+D₃/Ca on d 7 and 14. Rectal temperature was positively associated with plasma lipopolysaccharide-binding protein (r = 0.72), tumor necrosis factor-α (r = 0.74), C-reactive protein (r = 0.87), and with milk somatic cells (r = 0.75). Plasma 8-hydroxy-2-deoxyguanosine concentrations presented a 3-way interaction, where 8-hydroxy-2-deoxyguanosine was lower in HS than in PF on d 7 and 14, and lower in HS+D₃/Ca relative to HS on d 14 in the adequate vitamin E and Se treatment, but no effects were observed in the high vitamin E and Se group. Plasma superoxide dismutase concentrations increased over time, and were higher in HS relative to PF on d 14, whereas HS+D₃/Ca was similar to HS. Heat stress markedly reduced milk production and milk components while increasing markers of leaky gut and inflammation. In contrast, vitamin D₃ and Ca supplementation reduced hyperthermia (d 7–14), markers of leaky gut, and inflammation independent of dietary concentrations of vitamin E and Se.     

Measurement of humic and fulvic acid concentrations and dissolution properties by a rapid batch procedure

Although humic substances (HS) strongly facilitate the transport of metals and hydrophobic organic contaminants in environmental systems, their measurement is hampered by the time-consuming nature of currently available methods for their isolation and purification. We present and apply a new rapid batch method to measure humic (HA) and fulvic (FA) acid concentrations and dissolution properties in both solid and aqueous samples. The method is compared with the conventional procedures and is shown to substantially facilitate HS concentration measurements, particularly for applications such as geochemical modeling where HS purification is not required. The new method can be performed within 1.5-4 h per sample and multiple samples can be processed simultaneously, while the conventional procedures typically require approximately 40 h for a single sample. In addition, specific dissolution properties of HS are identified and are consistent with recent views on the molecular structure of HS that emphasize molecular interactions of smaller entities over distinct macromolecular components. Because the principles of the new method are essentially the same as those of generally accepted conventional procedures, the identified HA and FA properties are of general importance for the interpretation of the environmental occurrence and behavior of HS.     

Protein encapsulation by humic substances

Protein encapsulation by natural organic matter is hypothesized to preserve the activity of proteins in terrestrial and aquatic environments. Direct molecular-level evidence for encapsulation of net positively charged proteins lysozyme, trypsin, and ribonuclease A by a diverse set of humic substances (HS) in nanostructured films was collected using a combination of optical waveguide lightmode spectroscopy and quartz crystal microbalance measurements. The results suggest that protein-HS electrostatic attraction drives encapsulation of positively charged lysozyme by a soil humic acid at pH 5 to 8 and by six additional humic and fulvic acids from terrestrial and mixed terrestrial aquatic sources at pH 5 and 6. Encapsulation of trypsin and ribonuclease A, which had negatively charged surface patches under the studied conditions, suggested that localized protein-HS electrostatic repulsion is overcompensated by attractive forces, likely including contributions from the hydrophobic effect. Evidence is provided showing that encapsulation of lysozyme at pH 8 and of ribonuclease A at pH 5 and 6 involved partial disassembly of HA supramolecular associations. This work advances a molecular-level picture of protein encapsulation by HS and presents a novel approach to study the effects of encapsulation on protein enzymatic activity and susceptibility to abiotic and biotic transformations.     

Lanthanide--humic substances complexation. II. Calibration of humic ion-binding model V

The experimental complexation of the lanthanides (Sc, Y, and rare earth elements) with Suwannee river fulvic acid, Leonardite coal humic acid, and Elliot soil humic acid is described with Humic Ion-Binding Model V. The fitted intrinsic equilibrium constants for metal-proton exchange, pKMHA, for Eu3+ are similar to previously published experimental fits, and linear free energy relationship (LFER) estimated values. The experimentally observed lanthanide contraction effect in REE-humic complex stability is reflected in the gradual decrease in pKMHA from La to Lu. In Model V, a decrease in pKMHA from La to Lu indicates an increase in complex stability. Fitted pKMHA values for heavy REE are lower than those estimated by LFERs. Consequently, REE fractionation by humic substances complexation could be more pronounced than previously thought. Recommended pKMHA values for lanthanide-fulvic and -humic acid complexation are derived by superimposing the fitted trends in pKMHA for all REE, i.e., the decrease in pKMHA from La to Lu, on the average Eu pKMHA value for all literature datasets. These results will allow modeling assessments of organic matter induced REE fractionation in aquatic environments, taking into account changes in pH, ionic strength, and ion competition. A simulation of dissolved REE speciation in an average world river suggests that organic matter outcompetes carbonate complexation, even under alkaline conditions.     

Dietary starch level and rumen-protected methionine,lysine, and histidine: Effects on milk yield,nitrogen, and energy utilization in dairy cows fed diets low in metabolizable protein

Our objective was to investigate the interactions between starch level and rumen-protected Met, Lys, His (RP-MLH) on milk yield, plasma AA concentration, and nutrient utilization in dairy cows fed low metabolizable protein diets (mean = −119 g/d of metabolizable protein balance). Sixteen multiparous Holstein cows (138 ± 46 d in milk, 46 ± 6 kg/d in milk) were used in a replicated 4 × 4 Latin square with a 2 × 2 factorial arrangement of treatments. Each period lasted 21 d with 14 d for diet adaptation and 7 d for data and sample collection. Dietary starch level varied by replacing (dry matter basis) pelleted beet pulp and soyhulls with ground corn resulting in the following treatments: (1) 20% pelleted beet pulp and 10% soyhulls (reduced starch = RS), (2) RS plus RP-MLH (RS+AA), (3) 30% ground corn (high starch = HS), and (4) HS plus RP-MLH (HS+AA). Dietary starch concentrations averaged 12.3 and 34.4% for RS and HS basal diets, respectively. Diets were supplemented with RP-MLH products to supply digestible Met, Lys, and His. Compared with RS and RS+AA diets, HS and HS+AA diets increased yields of milk (37.9 vs. 40.1 kg/d) and milk protein (1.07 vs. 1.16 kg/d) and decreased dry matter intake (25.9 vs. 25.2 kg/d), milk urea N (12.6 vs. 11.0 mg/dL), and plasma urea N (13.3 vs. 11.6 mg/dL). Milk N efficiency was greater in cows fed the HS and HS+AA than RS and RS+AA diets (28.9 vs. 25%), and RP-MLH supplementation improved milk true protein concentration. Starch level × RP-MLH interactions were observed for plasma concentrations of Arg and Lys, with RP-MLH being more effective to increase plasma Arg (+16%) and Lys (+23%) when supplemented to the RS than the HS basal diet. Replacing pelleted beet pulp and soyhulls with ground corn lowered the plasma concentrations of all essential AA except Met and Thr. In addition, the plasma concentrations of His and Met increased with RP-MLH. The apparent total-tract digestibilities of neutral and acid detergent fiber were lower, and those of starch and ether extract greater in cows offered the HS and HS+AA diets than RS and RS+AA diets. Urinary excretion of urea N decreased by replacing pelleted beet pulp and soyhulls with ground corn. Enteric CH₄ production, CH₄ yield, and CH₄ intensity all decreased in the HS and HS+AA versus RS and RS+AA diets. Diets did not affect the intakes of gross energy, metabolizable energy, and net energy of lactation. In contrast, digestible energy intake increased with feeding the RS and RS+AA diets, whereas CH₄ energy decreased in cows fed the HS and HS+AA diets. Supplementation with RP-MLH had no effect on energy utilization variables. Overall, the lack of interactions between dietary starch level and RP-MLH supplementation on most variables measured herein showed that the effects of starch intake and RP-MLH were independent or additive.     

Humic substances are soft and permeable: evidence from their electrophoretic mobilities

Due to the complexity of the humic substances (HS), mathematical models have often been employed to understand their roles in the environment. Since no consensus exists with respect to the structure and conformation of the HS, models have alternatively given them properties corresponding to impermeable hard spheres or fully permeable polyelectrolytes. In this study, the hydrodynamic permeability of standard HS (Suwannee River fulvic, humic, and peat humic acids) are evaluated as a function of pH and ionic strength. A detailed theoretical model is used to determine the softness parameter (lambda0), which characterizes the degree of flow penetration into the HS on the basis of measured values of electrophoretic mobilities, diffusion coefficients, and electric charge densities. Their motion in an electric field is evaluated by a rigorous numerical evaluation of the governing electrokinetic equations for soft particles. The hydrodynamic impact of the polyelectrolyte chains is accounted for by a distribution of Stokes resistance centers and partial dissociation of the hydrodynamically immobile ionogenic groups distributed throughout the polyelectrolyte. The results demonstrate thatthe studied HS are small (radius ca. 1 nm), highly charged (500-650 C g(-1) when all sites are dissociated), and very permeable (typical flow penetration length of 25-50% of the radius, depending on pH). The HS also coagulate slightly when lowering the pH of the solution. Modeling of the HS as hard spheres with a charge and slip plane located at the surface is thus physically inappropriate, as are a number of analytical theories for soft particles that hold for low to moderate electrostatic potentials and large colloids. The shortcomings of these simpler approaches, when interpreting the electrophoretic mobilities of HS, are highlighted by comparison with rigorous theoretical predictions.     

Electrochemical analysis of proton and electron transfer equilibria of the reducible moieties in humic acids

Humic substances play a key role in biogeochemical and pollutant redox reactions. The objective of this work was to characterize the proton and electron transfer equilibria of the reducible moieties in different humic acids (HA). Cyclic voltammetry experiments demonstrated that diquat and ethylviologen mediated electron transfer between carbon working electrodes and HA. These compounds were used also to facilitate attainment of redox equilibria between redox electrodes and HA in potentiometric E(h) measurements. Bulk electrolysis of HA combined with pH-stat acid titration demonstrated that electron transfer to the reducible moieties in HA also resulted in proton uptake, suggesting decreasing reduction potentials E(h) of HA with increasing pH. This was confirmed by potentiometric E(h)-pH titrations of HA at different redox states. E(h) measurements of HA samples prereduced to different redox states by bulk electrolysis revealed reducible moieties in HA that cover a wide range of apparent standard reduction potentials at pH 7 from E(h)(0)* = +0.15 to -0.3 V. Modeling revealed an overall increase in the relative abundance of reducible moieties with decreasing E(h). The wide range of HA is consistent with its involvement in numerous environmental electron transfer reactions under various redox conditions.     

Quantitative evaluation of noncovalent interactions between glyphosate and dissolved humic substances by NMR spectroscopy

Interactions of glyphosate (N-phosphonomethylglycine) herbicide (GLY) with soluble fulvic acids (FAs) and humic acids (HAs) at pH 5.2 and 7 were studied by (1)H and (31)P NMR spectroscopy. Increasing concentrations of soluble humic matter determined broadening and chemical shift drifts of proton and phosphorus GLY signals, thereby indicating the occurrence of weak interactions between GLY and humic superstructures. Binding was larger for FAs and pH 5.2 than for HAs and pH 7, thus suggesting formation of hydrogen bonds between GLY carboxyl and phosphonate groups and protonated oxygen functions in humic matter. Changes in relaxation and correlation times of (1)H and (31)P signals and saturation transfer difference NMR experiments confirmed the noncovalent nature of GLY-humic interactions. Diffusion-ordered NMR spectra allowed calculation of the glyphosate fraction bound to humic superstructures and association constants (K(a)) and Gibbs free energies of transfer for GLY-humic complex formation at both pH values. These values showed that noncovalent interactions occurred most effectively with FAs and at pH 5.2. Our findings indicated that glyphosate may spontaneously and significantly bind to soluble humic matter by noncovalent interactions at slightly acidic pH and, thus, potentially pollute natural water bodies by moving through soil profiles in complexes with dissolved humus.