HPLC/UV determination of organic acids in fruit juices and nectars

A reversed phase HPLC method for separation and determination of organic acids in fruit juices and nectars is presented. The method is based on the reaction of free organic acids with O-(4 nitrobenzyl)-N,N'-diisopropylisourea (PNBDI) in presence of dioxane. Excess of reagent was removed with a strong cation-exchange resin. The p-nitrobenzyl esters were separated on a C₁₈ reversed phase column using gradient elution with water and acetonitrile and UV detection at 265 nm. Benzylmalonic acid was used as internal standard. The determinations were performed in the linear range of 0.05-2 g/l for lactic, acetic and succinic acids, 0.1-12 g/l for tartaric, malic and citric acids. The detection limits were 0.025 g/l, 0.017 g/l, 0.050 g/l, 0.039 g/l, 0.025 g/l and 0.060 g/l, respectively for lactic, acetic, tartaric, malic, succinic and citric acids. Validation of the method was carried out by the standard additions method, the recoveries ranged from 91.4 to 103.0%. The precision of the method was also evaluated and reported a CV% as less than 3.1%. Organic acid profiles of citrus fruit, pineapple and apple natural juices (home-made), commercial juices and nectars were established.     

Fluorescent Nanodiamonds Embedded in Biocompatible Translucent Shells

High pressure high temperature (HPHT) nanodiamonds (NDs) represent extremely promising materials for construction of fluorescent nanoprobes and nanosensors. However, some properties of bare NDs limit their direct use in these applications: they precipitate in biological solutions, only a limited set of bio‐orthogonal conjugation techniques is available and the accessible material is greatly polydisperse in shape. In this work, we encapsulate bright 30‐nm fluorescent nanodiamonds (FNDs) in 10–20‐nm thick translucent (i.e., not altering FND fluorescence) silica shells, yielding monodisperse near‐spherical particles of mean diameter 66 nm. High yield modification of the shells with PEG chains stabilizes the particles in ionic solutions, making them applicable in biological environments. We further modify the opposite ends of PEG chains with fluorescent dyes or vectoring peptide using click chemistry. High conversion of this bio‐orthogonal coupling yielded circa 2000 dye or peptide molecules on a single FND. We demonstrate the superior properties of these particles by in vitro interaction with human prostate cancer cells: while bare nanodiamonds strongly aggregate in the buffer and adsorb onto the cell membrane, the shell encapsulated NDs do not adsorb nonspecifically and they penetrate inside the cells.     

Serum levels of polybrominated diphenyl ethers (PBDEs) in foam recyclers and carpet installers working in the United States

Increased exposure to the flame retardants known as polybrominated diphenyl ethers (PBDEs) may be expected to occur during the recycling of polyurethane foam containing these chemicals. To date, no studies in the United States have investigated occupational exposure to these flame retardants during recycling processes. The objective of the present study was to determine if individuals working in foam recycling facilities, and/or carpet installers who may install carpet padding manufactured from recycled foam, possess significantly higher PBDE serum levels relative to that of the general U.S. population. As a control group, serum was collected from four spouses and one clerical worker. In addition, levels in workers were also compared to the recently published national health and nutrition examination survey (NHANES) data set on PBDEs in the general U.S. population. Serum samples were collected in duplicate and analyzed by two different laboratories as quality control. Total PBDE levels were found to be significantly higher (p < 0.05) in the individuals recycling foam and installing carpet (n = 15) relative to the control group (n = 5). Median sigmaPBDE levels in the foam recyclers, carpet layers, and control group were 160, 178, and 19 ng/g lipid, respectively. In contrast, concentrations of a polybrominated biphenyl (BB-153) and a polychlorinated biphenyl (CB-153) were equivalent among all groups tested. The PBDE congeners BDE-47, 99, 100, and 153 contributed 90% of the sigmaPBDE concentration in serum and no differences in congener patterns were apparent among the different groups. Relative to concentrations measured in the NHANES, foam recyclers and carpet layers have body burdens that are an order of magnitude higher. These data suggest individuals recycling foam-containing products, and/ or using products manufactured from recycled foam (i.e., carpet padding), have higher body burdens of PBDEs, and thus may be at higher risk from adverse health effects associated with brominated flame retardant exposure.     

Transport of testosterone and estrogen from dairy-farm waste lagoons to groundwater

Although concentrated animal feeding operations constantly generate physiologically active steroidal hormones, little is known of their environmental fate. Estrogen and testosterone concentrations in groundwater and their distribution in sediments below a dairy-farm wastewater lagoon were therefore determined and compared to a reference site located upgradient of the farm. Forward simulations of flow as well as estrogen and testosterone transport were conducted based on data from the sediment profile obtained during drilling of a monitoring well belowthe dairy-farm waste lagoon. Testosterone and estrogen were detected in sediments to depths of 45 and 32 m, respectively. Groundwater samples were directly impacted by the dairy farm, as evidenced by elevated concentrations of nitrate, chloride, testosterone, and estrogen as compared to the reference site. Modeling potential transport of hormones in the vadose zone via advection, dispersion, and sorption could not explain the depths at which estrogen and testosterone were found, suggesting that other transport mechanisms influence hormone transport under field conditions. These mechanisms may involve interactions between hormones and manure as well as preferential flow paths, leading to enhanced transport rates. These types of interactions should be further investigated to understand the processes regulating hormone transport in the subsurface environment and parametrized to forecast long-term fate and transport of steroidal hormones.     

Anaerobic oxidation of methane: mechanisms, bioenergetics, and the ecology of associated microorganisms

Microbially mediated anaerobic oxidation of methane (AOM) moderates the input of methane, an important greenhouse gas, to the atmosphere by consuming methane produced in various marine, terrestrial, and subsurface environments. AOM coupled to sulfate reduction has been most extensively studied because of the abundance of sulfate in marine systems, but electron acceptors otherthan sulfate are more energetically favorable. Phylogenetic trees based on 16S rRNA gene clone libraries derived from microbial communities where AOM occurs show evidence of diverse, methanotrophic archaea (ANME) closely associated with sulfate-reducing bacteria, but these organisms have not yet been isolated as pure cultures. Several biochemical pathways for AOM have been proposed, including reverse methanogenesis, acetogenesis, and methylogenesis, and both culture-dependent and independent techniques have provided some clues to howthese communities function. Still, questions remain regarding the diversity, physiology, and metabolic restrictions of AOM-related organisms.     

Effect of the stage of growth,wilting and inoculation in field pea (Pisum sativum L.) silages. II. Nitrogen fractions and amino acid compositions of herbage and silage

The aim of the study was to investigate the effects of stage of maturity, wilting and inoculant application on proteolysis in field pea herbage and silage in northern Italy. Semi‐leafless field peas were harvested at four progressive morphological stages (end of flowering, I; beginning of pod filling, II; advanced pod filling, III; beginning of ripening, IV). For each stage of growth, the herbage was field wilted to a dry matter (DM) content around 330 g kg^?1. The unwilted and wilted herbages were ensiled with (I) and without (C) a lactic acid bacteria (LAB) inoculant. The stage of growth significantly affected all the nitrogen fraction concentrations both in herbage and in silage. Extensive proteolysis took place in silages made at early morphological stages and characterised by a high crude protein content (around 240 g kg^?1 DM), as shown by the non‐protein nitrogen (NPN) value (around 700 g kg^?1 total N or higher). Neither inoculum nor wilting helped to reduce the protein degradation in these silages. The level of proteolysis was reduced in silages made from the pod filling stage onwards where most of the protein was localised in the seed and a better fermentation pattern was observed. The amino acid (AA) composition of silages made at stage IV was close to that of fresh herbage, with minimal losses of nutritionally essential amino acids for ruminants. Copyright © 2006 Society of Chemical Industry     

Removal of pharmaceuticals in sewage treatment plants in Italy

A listing of "priority pharmaceuticals" for human use in Italy resulted in the selection of 26 pharmaceuticals, belonging to 11 therapeutic classes. They were analyzed by liquid chromatography-tandem mass spectrometry, their occurrence was assessed in six sewage treatment plants (STPs), and the loads and the removal rates (RR) were studied. Total loads ranged from 1.5 to 4.5 g/day/1000 inhabitants in influents and 1.0 and 3.0 g/day/1000 inhabitants in effluents. Total RR in STPs were mostly lower than 40%. Pharmaceuticals could be divided into three groups according to their behavior in STPs: one group with RR higher in summer than in winter, one group with RR similar in summer and winter, and a last group not removed. Last, we studied the distribution and fate of residual pharmaceuticals in the surface waters receiving the effluents of the STPs and identified degradation and sorption as the major factors affecting attenuation. Ciprofloxacin, ofloxacin, sulfamethoxazole (antibiotics), atenolol (cardiovascular drug), ibuprofen (antiinflammatory), furosemide, hydrochlorothiazide (diuretics), ranitidine (gastrointestinal drug), and bezafibrate (lipid regulator) were the most abundant residual drugs, thus those of environmental concern.     

Experimental validation of a geographical information systems-based procedure for predicting pesticide exposure in surface water

A GIS-based procedure for predicting pesticide exposure in surface waters has been applied on a pilot river basin characterized by intensive agricultural activity. The predictive approach has been validated through experimental monitoring, performed by collecting manual and automatic water samples during the productive season. Five active ingredients (terbuthylazine, metolachlor, alachlor, linuron, fenitrothion) were selected for analysis to validate the predictive approach. Comparison between predicted and experimental values showed good agreement for terbuthylazine and metolachlor (used in large volumes within the basin), demonstrating the reliability of the approach. However, some anomalous results were obtained for some of the other chemicals, which serve to highlight the difficulties in getting reliable input data, in particular on application patterns (rate and time). Furthermore, the value of mapping pesticide exposure on the medium-large scale is described, and the limitations of the reported predictive approach are discussed.     

Factors influencing the national distribution of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in British soils

The polycyclic aromatic hydrocarbons (PAHs) naphthalene, acenaphthylene, acenaphthene, fluorene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, ideno[1,2,3,-cd]-pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene and the polychlorinated biphenyls (PCBs) 8, 18, 28, 29, 31, 52, 77, 101, 105, 114, 118, 123, 126, 128, 138, 141, 149, 153, 156, 157, 163, 169, 170, 171, 180, 183, 187, 189, 194, 199, 201, 206, and 209 were measured in -200 rural soils across Great Britain (GB). Dominance of soil PAH profiles by heavier compounds (4-6 rings) provided initial evidence for the importance of source in governing soil PAH concentrations. No relationship was found between soil organic matter (SOM) and sum concentration of total and "heavy" PAHs, although there was a weak positive relationship with lighter compounds. A spatial statistical technique showed that highest soil PAH concentrations were usually found close to industrial/urban centers where presumably source intensity is highest. PCBs clustered into seven groups, five of which contained a single "dioxin like" PCB, one contained lighter congeners (2-4 chlorines), and one contained heavy congeners (5-10 chlorines). Linear regressions with SOM explained up to 24.3% of variation for the sum concentration of penta- to deca- congeners, but <1% for the lighter congener groups. No significant relationships were found with latitude. Spatial statistical techniques showed clusters of high soil PCB concentrations predominantly in west and south east GB, either associated with urbanized areas or on the West coast.