Kinetics of desorption of organic compounds from dissolved organic matter

This study presents a new experimental technique for measuring rates of desorption of organic compounds from dissolved organic matter (DOM) such as humic substances. The method is based on a fast solid-phase extraction of the freely dissolved fraction of a solute when the solution is flushed through a polymer-coated capillary. The extraction interferes with the solute-DOM sorption equilibrium and drives the desorption process. Solutes which remain sorbed to DOM pass through the extraction capillary and can be analyzed afterward. This technique allows a time resolution for the desorption kinetics from subseconds up to minutes. It is applicable to the study of interaction kinetics between a wide variety of hydrophobic solutes and polyelectrolytes. Due to its simplicity it is accessible for many environmental laboratories. The time-resolved in-tube solid-phase microextraction (TR-IT-SPME) was applied to two humic acids and a surfactant as sorbents together with pyrene, phenanthrene and 1,2-dimethylcyclohexane as solutes. The results give evidence for a two-phase desorption kinetics: a fast desorption step with a half-life of less than 1 s and a slow desorption step with a half-life of more than 1 min. For aliphatic solutes, the fast-desorbing fraction largely dominates, whereas for polycyclic aromatic hydrocarbons such as pyrene, the slowly desorbing, stronger-bound fraction is also important.     

Molecular and structural characterization of dissolved organic matter from the deep ocean by FTICR-MS, including hydrophilic nitrogenous organic molecules

Dissolved organic matter isolated from the deep Atlantic Ocean and fractionated into a so-called hydrophobic (HPO) fraction and a very hydrophilic (HPI) fraction was analyzed for the first time by Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) to resolve the molecular species, to determine their exact masses, and to calculate their molecular formulas. The elemental composition of about 300 molecules was identified. Those in the HPO fraction (14C age of 5100 year) are very similar to much younger freshwater fulvic acids, but less aromatic and more oxygenated molecules are more frequent. This trend continues toward the HPI fraction and may indicate biotic and abiotic aging processes that this material experienced since its primary production thousands of years ago. In the HPI fraction series of nitrogenous molecules containing one, two, or three nitrogens were identified by FTICR-MS. Production spectra of the nitrogenous molecules suggest that the nitrogen atoms in these molecules are included in the (alicyclic) backbone of these molecules, possibly in reduced form. These mass spectrometric data suggest that a large set of stable fulvic acids is ubiquitous in all aquatic compartments. Although sources may differ, their actual composition and structure appears to be quite similar and largely independent from their source, because they are the remainder of intensive oxidative degradation processes.     

Persistent organic pollutants in farmed European sea bass (Dicentrarchus labrax,Linnaeus, 1758) from Sicily (Italy)

Farmed European sea bass (Dicentrarchus labrax, Linnaeus, 1758) were collected during 2016 from one Sicilian fish farm that uses two different rearing systems – sea cage and concrete tank – for determination of polychlorinated biphenyls (PCB), organochlorine pesticides (OCP) and polycyclic aromatic hydrocarbons (PAH) residues by HRGC-MS/MS. Moreover, commercial feed was analysed. This study aimed to determine whether the different rearing systems affect the concentration of these compounds, and to assess the safety of cultured fish. PCBs represent the pollutants with the highest concentration; in particular, PCB138 and 153 have the highest concentration in almost all samples. Among OCPs, only 4,4′-DDE, 4,4′-DDD and 4,4′-DDT residues have been detected. Concerning PAHs, only fluorene and phenanthrene were detected, in both rearing systems. Although some residues of organic pollutants were found in the analysed samples, they were always below the MRLs, so the results suggest that farmed sea bass are safe for human consumption.     

Photochemical mineralization of dissolved organic nitrogen to ammonium in the Baltic sea

Solar-radiation-induced photochemistry can be considered as a new source of nutrients when photochemical reactions release bioavailable nitrogen from biologically nonreactive dissolved organic nitrogen (DON). Pretreatments of Baltic Sea waters in the dark indicated that >72% of DON was recalcitrant to biological mineralization. When this DON (16-21.5 microM) was exposed to simulated solar radiation, the concentration of NH4+ increased 0.5-2.5 microM more in irradiated waters than in the dark controls. The photochemical production of NH4+ and the dose of absorbed photons were used to calculate the apparent quantum yield spectrum for photoammonification [mol NH4+ (mol photons)(-1) nm(-1)] at wavelengths (lambda) of 290-700 nm (phiNH4,lambda). The modeled mean rates of photoammonification based on phiNH4,lambda were 143 and 53 micromol NH4+ m(-2) d(-1) at the surface and in the whole water column, respectively, of Baltic Sea stations during summer. The results of this study indicate thatthe rate of photoammonification approximately equals and periodically exceeds the rate of atmospheric deposition of reactive inorganic nitrogen to the northern Baltic Sea. Forthese stratified surface waters beyond riverine input of labile nitrogen, photoammonification can periodically be the largest source of new bioavailable nitrogen.     

Binding of organic ligands with Al(III) in dissolved organic matter from soil: implications for soil organic carbon storage

The binding characteristics of organic ligands with Al(III) in soil dissolved organic matter (DOM) is essential to understand soil organic carbon (SOC) storage. In this study, two-dimensional (2D) FTIR correlation spectroscopy was developed as a novel tool to explore the binding of organic ligands with Al(III) in DOM present in soils as part of a long-term (21-year) fertilization experiment. The results showed that while it is a popular method for characterizing the binding of organic ligands and metals, fluorescence excitation-emission matrix-parallel factor analysis can only characterize the binding characteristics of fluorescent substances (i.e., protein-, humic-, and fulvic-like substances) with Al(III). However, 2D FTIR correlation spectroscopy can characterize the binding characteristics of both fluorescent and nonfluorescent (i.e., polysaccharides, lipids, and lignin) substances with Al(III). Meanwhile, 2D FTIR correlation spectroscopy demonstrated that the sequencing/ordering of organics binding with Al(III) could be modified by the use of long-term fertilization strategies. Furthermore, 2D FTIR correlation spectroscopy revealed that the high SOC content in the chemical plus manure (NPKM) treatment in the long term fertilization experiment can be attributed to the formation of noncrystalline microparticles (i.e., allophane and imogolite). In summary, 2D FTIR correlation spectroscopy is a promising approach for the characterization of metal-organic complexes.     

Chemical characterization, bioactive compounds, and antioxidant capacity of jussara (Euterpe edulis) fruit from the Atlantic Forest in southern Brazil

Samples of fruit from the jussara palm plant (Euterpe edulis), collected in different regions of the state of Santa Catarina, Brazil, were analyzed for chemical composition, phenolic acids, anthocyanins, flavonoids and fatty acids profile. Results indicated that the jussara fruit has a high lipid content (18.45-44.08%), oleic acid (44.17-55.61%) and linoleic acid (18.19-25.36%) are the fatty acids found in the highest proportion, and other components were proteins (5.13-8.21%), ash (1.55-3.32%) and moisture (34.95-42.47%). Significant differences were found in the total phenolic, total monomeric anthocyanins and other flavonoids for the samples from the five cultivation regions. The fruit from region E harvested in summer, with high temperatures and medium altitudes, had the highest contents of total phenolics (2610.86 ± 3.89 mg 100 g⁻¹ GAE) and monomeric anthocyanins (1080.54 ± 2.33 mg 100 g^− 1 cy-3-glu). The phenolic compound included ferulic, gallic, hydroxybenzoic and p-coumaric acids, as well as catechin, epicatechin and quercetin. The results show promising perspectives for the exploitation of this tropical fruit with a chemical composition comprising considerable phenolic acids and flavonoids compounds and showing activity antioxidant.     

Partial characterization of collagen from purple sea urchin (Anthocidaris crassispina) test

Summary As part of a study to establish an effective use of underutilized resources, purple sea urchin test collagen was prepared by limited pepsin digestion and characterized. This collagen consisted of two α chains and has a chain composition of (α1)₂α2 heterotrimer. The primary structure of the purple sea urchin collagen is different from that of a mammalian such as porcine. Sea urchin collagen has a denaturation temperature of 28 °C which is about 9 °C lower than that of the porcine skin collagen. The yield of collagen was about 35% on the basis of lyophilized dry weight. As the purple sea urchin has the potential as an alternative source of collagen for use in various fields such as foods, medicine, and cosmetics, it is necessary to improve the denaturation temperature of the sea urchin.     

Patterns of adenosine triphosphate catabolism as freshness indicators in fish species from the baltic sea

The breakdown products of adenosine triphosphate (ATP) were determined in order to evaluate the freshness of six Finnish fish species. The degradation of ATP was faster in white bream, in flounder and especially in pike than in other species.     

Photoformation of low-molecular-weight organic acids from brown water dissolved organic matter

This work describes the effects of simulated solar UV light on the bulk properties of dissolved organic matter (DOM) of bog lake water and on the formation of low-molecular-weight organic acids (LMWOAs). By means of size-exclusion chromatography it was shown that the more hydrophilic moieties of the DOM were preferentially photodegraded while the more hydrophobic ones remained relatively unaffected or were even formed. The combined photochemical-biological degradation proved to be more important than the pure photochemical mineralization. Formic, acetic, pyruvic, oxalic, malonic, and succinic acids were identified as important degradation products. Their contribution to the dissolved organic carbon increased from 0.31% before to 6.4% after 24 h irradiation. About 33% of the bioavailable photoproducts of DOM were comprised of these LMWOAs. The influence of nitrate on the formation of carboxylic acids could not be observed in the investigated system. Kinetic experiments indicated that degradation of LMWOAs occurred simultaneously during irradiation experiments, alpha-oxygen-substituted LMWOAs being more amenable to these processes. Dissolved iron acted as a catalyst of DOM photodegradation and LMWOA photoformation. Copper played an antagonistic role in the irradiation experiments, reducing the formation of formic, acetic, and malonic acids while increasing the formation of oxalic acid.     

海参肠组织蛋白酶D的提取及酶学特性研究

本研究以海参肠为原料,采用p H3.0 50 mmol/L甘氨酸-盐酸缓冲体系,按1∶6（w/v）的料液比,在4℃浸提1 h,获得海参肠组织蛋白酶D的粗酶液。以酸变性牛血红蛋白为底物,进行酶活测定,并研究了该酶的酶学性质。结果表明,海参肠组织蛋白酶D粗酶的最适p H为3.0,在p H3.0⁷.0之间稳定性较好;最适反应温度为50℃,在4⁴0℃具有较高稳定性。5 mmol/L的金属离子Mg²⁺、Ca²⁺、Ni²⁺、Zn²⁺、Cd²⁺和K⁺对该酶有激活作用,而Fe³⁺和Fe²⁺则对其有抑制作用。天冬氨酸蛋白酶抑制剂Pepstatin A对该酶活性有较强的抑制作用。上述结果说明,在本研究条件下提取获得的海参肠组织蛋白酶D粗酶是一种酸性蛋白酶,其组成以天冬氨酸蛋白酶为主。      

Terpenoids as major precursors of dissolved organic matter in landfill leachates,surface water,and groundwater

13C NMR analyses of hydrophobic dissolved organic matter (DOM) fractions isolated from a landfill leachate contaminated groundwater near Norman, OK; the Colorado River aqueduct near Los Angeles, CA; Anaheim Lake, an infiltration basin for the Santa Ana River in Orange County, CA; and groundwater from the Tomago Sand Beds, near Sydney, Australia, found branched methyl groups and quaternary aliphatic carbon structures that are indicative of terpenoid hydrocarbon precursors. Significant amounts of lignin precursors, commonly postulated to be the major source of DOM, were found only in trace quantities by thermochemolysis/gas chromatography/mass spectrometry of the Norman Landfill and Tomago Sand Bed hydrophobic DOM fractions. Electrospray/tandem mass spectrometry of the Tomago Sand Bed hydrophobic acid DOM found an ion series differing by 14 daltons, which is indicative of aliphatic and aryl-aliphatic polycarboxylic acids. The product obtained from ozonation of the resin acid, abietic acid, gave a similar ion series. Terpenoid precursors of DOM are postulated to be derived from resin acid paper sizing agents in the Norman Landfill, algal and bacterial terpenoids in the Colorado River and Anaheim Lake, and terrestrial plant terpenoids in the Tomago Sand Beds.     

Antibiotics in South Indian coastal sea and farmed prawns (Penaeus monodon)

Sulphonamides and chloramphenicol antibiotics were analysed by using liquid chromatography–tandem mass spectrometry (LC-MS/MS) in sea and farmed prawn (Penaeus monodon) samples obtained from the coastal region of southern India during 2011–2012. Average recoveries were 77–99% and precision was between 1% and 8%. The results revealed that in sea prawn samples neither of the two antibiotics was detected, but in farmed samples from coastal Andhra Pradesh some sulphonamides were detected in a concentration range greater than the maximum residual limit as set by Council Directive 2377/90 EC.     

Off-flavours in wines through indirect transfer of volatile organic compounds (VOCs) from coatings

This paper assesses the impact of volatile organic compounds (VOCs) from the drying of coatings on the sensory characters of corks and wines. According to Italian National Standard Method 11021:2002, a small-scale chamber was used (1) to expose wines to the drying of coatings with both low and high VOCs, and (2) to expose corks to the same coatings. After exposure to the coatings, the corks were then placed in direct contact with wine. Different styles of white, red and rosé wines were tested. In both directly exposed wines and in wines after contact with the exposed cork, the taste and smell off-flavour perception and intensity were assessed by a panel of eight experienced wine tasters using a five-point numerical scale according to International Organization for Standardization (ISO) standard methods. The results showed that the sensory characters of wines, especially taste, were influenced by the VOC content of the coatings. The taste off-flavour perception was found to be higher than the smell in wines exposed to coatings with either high or low VOCs contents. Analysis of variance (ANOVA) and Duncan analysis prove that: (1) panellist's answers were significantly different, (2) it was difficult to differentiate the off-flavour perception on the high-level scale, and (3) the panellist off-flavour perceptions versus wine style discriminated the wines into two groups (red and white/rosé). For all the wine styles, Pearson's test showed no significant correlation between off-flavour perception levels and the main chemical characters of the wines. For the wines that were in direct contact with the exposed corks, the panellists detect the off-flavours according to the levels of VOCs in the coating and wine styles and they assessed the highest levels of alteration were to the taste.     

Extraction optimization of bioactive compounds (crocin, geniposide and total phenolic compounds) from Gardenia (Gardenia jasminoides Ellis) fruits with response surface methodology

Response surface methodology (RSM) was employed to optimize the extraction parameters of crocin, geniposide and total phenolic compounds from gardenia fruits. The effects of three independent variables, namely ethanol concentration (EtOH, %), extraction temperature (°C) and time (min) on the yield of crocin, geniposide and total phenolic compounds were investigated. Results indicated that the data were adequately fitted into three second-order polynomial models. The independent variables, the linearity of extraction temperature and time, the quadratics of ethanol concentration and extraction time, the interactions between ethanol concentration and temperature, ethanol concentration and extraction time, as well as extraction temperature and time had a significant effect on the yield of crocin, geniposide or total phenolic compounds. The optimal extraction parameters were the EtOH of 51.3%, extraction temperature of 70.4 °C and time of 28.6 min according to the response surface analysis. Under this condition, the yield of crocin, geniposide and total phenolic compounds was 8.41 mg/g, 109.0 mg/g and 24.97 mg CAE/g dry powder of gardenia fruits, respectively.

Industrial relevance

There is a strong interest in the food industry in studying the extraction optimization of natural plants to produce higher quality products. Response surface methodology (RSM) is an effective technique for analyzing interactions among factors and optimizing the processes or products where multiple variables may influence the outputs. This work explores the extraction conditions for a natural pigment-gardenia yellow pigment by the RSM method and optimizes the extraction parameters to improve extraction yields of same main components of the natural pigment at the same time. The mathematical methods and models which can describe and predicate experimental data of the extraction would be extremely helpful in the extraction process of the natural products.     

Sorption of very hydrophobic organic compounds (VHOCs) on dissolved humic organic matter (DOM). 2. Measurement of sorption and application of a Flory-Huggins concept to interpret the data

Sorption phenomena of very hydrophobic compounds (VHOCs, log K(OW) > 5) on dissolved humic organic matter (DOM) are overwhelmingly based on partitioning processes. In this respect, DOM is very similar to "rubbery" soil/sediment OM. To exclude system adsorption effects, the DOM sorption coefficients (K(DOM)) of VHOCs were determined using a dynamic approach based on the VHOCs' aqueous solubility enhancement in the presence of DOM. Partition coefficients are strongly correlated to the analytes' Kow across the alkane, PAH, and PCB groups under study. These three "families" are regarded to be good models of hydrophobic partitioning. On the basis of a uniform one-parameter concept characterizing sorption on amorphous polymers, Hildebrand solubility parameters of amorphous polymeric sorbents, including DOM, and of sorbates can be calculated on the basis of partition coefficients. Likewise, partition coefficients can be estimated using Hildebrand solubility parameters. Literature-based partition coefficients on DOM fit very well in this universal one-parameter concept. On using our own sorption data of PAHs, PCBs, and alkanes on DOM, an almost identical solubility parameter for the DOM polymer under study is obtained. The concept is also very useful in understanding both waterborne and airborne bioconcentration processes, which are considered to be partitioning phenomena.     

Decomposition of hydrogen peroxide and organic compounds in the presence of dissolved iron and ferrihydrite

This work examines the contribution of solution phase reactions, especially those involving a chain reaction mechanism, to the decomposition of hydrogen peroxide (H2O2) and organic compounds in the presence of dissolved iron and ferrihydrite. In solutions at pH 4, where Fe was introduced as dissolved Fe(III), both H2O2 and 14C-labeled formic acid decomposed at measurable rates that agreed reasonably well with those predicted by a kinetic model of the chain reaction mechanism, using published rate constants extrapolated to pH 4. The ratio of the formic acid and H2O2 decomposition rates, as well as the dramatic effect of tert-butyl alcohol on these rates, confirmed that a solution chain reaction mechanism involving *OH controlled the decomposition kinetics of both compounds. In the presence of ferrihydrite as the iron source, the ratio of the rate of formic acid decomposition to that of H2O2 decomposition was significantly lower than that observed in the presence of only dissolved Fe. Moreover, neither rate diminished drastically upon addition of tert-butyl alcohol, indicating that the solution phase chain reaction is not a dominant decomposition pathway of H2O2 and formic acid. Relative decomposition rates of formic acid and a second *OH probe, benzoic acid, were consistent with oxidation of these compounds by *OH. These observations can be reproduced by a kinetic model including (a) decomposition of H2O2 at the iron oxide surface, producing *OH with lower yield than the reaction sequence with dissolved Fe, and (b) low concentrations of dissolved Fe in the presence of ferrihydrite, preventing propagation of the solution phase chain reaction.     

Complexation of copper(ll) in organic soils and in dissolved organic matter--EXAFS evidence for chelate ring structures

Associations with functional groups of natural organic matter (NOM) are of great importance for bioavailability, toxicity, and mobility of trace metals in soils and waters. In this study, the coordination chemistry of copper, Cu(ll), in organic soils and dissolved organic matter (DOM) from soils and streams was investigated by extended X-ray absorption fine structure (EXAFS) spectroscopy. In both soil organic matter (SOM) and DOM (990-11 000 microg Cu g(-1) dryweight, pH 2.8-6.3), Cu(ll) was coordinated by 4 oxygen/ nitrogen (O/N) atoms at a distance of 1.92-1.95 angstroms in the first coordination shell. These four atoms are positioned in the equatorial plane of a Jahn-Teller distorted octahedron. In samples with a pH of 4.8-6.3, a second coordination shell with 2.0-3.8 C atoms was located at a distance of 2.76-2.86 angstroms. A significant improvement (19-39%) of the fit was obtained by including a third coordination shell with 2.0-3.8 O/C atoms involved in single scattering at an average distance of 3.69 angstroms and multiple scattering at an average distance of 4.19 angstroms. Our results provide evidence for inner-sphere complexation of Cu(ll) in NOM and suggest that Cu(ll) is complexed by either one or two five-membered chelate rings involving possible combinations of amino, carboxyl, or carbonyl functional groups. Ion activity measurements showed that less than 0.2% of total Cu was in the form of free Cu2+ in our samples at pH 4.8-6.3.     

用于有机颜料合成及表面改性处理的助剂(二)

(8)非离子聚氧乙烯醚表面活性剂这类表面活性剂经常用于有机颜料合成或作表面处理剂。例如平平加OS 15用于偶合组分溶液中,在酸析时使析出的偶合组分粒子微细,加速偶合反应,防止包芯现象。常用的聚氧乙烯醚非离子表面活性剂可作为润湿剂、分散剂和乳化剂。选用这类表面活性