Monocyclic and monoaromatic naphthenic acids: synthesis and characterisation

Characterisation of the complex mixtures of carboxylic acids (naphthenic acids) occurring in crude oils and in degraded oil sands is environmentally important. Indeed some acids in waters from oil platforms are apparently hormonally active, and the oil sands acids are said to be toxic to a wide range of biota. Previous attempts to identify monocyclic and monoaromatic naphthenic acids have been hampered by the lack of authenticated synthetic reference compounds. Some studies have indicated that acids with ethanoic acid side chains are present in the naphthenic acids mixtures, so in the present study, we synthesised and characterised by mass spectrometry, a range (C_8–14) of monoaromatic and monocyclic ethanoic acids. Using 2-D comprehensive gas chromatography–mass spectrometry, we then compared the retention times and mass spectra of the synthetic acids with those of a commercial naphthenic acids mixture. Some alicyclic and numerous aromatic acids were successfully identified.     

低分子量有机酸对可变电荷土壤吸附铝的影响机制

通过吸附性铝的解吸实验研究了低分子量有机酸对三种可变电荷土壤(2种砖红壤和1种赤红壤)吸附铝的影响机制，结果表明，柠檬酸、苹果酸和酒石酸等带有3个及3个以上活性官能团的有机酸在低pH条件下可以通过形成土壤一有机酸一铝三元表面络合物和增加土壤的表面负电荷两种机制显著增加土壤对铝离子的吸附量，但以前一种影响机制为主。乳酸、水杨酸、草酸和丙二酸等带有2个活性官能团的有机酸仅通过改变土壤的表面负电荷影响铝的吸附。土壤氧化铁是土壤吸附有机酸的主要载体，当用化学方法将土壤中的氧化铁除去后，有机酸对铝吸附的影响变小。在pH5．0时有机酸主要通过形成可溶性有机铝络合物减小土壤对铝的吸附，但有机酸的存在增加了Al^3 在吸附性铝中所占的比例，导致铝的解吸率增加。土壤中大量氧化铁的存在使其即使在低pH下也能对铝离子发生专性吸附，导致吸附性铝的解吸率减小。     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

Amino acids during development of mountain birch leaves

Summary. The nutritive value of tree foliage for herbivores decreases rapidly with leaf maturation, due in particular to the decline in leaf nitrogen content. Since the amino acid content of plants differs from the need of herbivores for individual amino acids, we examined developmental changes in the contents of amino acids throughout the growth season of mountain birch. The contents of free and protein-bound amino acids, as well as essential and nonessential ones, displayed different patterns with leaf maturation, suggesting that total nitrogen or protein levels are poor predictors of the nutritive status of leaves. The contents of protein-bound amino acids were 100 times higher than those of free amino acids, indicating that the role of free amino acids in nutrition of herbivores is probably less important than that of protein-bound amino acids. Among protein-bound amino acids, both the absolute and the relative contents of two nitrogen-rich essential amino acids, lysine and arginine, decreased during early leaf growth, presumably reducing nitrogen availability in developing leaves. Essential amino acids were mainly positively related to each other, suggesting the co-ordinated regulation of their synthesis. Changes in correlations among individual free amino acids reflected developmental changes in allocation preferences between biosynthesis pathways with leaf growth. Received 31 January 2003; accepted 17 March 2003. R1D=" Correspondence to: Teija Ruuhola, e-mail: teiruu@utu.fi     

Strong adsorption of DNA molecules on humic acids

Analysing soil microbial communities is often hampered by DNA adsorption on soil organic compounds such as humic acids. However the role of humic acids in DNA adsorption and stability in soils remains controversial. To characterize DNA–humic acid interactions, we studied DNA adsorption on two commercially available humic acids and a soil humic acid extracted from an Andosol. Desorption of the adsorbed DNA using 4 different solutions—distilled water, 0.1 M NaCl, 0.1 M sodium phosphate buffer (pH 6.0), and 1% sodium dodecyl sulfate solution—was also studied to understand the mechanism of DNA adsorption on humic acids. Here, we show that humic acids play an important role in DNA adsorption to soils. DNA molecules were adsorbed on the humic acids, with adsorption increasing proportionally with the DNA concentrations in the solution. The adsorption on all humic acid samples was fitted with Freundlich equation, and the parameters obtained from the equation indicated a high affinity between the humic acids and DNA molecules. The total amount of DNA desorbed by the 4 solutions was less than 2% of the total DNA adsorbed on all the humic acids. The results demonstrate that DNA molecules are able to bind strongly to humic acids by ligand binding, hydrophobic interaction, aggregation, or precipitation.     

氯化消毒饮用水中强致突变物MX[3-氯-4-(二氯甲基)-5-羟基-2(5H)-呋喃酮]的形成

利用一系列XAD吸附树脂及大孔阴、阳离子交换树脂,将太湖水中溶解态有机物分离为溶解态富里酸类、腐殖酸类、憎水弱酸类、憎水碱类、憎水中性物类、亲水酸类、亲水碱类七种组分,分别对不同组分的有机物进行氯化处理后,用GC/MS选择离子峰面积法测定了产物中的MX[3-氯-4-（二氯甲基）-5-羟基-2（5H）-呋喃酮]。结果表明,太湖水体中的溶解态腐殖酸类可能是生成MX的重要前驱物。     

On the ability of Anemonia sulcata (Coelenterata: Anthozoa) to absorb charged and neutral amino acids simultaneously

Reciprocal inhibition experiments concerning the simultaneous absorption of acidic, basic and neutral amino acids give evidence that Anemonia sulcata Pennant (Coelenterata: Anthozoa) possess at least three distinct uptake systems for amino acids. The absorption of amino acids belonging to the same class is mutually inhibited. Increasing inhibitor concentrations reduce the uptake of the substrate successively, indicating that the receptors are saturated only at high substrate concentrations; this is not the case under natural conditions. The uptake system for acidic amino acids is highly specific; uptake is not inhibited by either basic or neutral amino acids. The specificity for basic amino acids is lower; uptake is influenced by neutral amino acids. Neutral amino acids are absorbed either by one single system with broad specificity or by several systems with overlapping specificity. D- and L-isomers seem to be absorbed by the same system, as the uptake is reciprocally inhibited. The restricted specificity of the amino-acid uptake systems, especially those for neutral amino acids, could be explained as an adaptation to avoid accumulation of certain amino acids in a most economic way. Moreover, a broad spectrum of various dissolved organic materials can thus be utilized. The experiments also give evidence that anemones are able to supply their metabolism completely with the necessary substances by absorbing dissolved organic material. The absorbed substances may, furthermore, be vital for the metabolism, although their individual energy content may be negligible. Anemones display optimum fitness to an important environmental factor-dissolved organic material — on a macromolecular level, in addition to structural and physiological adaptations.     

Sources of cyclopropanoid fatty acids in the mummichog Fundulus heteroclitus

The saturated fatty acids in lipids of the mummichog Fundulus heteroclitus (L.) contain the characteristic bacterial cis-9,10-methylenehexadecanoic and cis-9,10-methyleneoctadecanoic acids in addition to straight-chain, iso, anteiso and multi-branched fatty acids. To ascertain whether the cyclopropanoid fatty acids (CFA) might be used as a marker for bacterial components in the mummichog diet, the saturated fatty acids of detritus were compared with those of fish intestines and their contents, and with those of eviscerated fish. The relative amounts of individual fatty acids in each sample indicated that microorganisms or invertebrate animals that consume microorganisms constitute a part of the mummichog's diet. A similar analysis of anterior and posterior sections of the fish intestines showed a higher concentration of CFA in the posterior section, suggesting that at least some of the cyclic acids might originate from the resident bacterial gut population. When a group of mummichogs was maintained on a beef-liver diet devoid of cyclic acids, carcass lipids were not depleted of CFA. Instead, an increase in concentration was observed. It was concluded that the intestinal microflora have a role in supplying CFA to mummichog lipids. Since the overall results indicate that these acids are derived from commensal bacteria as well as from bacteria associated with the diet, it is not possible to use such compounds as food-chain markers.     

Chloroacetic acids in environmental processes

The fate of chloroacetic acids (CAA) in forest soils was studied using radio-indicator methods. We showed that chloroacetic acids are both microbially degraded and simultaneously formed by chloroperoxidase-mediated chlorination of acetic and humic acids. The degree of biodegradation of chloroacetic acids in soil depends on their concentration. Dichloroacetic acid (DCA) is degraded faster than trichloroacetic acid (TCA). Chlorination of acetic acid led to a fast formation of dichloroacetic acid, whereas chlorination of humic acids gave rise to trichloroacetic acid. Both processes lead to a steady state in soil, participate in the chlorine cycle and possibly also in decomposition of organic matter in forest ecosystems.     

Investigations of some trace elements in the Bay of Lim

Sea water was collected at several stations in the Bay of Lim at a depth of one meter below the surface, and before analysis, was filtered with 0.45-μm Millipore filters. Shallow water sediments were collected at the same locations. Humic acids used in this work were separated from near-shore sediments taken from various saline waters of the Bay of Lim. The prepared humic acids were then analysed for their elementary composition and also for positions of their hydrolytic products to obtain more data on how and to which characteristic part, the trace elements were related. The hydrolysis of humic acids was done by chemical methods in order to obtain four main components: amino acids, sugars, phenols and condensed benzene core. Neutron activation analysis was used for trace element analysis in evaporated portions of filtered sea water, sediments, soil, living organisms, humic acids and their hydrolytic products. This work was undertaken to obtain more data on the organic matter present in sediments and in seagrass flats, and also to collect more data on trace elements that are associated with typical and representative samples for the Bay of Lim. Analyses of trace elements associated with either humic acids or their hydrolytic products were performed with the purpose of gaining evidence as to which part of humic acids metals are bound. Humic acids or their decomposition products play an important role in the distribution and availability of a number of essential or nonessential trace elements. Results of this work indicate that humic acids influence the process of redistribution of trace elements in the investigated local coastal area.     

Characterization of soil low-molecular-weight organic acids in the Karst rocky desertification region of Guizhou Province, China

Soil low-molecular-weight (LMW) organic acids play important roles in the soil-forming process and the cycling of nutrients in Karst regions. In this study, we quantified the contents of LMW organic acids (including lactate, acetate, formate, malate, and oxalate) in soil solution over the Karst region of Guizhou Province, China using ion chromatography. The concentration of total LMW organic acids in topsoil solution ranged from 0.358 to 1.823 μmol·g^-1, with an average of 0.912 μmol·g^-1. The mean concentrations of lactate, acetate, formate, malate, and oxalate were 0.212±0.089, 0.302±0.228, 0.301±0.214, 0.014±0.018 and 0.086±0.118 μmol·g^-1, respectively. There were also significant difference in the contents of these acids among four phases of rocky desertification, and their concentrations decreased with the aggravation of rocky desertification. The concentrations of the LMW organic acids were significantly positive correlated each other. Significant positive correlations were also observed among individual LMW organic acids in soil solution, and between them and soil available P, available K, exchangeable Ca, respectively. Furthermore, the concentrations of LMW organic acids were significantly positively correlated with inorganic anions (chlorides, nitrates, and sulfates) in Karst topsoil solution. Therefore, the concentrations of soil LMW organic acids might be one of driving force in the Karst rock desertification process in Guizhou Province.     

Acetate incorporation into the lipids of the anemone Anthopleura elegantissima and its associated zooxanthellae

Anthopleura elegantissima containing zooxanthellae, as well as isolated zooxanthellae, incubated with acetate-1-¹⁴C under both light and dark conditions readily incorporate radioactivity into their total lipid pools. In both cases, the specific activity was greatly increased in the light. Dark-incubated anemones and isolated zooxanthellae incorporate activity predominantly into polar lipid; the remainder being present principally in the triglyceride moiety. Light-incubated organisms, however, show a dramatic redistribution of isotope towards greatly increased triglyceride and was ester incorporation, with a concomitant drop in polar lipid. onder light conditions, 70 to 75% of the radioactivity found in the fatty acids of the total zooxanthellae lipid was present in hexadecanoic (16:0) and octadecenoic (18:1) fatty acids. These are also the two major fatty acids by mass. Octadecanoic acid (18:0) is less than 5% by mass. Isotope incorporation patterns suggest that octadecenoic acids arise by elongation of hexadecenoic acids and that this conversion is blocked in the dark. Isotope incorporation patterns for anemones suggest that fatty acids, primarily in the form of saturated or monoenoic fatty acids, are translocated from algal to animal cells. No activity was found in either octadecadienoic (18:2) or octadecatrienoic (18:3) acids. The significance of these data is discussed.     

The reduction of selenate by fulvic acids in soils of a high gastric cancer risk area in Sri Lanka∗

In order to elucidate the probable etiological factors for the incidence of gastric cancer, the interaction between selenate and fulvic acids was investigated under chemically controlled conditions. The reduction ability of selenate by fulvic acids was enhanced in acidic conditions. The fulvic acids may play an important role in the nitrosation process. Thus the investigations of the mechanism by which selenate interact with fulvic acids will provide a new insight into the chemical activation process by which selenium supplementation is supposed to act as an anticarcinogen.     

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

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

有机酸对珠江三角洲水稻土镉解吸行为的影响

用批平衡实验方法,研究了3种有机酸及其两两混合酸在一系列pH值梯度下(pH3~7)对珠江三角洲沉积型水稻土镉(Cd)解吸的影响.结果表明,只有柠檬酸及含柠檬酸的混合酸在较低酸度区(pH>5)可以显著促进Cd的解吸,这一效应与浓度成正相关,而苹果酸、草酸及二者的混合酸在所试验酸度范围均促进了Cd吸附,特别是草酸,促进作用随浓度的升高而增强.在较低pH区(pH<5),苹果酸最有利于Cd解吸,在高pH区(pH≥5),柠檬酸最有利于Cd解吸,草酸的Cd解吸能力最低.混合有机酸交互作用不显著,对Cd解吸的影响约等于各个单独酸的作用之和,但在一些酸度条件下,可存在颉颃作用.图3表2参22     

Antioxidant effect of lignite humic acids and its salts on the thermo-oxidative stability/degradation of polyvinyl alcohol blends

We demonstrate the antioxidant potential of humic acids in (green) polymer chemistry. Lignite humic acids and its sodium and ammonium salts were mixed at different concentrations with polyvinyl alcohol and thermogravimetry was used to assess the influence on the thermo-oxidative stability of resulted blends. Both protonized form and ammonium salt of humic acids caused increased stability of investigated polymers in the studied concentration range (0.5–10% of humic acids in polymer). In contrast to protonized form, the ammonium salt also showed moderating effect on polymer degradation kinetics. Sodium salts caused substantially lower stabilizing effect and presence of 10% of humic matter caused even destabilization. In all cases, however, when the degradation has already started, the presence of humic acids and its salts caused more intensive polymer decomposition, which resulted in lower weight of char.     

Identification and quantitative analysis of the amino acids present in protein of the brown shrimp Penaeus aztecus

In order to better formulate an artificial shrimp diet, the protein composition of shrimp was assessed and the essential amino acids determined. Penaeus aztecus were treated to remove lipids, carbohydrates and other interfering substances, and the protein was hydrolyzed to its constituent amino acids. The amino acids were then quantitatively analyzed by gasliquid chromatography as their trimethylsilyl derivatives. The essential amino acids were then determined. Shrimp were injected with ¹⁴C-labeled glucose and analyses performed to determine which amino acids then exhibited radioactivity, i.e., were synthesized from the labeled glucose. Those amino acids which were not manufactured from the glucose were categorized as essential.     

Plant availability of cadmium in presence of organic acids: an interactive aspect

The present communication reports the effect of various carboxylic and amino acids on the uptake and translocation of root-absorbed Cd by maize (Zea mays). Statistically significant increases in Cd accumulation in various plant tissues with increasing supplementation of organic acids suggested the existence of Cd-organic acid interaction in soil-rhizosphere environment of the plant. The potentiality of phytochelators (organic acids) to form plant available organically bound Cd is discussed.     

不同pH下低分子量有机酸对黄壤中铝活化的影响

用一次平衡的方法研究了不同pH下低分子量有机酸对黄壤中铝活化的影响.结果表明,低分子量有机酸体系可以通过质子和有机酸阴离子两个因素促进黄壤中铝的活化.当pH>4.3时,有机酸通过络合作用促进铝溶解的大小顺序为:柠檬酸>草酸>水杨酸>乳酸,与有机酸和铝形成络合物的稳定常数大小一致.有机酸阴离子可以通过自身的吸附增加土壤交换态铝的量,但质子作用对黄壤交换态铝的活化比有机酸阴离子的吸附起着更为重要的作用,随pH值的降低这种趋势更加明显.有机酸对交换态铝的活化作用随pH值的降低而增加.低分子量有机酸活化的铝主要分布在土壤表面的交换位上,但在柠檬酸和草酸体系中,当pH值分别大于4.40和4.55时,活化铝主要分布在土壤溶液中.     

Plasma nonesterified fatty acids of marine teleost and elasmobranch fishes

The plasma nonesterified fatty acids (NEFA) of five species of temperate zone marine teleost fishes (Northwestern Atlantic), one Arctic marine teleost (Eastern Canadian Arctic), and four species of marine elasmobranchs (Northwestern Atlantic) are reported. Four fatty acids, 16:0, 18:1n9, 20:5n3 and 22:6n3, comprised 70 to 83% of total NEFA in the plasma of all temperate teleost species examined. With the sole exception of 18:1, these differed from the predominant fatty acids, 14:1, 16:1, 18:1 and 20:5n3, in the Arctic species. The predominant fatty acids in elasmobranch NEFA were 16:0, 22:6n3 and 18:1n9 in all species but saturated fatty acids (14:0, 16:0 and 18:0) accounted for 40% of all NEFA in all elasmobranchs examined. Monoenes represented a greater, and polyenes a smaller, percentage of the fatty acids in the Arctic sculpin compared to the temperate sculpin. Fatty acids of the n3 series were lower in the plasma of the Arctic sculpin compared to the temperate sculpin. Comparisons with published values for freshwater fish using the same method indicate the n3:n6 ratio is higher in the marine teleost fishes. Ratios of n3:n6 fatty acids ranged from 1.80 to 7.94 for the elasmobranchs and were on average lower than those for the marine teleosts. Total levels of NEFA for the elasmobranchs were between 193 and 399 nmol ml^-1, lower than the values reported here for teleosts but within the range reported by others for some teleost fishes.