In situ examination of the protonation behavior of fulvic acids using differential absorbance spectroscopy

The effects of pH changes on the absorbance spectra of fulvic acids, which constitute a major part of natural organic matter (NOM) were examined based primarily on the example of standard Suwannee River fulvic acid (SRFA). Differential absorbance spectra of SRFA generated at varying pH values were determined to be rich in features that are absent in the conventional spectra. Analysis of the differential absorbance revealed the existence of two predominant types of pH-active chromophores which produced features that emerged in the pH ranges associated with carboxylic and phenolic functional groups of fulvic acids. Comparison of the differential absorbance spectra of SRFA and those of the fraction of hydrophobic acids of South Platte River fulvic acid show the existence of differences indicative of fulvic acids's site-specificity. The evolution of the pH-differential spectra of fulvic acids was in accord with predictions made based on the NICA-Donnan theory. These results show that pH-differential absorbance spectroscopy can be used to quantify in situ the protonation and site-specificity of fulvic acids.     

近红外光谱分析法快速测定稻谷常规化学指标

采集150份有代表性的我国南方地区稻谷样品的近红外光谱,用偏最小二回归分析法(PLS),建立了稻谷的水分、直链淀粉、蛋白以及胶稠度的近红外定量分析模型,并对30份预测集样品进行了验证。水分、直链淀粉、蛋白以及胶稠度的校正集模型的决定系数所(R2)分别为0.990 3、0.560 3、0.913 2以及0.678 0,交互验证均方根误差(RMSECV)分别为0.372 8%、1.456 9%、0.305 4%以及5.031 5%;验证集标准预测偏差(RMSEP)分别为0.382 5%、1.465 0%、0.510 0%以及5.052 1%。结果表明,近红外光谱分析法可以满足快速分析的要求。     

果汁中苯甲酸钠的含量的差示紫外分光光度法测定

以无苯甲酸钠果汁为本底,绘制标准曲线。将果汁制品经乙醚提取分离后,采用差示紫外分光光度法测定果汁中苯甲酸钠的含量,简化样品处理步骤,方法简便可靠,经对实样分析,得到了与国家标准检验方法（紫外分光光度法）基本一致的结果。可以作为测定果汁中苯甲酸钠含量的有效方法之一。     

Activity and thermal stability of antioxidants by differential scanning calorimetry and electron spin resonance spectroscopy

Heat flux differential scanning calorimetry (DSC) and electron spin resonance spectroscopy (ESR) were used to assess the activity and the thermal stability of antioxidants in four vegetable oils. Sunflower oil (SO) and high oleic sunflower oil (HOSO), both rich in diunsaturated fatty acids (FA), low trans oil (LT) and partially hydrogenated palm oil (PHPO), both containing monounsaturated FA, were analyzed by isothermal heat flux DSC, with or without 300 mg/kg of antioxidant: ascorbyl palmitate (AP), α-tocopherol (αT), δ-tocopherol (δT) and propyl gallate (PG). DSC experiments showed that δT is the most effective antioxidant for SO and PG for the less unsaturated oils. SO and PHPO were also analyzed by ESR at 120 and 145 °C, respectively. ESR results confirm the strongest antioxidant activity of δT and PG for SO and PHPO, respectively. Therefore, the present study demonstrates that DSC and ESR are valuable technologies to study activity and stability of antioxidants at high temperature. Moreover, experiments performed in the presence of the spin-trap N-tert-butyl-α-phenylnitrone (PBN), suggest that δT delay lipid oxidation through a different reaction mechanism when compared to αT. A different mechanism between tocopherols isomers in delaying lipid oxidation has been hypotized.     

NOM removal by adsorption and membrane filtration using heated aluminum oxide particles

Heated aluminum oxide particles (HAOPs) are a newly synthesized adsorbent with attractive properties for use in hybrid adsorption/membrane filtration systems. This study compared removal of natural organic matter (NOM) from water by adsorption onto HAOPs with that by adsorption onto powdered activated carbon (PAC) or coagulation with alum or ferric chloride (FeCl3); explored the overlap between the NOM molecules that preferentially adsorb to HAOPs and those that are removed by the more conventional approaches; and evaluated NOM removal and fouling in hybrid adsorbent/membrane systems. For equivalent molar doses of the trivalent metals, HAOPs remove more NOM, and NOM with higher SUVA254, than alum or FeCl3. Most of the HAOPs-nonadsorbable fraction of the NOM can be adsorbed by PAC; in fact, that fraction appears to be preferentially adsorbed compared to the average NOM in untreated water. Predeposition of the adsorbents on a microfiltration membrane improves system performance. For the water tested, at a flux of 100 L/m2-hr, predeposition of 11 mg/L PAC and 5 mg/L HAOPs (as Al3+) allowed the system to operate 5 times as long before the transmembrane pressure increased by 1 psi and to remove 10-20 times as much NOM as when no adsorbents were added.     

Electrochemical properties of natural organic matter (NOM), fractions of NOM, and model biogeochemical electron shuttles

In this study, cyclic voltammetry was used to characterize the redox properties of natural organic matter (NOM). Using a stationary platinum working electrode, minimal concentrations of electrolyte, and dimethyl sulfoxide (DMSO) as the solvent, we were able to resolve two pairs of oxidation and reduction peaks for a fraction of Georgetown NOM that is enriched in polyphenolic moieties (NOM-PP). Applying our method to other fractions of Georgetown NOM, and to samples of NOM from a wide range of other sources, gave cyclic voltammograms (CVs) that generally contained fewer distinguishing features than those obtained with NOM-PP. For comparison, CVs were also obtained using our method on six quinone model compounds: anthraquinone-2,6-disulfonate (AQDS), lawsone, juglone, menadione, menaquinone-4, and ubiquinone-5. The CVs of these quinones were similar in shape to the CV of NOM-PP, consistent with the notion that quinones are the dominant redox-active moieties associated with NOM. Quantitative analysis of the peaks in these CVs showed that the peak potentials (Ep) were separated by more than 0.059 V and that the peak currents (i(p)) were linearly related to the square root of the scan rate (v0.5) and concentration (C) for both NOM-PP and the model quinones. Equivalent results were obtained with a rotating Pt disk electrode. From this we conclude that NOM-PP and the model quinones undergo similar sequences of two one-electron, quasi-reversible, diffusion controlled, electron transfers at the Pt electrode surface in DMSO. Although it is difficult to relate these results to Nernstian standard potentials vs the standard hydrogen electrode (SHE) under aqueous conditions, it is clear that the apparent formal potential for NOM-PP lies between the corresponding potentials for menadione and juglone and well above that of AQDS. Attempts to derive correlations between Ep and i(p) for the NOMs with quantifiable electrode response and other measurable properties of NOM (including trace metal content and UV-vis absorbance) did not yield any strong relationships.     

微分脉冲催化极谱法及等离子发射光谱法测定奶粉中铬含量

研究了2种测定奶粉中铬含量的方法,微分脉冲催化极谱法和等离子发射光谱法,并对2种方法的特点及存在的问题进行了讨论。     

Differences between conventional and glyphosate tolerant soybeans and moisture effect in their discrimination by near infrared spectroscopy

Previous studies showed that Near Infrared Spectroscopy (NIRS) could distinguish between Roundup Ready® (RR) and conventional soybeans at the bulk and single seed sample level, but it was not clear which compounds drove the classification. In this research the varieties used did not show significant differences in major compounds between RR and conventional beans, but moisture content had a big impact on classification accuracies. Four of the five RR samples had slightly higher moistures and had a higher water uptake than their conventional counterparts. This could be linked with differences in their hulls, being either compositional or morphological. Because water absorption occurs in the same region as main compounds in hulls (mainly carbohydrates) and water causes physical changes from swelling, variations in moisture cause a complex interaction resulting in a large impact on discrimination accuracies.     

Natural organic matter (NOM) adsorption to multi-walled carbon nanotubes: effect of NOM characteristics and water quality parameters

The effect of natural organic matter (NOM) characteristics and water quality parameters on NOM adsorption to multiwalled carbon nanotubes (MWNT) was investigated. Isotherm experiment results were fitted well with a modified Freundlich isotherm model that took into account the heterogeneous nature of NOM.The preferential adsorption of the higher molecular weight fraction of NOM was observed by size exclusion chromatographic analysis. Experiments performed with various NOM samples suggested that the degree of NOM adsorption varied greatly depending on the type of NOM and was proportional to the aromatic carbon content of NOM. The NOM adsorption to MWNT was also dependent on water quality parameters: adsorption increased as pH decreased and ionic strength increased. As a result of NOM adsorption to MWNT, a fraction of MWNT formed a stable suspension in water and the concentration of MWNT suspension depended on the amount of NOM adsorbed per unit mass of MWNT. The amount of MWNT suspended in water was also affected by ionic strength and pH. The findings in this study suggested that the fate and transport of MWNT in natural systems would be largely influenced by NOM characteristics and water quality parameters.     

Assessment of conventional and microwave heating induced degradation of carotenoids in olive oil by VIS Raman spectroscopy and classical methods

Raman spectroscopy, as a fast non-destructive method, has shown its potential in revealing heat-induced degradation of extra virgin olive oil carotenoids during microwave versus conventional heating processes. A progressive degradation in carotenoids was observed, starting at 180 °C and 140 °C in microwave and conventional heating processes respectively; this was followed by a rapid degradation at 180 °C only with conventional heating. As the main difference, the Raman bands due to carotenoids completely disappeared at 203 °C with conventional heating, while these bands could still be observed even up to 225 °C with microwave heating. Furthermore a loss of cis double bonds and slightly changes in free fatty acid was also observed in both heating processes. A precise calibration model was established using partial least squares regression, which can be used for monitoring carotenoids content degradation during heating. The accuracy of the model was estimated using the root mean square errors and the correlation coefficient.     

Antioxidative activity of lactobacilli measured by oxygen radical absorbance capacity

The reducing ability and antioxidative activity of some species of Lactobacillus were compared under in vitro conditions. Cultures of Lactobacillus delbrueckii ssp. lactis, Lactobacillus delbrueckii ssp. bulgaricus, Lactobacillus acidophilus, and Lactobacillus casei were grown at 37 degrees C in de Man, Rogosa, Sharpe (MRS) broth supplemented with 0.5% 2,3,5 triphenyl tetrazolium chloride (TTC) to evaluate reducing activity. Reduced TTC was extracted from the cultures with acetone, and the intensity of the red color measured colorimetrically at 485 nm was an indication of reducing activity. The lactobacilli varied significantly in relative ability to reduce TTC when grown in MRS broth for 15 h. The relative amounts of growth as indicated by pH values at 18 h appeared to influence the amount of reduction. Antioxidative activity was evaluated by the ability of the whole cells or the cell-free extracts from cultures to protect a protein from being attacked by free radicals. These analyses were performed using the oxygen radical absorbance capacity method. All cultures tested exhibited some degree of antioxidative activity. Among the treatments, the cell-free extracts from cells grown in MRS broth exhibited significantly higher values than did whole cells. There was no apparent relationship between the reducing and antioxidative activities of the cultures evaluated. The results from this study show that these cultures can provide a source of dietary antioxidants. Furthermore, selection of cultures that produce antioxidants as starters could provide yet another health or nutritional benefit from cultured or culture-containing dairy products.     

Displacement effect of NOM on atrazine adsorption by PACs with different pore size distributions

This study investigated displacement of atrazine by the strongly competing fraction of natural organic matter (NOM) in batch and continuous-flow powdered activated carbon/PAC) adsorption systems. Due to the displacement effect, atrazine adsorption capacity in a continuous flow PAC/microfiltration (MF) system, where the carbon retention time is greater than the hydraulic retention time, decreased with time or NOM throughput. The capacity was lower than that measured in a batch reactor or predicted by the equivalent background compound-ideal adsorbed solution theory (EBC-IAST) method. A mathematical model previously developed to simulate the adsorption process in the PAC/MF system was modified to take into account the displacement effect. Two types of PACs were tested using a range of influent atrazine concentrations and carbon doses. The extent of atrazine displacement by NOM was found to depend on the type of PAC, while the rate of displacement was a function of PAC type as well as carbon dose. The PAC lost its adsorption capacity for atrazine faster at a lower carbon dose. PAC B, which has a higher percentage of mesopores, lost more atrazine adsorption capacity but at a slower rate than PAC A.     

Examination of arsenic speciation in sulfidic solutions using X-ray absorption spectroscopy

Both thioarsenites and thioarsenates have been demonstrated to exist in sulfidic waters, yet there is uncertainty regarding the geochemical conditions that govern the formation of these arsenic species. The purpose of this research was to use advanced spectroscopy techniques, speciation modeling, and chromatography to elucidate the chemical speciation of arsenic in sulfidic solutions initially containing arsenite and sulfide. Results of X-ray absorption spectroscopy (XAS) show that experimental solutions contained mixtures of arsenite and thioarsenites with increasing substitution of sulfur for oxygen on arsenic as the sulfide concentration increased. Experimental samples showed no evidence of polymeric arsenic species, or transformation of thioarsenites to thioarsenates. The arsenic speciation measured using XAS was similar to predictions obtained from a thermodynamic model for arsenic speciation, excluding thioarsenate species in sulfidic systems. Our data cast some doubt on the application of chromatographic methods for determining thioarsenates and thioarsenites (or mixtures) in natural waters in cases where the arsenic oxidation state cannot be independently verified. The same chromatographic peak positions proposed for thioarsenates can be explained bythioarsenite species. Furthermore, sample dilution was shown to change the species distribution and care should be taken to avoid sample dilution prior to chromatographic analysis.     

Formation of chloroform and other chlorinated byproducts by chlorination of triclosan-containing antibacterial products

Triclosan is a widely used antibacterial agent found in many personal hygiene products. Although it has previously been established that pure triclosan and free chlorine readily react, interactions between triclosan-containing consumer products and free chlorine have not previously been analyzed in great depth. Sixteen double-blinded solutions including both triclosan-containing (1.14-3.12 mg triclosan/g product) and triclosan-free products were contacted with free chlorine at pH 7. Products detected included (chlorophenoxy) phenols, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and chloroform. The daughter product yields were found to be highly variable and were dependent on the antimicrobial product investigated, the free chlorine to triclosan ratio, and the temperature at which the study was conducted. Lowering the temperature from 40 to 30 degrees C resulted in a decreased average chloroform yield from 0.50 to 0.37 mol chloroform/mol triclosan consumed after 1 min of reaction time for an initial free chlorine concentration of 4.0 mg/L as Cl2. At 40 degrees C the average molar chloroform yields decreased to 0.29 and <0.1 when the initial free chlorine concentration was decreased to either 2.0 or 1.0 mg/L as Cl2, respectively. Field experiments, in which Atlanta, GA and Danville, VA tap waters were augmented with various soap products, exhibited results varying from the laboratory experiments in that different productyields were observed. These differences are attributed to the chlorine demand of constituents in the tap water. A simple exposure model suggests that exposure to chloroform can be significant under some conditions.     

Separation and characterization of NOM by high-performance liquid chromatography and on-line three-dimensional excitation emission matrix fluorescence detection

By using high-performance size exclusion chromatography (HPSEC) and reversed-phase high-performance liquid chromatography with on-line three-dimensional excitation emission matrix fluorescence detection, we measured fluorescence properties of natural organic matter (NOM) as a function of molecular size (MS) and polarity. The work was carried out with Suwannee River Fulvic Acid, Aldrich Humic Acid, and a naturally occurring river NOM sample. Significant differences in fluorescence maximum pattern were found as NOM was separated chromatographically based on MS and polarity. There existed a strong relationship between MS, fluorescence pattern, and polarity. Humic-, fulvic-, and protein-like fluorescence fractions had distinct hydrophilic/hydrophobic nature. The results suggest that HPSEC may be better for characterizing major fulvic-like fluorescence and smaller MS fractions but not those having humic- and protein-like fluorescence and larger MS, which may be strongly adsorbed onto the HPSEC column because of their hydrophobic nature. This study has significant implications for further understanding the nature of NOM and its complexation with trace metals.     

Transformation of acetaminophen by chlorination produces the toxicants 1,4-benzoquinone and N-acetyl-p-benzoquinone imine

The reaction of the common pain reliever acetaminophen (paracetamol, 4-acetamidophenol) with hypochlorite was investigated over time under conditions that simulate wastewater disinfection. Initially, the reaction was studied in pure water at neutral pH (7.0), a range of reaction times (2-90 min), and a molar excess of hypochlorite (2-57 times) relative to the acetaminophen concentration. The reaction was monitored using reversed-phase liquid chromatography (LC) with ultraviolet absorbance, electrochemical, and mass spectrometric detection. At 1 micromol/L (150 ppb) and 10 micromol/L (1.5 ppm) levels, acetaminophen readily reacted to form at least 11 discernible products, all of which exhibited greater LC retention than the parent. Two of the products were unequivocally identified as the toxic compounds 1,4-benzoquinone and N-acetyl-p-benzoquinone imine (NAPQI), which is the toxicant associated with lethality in acetaminophen overdoses. With a hypochlorite dose of 57 micromol/L (4 ppm as Cl2), 88% of the acetaminophen (10 micromol/L initial) was transformed in 1 h. The two quinoidal oxidation products 1,4-benzoquinone and NAPQI accounted for 25% and 1.5% of the initial acetaminophen concentration, respectively, at a 1 h reaction time. Other products that were identified included two ring chlorination products, chloro-4-acetamidophenol and dichloro-4-acetamidophenol, which combined were approximately 7% of the initial acetaminophen concentration at 1 h. The reaction was also studied in wastewater, where similar reactivity was noted. These results demonstrate that acetaminophen is likely to be transformed significantly during wastewater chlorination. The reactivity of the chlorine-transformation products was also studied with sulfite to simulate dechlorination, and 1,4-benzoquinone and NAPQI were completely reduced.     

Forward modeling of metal complexation by NOM: II. prediction of binding site properties

An a priori model of metal complexation by natural organic matter (NOM) has previously been shown to predict experimental data at pH 7.0 and 0.1 M ionic strength (Cabaniss, S. E. Environ. Sci. Technol. 2009). Unlike macroscopic models based only on stoichiometry and thermodynamics, this a priori model also predicts the ligand groups and properties of complexed (occupied) molecules. Ligand molecules with strong binding sites form complexes at low metal concentrations and have average properties (molecular weight, charge, aromaticity) which can differ significantly from the average properties of bulk NOM. Cu(II), Ni(II) and Pb(II) preferentially bind to strong amine-containing sites which are often located on small (MW < 1000), lower-aromaticity molecules. Cd(II) and Zn(II) show generally weaker binding, although they also prefer amine-containing sites to pure carboxylates and bind to smaller, less aromatic molecules. Ca(II) shows no real preference for amine over carboxylate ligand groups, preferentially binding to larger and more negatively charged molecules. Al(III) has a unique preference for phenol-containing sites and larger, more aromatic molecules. While some predictions of this model are consistent with a variety of experimental data from the literature, others await validation by molecular-level analysis.     

Quality of minimally processed carrots as affected by warm water washing and chlorination

Different applications of cold and warm tap water (4 °C and 50 °C) with and without chlorination, respectively, in the washing of uncut peeled carrots (Daucus carota L.) were conducted, and their effects on sensory and microbiological properties during storage for 9 days at 4 °C were assessed. To minimise cross-contamination of almost sterile inner root parts with the highly contaminated outer cortex during processing the peeled carrots were washed prior to cutting. The washing treatments were carried out using a commercial processing line, thus facilitating the scale-up to industrial production. Populations of aerobic mesophilic bacteria, lactic acid bacteria and enterobacteria on these minimally processed carrots were determined, and the sensorial quality of shredded carrots was evaluated by a sensory panel throughout storage. Additionally, colour, texture, sugars, and trichloromethanes were analysed. Washing uncut carrots with cold chlorinated water (200 mg/l, 4 °C) and warm tap water (50 °C) ensured sugar retention and reduced aerobic mesophilic bacteria by 1.7 and 2.0 log₁₀ colony forming units per gram (cfu/g), respectively, while washing with warm chlorinated water (200 mg/l) resulted in a 2.3 log₁₀ cfu/g reduction. By-product formation due to chlorination was negligible. Sensorial properties of the latter samples were slightly affected. It was shown that both washing uncut knife-peeled carrots with cold chlorinated water (4 °C) and warm tap water (50 °C), respectively, provided good microbiological safety paired with improved sensorial properties. Moreover, fresh-like character of the products was retained, as indicated by the persisting respiration of the living tissues.Industrial relevanceMinimally processed vegetables are an increasing market. Shelf-life extension and consumer safety are of immense relevance for the fresh-cut industry; therefore, the application of antimicrobial agents such as chlorine is widespread. However, various consumer groups object to the use of chlorinated water. The present study aimed at comparing the efficacy of cold and warm tap water with and without chlorination, respectively, in washing uncut carrots during the production of shredded, packaged carrots while operating on pilot-plant scale under conditions of industrial practice. In view of microbial reduction and maintenance of sensory properties, the use of cold chlorinated water and warm tap water, respectively, proved to be effective for washing peeled carrots. By-product formation due to chlorination was negligible.