Fractionation and Distribution of Metals in Guadiamar River Sediments (SW Spain)

Traditionally, the Guadiamar River (Seville, Southwest Spain) has received pollution from two different sources, in its upper section, from a pyrite exploitation (Los Frailes mine) and, in its lower section, from untreated urban and industrial wastes and from intensive agricultural activities. In 1998, the accidental spillage of about 6 million m³ of acid water and sludge from mine tailings to Guadiamar River worsened the pollution of an already contaminated area. The main polluting agents of the spillage were heavy metals. The total concentration of a metal provides scarce information about the effects on environmental processes or about the toxicity of the sediment samples. A more sophisticated fractionation of the sediment samples based on a species distribution can help to understand the behaviour and fate of the metals. This article describes a distribution study of the metals Al, Cd, Cu, Fe, Mn, Pb and Zn by fractionation analysis of sediments from eleven sample sites alongside the Guadiamar Riverbed. The samples were collected in summer 2002, four years after the spillage and after the area had been cleaned. Sequential extraction analysis resulted in the definition of four fraction categories: exchangeable metal (the most available fraction), reducible metal (bound to hydrous oxides of Fe and Mn), oxidizable metal (bound to organic matter and sulphides) and a residual fraction (bound to minerals). Significant increases in the available fraction of several potentially toxic metal ions like Cd, Mn and Zn were found. The distribution pattern was variable along the River. At the site closest to the mineworks, the soluble forms of Cd, Mn and Zn were significantly more abundant that those downstream. Cu and Pb were present in the reducible fraction while Fe was present associated in the residual fraction.     

Melanoidins from coffee infusions. Fractionation, chemical characterization, and effect of the degree of roast

A method involving fractionation in ethanol aqueous solutions, anion exchange chromatography, and immobilized copper chelating chromatography was developed to obtain high molecular weight anionic melanoidin populations from coffee infusions. Six anionic fractions with different physicochemical properties (ethanol solubility and chelating ability) and chemical composition regarding carbohydrate as well as protein nature and content were isolated. Fractions with similar chemical composition were obtained for light-, medium-, and dark-roasted coffee infusions. These melanoidin fractions accounted for 30-33% of the cold-water soluble high molecular weight material, independently of the degree of roast in coffee. The nature and abundance of the different polysaccharides in each fraction were dependent on their ethanol solubility. The 50% ethanol insoluble melanoidin populations contained mostly galactomannan-like carbohydrates, and the fractions obtained with 75% ethanol contained mostly arabinogalactan-like carbohydrates. The melanoidin populations with chelating properties presented significantly lower carbohydrate content and, from these, the 75% ethanol soluble fractions were almost devoid of carbohydrate material. The results obtained suggest that the chelating ability of these coffee melanoidins is modulated by their carbohydrates.     

Changes in the lipid composition of powdered infant formulas during long-term storage

Changes in the lipid composition of two standard infant formulas induced by 4 years of storage were determined. Lipids were thoroughly analyzed using different gas-liquid and liquid-liquid chromatographic techniques. Oleic acid and linoleic acid, which accounted for almost the total monounsaturated and polyunsaturated fatty acids, respectively, showed slight but significant decreases (P < 0.05) during the 4 years of storage (from 41.52 to 39.83% for oleic acid and from 17.35 to 15.99% for linoleic acid). Total trans fatty acid isomers showed low initial level (0.22% of total fatty acids), and such level remained unchanged during the storage period. Nonvolatile oxidation compounds including oxidized, dimeric, and polymeric triglycerides did not significantly increase during the storage period, although a significant loss of tocopherols was found in the surface oil fraction (10-15%). In general, the results obtained indicate that, although small losses of oleic and linolenic acid as well as tocopherols were found, the 4 year storage period did not lead to relevant changes in the lipid fraction of infant formulas.     

Vascular effects, angiotensin I-converting enzyme (ACE)-inhibitory activity, and antihypertensive properties of peptides derived from egg white

In this study, we have identified novel antihypertensive peptides derived from egg-white proteins. The sequences YRGGLEPINF and ESIINF produced an acute blood-pressure-lowering effect in spontaneously hypertensive rats upon a single oral administration. Our results suggest that the antihypertensive action could be attributed to a vascular-relaxing mechanism that would occur in vivo independently of angiotensin I-converting enzyme (ACE) inhibition, because neither these peptides nor their main digestion fragments, except for the dipeptide YR, acted as ACE inhibitors in vitro. The vasodilator and antihypertensive activity of the sequences ESI and NF would explain the blood-pressure-lowering effect of ESIINF. With regard to YRGGLEPINF, in addition to NF, YR appeared as the main fragment responsible for its activity. The dipeptide YR, named kyotorphin and previously identified as an endogenous analgesic neuropeptide in the central nervous system, showed strong vasodilator and antihypertensive properties. The structure-activity features of the vasodilator peptides are discussed.     

Photocatalytic ozonation of winery wastewaters

The combination of UV-A/vis radiation and ozone, in the presence of titanium dioxide, has been investigated as a potential destructive technology for the treatment of winery wastewaters. The contribution of the adsorption stage, single ozonation, photolytic ozonation, and photocatalysis has previously been assessed. Adsorption onto the TiO 2 surface accounts for a 15-20% removal of the initial chemical oxygen demand (COD). The rest of the subsystems attain COD conversion values in the range of 37-43%. The photocatalytic ozonation of the effluent, under the operating conditions investigated, increases the COD depletion to a value close to 80%. The working pH was studied in the range of 3-11, the optimum value being located in the acidic region (pH 3). A saturation-like behavior is experienced when the amount of TiO 2 used is varied in the interval of 0-3 g L(-1). Contrary to the use of ozone alone, the system UV-A/vis/O3/TiO2 leads to the total mineralization of the COD removed. A proposed pseudoempirical model suggested the existence of a synergistic effect when radiation, ozone, and titanium dioxide are combined.     

Effects of preoperative epidural administration of racemic ketamine for analgesia in sheep undergoing surgery

OBJECTIVE: To investigate the effects of preoperative epidural administration of racemic ketamine to provide analgesia in sheep undergoing experimental hind limb orthopedic surgery. ANIMALS: 12 adult sheep (weight range, 51.4 to 67.2 kg). PROCEDURE: Sheep were anesthetized with guaifenesin, thiopental, and isoflurane; after induction of anesthesia, sheep received a lumbosacral epidural injection of ketamine (1 mg/kg; n = 6) or saline (0.9% NaCl) solution (1 mL/7 kg; 6 [control group]). Respiratory and cardiovascular variables were recorded before and at intervals during and for 6 hours after anesthesia. During that 6-hour postoperative period, analgesia was evaluated subjectively with a numeric ranking scale that included assessments of comfort, posture, movement, and response to wound palpation; buprenorphine was administered when a score > 3 (maximum score, 10) was achieved. Rectal temperature, heart and respiratory rates, and lameness were evaluated daily for 2 weeks after surgery. RESULTS: At all evaluations, cardiovascular and respiratory variables were comparable between the 2 groups. Compared with control sheep, time to first administration of rescue analgesic was significantly longer and total dose of buprenorphine administered during the 6- hour postoperative period was significantly decreased for ketamine-treated sheep. During the second week following surgery, ketamine-treated sheep had significantly less lameness than control sheep. CONCLUSIONS AND CLINICAL RELEVANCE: In sheep undergoing hind limb surgery, preoperative epidural administration of ketamine appears to provide analgesia in the immediate postoperative period and has residual analgesic effects, which may contribute to more rapid return of normal function in surgically treated limbs.     

Evaluation of histamine release during constant rate infusion of morphine in dogs

OBJECTIVE: To evaluate histamine release and selected physiologic variables during constant rate infusion (CRI) of morphine in dogs. ANIMALS: Five healthy, conscious, intact female dogs. MATERIAL AND METHODS: Using a Latin square, repeated-measures design, dogs were randomly assigned to three treatment groups to receive a 4-hour CRI of saline (SAL), or a loading dose of morphine at 0.3 mg kg(-1) (LM), or 0.6 mg kg(-1) (HM), followed by an infusion of 0.17 mg kg(-1) hour(-1) (LM) and 0.34 mg kg(-1) hour(-1) (HM) respectively. Dogs received each of the three treatments at intervals of at least 7 days. Plasma histamine concentration, skin flushing, edema and wheals, heart rate and rhythm and non-invasive arterial blood pressure were measured before the loading dose and at 1, 2, 5, 15, 30, 60, 120, 180 and 240 minutes during the CRI, or at the time of occurrence. RESULTS: The loading dose induced the highest histamine release in the HM group being statistically higher than the SAL group. The histamine release obtained in the LM group after the loading dose did not differ from SAL. During the infusion, plasma histamine levels were numerically higher in the LM group. Besides one dog that developed hypotension for 2 minutes after the loading dose in the HM group and one dog that showed occasional ventricular premature contractions during both morphine infusions, cardiovascular variables were similar among the three treatment groups. CONCLUSIONS AND CLINICAL RELEVANCE: Both doses of morphine induced variable histamine release with minimal adverse cardiovascular effects in these conscious, healthy dogs. The plasma histamine levels obtained may be associated with significant hemodynamic changes in patients with limited cardiovascular reserve and sympathetic nervous tone.     

Physicochemical properties of natural phenolics from grapes and olive oil byproducts and their antioxidant activity in frozen horse mackerel fillets

The reducing and chelating capacities and the affinity for the incorporation into the fish muscle of grape procyanidins, hydroxytyrosol, and propyl gallate were studied together with their antioxidant activity in frozen horse mackerel (Trauchurus trauchurus) fillets. Fillets were supplemented with phenolic antioxidants by (a) spraying an aqueous phenolic solution, (b) glazing with an aqueous phenolic solution, and (c) a previous washing of fillets with water plus spraying an aqueous phenolic solution. The effect of washing on the endogenous pro-oxidant/antioxidant balance of the fillets was also determined. All phenolic compounds were effective delaying lipid oxidation in the fish fillets. The order of antioxidant efficiency in spraying and glazing was propyl gallate > hydroxytyrosol > procyanidins, which was similar to the reducing power of these phenolics, but did not show any correlation with their chelating capacity and their affinity to the fish muscle. Washing the fillets with water prior to spraying phenols increased synergistically the antioxidant activity of grape procyanidins and changed the relative antioxidant efficiency to propyl gallate approximately procyanidins > hydroxytyrosol. This synergism may be a result of a better distribution of the procyanidins onto the fillet surface because of the residual water that remained on the fillets surface after washing.     

Selective recovery of tagatose from mixtures with galactose by direct extraction with supercritical CO2 and different cosolvents

A selective fractionation method of carbohydrate mixtures of galactose/tagatose, using supercritical CO(2) and isopropanol as cosolvent, has been evaluated. Optimization was carried out using a central composite face design and considering as factors the extraction pressure (from 100 to 300 bar), the extraction temperature (from 60 to 100 degrees C), and the modifier flow rate (from 0.2 to 0.4 mL/min, which corresponded to a total cosolvent percentage ranging from 4 to 18% vol). The responses evaluated were the amount (milligrams) of tagatose and galactose extracted and their recoveries (percent). The statistical analysis of the results provided mathematical models for each response variable. The corresponding parameters were estimated by multiple linear regression, and high determination coefficients (>0.96) were obtained. The optimum conditions of the extraction process to get the maximum recovery of tagatose (37%) were 300 bar, 60 degrees C, and 0.4 mL/min of cosolvent. The predicted value was 24.37 mg of tagatose, whereas the experimental value was 26.34 mg, which is a 7% error from the predicted value. Cosolvent polarity effects on tagatose extraction from mixtures of galactose/tagatose were also studied using different alcohols and their mixtures with water. Although a remarkable increase of the amount of total carbohydrate extracted with polarity was found, selective extraction of tagatose decreased with increase of polarity of assayed cosolvents. To improve the recovery of extracted tagatose, additional experiments outside the experimental domain were carried out (300 bar, 80 degrees C, and 0.6 mL/min of isopropanol); recoveries >75% of tagatose with purity >90% were obtained.     

Generation of saffron volatiles by thermal carotenoid degradation

Generation of volatiles by thermal treatments has been studied in saffron spice for two reasons: (a) to determine volatile profile changes during simulated aging processes and (b) to study the volatile generation pathway. During the aging process, while the amounts of C10 compounds such as safranal and HTCC increase, the amounts of C9 compounds such as isophorone and 2,6,6-trimethylcyclohexane-1,4-dione decrease. A new compound tentatively identified as 4,5,6,7-tetrahydro-7,7-dimethyl-5-oxo-3H-isobenzofuranone seems to play a very important role in the aging process. The importance of this compound, structurally similar to dihydroactindiolide, was also confirmed when the saffron volatile fraction was analyzed via the degradation of the linear chain of crocetin and crocetin esters and is reported for the first time in this paper. Thermal degradation studies of zeaxanthin, crocetin, and trans and cis crocetin esters isomers allowed us to propose different mechanisms which explain saffron volatile generation depending on the crocetin ester isomer structure.