Structural characterisation of the olive pomace pectic polysaccharide arabinan side chains

An arabinan (97% of Ara and 3% of hexuronic acid) was isolated from the alcohol-insoluble residue (AIR) of olive pomace by treatment with 0.02 M HNO(3), at 80 degrees C, followed by graded precipitation with ethanol. It was separated from acidic pectic polysaccharides by anion-exchange chromatography, and by size-exclusion chromatography its molecular weight was estimated as 8.4 kDa. By methylation analysis, the linkage composition was established as 5:4:3:1 for (1-->5)-Araf, T-Araf, (1-->3,5)-Araf and (1-->3)-Araf, respectively. 13C NMR spectroscopy confirmed this linkage composition, and allowed to assign the alpha anomeric configuration for the arabinofuranosyl residues, except for some terminally linked ones, that were seen to occur as T-beta-Araf. By 2D NMR spectroscopy (1H and 13C), it was possible to conclude that the T-beta-Araf was (1-->5)-linked to a (1-->5)-Araf residue. Also, in the arabinan (1-->5)-Araf backbone, the branched (1-->3,5)-Araf residues were always adjacent to linear (1-->5)-Araf residues. A tentative structure is proposed.     

Modulation of cytokine secretion by pentacyclic triterpenes from olive pomace oil in human mononuclear cells

Olive pomace oil, also known as "orujo" olive oil, is a blend of refined-pomace oil and virgin olive oil, fit for human consumption. Maslinic acid, oleanolic acid, erythrodiol, and uvaol are pentacyclic triterpenes, found in the non-glyceride fraction of orujo oil, which have previously been reported to have anti-inflammatory properties. In the present work, we investigated the effect of these minor components on pro-inflammatory cytokine production by human peripheral blood mononuclear cells in six different samples. Uvaol, erythrodiol, and oleanolic acid significantly decreased IL-1beta and IL-6 production in a dose-dependent manner. All three compounds significantly reduced TNF-alpha production at 100microM; however, at 10microM, uvaol and oleanolic acid enhanced the generation of TNF-alpha. In contrast, maslinic acid did not significantly alter the concentration of those cytokines, with the exception of a slight inhibitory effect at 100microM. All four triterpenes inhibited production of I-309, at 50microM and 100microM. However, uvaol enhanced I-309 production at 10microM. The triterpenic dialcohols had a similar effect on MIG production. In conclusion, this study demonstrates that pentacyclic triterpenes in orujo oil exhibit pro- and anti-inflammatory properties depending on chemical structure and dose, and may be useful in modulating the immune response.     

Biological conversion of olive pomace into compost by using Trichoderma harzianum and Phanerochaete chrysosporium

Olive pomace was composted by using a reactor for a period of 50 days in four bioreactors. Urea was added to adjust C/N ration between 25–30. At the end of 50 days of composting using Trichoderma harzianum and Phanerochaete chrysosporium, cellulose and lignin were highly degraded. It was found that after 30 days, P. chrysosporium and T. harzianum degraded approximately 71.9% of the lignin and 59.25% of the cellulose, respectively. The percent of ash content in the raw waste mixture was 13%. This percentage increased from 13% to 18.55% in treatment bioreactors and from 13% to 13.55% in control reactors during 50 day of composting process. The amount of CO₂ produced by the treated sample was 3 mg of CO₂/g organic carbon which is indicated that the treated sample was considered as stable compost. The results proved that the use of accelerating agents was found to be efficient in producing mature stable with nearly non-phytotoxicity compared to control sample in less than 50 days.     

Operationally determined chemical speciation of barium and chromium in drilling fluid wastes by sequential extraction

ABSTRACT

A study has been conducted to determine the influence of pH on the speciation and distribution of barium and chromium in drilling mud. Samples in equilibrium under controlled conditions were subjected to sequential extraction procedure to fractionate the heavy metals into the designated forms of exchangeable, adsorbed, organically bound, carbonate and residual phases. This provides an insight into the potential availability of the heavy metals for possible release into groundwaters and/or surface waters. The major portion of both the metals studied was found in the carbonate and residual forms with the relative distribution depending on the pH. Generally, decreasing pH caused a shift from the residual form towards the carbonate or organic forms of metals. The occurrence of metals in more stable organic, carbonate and residual forms in drilling mud, coupled with no significant release to the aqueous phase upon varying the pH indicates the resistance of these metals to remobilisation from drilling mud.     

橄榄果渣乙醇提取物成分分析及抗氧化和抑菌性能研究

橄榄果渣中生物活性成分丰富。本文主要研究橄榄果渣提取物成分及其对灰葡萄孢的抑菌性能。首先以橄榄果渣为原料,采用加热回流法,分别以H₂O、50%乙醇、70%乙醇和90%乙醇为提取剂,得到四种提取物并采用HPLC和GC-MS对提取物进行成分分析。其次测定了提取物的总酚含量、抗氧化性和对灰葡萄孢的抑菌性能。研究表明,90%乙醇提取物的酚类含量较高,抗氧化水平优良,并且对灰葡萄孢有明显的抑制作用。该研究为橄榄果渣活性成分在抑菌性能方面的研究提供了一定的理论依据。     

Voltammetric determination of dissolved iron and its speciation in freshwater

Analytical methods were developed to determine the concentration of total dissolved iron and its chemical speciation in freshwater using cathodic stripping voltammetry (CSV) with 1-nitroso-2-naphthol (NN) at pH 8.1. The concentrations of total dissolved iron in river water that iron concentration was certified and in natural water samples from Lake Kasumigaura were determined successfully. The natural iron ligand concentration and the conditional stability constant were determined by ligand competition between NN and the natural ligands present in the sample. In the water samples from Lake Kasumigaura, the concentrations of total dissolved iron and natural ligand were 47.8 ± 4.4nM and 80.0 ± 19.6nM and the conditional stability constant (K_FeL) was 10^25.9±0.4M^–1 (n = 3). The value of K_FeL was greater than any reported K_FeL for seawater. More than 99.9% of the dissolved iron existed as organic species due to the very high value of the conditional stability constant. The inorganic iron concentration calculated from these results was 10^–13.4M, indicating that the inorganic iron level in Lake Kasumigaura was similar to that in the open ocean and therefore that iron can be a limiting factor for algal growth in Lake Kasumigaura. This is the first report of the complexation of iron(III) and inorganic iron levels in lake water determined by CSV.     

Optimization of polyphenol extraction from red grape pomace using aqueous glycerol/tartaric acid mixtures and response surface methodology

Grape pomace is a food industry waste containing a high burden of antioxidant polyphenols and several methodologies have been developed for their efficient extraction. However, a sustainable and environmentally friendly process should involve recovery means composed of benign, non-toxic solvents, such as tartaric acid and glycerol, which are natural food constituents. In this line, this study examined the extraction of polyphenols using aqueous tartaric acid/glycerol solutions. The aim was to assess the role of acid and glycerol concentration in the extraction yield, employing a Box-Behnken experimental design and response surface methodology. The results showed that solutions containing only glycerol (20%, w/v) are more suitable for retrieving polyphenols, flavonoids, and pigments from grape pomace, while tartaric acid exerted a negative effect in this regard, when tested at concentrations up to 2% (w/v).     

反相HPLC法测定静注人免疫球蛋白中残余胆酸钠含量研究

用反相高效液相色谱法(R—HPLC)测定静注人免疫球蛋白(IVIG)中残余胆酸钠含量。首先用固相提取柱吸附、浓缩制品中残余胆酸钠,然后加入一定量胆酸钠,使样品中胆酸钠含量达到可检测水平后,依外标法进行测定。结果表明,用R—HPLC法测定胆酸钠准确性及重复性较好,是一种相对准确快速的方法。     

Spectrofluorimetric determination of atenolol from human urine using high‐affinity molecularly imprinted solid‐phase extraction sorbent

This study presents a novel, sensitive and selective molecularly imprinted solid‐phase extraction (MISPE)–spectrofluorimetric method for the removal and determination of atenolol from human urine. Molecularly imprinted and non‐imprinted polymers were synthesized thermally using a radical chain polymerization technique and used as solid‐phase extraction sorbents. Acrylic acid ethylene glycol dimethacrylate, dibenzoyl peroxide and dichloroethane were used as a functional monomer, cross‐linker, initiator and porogen, respectively. The calibration curve was in the range of 0.10–2.0 μg/ml for the developed method. Limit of detection and limit of quantification values were 0.032 and 0.099 μg/ml, respectively. Owing to the selectivity of the MISPE technique and the sensitivity of spectrofluorimetry, trace levels of atenolol have been successfully determined from both organic and aqueous media. Relatively high imprinting factor (4.18) and recovery results (74.5–75.3%) were obtained. In addition, intra‐ and interday precision values were 0.38–1.03% and 0.47–2.05%, respectively, proving the precision of the proposed method. Thus, a selective, sensitive and simple MISPE–spectrofluorimetric method has been developed and applied to the direct determination of atenolol from human urine.     

Carbon exchange and water use efficiency of a growing, irrigated olive orchard

We measured eddy covariance fluxes of CO₂ and H₂O over a flat irrigated olive orchard during growth, in different periods from Leaf Area Index (LAI) of 0.3–1.9; measurements of soil respiration were also collected. The daily net ecosystem exchange flux (F_NEE) was practically zero at LAI around 0.4 or when the orchard intercepted 11% of the incoming daily radiation; at the end of the experiment, with LAI of 1.9 (and the fraction of intercepted daily radiation close to 0.5), F_NEE was around 10 g CO₂ m⁻² day⁻¹. The night-time ecosystem respiration (R_eco), calculated from eddy fluxes in well-mixed night conditions, show a clear but non-linear dependence with LAI; it ranged from 0.05 to 0.15 mg CO₂ m⁻² s⁻¹ (in average), being the lower limit ideally close to the heterotrophic soil respiration at the site. The gross primary production flux (F_GPP) was linearly related to LAI within the LAI range of this experiment (with 11 g CO₂ m⁻² day⁻¹ increments per unit of LAI) and to the fraction of intercepted radiation. The maximum rates of F_GPP (0.75 mg CO₂ m⁻² s⁻¹) were obtained in the summer mornings of 2002, at LAI close to 1.9. F_GPP was strongly modulated by vapour pressure deficit (VPD) through the canopy conductance, even in absence of water stress. Hence, especially in the summer, the maximum rates of carbon assimilation are reached always before noon. The daily course of F_GPP shows a two-phase pattern, first related to irradiance and then to canopy conductance. The water use efficiency (WUE) was, in average, 3.8, 6.3 and 7 g CO₂ L⁻¹ in 1999, 2001 and 2002, respectively, with maxima always in the early morning. Hourly WUE was strongly related to VPD (WUE = −10.25 + 22.52 × VPD^−0.34). Our results suggest that drip irrigated orchards in general, and olive in particular, deserve specific carbon exchange and carbon budget studies and cannot be easily included in other biomes.     

Solid-phase extraction of liquiritin and glycyrrhizin from licorice using porous alkyl-pyridinium polymer sorbent

Introduction – Liquiritin and glycyrrhizin are valuable components of licorice. An effective separation and determination procedure is needed to separate the liquiritin and glycyrrhizin from the licorice extract. Methodology – A polymer‐confined, ionic liquid sorbent was developed using a process involving polymerisation and modification. The obtained porous particles were used as a sorbent in a solid‐phase extraction process to isolate liquiritin and glycyrrhizin from licorice with different washing and elution solvents. The porous alkyl‐pyridinium polymer sorbent was compared with the C₁₈ sorbent. Results – A simple and convenient method was established to the selectively separate and determinate of liquiritin and glycyrrhizin using a porous ionic liquid‐based polymer coupled with HPLC. Additionally, this study evaluated the application of this sorbent for the detection of these two compounds in commercial medicines. Conclusion – This method was a viable tool that was compatible with the existing HPLC methods and was used to separate and analyse the content of liquiritin and glycyrrhizin in licorice. Copyright © 2010 John Wiley & Sons, Ltd.     

Assessing the impact of agro-industrial olive wastes in soil water retention: Implications for remediation of degraded soils and water availability for plant growth

Olive solid waste (OSW) is a toxic by-product of olive oil production. Disposal of OSW is a major problem in many Mediterranean countries leading to increased interest in its potential as an organic fertiliser. Relatively little is known regarding the impact of augmentation with OSW and olive solid waste compost (OSWC) on soil hydraulic properties. The effect of OSW and OSWC on the hydraulic characteristics of common agricultural soils with high sand but very different silt and clay contents was analysed. Increased organic inputs induced reductions in soil bulk density and increases in air capacity, hydraulic conductivity and the water content available for plant growth (AWC) in the Sandy Clay Loam (SCL) soil. Similar patterns were observed in Loamy Sand (LS) soil augmented with OSW, but OSWC caused reductions in hydraulic conductivity, air capacity and AWC. Nonetheless, over longer timescales OSWC may benefit the hydraulic properties of loamy sand soils as the compost becomes fully incorporated within the soil structure. Augmentation with organic olive waste induced the hydraulic parameters of the sandy clay loam soil to become identical to those loamy sand (LS) with a higher available water capacity; suggesting that soil augmentation with OSW and OSWC may be an effective tool in remediating and improving degraded or organic poor soils. In terms of the improvement of hydraulic parameters, application rates of 6–8% OSW/OSWC were most beneficial for both soil types.     

A comparison of alternative sample preparation procedures for the analysis of swainsonine using LC‐MS/MS

Introduction – Swainsonine, a polyhydroxy indolizidine alkaloid and known glycosidase inhibitor, is found in a number of different plants that cause a lysosomal storage disease known as locoism in the western USA. Most recently swainsonine has been analysed by LC‐MS/MS after sample extraction and preparation from ion‐exchange resins. Objective – To compare previously published sample preparation procedures with several new alternative procedures to provide methods using either commercially available solid‐phase extraction equipment or procedures which significantly reduce sample preparation time. Methodology – A previously reported and validated sample preparation method using ion‐exchange resin was compared with methods using a commercially available solid‐phase extraction cartridge, a solvent partitioning procedure or a single solvent extraction procedure using one of two solvents. Twenty different plant samples of varying swainsonine concentrations were prepared in triplicate and analysed by LC‐MS/MS. The measured concentration of swainsonine was then statistically compared between methods. Results – There were no statistically significant differences found between four of the five different sample preparation methods tested. Conclusion – A commercially available SPE cartridge can be used to replace the previously used ion‐exchange resin for swainsonine analysis. For very rapid analyses the SPE procedure can be eliminated and a simple, single solvent extraction step used for sample preparation. Published in 2010 by John Wiley & Sons, Ltd.     

Molecular microbial and chemical investigation of the bioremediation of two-phase olive mill waste using laboratory-scale bioreactors

Two-phase olive mill waste (TPOMW) is a semi-solid effluent that is rich in contaminating polyphenols and is produced in large amounts by the industry of olive oil production. Laboratory-scale bioreactors were used to investigate the biodegradation of TPOMW by its indigenous microbiota. The effect of nutrient addition (inorganic N and P) and aeration of the bioreactors was studied. Microbial changes were investigated by PCR-temperature time gradient electrophoresis (TTGE) and following the dynamics of polar lipid fatty acids (PLFA). The greatest decrease in the polyphenolic and organic matter contents of bioreactors was concomitant with an increase in the PLFA fungal/bacterial ratio. Amplicon sequences of nuclear ribosomal internal transcribed spacer region (ITS) and16S rDNA allowed identification of fungal and bacterial types, respectively, by comparative DNA sequence analyses. Predominant fungi identified included members of the genera Penicillium, Candida, Geotrichum, Pichia, Cladosporium, and Aschochyta. A total of 14 bacterial genera were detected, with a dominance of organisms that have previously been associated with plant material. Overall, this work highlights that indigenous microbiota within the bioreactors through stimulation of the fungal fraction, is able to degrade the polyphenolic content without the inoculation of specific microorganisms.     

Simultaneous determination of sucrose and trehalose in olive leaves by spectrophotometry utilizing partial least squares method

This study deals with the simultaneous determination of sucrose and trehalose in olive leaf samples, with easy sample preparation step, by second derivative UV–Vis spectrophotometry and partial least squares technique. A training set consisting of 31 binary mixture solutions was applied for the construction of PLS model. The proposed procedure was successfully applied for the simultaneous determination of both carbohydrates in laboratory prepared mixtures and in real samples. The real samples were from different growth stages of olive plant. The root mean square error of prediction was determined to be 1.95 and 2.06 for sucrose and trehalose, respectively. Also, limit of detection was 0.21 ppm for sucrose and 0.26 ppm for trehalose. The proposed procedure is rapid, simple, and easy to perform which can be used for routine analysis of both carbohydrates in plant leaves.     

Uptake, distribution, and speciation of chromium in Brassica juncea

Brassica juncea (Indian mustard) has been widely used in phytoremediation because of its capacity to accumulate high levels of chromium (Cr) and other metals. The present study was conducted to investigate mechanism(s) involved in Cr binding and sequestration by B. juncea. The plants were grown under greenhouse conditions in field-moist or air-dried soils, amended with 100 mg kg(-1) of Cr (III) or VI). The plant concentrated Cr mainly in the roots. B. juncea removed an average of 48 and 58 microg Cr per plant from Cr (III) and Cr (VI)-treated soils, respectively. The uptake of Cr was not affected by the moisture status of the soils. X-ray absorption near-edge spectroscopy measurements showed only Cr (III) bound predominantly to formate and acetate ligands, in the bulk and rhizosphere soils, respectively. In the plant tissues, Cr (III) was detected, primarily as acetate in the roots and oxalate in the leaves. X-ray microprobe showed the sites of Cr localization, and probably sequestration, in epidermal and cortical cells in the roots and epidermal and spongy mesophyll cells in the leaves. These findings demonstrate the ability of B. juncea to detoxify more toxic Cr (VI), thereby making this plant a potential candidate for phytostabilization.     

污染条件下VAM玉米元素积累和分布与根际重金属形态变化的关系

为了了解重金属Cu、Zn、Pb、Cd在土壤－根际－植物系统中的行为,揭示VAM植物减弱土壤中过量重金属对植物生理毒的抗性机理,采用原子吸收光谱测定Cu、Zn、Pb、Cd在污灌土壤中生长的VA菌根玉米和无菌根玉米中的积累和分布,并用连接形态分析技术分析了菌根际中Cu、Zn、Pb、Cd的形态分布和变化趋势,结果表明,Cu、Zn、Pb、Cd在菌根玉米中的积累量比非攻根中积累量分别减少10％、18％和29％,Cd积累量没有改变,生长7周后,菌根玉米是非菌根玉米生物量的1．5倍,与对照土壤相比,根际中除Cu交换态显著增加外,Zn、Pb、Cd各形态相对改变量显著大于非菌根,且菌根根际上中Cu、Zn、Pb有机结合态增加量显著大于非根际土,说明菌根际金属向稳定状态转移的程度显著大于非菌根际,同时,讨论了根际金属形态对金属有效性的影响,及其与菌根植物金属抗性机理的关系。     

Imaging and speciation of trace elements in biological environment

Mineral elements, often at the trace level, play a considerable role in physiology and pathology of biological systems. Metallogenomics, metalloproteomics, and metallomics are among the emerging disciplines which are critically dependent on spatially resolved concentration maps of trace elements in a cell or tissue, on information on chemical speciation, and on that on metal-binding coordination sites. The mini-review discusses recent progress in analytical techniques for element profiling on the genome scale, biological trace element imaging, and probing, identification and quantification of chemical species in the biological environment. Imaging of the element distribution in cells and tissue sections is becoming possible with sub-micrometer spatial resolution and picogram-level sensitivity owing to advances in laser ablation MS, ion beam and synchrotron radiation X-ray fluorescence microprobes. Progress in nanoflow chromatography and capillary electrophoresis coupled with element specific ICP MS and molecule-specific electrospray MS/MS and MALDI enables speciation of elements in microsamples in a complex biological environment. Laser ablation ICP MS, micro-SXRF, and micro-PIXE allow mapping of trace element distribution in 1D and 2D proteomics gels. The increasing sensitivity of EXAFS and XANES owing to the use of more intense synchrotron beams and efficient focusing optics provide information about oxidation state, fingerprint speciation of metal sites and metal-site structures.     

Application of Poly 1,8‐diaminonaphthalene/multiwalled carbon nanotubes‐COOH hybrid material as an efficient sorbent for trace determination of cadmium and lead ions in water samples

Poly 1,8‐diaminonaphthalene/multiwalled carbon nanotubes‐COOH hybrid material as an effective sorbents in solid phase extraction has been developed for the separation and preconcentration of Cd(II) and Pb(II) at trace levels in environmental water samples. The results indicate that the novel nanocomposite show a high affinity for these heavy metals due to the presence of several good extractive sites, which are introduced to the synthesized nanocomposite The maximum adsorption capacity of the synthesized sorbent for cadmium and lead ions was found to be 101.2 and 175.2 mg g^?1, respectively. The detection limits of this method were 0.09 and 0.7 ng ml^?1 for Cd(II) and Pb(II), respectively. Copyright © 2014 John Wiley & Sons, Ltd.