Ultraviolet-absorbing compounds in milk are related to forage polyphenols.

The aim of this work was to characterize UV-absorbing compounds (UAC) in milk in relation to diet. In winter, 4 groups of cows each received a different diet: concentrate rich containing 35% cocksfoot hay (CCH), maize silage (MS), rye grass silage (RS), or rye grass hay (RH). In summer, 2 additional diets were given: mountain grassland hay (GH) and mountain grassland pasture (GP). Polyphenols were analyzed by HPLC and Folin reaction on forages and UAC were extracted from milks and analyzed by HPLC. In forages, the number of polyphenols was lowest in MS (57) and greatest in GP (85). Twenty-four peaks were identified, accounting for 28 to 47% peak area at 280 nm. Caffeoyl compounds and flavonoid glycosides were mainly found in RH, GH, and GP. Hydrolyzed compounds such as hydroxycinnamic acids and aglycones were found in MS and RS. Estimated amounts of polyphenols were lowest for MS (3.7 g/kg), roughly similar for CH, RS, and RH (about 15 g/kg), and greatest for GH and GP (21.6 and 35.3 g/kg, respectively). About 230 different peaks were separated in milks. Milks from RH and GP contained the lowest (87) and the greatest (127) numbers of peaks, respectively. Only 10 peaks were identified, accounting for 21 to 54% of the total spectra area. In addition to the major compound hippuric acid, phenylacetic acid, benzoic acid, 4-hydroxybenzoic acid benzaldehyde, catechol, and small amounts of ferulic acid were found in varying amounts depending on the diet. Flavonoids such as quercetin, luteolin, and apigenin were also present. Hippuric acid was clearly related to the presence of caffeoylquinic compounds in forages. Other identified UAC may originate essentially from forage simple polyphenols or from cell wall aromatics. Some of the several unknown compounds may also originate from the transformation of other nutrients. Estimated amounts of UAC were widely variable within each animal group. They were surprisingly high in CCH and roughly similar in all milks from preserved forages (about 3.6 mg/L), with generally greater values for GH milks, whereas the greatest amount was found in GP milks (13.3 mg/L). Hierarchical clustering clearly discriminated the 6 diets, showing that there were major differences in GP milks. Some UAC were specific to one or a group of diets. Ultraviolet-absorbing compounds are therefore a potential tool to distinguish between milks according to diet. In addition, they may have a bioactive effect on milk component conservation or on human health.

One-dimensional modelling of the interactions between heavy rainfall-runoff in an urban area and flooding flows from sewer networks and rivers.

Many investigations have been carried out in order to develop models which allow the linking of complex physical processes involved in urban flooding. The modelling of the interactions between overland flows on streets and flooding flows from rivers and sewer networks is one of the main objectives of recent and current research programs in hydraulics and urban hydrology. This paper outlines the original one-dimensional linking of heavy rainfall-runoff in urban areas and flooding flows from rivers and sewer networks under the RIVES project framework (Estimation of Scenario and Risks of Urban Floods). The first part of the paper highlights the capacity of Canoe software to simulate the street flows. In the second part, we show the original method of connection which enables the modelling of interactions between processes in urban flooding. Comparisons between simulated results and the results of Despotovic et al. or Gomez & Mur show a good agreement for the calibrated one-dimensional connection model. The connection operates likes a manhole with the orifice/weir coefficients used as calibration parameters. The influence of flooding flows from river was taken into account as a variable water depth boundary condition.

PCB, PCDD/F and PBDE levels and profiles in crustaceans from the coastal waters of Brittany and Normandy (France).

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analysed in the muscle of various edible marine crustaceans (spider crab, edible crab, velvet swimming crab and Norway lobster) from the Brittany and Normandy coasts (France). The highest concentrations were measured in species collected from Antifer (Seine Bay). PCB and PBDE patterns in crustacean muscles were similar and independent of the geographical area with the predominance of the high chlorinated PCBs (CB153, 138, 118 and 180), and of a few PBDE congeners (BDE47, BDE99, BDE100 and BDE28). Oppositely, dioxin contamination differed with site. The major component in crustaceans from the Seine Bay was 2378-TCDF, whereas specimens from cleaner areas had higher relative concentrations of OCDD. Finally, the comparison of the spider crab contaminant profiles to those measured in mussel and sea bass highlighted two different trends: decapod crustaceans possess relatively strong capacity to metabolise PCBs and PBDEs; however these species might be used as bioindicators for dioxin pollution monitoring in the marine coastal environment.

Broad spectrum analysis of 109 priority compounds listed in the 76/464/CEE Council Directive using solid-phase extraction and GC/EI/MS

A single multiresidue method was developed to determine 109 priority organic compounds included in the 76/464/EEC Council Directive on Pollution of the European Union. Such Directive includes 132 priority pollutants with a broad spectrum of polarities to be analyzed in drinking and surface waters, with the aim to protect water quality. From this list, the compounds analyzed included benzidines, chloroanilines, chloronitrobenzenes, chloronitrotoluenes, chlorophenols, chloronitrotoluidines, PAHs, PCBs, pesticides, phenylurea, and triazine herbicides. The method was developed in four steps. First, automated off-line solid-phase extraction using polymeric sorbent Oasis 60 mg cartridges was optimized to trap 109 compounds. Second, gas chromatography coupled to mass spectrometry with electron impact ionization (GC/EI/MS) was used in selected ion monitoring (SIM) mode for tentative identification of target analytes. Third, GC/EI/MS under full scan conditions was used for spectrum identification and analyte confirmation. Last, quantification was performed from SIM chromatogram using surrogates and internal standard. This method offered excellent sensitivity and selectivity, and the preconcentration of 200 mL permitted the achievement of limits of detection at the low nanogram/liter level and recoveries between 70 and 120%. Such methodology was applied to determine 109 organic compounds in French surface waters, and several pollutants were detected at levels from ppt to ppb. This multiresidue method developed was highly reproducible and robust and permitted a high sample throughput.

Urinary testosterone (T) to epitestosterone (E) ratios by GC/MS. I. Initial comparison of uncorrected T/E in six international laboratories.

Six laboratories in six countries collaborated to investigate the analytical method for estimating the testosterone to epitestosterone ratio (T/E) in urine by gas chromatography/mass spectrometry in the context of detecting the application of T as a doping agent in sport. The protocol specified many but not all details of reagents and instrument conditions. The design included the distribution and analysis of four urines with different T/E values, three replicates per value, and one standard. The ranges of mean T/E values for the four urines estimated by peak area (PA) were 0.32-0.42, 0.72-0.94, 0.91-1.14 and 3.19-5.48. The analyses of variance for these data and for the peak height (PH) data were significant for the laboratory factor (p < 0.0001). In addition there was a significant interaction between the urine factor and the laboratory factor which indicates the complexity of the analysis. T/E calculated using PA was not significantly different from that using PH. For within-laboratory precision all values for PH and PA were < 8.3%, and for between-laboratory precision all values were < 11.7% except for one (20.1%). The data represent a baseline for future experiments designed to elucidate the sources of within-and between-laboratory variance, and to harmonize estimates of T/E.

Efficient solid-phase extraction procedures for trace enrichment of priority phenols from industrial effluents with high total organic carbon content.

Polymeric solid-phase extraction (SPE) cartridges and Speedisks were used to extract 17 phenols from HPLC-grade water, tap water, river water and industrial effluents. With SPE cartridges, recoveries between 60 and 120% were obtained for waters with a total organic carbon (TOC) content below 20 mg C/l. However, when extracting industrial effluent waters with higher TOC values (75 mg C/l), only the polar phenols were recovered from the water fraction. Nonpolar compounds (di-, tri- and tetrachlorophenols) remained attached to the particulate matter and were recovered from the 0.45-microm filter membrane disks by Soxhlet extraction. Speedisks offered a high efficiency and permitted one to extract phenols without a prior filtration step. Acceptable recoveries were obtained when processing heavily charged industrial effluents with a TOC of 505 mg C/l. Liquid chromatography with electrochemical detection was used for the routine determination of 17 priority phenols.

[Not Available]. / Microdosage du carbone dans les composés organiques par combustion quasi-instantanée et titrage coulometrique automatique du dioxyde de carbone.

A rapid simple method is described for the determination of carbon in organic compounds. The technique is based on a flash-combustion of the weighed sample (1-3 mg) in a hot empty combustion chamber at 950-1050 degrees and swept by a stream of oxygen at a rate of 80-100 ml min . Together with this flash and dynamic combustion in oxygen, a cupric oxide filling at 850 degrees is necessary. Halogens and sulphur oxidation products are retained by means of a silvered alumina filling at 750-800 degrees . Water and acidic oxides of nitrogen are absorbed at room temperature by means of magnesium perchlorate and manganese dioxide respectively. Carbon dioxide is absorbed in the cathodic compartment of an automatic coulometer and generates H(+) ions which are neutralized by OH(-) obtained by electrolysis. This method makes possible the determination of carbon in compounds containing halogens (including fluorine), phosphorus and metals. However, some metal compounds with polynuclear rings in their molecules give low results and require the addition of an oxidant to the sample in the boat for complete combustion. Vanadium pentoxide seems to be the best oxidant in the present working conditions. Solid samples are weighed and analysed in platinum or porcelain boats; liquid samples are weighed in Pyrex capillaries which are laid in platinum boats and covered with a small piece of platinum gauze. When normal liquid samples are analysed, one tip of the capillary is broken before its introduction into the combustion tube but in the case of volatile liquid samples the sealed capillary is introduced into the combustion chamber, where it explodes. The precision obtained is better than that of the classical methods.

[Not Available]. / Sur le microdosage du soufre dans les composes organiwues, en presence d'halogenes, par combustion et titrage coulometrique automatique du dioxyde de soufre.

The method for the determination of sulphur in organic compounds (E. Debal and R. Levy, Bull. Soc. Chim. France, 1968, 426; 1971, 3374) by combustion in oxygen at 1310-1320 degrees C and coulometric titration of the sulphur dioxide formed is improved. Silver and 8-hydroxy-quinoline are successfully used to remove halogens (fluorine included) from combustion products. A new glass cell for the acidimetric titration of sulphur dioxide with an automatic coulometer is devised, with a water-jacket for its cathodic and reference compartments. The constant-temperature water-flow makes this determination easy to carry out with no drawbacks, even in varying ambient temperature.

[Not Available]. / Dosage microanalytique du deuterium dans les composes organiques.

A simple method is described for the microdetermination of deuterium in organic compounds. It involves a flash combustion of the weighed sample in a hot empty chamber at 950-1050 degrees and swept by oxygen at 60 ml/min. Together with this combustion in the gaseous phase, an oxidation of the primary combustion gases on cupric oxide at 850 degrees is necessary. Oxidation products containing halogens and sulphur are retained on silvered alumina at 750-800 degrees . Combustion water containing deuterium oxide and hydroxide is frozen out from the combustion gases in a special trap with two five-way stop-cocks which make possible the simultaneous flow of oxygen and hydrogen; the latter is used as a carrier-gas in the apparatus from the trap downwards. The frozen water is then vaporized by heating in a hydrogen flow of 30 ml/min and reduced on magnesium at 600 degrees . Deuterium is obtained as deuterium hydride in hydrogen; it is measured versus pure hydrogen, with a thermal conductivity detector. A Determination within a series can be completed in 15 min. The precision of the results is that obtained in classical organic microanalysts.

A survey of PCDD and PCDF in French long-life half-skimmed drinking milk.

A national survey was carried out in order to assess the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in long-life half-skimmed drinking milk produced and consumed in France. 151 Samples were collected from 33 dairy establishments selected for their production amounts following a random sampling scheme. 148 of the 151 results were finally used for statistical assessment. The mean concentration of 2,3,7,8-TCDD toxicity equivalent found is 0.65 pg/g of milk fat. This result is far below the threshold recommended by the European Union.

Dioxins in adipose tissue of non-occupationally exposed persons in France: correlation with individual food exposure.

We evaluated individual adipose tissue (subcutaneous lipomas) dioxin contamination in non-occupationally exposed persons living in France (adult patients undergoing a surgical ablation of benign lipomas), in relation to the corresponding individually evaluated mean daily dietary dioxin intake (DDDI). The diet survey (questionnaire) included information on consumption of meat, fish, milk and dairy products, from which the individual DDDI was calculated. Sixteen subjects participated in this study. DDDI ranged between 1.06 and 3.31 pg I-TEQ/kg body weight, bw (mean value: 2.05+/-0.72). Adipose tissue polychlorinated dibenzo-p-dioxins (PCDD)/polychlorinated dibenzofurans (PCDF) levels ranged between 18.5 and 76.9 pg I-TEQ/g lipids (mean value: 35.6+/-14.8). No relation was found between the DDDI and adipose tissue PCDD/PCDF concentrations. The mean DDDI in France does not fundamentally differ from those found in other industrialised countries, is within the range of 1-4 pg I-TEQ/kg/day recently suggested by WHO-ECEH/ICPS for the tolerable daily intake of dioxins. Adipose tissue PCDD/PCDFs levels are similar to levels in other European countries and USA without relation to sex or age, and can be considered representative European background concentrations. Globalisation of alimentary production leads to a similar food exposure in Western European countries, in spite of dioxins accidental selective contaminations that are epiphenomenon and thus do not have any impact in human dioxin background levels.

Major dicaffeoylquinic acids from Artemisia vulgaris.

The two major caffeoylquinic acids, 3,5-di-O-caffeoylquinic acid and 1,5-di-O-caffeoylquinic acid, were new-isolated from the flowering tops of Artemisia vulgaris (yield 2.0% and 0.3% on dry weight, respectively) and characterized by spectroscopic analysis.

The aromatic and polyphenolic composition of Roman camomile tea.

The qualitative and quantitative composition of the main aromatic and polyphenolic constituents of infusion from Chamaemelum nobile flowers was examined. The camomile tea contained a large amount of polyphenolic compounds (340 mg/l), the most important being chamaemeloside (155 mg/l). Only traces of essential oil were recovered in tea (7 mg/l).

Luteolin 3'-glucuronide, the major flavonoid from Melissa officinalis subsp. officinalis.

Luteolin 3'-O-beta-D-glucuronide (1) was isolated from the leaves of Melissa officinalis subsp. officinalis and characterized by spectroscopic analysis.

Quercetin 3-arabinopyranoside, a major flavonoid compound from Alchemilla xanthochlora.

Quercetin 3-O-alpha-L-arabinopyranoside (1) was isolated from the aerial parts of Alchemilla xanthochlora and characterized by spectroscopic analysis.

[Quality of blood salvaged in orthopedic surgery by washing swabs]. / Qualité du sang récupéré en chirurgie orthopédique par le lavage des compresses.

OBJECTIVE: To establish the feasibility and safety of recuperating blood absorbed by swabs used during orthopaedic surgery. STUDY DESIGN: Open, prospective study. PATIENTS: Included were children undergoing potentially haemorrhagic orthopaedic surgery for whom intraoperative blood salvage seemed possible. Excluded were those with contraindications for this procedure such as septic surgery and cancer surgery. METHOD: Intraoperative swabs used within the surgical field were collected by a surgical assistant, also in charge of weighing and washing them. The liquid was collected by the aspiration system of a recuperation-washing machine (RWM). The salvaged red blood cells were collected and retransfused at the end of surgery. Several samples of the washing liquid of the swabs and salvaged blood were taken during the procedure. The correlation between the quantity of blood shed and salvaged was calculated. The biological and clinical tolerance of the transfusion was assessed. RESULTS: Twelve patients undergoing surgery for scoliosis have been included. An average of 278 mL of blood were salvaged. In the washed cell concentrates the haematocrit was 54% and the free haemoglobin concentration was 3.84 g.L-1. All the bacteriological tests were negative over the first 24 hours. CONCLUSION: Provided that a strict operatory protocol is followed, this study demonstrates the possibility of recuperating blood from swabs used during major orthopaedic surgery.

[Polyphenolic composition of the leaf of bilberry]. / Composition polyphénolique de la feuille de myrtille.

Dried leaves of 14 harvested batches and one batch from commercial origine of Vaccinium myrtillus L present a similar polyphenolic pattern. The mean levels of the harvested batches and the levels of the commercial batch were respectively: total polyphenol compounds 12.98 and 10.62%, tannins 7.84 and 7.43%, total flavonoid compounds 2.98 and 2.20% (spectrophotometry), 1.41 and 1.16% (HPLC), quercetin 3-glucuronide 1.02 and 0.83%, hyperoside 0.22 and 0.16%, chlorogenic acid 3.66 and 1.58%. The levels were higher in young leaves and lower in old leaves. A specific chromatographic profile of the flavonoid compounds and a determination method of the tannin or the total polyphenol content were proposed in a standardization purpose.

[Standardization of the birch leaf]. / Standardisation de la feuille de bouleau.

Dried leaves of Betula pendula Roth (14 batches) and B. pubescens Ehrh. (3 batches) present a similar flavonoid pattern. The mean levels of the principal flavonoid compounds were respectively: total flavonoids 3.29 and 2.77%, hyperoside 0.80 and 0.77%, avicularin (two forms) 0.57 and 0.26%, galactosyl-3 myricetol 0.37 and 0.18%, glucuronyl-3 quercetol 0.25 and 0.36%, quercitrin 0.14 and 0.12%. The flavonoid levels were higher in young leaves and lower in old leaves of B. pendula. 14 batches of commercial origin were also examined for a comparative study. Pharmacopoeial specifications are proposed for a revision of the monograph "Betulae folium".

[Standardization of the aerial parts of Alchemilla]. / Standardisation des parties aériennes d'alchémille.

Dried aerial parts of Alchemilla xanthochlora Rothm. (16 batches), A. glabra Neygenf. (1 batch), A. coriacea Buser (2 batches) and A. filicaulis Buser (3 batches) present a similar flavonoid and tanin pattern. In the case of A. xanthochlora, the mean levels of the principal compounds were: total flavonoids 2.22%, glucuronyl-3 quercetol 1.18%, tanins 16.0% and ellagic acid 0.36%. The flavonoid levels were higher before flowering and the tanin levels higher during flowering. Four commercial batches were examined for a comparative study. Pharmacopoeial specifications were proposed for a revision of the monograph "Alchemillae herba".

[Standardization of hazel leaf]. / Standardisation de la feuille de noisetier.

Dried leaves of 9 harvested batches and 5 batches of commercial origin from Corylus avellana L. were examined. The levels of principal polyphenolic compounds averaged respectively: total flavonoids 2.58 and 2.58%, myricitrin 1.09 and 1.35%, quercitrin 0.30 and 0.40%, tannins 5.2 and 6.5%. Specifications were discussed for a French Pharmacopoeial monography.