Impact of natural organic matter on the physicochemical properties of aqueous C60 nanoparticles

Existing toxicity data indicate that industrial-scale production of C60 fullerene poses a potential threat to the environment. Evaluating the environmental impact of C60 requires careful characterization of its physicochemical properties in the natural aqueous environment. Our study aims to determine the effects of aquatic natural organic matter (NOM) on the physicochemical properties of aqueous C60 nanoparticles, nC60. Stable nC60 suspensions were formed using three different solvent exchange protocols. They were thoroughly characterized for particle size, morphology, and electrophoretic mobility in the absence or presence of two model NOM components, Suwannee River humic acid and fulvic acid. NOM caused disaggregation of nC60 crystals and aggregates under typical solution conditions of natural water, leading to significant changes in particle size and morphology. Such effect increased with increasing NOM concentration. The changes in nC060 size and morphology strongly depended on the nC60 formation pathway. Results from this study indicate that NOM may play a critical role in the transport and toxicity of C60 in the natural aqueous environment.     

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.     

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.     

Sorption of tetracycline and chlortetracycline on K- and Ca-saturated soil clays, humic substances, and clay-humic complexes

Tetracycline (TC) and chlortetracycline (CTC) are used extensively for growth promotion and therapeutic purposes in livestock production. The sorption of TC and CTC on clays, humic substances (HS), and clay-humic complexes (clay-HC) derived from two agricultural soils was quantified using dilute CaCl2 (Ca) and KCI (K) as background solutions. In all systems, the soil components sorbed > 96% of added tetracyclines. Strongest sorption was observed for clays, followed by HS, and then clay-HC. Greater sorption by the Ca systems than the K systems and decreased sorption with increasing pH suggests that cation bridging and cation exchange contribute to sorption. X-ray diffraction analysis showed that TC and CTC were sorbed in the interlayers of smectites and that the presence of HS reduced interlayer sorption of tetracyclines by smectites in clay-HC. The results indicate that tetracyclines are dominantly sorbed on soil clays and that HS in clay-HC either mask sorption sites on clay surfaces or inhibit interlayer diffusion of tetracyclines.     

Highly Sensitive Detection of Organophosphorus Pesticides Represented by Methamidophos via Inner Filter Effect of Au Nanoparticles on the Fluorescence of CdTe Quantum Dots

A sensitive fluorescence detection method of organophosphate pesticides (OPs) represented by methamidophos was developed using the inner filter effect (IFE) of Au nanoparticles (AuNPs) on CdTe quantum dots (QDs). The fluorescence of CdTe QDs was remarkably quenched with the presence of AuNPs via IFE. Acetylcholinesterase (AChE) catalyzed the hydrolysis of acetylthiocholine into thiocholine, which could induce the aggregation of AuNPs and decrease their characteristic absorption, making IFE-decreased fluorescence of CdTe QDs recovered. OPs can inhibit the activity of AChE, thus preventing the aggregation of AuNPs and the fluorescence recovery of CdTe QDs. Therefore, the IFE of fluorescence between AuNPs and CdTe QDs could convert the absorption signal to fluorescence signal, which improved the detection sensitivity of OPs in vegetables. Under the optimum conditions, the response was linearly proportional to the concentration of methamidophos in the range of 0.06～0.78 mg/kg with a detection limit of 2 μg/kg (3σ) which was superior to the method of GB/T 5009.199-2003. The proposed assay exhibited good reproducibility and accuracy, providing a simple and rapid method for the screening of OPs.     

Distinct effects of humic acid on transport and retention of TiO2 rutile nanoparticles in saturated sand columns

The distinct effects of humic acid (HA, 0-10 mg L(-1)) on the transport of titanium dioxide (rutile) nanoparticles (nTiO(2)) through saturated sand columns were observed under conditions of environmental relevance (ionic strength 3-200 mM NaCl, pH 5.7 and 9.0). Specifically, the transport of nTiO(2) was dramatically enhanced in the presence of HA at pH 5.7, even at a low HA concentration of 1 mg L(-1). The mobility of nTiO(2) was further increased with greater concentrations of HA. In contrast, this enhancement of the nTiO(2) transportability due to the presence of HA was limited at pH 9.0 because of the negligible adsorption of HA onto nTiO(2), regardless of the concentrations of HA examined in this study. The distinct effects can be explained by the adsorption behaviors of HA to nTiO(2) and sand surfaces and the resulting interactions between nTiO(2) and sand surfaces under different conditions, which resulted in a large variation of the nTiO(2) transport and deposition behaviors at various conditions. In addition, theoretical interaction energy calculations and additional elution experiments indicate that the secondary energy minimum played an important role in controlling the nTiO(2) transport and deposition in porous media observed in this study. Moreover, the interaction energy calculations suggest that at pH 5.7, HA affected nTiO(2) transport by increasing the negative surface charge of nTiO(2) at low HA adsorption densities; whereas, combinations of increased electrostatic and steric interactions due to the presence of HA were the main mechanisms of enhanced transportability of nTiO(2) at high HA adsorption densities. Overall, results from this study suggest that natural organic matter and solution pH are likely key factors that govern the stability and mobility of nTiO(2) in the natural aquatic environment.     

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.     

Sensitive fluorescent detection of melamine in raw milk based on the inner filter effect of Au nanoparticles on the fluorescence of CdTe quantum dots

A simple, rapid and sensitive fluorescent assay for determination of melamine has been developed based on inner filter effect (IFE) of gold nanoparticles (AuNPs) on the fluorescence of CdTe quantum dots (QDs). When thioglycolic acid-capped CdTe QDs was mixed with citrate-stabilized AuNPs, the fluorescence of CdTe QDs was significantly quenched via the IFE of AuNPs. With the presence of melamine, melamine could induce the aggregation and corresponding absorbance change of AuNPs, which then resulted in the recovery of IFE-decreased emission of CdTe QDs. Under the optimum conditions, the detection limit for melamine in raw milk was 0.02mgL(-1). The application of this method in samples of melamine-spiked raw milk suggested a recovery between 103% and 104%. Therefore, the obvious merits provided by the present assay, such as simplicity, rapidity, low cost, and high sensitivity, would make it promising for on-site screening of melamine adulterant in raw milk.     

Anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA)

The potential for anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) was investigated in laboratory incubations of sediments from a petroleum-contaminated aquifer and in aquatic sediments. The addition of humic substances (HS) stimulated the anaerobic degradation of MTBE in aquifer sediments in which Fe(III) was available as an electron acceptor. This is attributed to the fact that HS and other extracellular quinones can stimulate the activity of Fe(III)-reducing microorganisms by acting as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. MTBE was not degraded in aquifer sediments without Fe(III) and HS. [14C]-MTBE added to aquatic sediments adapted for anaerobic MTBE degradation was converted to 14CO2 in the presence or absence of HS or the HS analog, anthraquione-2,6-disulfonate. Unamended aquatic sediments produced 14CH4 as well as 14CO2 from [14C]-MTBE. The aquatic sediments also rapidly consumed TBA under anaerobic conditions and converted [14C]-TBA to 14CH4 and 14CO2. An adaptation period of ca. 250-300 days was required prior to the most rapid anaerobic MTBE degradation in both sediment types, whereas TBA was metabolized in the aquatic sediments without a lag. These results demonstrate that, under the appropriate conditions, MTBE and TBA can be degraded in the absence of oxygen. This suggests that it may be possible to design strategies for the anaerobic remediation of MTBE in petroleum-contaminated subsurface environments.     

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.     

Influence of collector surface composition and water chemistry on the deposition of cerium dioxide nanoparticles: QCM-D and column experiment approaches

The deposition behavior of cerium dioxide (CeO(2)) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied in quartz crystal microbalance with dissipation (QCM-D) to examine the effect of these mineral phases on CeO(2) deposition in NaCl solution (1-200 mM). Frequency and dissipation shift followed the order: silica > iron oxide > alumina in 10 mM NaCl at pH 4.0. No significant deposition was observed at pH 6.0 and 8.5 on any of the tested sensors. However, ≥ 94.3% of CeO(2) NPs deposited onto Ottawa sand in columns in 10 mM NaCl at pH 6.0 and 8.5. The inconsistency in the different experimental approaches can be mainly attributed to NP aggregation, surface heterogeneity of Ottawa sand, and flow geometry. In QCM-D experiments, the deposition kinetics was found to be qualitatively consistent with the predictions based on the classical colloidal stability theory. The presence of low levels (1-6 mg/L) of Suwannee River humic acid, fulvic acid, alginate, citric acid, and carboxymethyl cellulose greatly enhanced the stability and mobility of CeO(2) NPs in 1 mM NaCl at pH 6.5. The poor correlation between the transport behavior and electrophoretic mobility of CeO(2) NPs implies that the electrosteric effect of OM was involved.     

Quantification of the interaction of Tc with dissolved boom clay humic substances

Technetium-99 (Tc), a fission product of uranium-238, is an important radionuclide because of its long half-life and its high yield in radioactive waste. To elucidate the Tc geochemical behavior in reducing environments relevant to geological disposal and in the presence of humic substances (HS), experiments were set up that resulted forthe first time in the determination of an interaction constant for Tc with dissolved humic substances. A number of lab-scale Boom Clay (a possible geological underground High-Level Radioactive Waste storage site in Mol, Belgium) batch experiments were set up, combining both different initial Tc(VII) concentrations and different solid/liquid ratios. On these batches several sequential extraction steps with HS-free synthetic Boom Clay water were performed. Equilibration times were fixed at 1 week for each extraction step. Tc(VII) was found to be readily reduced to Tc(IV) by the solid Boom Clay phase. This solid phase was able to sorb Tc(IV) to a very large extent (log Kd approximately 2.5-4.0), and two sorption sinks (one of which is humic substances) were detected. In solution, Tc(IV) was mainly associated with HS. Concentrations in solution were found up to the order of 2 x 10(-6) M. The results were quantitatively described as a competition for Tc(IV) between the solid phase and the dissolved HS (Schubert-like approach). It was concluded that a hydrophobic sorption of uncharged Tc(IV) species in solution would act as the dominating interaction mechanism with HS, with an interaction constant log K(HS) = 5.3 +/- 0.3.     

Strong copper-binding behavior of terrestrial humic substances in seawater

In coastal areas, strong complexation of copper generally reduces its toxicity; our ability to monitor and regulate copper as a toxin therefore depends on our understanding of the sources and sinks of the copper-binding ligands. Terrestrial humic substances (HS) are well-recognized contributors to weak ligand concentrations in aquatic systems. In this work, we show that HS are likely contributors to both stronger and weaker ligand classes controlling copper speciation in coastal areas receiving typical inputs of terrestrial organic matter. We used competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-ACSV), with the added ligands benzoylacetone and salicylaldoxime, to examine copper binding by terrestrial HS in a seawater matrix, at HS and copper concentrations typical of coastal waters. Copper titration data of 1 mg/L Suwannee River humic acid (SRHA) in seawater could be modeled using conditional stability constants of 10(12.0) and 10(10.0) and total ligand concentrations of 10.4 and 199 nM for a stronger and weaker ligand, respectively. Similar results were obtained for Suwannee River fulvic acid (SRFA). Strong copper binding by SRFA in seawater was weaker than previously reported for a freshwater at similar pH, possibly indicating effects of Ca and Mg competition or ionic strength. Nevertheless,the concentrations and binding strengths of copper ligands we observed are comparable to the range reported in previous coastal speciation studies. In addition, we show that the weaker copper ligands cause internal calibration techniques to significantly underestimate the sensitivity of ACSV in the presence of HS concentrations typical of coastal waters. To address this issue, we demonstrate the use of "overload titrations", using a high enough concentration of added ligand to outcompete all natural ligands as an alternative calibration technique for analysis of coastal samples.     

Precipitation and growth of zinc sulfide nanoparticles in the presence of thiol-containing natural organic ligands

In sulfidic aquatic systems, metal sulfides can control the mobility and bioavailability of trace metal pollutants such as zinc, mercury, and silver. Nanoparticles of ZnS and other metal sulfides are known to exist in oxic and anoxic waters. However, the processes that lead to their persistence in the aquatic environment are relatively unknown. The objective of this study was to evaluate the importance of dissolved natural organics in stabilizing nanoparticulate ZnS that precipitates under environmentally relevant conditions. Precipitation and growth of ZnS particles were investigated in the presence of dissolved humic acid and low-molecular weight organic acids that are prevalent in sediment porewater. Dynamic light scattering was used to monitor the hydrodynamic diameter of particles precipitating in laboratory solutions. Zn speciation was also measured by filtering the ZnS solutions (< 0.2 microm) and using anodic stripping voltammetry to confirm that Zn was coordinated to sulfide during the precipitation experiments and not to the dissolved organic ligands. X-ray photoelectron spectroscopy and electron microscopy were used to confirm that amorphous particles containing Zn and S were precipitating in the suspensions. Observed growth rates of ZnS particles varied by orders of magnitude, depending on the type and concentration of organic ligand in solution. In the presence of humic acid and thiol-containing ligands (cysteine, glutathione, and thioglycolate), observed growth rates decreased by 1-3 orders of magnitude relative to controls without the ligands. In contrast, growth rates of the particles were consistently within 1 order of magnitude of the ligand-free control when oxygen- and amine-containing ligands (oxalate, serine, and glycolate) were present Furthermore, particle growth rates decreased with an increase in thiol concentration and increased with NaNO3 electrolyte concentration. These studies suggest that specific surface interactions with thiol-containing organics may be one factor that contributes to the persistence of naturally occurring and anthropogenic nanoparticles of ZnS and other metal sulfides in the aquatic environment.     

On the origin of the optical properties of humic substances

Absorption and fluorescence spectroscopy and laser photobleaching experiments were employed to probe the origins of the optical properties of humic substances (HS). Luminescence quantum yields and the wavelengths of maximum emission were acquired for Suwannee River humic acid (SRHA) and fulvic acid (SRFA) at an extensive series of excitation wavelengths across the ultraviolet and visible. Laser irradiation at a series wavelength across the ultraviolet and visible was further employed to destroy selectively chromophores absorbing at specific wavelengths, using absorption spectroscopy to follow the absorption losses with irradiation time. The results provide unequivocal evidence that the absorption and emission spectra of these materials cannot result solely from a simple linear superposition of the spectra of numerous independent chromophores. Instead, the long wavelength absorption tail of HS (>350 nm) appears to arise from a continuum of coupled states. We propose that this behavior results from intramolecular charge-transfer interactions between hydroxy-aromatic donors and quinoid acceptors formed by the partial oxidation of lignin precursors. We further propose that these donor-acceptor interactions may be a common phenomenon, occurring within all natural hydroxy- or polyhydroxy-aromatic polymers that form appropriate acceptors upon partial oxidation. Examples of such species include lignin, polyphenols, tannins, and melanins.     

Diffusion coefficients of humic substances in agarose gel and in water

Measurements of the diffusion coefficients of five different humic substances (HS) have been performed in water and in agarose hydrogels at several pH values (in the range of 3-10) and gel concentrations (in the range of 0.7-3% w/w). Fluorescence correlation spectroscopy (FCS) and classical diffusion cells were used in parallel to probe diffusion over both microscopic and mesoscopic distance scales. In general, agreement between the techniques was reasonable, which indicated that local nonhomogenities in the gel did not play an important role. Diffusion coefficients (D) in the gel were generally in the range of 0.9-2.5 x 10(-10) m2 s(-1) but were generally only 10-20% lower than in solution. At low pH values, one of the studied humic substances (a peat humic acid, PPHA) formed large aggregates that could not penetrate into the gel and therefore could not be defined by a single D value. The observed decreases of D in the gel for other HS were too large to be explained by the tortuousity and obstructive effects of the gel alone. D decreased slightly with increasing gel concentration and increased slightly with pH. Because modifications of D due to pH were similar in both the gel and the free solution, it is unlikely that complexation with the gel was greatly influenced by the pH. Rather, the main effect that appeared to decrease the diffusive flux in gels was likely small increases in the hydrodynamic radii of the humic macromolecules. An anomalous diffusion model was used to describe the FCS data in the gel. The characteristic exponent determined by fitting the autocorrelation functions with this model decreased only slightly (from 0.96 to 0.90) with increasing gel concentration providing support that HS complexation with the gel fibers was not very important. The results have important implications for our understanding of the fate and behavior of the HS and their associated pollutants and for interpreting metal speciation data obtained using gel-covered analytical sensors.     

Fluorescence quenching and luminescence sensitization in complexes of Tb3+ and Eu3+ with humic substances

Intrinsic fluorescence quenching of humic substances (HS) and the sensitization of Ln3+ luminescence (Ln3+ = Tb3+, Eu3+) in HS complexes were investigated. Both measurements yielded complementary information on the complexation of metals by HS. Large differences between fulvic acids (FA) and humic acids (HA) were found. From time-resolved luminescence measurements it is concluded that a combination of energy transfer and energy back transfer between HS and Ln3+ is responsible for the observed luminescence decay characteristics. In the case of Eu3+, an additional participation of charge-transfer states is suggested. A new concept for the evaluation of the sensitized luminescence decays of Ln3+ was adapted.     

Effects of humic substances on precipitation and aggregation of zinc sulfide nanoparticles

Nanoparticulate metal sulfides such as ZnS can influence the transport and bioavailability of pollutant metals in anaerobic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences the stability of zinc sulfide nanoparticles as they nucleate and aggregate in water with dissolved NOM. We compared NOM fractions that were isolated from several surface waters and represented a range of characteristics including molecular weight, type of carbon, and ligand density. Dynamic light scattering was employed to monitor the growth and aggregation of Zn-S-NOM nanoparticles in supersaturated solutions containing dissolved aquatic humic substances. The NOM was observed to reduce particle growth rates, depending on solution variables such as type and concentration of NOM, monovalent electrolyte concentration, and pH. The rates of growth increased with increasing ionic strength, indicating that observed growth rates primarily represented aggregation of charged Zn-S-NOM particles. Furthermore, the observed rates decreased with increasing molecular weight and aromatic content of the NOM fractions, while carboxylate and reduced sulfur content had little effect. Differences between NOM were likely due to properties that increased electrosteric hindrances for aggregation. Overall, results of this study suggest that the composition and source of NOM are key factors that contribute to the stabilization and persistence of zinc sulfide nanoparticles in the aquatic environment.     

量子点标记免疫技术在食品中小分子有害物检测中的应用

量子点（quantum dots,QDs）是一种荧光纳米颗粒,具有荧光量子产率高、发射光谱窄、发射波长可调等优点,是近几年发展起来的一种新型荧光标记物,在食品中小分子有害物免疫检测中的应用已成为研究热点。本文总结介绍了3 种常用的QDs与抗体/抗原偶联方法及其各自优缺点,并对基于QDs的荧光免疫分析方法在食品小分子有害物检测中的应用进行了详细综述。