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A study of the pigment composition in the water column particulates and bottom sediment column of an anoxic lake, Lake Ciso (Catalonia, Spain), has been carried out. The depth-dependencies of the carotenoid and chlorophyll distributions in the water column during stratification and holomixis, as well as during the diurnal cycles, have been determined. In the sediment, the composition of the pigments has been studied over the top 25 cm. The analyses were carried out by high performance liquid chromatography (HPLC) and HPLC coupled to mass spectrometry. The distributions of carotenoids, bacteriochlorophylls and chlorophylls in the water particulates closely follow the population dynamics of the photosynthetic organisms during stratification and holomixis. Among these, only chlorophyll a transformation products are found in the water column, namely phaeophytin a , pyrophaeophytin a and pyrophaeophorbide a . These derivatives also occur in the sediment, where they are found together with bacteriophaeophytin a and pyrobacteriophaeophytin a . This compartment-dependent occurrence corresponds to a higher degree of preservation of the bacterial vs algal pigments. The former occur in the anoxic hypolimnion or mixed water column during holomixis, and the latter in the oxic epilimnion. The presence of these compounds and the very low abundance of phaeophorbide a and absence of bacteriophaeophorbide a point to a transformation pathway where, in the absence of zooplankton grazing or high abundances of the enzyme chlorophyllase, the loss of the phytyl chain occurs predominantly after loss of the C-13 2 carbomethoxyl group. Okenone, alloxanthin, α-carotene and zeaxanthin/lutein are the major water column carotenoids. Their relative abundances contrast with their distribution in the sediments where okenone is the predominant compound and zeaxanthin/lutein are below detection limit. This effect may be in part a consequence of a more uniform okenone concentration in the water particulates over the year, leading to a higher annual sedimentation flux. Again, it may also be influenced by the higher degree of preservation of the bacterial vs algal carotenoids. A similar situation is observed for the relative abundances of chlorophyll a and bacteriochlorophyll a in water particulates and sediments.

The distributions of carotenoids, chlorophylls, and their degradation products have been studied in two microbial mat systems developed in the calcite and calcite/gypsum evaporite domains of a solar saltern system. Phormidium valderianum and Microcoleus chthonoplastes are the dominant cyanobacterial species, respectively, and large amounts of Chloroflexus-like bacteria occur in the carbonate/gypsum mat. In both systems, the major pigments are chlorophyll a, zeaxanthin, β-carotene and myxoxanthophyll, which originate from these mat-building cyanobacteria. This common feature contrasts with differences in other pigments that are specific for each mat community. Thus, chlorophyll c and fucoxanthin, reflecting diatom inputs, are only found in the calcite mat, whereas the calcite/gypsum mat contains high concentrations of bacteriochlorophylls c produced by the multicellular green filamentous bacteria. In both cases, the depth concentration profiles (0–30 and 0–40 mm) show a relatively good preservation of the cyanobacterial carotenoids, zeaxanthin, β-carotene, myxoxanthophyll, and echinenone. This contrasts with the extensive biodegradation of cyanobacterial remains observed microscopically. Fucoxanthin in the calcite mat is also transformed at a faster rate than the cyanobacterial carotenoids. Chlorophyll a, the major pigment in both mats, exhibits different transformation pathways. In the calcite/gypsum mat, it is transformed via C-132 carbomethoxy defunctionalization prior to loss of the phytyl chain, leading to the formation of pyrophaeophytin a and, subsequently, pyrophaeophorbide a. On the other hand, the occurrence of the enzyme chlorophyllase, attributed to diatoms in the calcite mat, gives rise to extensive phytyl hydrolysis, with the formation of chlorophyllide a, pyrophaeophorbide a and, in minor proportion, phaeophorbide a. Studies of the sources of the photosynthetic pigments and of their transformation pathways in such simplified ecosystems provide a basis for the understanding of the distribution patterns of these compounds in more complex aquatic environments.

The tetrapyrroles in a highly immature Late Pliocene lacustrine sediment (Willershausen, Germany) show a simple distribution of both chlorin and porphyrin components as the free bases. The major components are C[sub 32] desoxophylloerythroaetioporphyrin (DPEP), a C[sub 33] bicycloalkano porphyrin, the chlorine analogue of the latter, and desoxophylloerythrin and its chlorin counterpart. The structure of the novel bicycloalkano chlorin was determined using a combination of two-dimensional phase-sensitive COSY NMR and nOe studies. Measurements of [delta][sup 13]C and other data indicate that DPEP and the bicycloalkano porphyrin were derived from the chlorophyll(s) of photosynthetic organisms utilizing a common source of CO[sub 2], probably diatoms. The occurrence of DPEP and other minor alkyl porphyrins indicates that the chlorophyll defunctionalization pathway leading to these components can occur at low temperature and was probably biologically mediated, as was the condensation reaction leading to the fused ring components.

Isotope ratio monitoring GC-MS (irm-GCMS) analyses of individual hydrocarbons isolated from the surface sediment of a small eutrophic lake (Priest Pot, U.K.) and a phytoplankton tow sample from the upper water column have been undertaken in order to assign sources of sedimentary lipids. The δ 13C values for the sedimentary n-alkanes showed no clear distinction between lower molecular weight components (C17–C19) of presumed algal origin and higher members (C23–C33) of presumed higher plant origin, thus indicating a limitation to the use of compound specific isotope analysis in the freshwater system studied. In contrast, the δ 13C values of sedimentary hopenes were markedly depleted (by over 20%) compared with those in the phytoplankton sample from the upper water column. Hop-22(29)-ene in the surficial sediment had a δ 13C value of −55.2%, which contrasts witht he value of the phytoplankton component (−32.7%), attributed to cyanobacteria. These values indicate that a highly 13C-depleted source provides a major contribution to the sedimentary component. It is proposed that the sedimentary hopenes originate in part from methanotrophic bacteria, demonstrating the presence of a bacterial methane cycle in this environment.

To obtain further information about the origin of sedimentary tetrapyrroles such as the alkyl porphyrin desoxophylloerythroaetioporphyrin, the defunctionalization of chlorophyll a has been studied in batch cultures of the marine diatom Phaeodactylum tricornutum, which were induced to undergo senescence by the exclusion of light. Identification of pigments by combined reversed phase high-performance liquid chromatography-mass spectrometry (LC-MS), with on-line photo-diode array detection, revealed conversion of chlorophyll a to phaeophytin a and pyrophaeophorbide a. The results demonstrate that certain chlorophyll a transformation products which occur commonly in aquatic sediments can be formed in part by the action of algal enzymes in the water column. The study provides the first unambiguous identification of pyrophaeophorbide a during senescence of a non-mutant alga.

The abundances and distribution patterns of mono-, di- and trimethylated 2-methyl-2-(4,8,12-trimethyltridecyl) chromans (MTTCs) and long-chain alkylbenzenes in extracts of marl (66 samples), anhydrite (15) and halite (1) strata of the Salt IV Formation of the Oligocene Mulhouse Basin are reported. The distributions of the methylated MTTCs indicate salinity changes of the upper part of a density stratified water column of the basin. These variations are explained by a tectonically or climatically induced change in the supply of water of relative lower salinity to form a layer overlying the deeper water brine. Hence, it is suggested that mesohaline (3.5–15%) conditions in the surface waters were established as a result of periodic incursions of marine water and subsequent evaporation. Conversely, during periods when the surface water was derived mainly from fresh water from the hinterland, lower average salinity in the surface layer resulted. The distributions of long-chain alkylbenzenes also appear to record these changes.

The lower Oligocene evaporite sequence of the Mulhouse Basin (France) contains organic matter-rich marl deposits. These marls display an overall cyclic variation of sedimentation rate, organic carbon content, hydrogen index and selected molecular parameters over a 30 m thick stratigraphic interval. The integration of all sedimentological and geochemical parameters has allowed the reconstruction and characterization of the paleoenvironment of deposition. The marls were deposited in a perennial lake that was at times connected to the sea. Two organic facies end members could be assigned to a lake stage with a marine connection and a lake stage that received dominantly continental water input. The overall stratigraphic variation in the organic matter content is interpreted to reflect the adaptation of the Oligocene flora to the changing paleoclimate and environmental conditions.

Principal components analysis (PCA) has been used to investigate changes in concentrations of the components of the hydrocarbon fractions extracted from 71 marl samples, selected to cover two total organic carbon (TOC) maxima in the lower part of the Salt IV formation, a Lower Oligocene evaporitic sequence from the Mulhouse Basin, France. The analysis indicates that the fractions can be ascribed as lying between two end member distributions. The changes in these distributions are gradual, suggesting that they resulted from fairly gradual changes in the depositional palaeoenvironment. These changes are related to increased algal productivity associated with the evolution of a restricted lacustrine environment through to one with a greater marine influence. Systematic variations in the concentrations of selected components relative to the TOC profile point to a repeated sequential evolution in the biological assemblage during deposition of the sequence.

— This paper reports a new method for monitoring the allomerization reactions of chlorophyll a and pheo-phytin a. Complex mixtures are generated from illuminating pure compounds and monitored using both diode array high-performance liquid chromatography (DAD-HPLC) and liquid chromatography-mass spectrometry (LC-MS). LC-MS allows molecular weight and fragment ion analysis of significant HPLC peaks. Five products of the degradation of chlorophyll a can be simultaneously detected in a mixture, namely the monohydroxy allomer, the methoxylactone allomer, pheophytin a and the two corresponding allomers of the pheophytin. It is demonstrated that more than one pathway must be involved in the in vitro photodegradation of chlorophyll a as shown by the simultaneous existence of several intermediates.

A suite of steryl esters of pyrophaeophorbide a ( 1a ), a water column degradation product of phytoplankton chlorophyll a, has been prepared in good yield using dicyclohexylcarbodiimide as dehydrating agent. Comparison and co-injection of these standards with the complex mixtures of steryl chlorin esters in various recent sediments, using negative ion HPLC-MS, has confirmed the structures of a number of the natural components.

Dawn Johnson Bernadette Hardware Mwidimi Ndosi Tracey Young Claire Hale James Maxwell Euthalia Roussou Ade Adebajo

The (22 R )-30a,30b-dihomohopan-30b-yl and tetrahymanyl esters of pyrophaeophorbide a , chlorophyll a transformation products resulting from zooplankton herbivory, occur in an extract of surface sediment from Lake Valencia (Venezuela). The former was identified by HPLC-PDA-MS comparison with a standard and the latter after reduction of the extract and GC-MS analysis of the released alcohols.

Objective. To investigate the association between frequency of alcohol consumption and the risk and severity of RA. Methods. Frequency of alcohol consumption was recorded by patients and controls in a self-completed questionnaire. Odds ratios (ORs) for RA risk were calculated according to alcohol consumption, adjusted for age, gender and smoking status. Median values of all RA severity measures were then calculated according to the frequency of alcohol consumption, and the non-parametric trend test was used to assess association. A negative binomial regression model was used to adjust for potential confounding. Results. Eight hundred and seventy-three patients with erosive RA, and 1004 healthy controls were included in the study. Risk of RA decreased according to frequency of alcohol consumption, such that non-drinkers had an OR for RA of 4.17 (3.015.77) compared with subjects consuming alcohol on >10 days per month (P for trend

Reduction of a sulphur-rich asphaltene from a crude oil (Rozel Point) with lithium in ethylamine (Li/EtNH2) affords an alkane fraction similar to that obtained from desulphurisation with Raney nickel, but in higher yield. Using Li/EtND2, deuterium-labelled alkanes were obtained, thereby confirming the presence of sulphide linkages in the asphaltene fraction. Reduction of two sulphur-rich kerogens with similar sulphur contents, Serpiano shale (M. Triassic) and Jurf Ed Darawish (JED, U. Cretaceous) afforded significant quantities of polar solvent-extractable material. Both kerogens also yielded low amounts of hydrocarbons although the amount released from JED kerogen was significantly higher. The results indicate that, whereas the kerogens contain hydrocarbon moieties intermolecularly linked by sulphide bridges, the distributions of the precursors lipids which were incorporated were different. For example, GC-MS analysis of the labelled products from JED kerogen revealed them to be dominated by steranes of algal origin, with the position(s) of deuterium labelling providing evidence of sulphide linking and cross-linking. On the other hand, the labelled products from Serpiano kerogen were dominated by hopanes of bacterial origin which were linked terminally via the side chain.

Combined liquid chromatography-mass spectrometry studies of the pigment distributions of a variety of lake and marine sediments from different depositional settings reveal the presence of steryl chlorin esters as significant components of the chlorin assemblages. The components are water column transformation products of phytoplankton chlorophyll a, and it is suggested that they form through an enzymatic esterification or transesterification process during senescence or decay. Remarkably, the steroidal alcohols are esterified mainly to a common nucleus, pyrophaeophorbide a. The transformation pathway involved appears to be a ubiquitous one in marine and lacustrine environments, and the components represent a significant sedimentary “sink” for the chlorophyll biosynthesised in the euphotic zone. Future water column studies of the changes in photosynthetic pigments in phytoplankton blooms and of pigment fluxes should take into account the likely presence of steryl chlorin esters.

The distribution patterns of sedimentary A-ring methylated steranes have changed markedly over geological time. Although dinosterane and its isomer 24-ethyl-4α-methylcholestane have been tentatively identified in three Proterozoic rock units, they are either not detectable or occur in low abundance relative to 3-methyl steranes throughout most of the Palaeozoic. Between Permian and middle Triassic times (260-220 Ma ago), 4-methyl sterane abundances in marine sediments increased markedly. The presence of dinosterane in some middle Triassic marine sediments is contemporaneous with the appearance of fossil cysts of uncontested dinoflagellate affinity. 4-Methyl steranes, including dinosterane or their precursor sterenes and sterols, then show a continuous presence, often in high abundance, in marine sediments from the late Triassic through to the present day. Assemblages of 4-methyl steranes and their precursors, but with dinosterane absent or in low relative abundance, are often the predominant steroids in lacustrine sediments in the Cainozoic. Dinosterane appears to arise predominantly from marine dinoflagellates and, as a consequence, is a useful biological marker for Mesozoic and Cainozoic marine organic matter. The isomer 24-ethyl-4α-methylcholestane is likely to have multiple origins although its very high abundance in Tertiary lacustrine sediments and oils, compared to older materials, suggests that dinoflagellates could also be the source in these cases.

Genome-wide association studies (GWAS) have contributed to the identification of at least 14 rheumatoid arthritis (RA) susceptibility loci.1 One of the first RA GWAS included 1522 cases and 1850 controls from the USA/Sweden and identified TRAF1/C5 as a novel RA locus.2 This GWAS was recently repeated after including an additional 1550 cases and 3310 controls from the USA and restricting analysis to US subjects.3 In the expanded sample, two novel single nucleotide polymorphisms (SNP) mapping to the REL locus showed association with RA. REL encodes c-Rel, a member of the nuclear factor kappa B family of transcription factors and one of the associated SNP (rs13031237) maps to an intron of this gene. The association was validated in an independent sample of 2604 RA cases and 2882 controls from the USA/Canada, with strong evidence for association in the combined samples (rs13031237, p=3.1×10−14). We aimed to test the …

The occurrence in sediments of chlorophyll-derived tetrapyrroles provides evidence for primary photosynthetic communities in palaeo water columns. In ancient sedimentary rocks the components occur mainly as nickel or vanadyl complexes of alkyl porphyrins, and to a lesser extent carboxylic acids. Although extensive loss of functional groups has occurred, the structures of a number of the components reveal that chlorophyll carbon skeletons can survive intact or virtually intact, although in other cases the skeletons have been modified by rearrangement. The structures of a few components indicate an origin from the chlorophyllsc, and thus an algal input, whereas an origin from photosynthetic bacterial chlorophylls is apparent from the carbon skeletons of other components. Such studies, taken with other distributional features (e.g. ratio of nickel to vanadyl components, extent of tetrapyrrole preservation) can provide information about the productivity and preservation of organic matter and presence of water column anoxia at the time of deposition. Studies of the tetrapyrrole components in one recent and two highly immature older sediments have provided further evidence for the pathway of defunctionalization, through the identification of the minimum number of components necessary to link a chlorophyll, such as chlorophylla, to the major alkyl porphyrin in sedimentary organic matter. Additionally, evidence for an early and unexpected transformation pathway comes from the recent identification in sediments of chlorin acids esterified with sterols.

Negative-ion liquid chromatographic-mass spectrometric analysis of the pigment composition of the bottom sediment (15–20 cm) of a eutrophic lake revealed the presence of a novel series of chlorophyll transformation products, in which a series of C 27 C 30 sterols and stanols are esterified to a pyrophaeophorbide a nucleus of algal origin. The major components are algal-derived chlorophyll a and b degradation products, and the presence of a bacteriochlorophyll-related phaeophytin indicates the presence of anoxic conditions extending into the photic zone when the sediment was laid down.

The major esterified tetrapyrrole in a Miocene oil shale (Marau, Brazil) is a free base chlorin, most likely pyrophaeophorbide a, esterified to 24-ethyl-4α-methyl-5α(H)-cholestan-3β-ol, the structure being assigned by FAB-MS and 1H NMR, and by GC-MS analysis of the sterol liberated by hydrolysis. FAB-MS and electronic absorption spectrophotometric data for the second most abundant component are consistent with the mesopyrophaeophorbide counterpart. Only one other minor esterified chlorin was detected, implying a highly specific and, hence, biologically-mediated esterification. It is not clear whether the reaction took place during biosynthesis of an unknown precursor chlorophyll or resulted from esterification of a hydrolysis product(s) from a known chlorophyll (most likely chlorophyll a) after cellular disruption, although the second possibility is considered more likely.

An unusual series of quinone pigments in a pink Eocene (c. 45x106 yr) sepiolite (quincyte, France) has been characterised by spectroscopy. The structure of the major pigment (c. 75% of total), 2,8-di-isopropyl-peri-xanthenoxanthene-4,10-quinone, was confirmed by synthesis. Spectroscopy revealed six minor related components with various oxygenated C-2 substituents (C1–C3) and, generally, a C-8 isopropyl group. Although the origin of the pigments is unknown, they (or their precursors) appear to have been biosynthesised by the acyl-malonate pathway.

The identities of the two major tetrapyrroles in the bottom sediment of a eutrophic lake, assigned previously by spectral comparison with standards, have been confirmed as phaeophytin a and pyrophaeophytin a through the use of 2D COSY and nOe difference NMR techniques. This provides the first unambiguous characterization of sedimentary chlorins, the components being early products in the degradative pathway of chlorophyll a in the aquatic environment.

Anti-tumour necrosis factor (TNF) agents have revolutionized the treatment of patients with rheumatoid arthritis (RA). These therapies are, however, expensive and 30% of patients fail to respond. In a large cohort of Caucasian RA patients treated with anti-TNF medications (total n = 1050, etanercept n = 455, infliximab n = 450), we investigated whether genotypes of eight single nucleotide polymorphisms in the region containing the TNF gene were associated with response to anti-TNF therapy. Linear regression analyses adjusted for baseline 28 joint disease activity score (DAS28), baseline health assessment questionnaire score, gender and concurrent disease modifying anti-rheumatic drug treatment were used to assess association of these polymorphisms with treatment response, defined by change in DAS28 after 6 months. Analyses were performed in the entire cohort, and also stratified by anti-TNF agent. Association between DAS28 response and TNF-308 (rs1800629) genotype (P = 0.001) was detected across the whole cohort. After stratification by anti-TNF agent, the rare TNF-308AA genotype was associated with a significantly poorer response compared with TNF-308GG in etanercept (P = 0.001, n = 7) but not infliximab (P = 0.8, n = 17) treated patients. Conversely, the GA genotype at TNF-238 (rs361525) was associated with a poorer response to infliximab (P = 0.028, n = 40), but not etanercept (P = 0.6, n = 33). Owing to the small numbers of patients in some of the genotype groups examined, our data must be regarded as preliminary and will require replication in further large cohorts of anti-TNF-treated patients. If confirmed, our findings suggest the potential for genotype at these markers to aid selection of anti-TNF agent in patients with RA.

To test the hypothesis that premedication with acetaminophen, ibuprofen, and/or 4% lidocaine gel would decrease discomfort and improve satisfaction with screening mammography in women who expect a higher level of discomfort.In this HIPAA-compliant, institutional review board-approved, prospective, double-blinded, placebo-controlled clinical trial, 418 women aged 32-89 years who expected substantial discomfort with screening mammography were randomly divided to receive premedication with acetaminophen, ibuprofen, and/or 4% lidocaine gel. Subjects provided informed written consent. The primary outcome was discomfort. Secondary outcomes were satisfaction and plans for future mammography on the basis of discomfort. Subjects completed structured questionnaires with visual analog scales to measure discomfort and satisfaction. A generalized linear mixed-models framework was used to assess the effect of medications on discomfort during mammography, and satisfaction with technologist and machine combinations was included as a random effect. The "plans for mammography next year" outcome was modeled by using a binary distribution and logit link function.Discomfort was significantly lower in the lidocaine gel group (P = .01). Satisfaction was significantly negatively correlated with discomfort (P.001). Satisfaction and whether or not the subject had delayed her mammography because of fear of discomfort had significant effects on plans to undergo mammography next year (P.001 for both). There were significant differences in discomfort between different combinations of technologists and machines.Premedication with 4% lidocaine gel significantly reduced discomfort during screening mammography, and reduced discomfort may improve the likelihood of future mammographic screening and early detection of breast cancer.

Fast atom bombardment (FAB) mass spectra of a number of functionalized tetrapyrroles derived from chlorophylls a and b have been obtained and MS/MS studies used to investigate aspects of the fragmentation behavior of some of them. The application of this approach is demonstrated by the assignment of pheophytin b isolated from a lake sediment where the amount and purity were insufficient for 1 H nuclear magnetic resonance spectroscopic studies

This paper briefly reviews recent developments in 1 H NMR studies of chlorins and porphyrins of sedimentary origin, with particular reference to correlated spectroscopy (COSY), which allows elucidation of spin-coupled systems

The Treibs hypothesis linking sedimentary 13,15-ethanoporphins to an origin from chlorophylls requires the natural occurence of a suite of intermediates on the proposed degradative pathway. Few of the putative intermediates have been isolated and identified. Through examination of the tetrapyrrole distributions of three selected sediments, the minimum number of «intermediates» necessary for the operation of a pathway of defunctionalization has been assigned, linking a precursor such as chlorophyll a to a sedimentary porphyrin with the same carbon skeleton (deoxophylloerythroetioporphyrin). This provides further structural evidence for the defunctionalization of chlorophylls to give sedimentary 13,15-ethanoporphyrins

The on-line coupling of a high-performance liquid chromatograph to a mass spectrometer (LC/MS) has allowed the analysis of a number of tetrapyrrole pigments of sedimentary significance. Fragmentation processes were found to be restricted to the periphery of the structures. In the posivite-ion mode the extent of fragmentation could be manipulated, allowing molecular weight information to be obtained, as well as specific fragmentation patterns. These findings have suggested a number of applications of LC/MS in the investigation of sedimentary tetrapyrrole distributions. In particular, the assignment of individual components in mixtures is possible from comparison of mass spectra with those of coinjected standards

The major chlorin in Messel oil shale (Eocene, lacustrine, F.R.G.) has been isolated and assigned as the nickel complex of mesopyrophaephorbide a by spectral comparison with a synthesised standard. The component, whose structure clearly indicates a chlorophyll origin and which co-occurs with its free-base counterpart, has the same carbon skeleton as the major nickel porphyrin acid assigned previously, but is present in much lower abundance and still retains the C-131 carbonyl group found in all chlorophylls. It appears that mesopyrophaeophorbide a represents the major part of the residual chlorin fraction which has survived aromatisation and carbonyl reduction and, like the alkyl porphyrins and carboxylic acids, has become metallated with nickel.

A knowledge of past changes in the biological productivity of the oceans is important for understanding the interactions between carbon cycling and climate. Phytoplankton productivity in today's oceans can be estimated from the concentrations of chlorophyll in sea water1, but chlorophyll is not preserved in the sediments. Existing proxies for past algal productivity do not represent total productivity; for example, biogenic opal2 reflects the contribution of only part of the phytoplankton community, and the organic carbon record can be subject to contamination from terrestrial inputs2,3. Although chlorins, the pigment-transformation products of chlorophyll, are widespread in Quaternary marine sediments, their potential as proxy measures of past variations in primary productivity has not been convincingly demonstrated. Here we report a high-resolution molecular stratigraphic record of chlorin concentrations over the past 350,000 years in a sediment core from the subtropical Atlantic continental margin. Maxima in the chlorin accumulation rate coincide with significant peaks in the accumulation rates of biogenic opal (at the end of glacial terminations) and organic carbon (between terminations). These results suggest that chlorins, unlike other proxies, can serve as a measure of total primary productivity variations.

To evaluate effectiveness of oral anxiolytic medication versus relaxation technique for anxiety reduction in women undergoing breast core-needle biopsy (CNB).The institutional review board reviewed and approved the study. Informed consent was obtained from 143 consecutive women scheduled for breast CNB. Women were randomized as follows: no anxiety intervention (usual care group), relaxation therapy with an audiotape of classical music and ocean sounds during CNB (relaxation group), and 0.5-mg of alprazolam administered orally 15 minutes before CNB (medication group). Anxiety before, during, and 24 hours after the procedure was assessed with State-Trait Anxiety Inventory and self-reported visual analog scale from 0 (no anxiety) to 10 (worst anxiety). Data analysis was performed with statistical software. Descriptive statistics were computed for all variables. Group differences were determined with analysis of variance. Differences in mean values were assessed with Bonferroni multiple comparison procedure. Categorical demographic differences were assessed with chi(2) statistic.Preprocedural State-Trait Anxiety Inventory scores indicated that women were not inherently anxious: usual care group, score of 44.63; relaxation group, 45.74; and medication group, 49.1. Scores represented significantly elevated anxiety for women in all three groups when compared with the normative value of 35.12 (P.0001), with no statistically significant differences between the scores of the three groups. Women in medication group reported significant reductions in anxiety (-44%) from levels determined before the procedure to levels determined during the procedure (P = .02) and significant reduction during the procedure when compared with changes in usual care (+15%) and relaxation (-8%) groups (P = .02). Women in all three groups reported significant reduction in anxiety from levels determined before the procedure to levels determined at 24 hours after it (P.0001). There was no significant difference (P = .95) in 24-hour postprocedural anxiety levels among the three groups.Use of oral anxiolytic medication before breast CNB can significantly reduce anxiety women experience during the procedure.

We discuss a patient with an occult, densely calcified synovial sarcoma of the hip who came to clinical attention because of pulmonary metastases. When synovial sarcomas present with dense and conglomerate calcification, they may be confused with benign processes such as myositis ossificans or tumoral calcinosis. Malignancies such as extraskeletal osteogenic sarcoma, extraskeletal chondrosarcoma, and mesenchymal chondrosarcoma must also be considered in the differential diagnosis.

A multi-user integrated suite of instruments designed to optimize the search for evidence of life on Mars is described. The package includes: - Surface inspection and surface environment analysis to identify the potential Mars landing sites, to inspect the surface geology and mineralogy, to search for visible surficial microbial macrofossils, to study the surface radiation budget and surface oxidation processes, to search for niches for extant life. - Subsurface sample acquisition by core drilling- Analysis of surface and subsurface minerals and organics to characterize the surface mineralogy, to analyse the surface and subsurface oxidants, to analyse the mineralogy of subsurface aliquots, to analyse the organics present in the subsurface aliquots (elemental and molecular composition, isotopes, chirality). - Macroscopic and microscopic inspection of subsurface aliquots to search for life's indicators (paleontological, biological, mineralogical) and to characterize the mineralogy of the subsurface aliquots. The study is led by ESA Manned Spaceflight and Microgravity Directorate.

Low molecular weight hydrocarbon (LMWH) distributions were examined in sediments from Sites 1109 and 1115 in the western Woodlark Basin using purge-trap thermal adsorption/desorption gas analysis. A number of different hydrocarbon components >C1, which were not detected during shipboard gas analysis, were detected at both sites using the purge-trap procedure. Concentrations of ethane, propane, and butane remained relatively low (

The objective of this study was to evaluate and document pain and psychological distress related to imaging-guided core needle biopsy (CNB) of the breast. This prospective study of 52 consecutive patients undergoing CNB of the breast assessed anxiety, pain, acute stress disorder, and activities of daily living both preprocedure and at 24 hours, 5 days, and 30 days postprocedure. Survey instruments included the State-Trait Anxiety Inventory (STAI), a visual analog pain scale, the SF-36 Physical Functioning Scale, and DSM IV criteria for acute stress disorder. Preprocedure the mean scores for self-reported levels of state and trait anxiety were 47.11 ( SD = 13.53) and 37.71 ( SD = 11.24), respectively. At 24 hours postprocedure, the mean score for self-reported state anxiety was 38.74 ( SD = 17.77), a significant reduction from the preprocedure level reported by patients (p < 0.005). Further reductions in state anxiety levels were reported at 5 and 30 days postprocedure. The mean scores for state anxiety fell within the normal range at 30 days postprocedure (mean 32.75, SD = 10.97). However, at 5 days post-CNB, patients with confirmed malignancies reported significantly more anxiety than patients without malignancies ( p = 0.002). This difference was not present at 30 days post-CNB ( p = 0.17). Patients reported average pain scores of 2.0 (on a scale of 0–10) during the biopsy. This decreased to 1.3 at 24 hours, 0.3 at 5 days, and 0.2 at 30 days. Reported symptoms of acute stress related to the procedure significantly increased over the period between the 5-day interview and the 30-day interview. One (2%) patient reported avoidance of thoughts about CNB 5 days postprocedure and 5 (12%) patients reported this at 30 days postprocedure (p < 0.05). Patients undergoing CNB reported significant levels of state anxiety which were greatest at the time of biopsy. A significant decrease was observed at 24 hours postprocedure, despite the fact that biopsy results were not available to the patients. Self-reported levels of anxiety for the group, regardless of biopsy results, fell within the normal range by 30 days. Further research and interventions are recommended to address the management of anxiety for patients undergoing CNB.

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH2 and HI/LiAlH4) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.

A method is described for the high-performance liquid chromatography (HPLC) mass spectrometry analysis of porphyrin mixtures by using an atmospheric pressure interface, which can operate in two modes: pneumatically assisted elecrrospray and atmospheric pressure chemical ionization (APCI). Optimization of the conditions and evaluation of spectral information has been carried out by using direct injection of free-base and metallo porphyrin standards. The most effective results were obtained using APCI. HPLC-APCI mass spectrometry analysis of the demetallated vanadyl porphyrin fraction from the Triassic Serpiano oil shale has allowed rapid characterization of the distribution; more than 50 significant components are present. The presence of trace amounts of high molecular weight ( > C33) cycloalkano porphyrins indicates the occurrence of photic zone anoxia in the ancient water column. This example illustrates the potential of the approach for studies of porphyrin mixtures of environmental or biological significance, which should be applicable to other types of metallo and free-base components that can be separated by HPLC under normal or reversed-phase conditions, (J Am Soc Mass Spectrom 1996, 7, 965–971)

Bacterial populations and activity were quantified at four Ocean Drilling Program Leg 146 sites in the Cascadia Margin accretionary wedge, off the west Canadian/American coast. At two sites the sediments contained gas hydrates: Site 889/890 had a discrete hydrate zone for -10 m above the bottom-simulating reflector (BSR) at 225 m below the sea floor (mbsf), and Site 892 had disseminated hydrate in the top -20 mbsf and a BSR at 73 mbsf. Site 891 had fault zones and discrete zones of active fluid venting. The other site, 888, was a control site without gas hydrates or substantial fluid venting. Bacterial populations were present at all sites with deepest samples from Site 888 at 564 mbsf. The control Site 888 and the top -90 mbsf of Site 889/890 had bacterial distributions similar to previous sites studied in the Pacific Ocean. In the top -20 m of Site 892, however, bacterial populations were much lower than in the other two sites; they may have been inhibited by the high concentrations of hydrogen sulfide within the hydrate zone. Below this depth, bacterial populations increased to concentrations consistent with other sites, apart from local decreases in Hole 892A associated with thermally generated aromatic hydrocarbons, which might be toxic to a portion of the bacterial community. Near-surface bacterial populations at 891A were -4.5 times higher than expected, probably reflecting fluid venting near this site. Below about 50 mbsf at this site (Hole 891B), bacterial populations were also elevated and peaks corresponded to geochemical anomalies resulting from fluid venting. Bacterial processes generally decreased with increasing depth at the control site, which was dominated by sulfate reduction, and rates of methane oxidation in the top 90 m were low, ranging from 0.002 to 0.033 nmol/cm3/d. Fluid and gas venting have a marked effect on deep bacterial processes at Sites 891 and 889/890: in contrast to the control site, maximum bacterial activities occur and bacterial populations are elevated at depth (sub-200 mbsf), reflecting marked increases in methane oxidation. At Site 889/890, bacterial populations and activity were stimulated in the discrete hydrate zone. Methane oxidation rates increased in the middle of this zone to 134.5 nmol/cm3/d, and this resulted in a significant increase in the total bacterial population. The anaerobic process(es) responsible for methane oxidation remain unclear, but fluid flux into accretionary wedge sediments may be an important process in providing electron acceptors to maintain these high rates of methane oxidation. Variation in bacterial profiles between cores at the same site (891 and 892), only a few meters apart, closely reflect spatial heterogeneity in geochemistry and fluid expulsion in these accretionary sediments, demonstrating that bacterial processes are a sensitive index for the fluid and gas venting that may drive many of the geochemical changes.

Infrared multispectral sensors are being investigated as a means for day and night target detection. Infrared multispectral sensors would exploit high spectral band-to-band correlation to reject high background clutter. An infrared Fourier transform spectrometer-based field measurement system was used to collect spectral signature data of targets and desert scrub and sand backgrounds from a 100 foot tower at White Sands Missile Range. The measurements include target-to-background spectral contrast, subpixel targets, background spectral correlation, and background spatial power spectra. The measurements have been analyzed to determine multispectral signal-to-clutter ratios versus target, background, diurnal, and weather variations, background correlation versus temperature clutter variations, and spectral correlation versus spatial scale. These measurements contribute to the expanding target and background infrared hyperspectral signature database. The results of the analysis demonstrate the utility and robustness of infrared multispectral techniques for target detection.

Proposes a framework for classifying and mapping aquatic systems at various scales using ecologically significant physical and biological criteria. Classification and mapping concepts follow tenets of hierarchical theory, pattern recognition, and driving variables. Criteria are provided for the hierarchical classification and mapping of aquatic ecological units of riverine, lacustrine, and ground-water systems within their geoclimatic and watershed settings. Some hydrogeomorphic criteria for classifying wetlands are also proposed.

Infrared spectra were collected of targets and tree and grass backgrounds during 9 days over a 2-month period, from September 24 to November 29, 1993, at Wright Laboratory/Wright-Patterson Air Force Base, Dayton Ohio. A description of the infrared spectrometer, the experiments conducted, and the data obtained are given. High spectral correlations in backgrounds were observed during the 2-month period, with the highest correlation observed near midday at the beginning of the 2-month period. There is evidence of seasonal variations in correlation as well as observed radiance. jg

Marketing case studies provide context for analysis and decision-making designs in different business situations, companies, and industries. In most marketing courses, students use cases about actual companies to practice strategic marketing analysis and to gain some experience in the tasks of crafting and implementing marketing strategy. A case sets forth, in factual manner, the events and organizational circumstances surrounding a particular marketing managerial situation. The purpose of this paper is to look at why case studies are used, problems using them and recommendations using standard and innovative methodologies for using them effectively.

When the thermal contrast between a target and the background is large it is usually sufficient to use a single spectral band for detection purposes and consequently spectral emissivity variations are ignored. We consider the problem of detection and estimation of spectral emissivity in the thermal infrared emphasizing the particular detection situation where the target thermal contrast is small. More generally, we show that temperature can be considered as random interference of low rank. This leads to a procedure of optimally estimating both the temperature and spectral emissivity components. of radiance measurements. In addition to temperature and spectral emissivity estimation we outline a phenomenology based optimal detector that is invariant to unknown levels of temperature variation and unknown levels of target thermal contrast.

Genome-wide association studies of rheumatoid arthritis (RA) have identified an association of the disease with a 6q23 region devoid of genes. TNFAIP3, an RA candidate gene, flanks this region, and polymorphisms in both the TNFAIP3 gene and the intergenic region are associated with systemic lupus erythematosus. We hypothesized that there is a similar association with RA, including polymorphisms in TNFAIP3 and the intergenic region.To test this hypothesis, we selected tag-single nucleotide polymorphisms (SNPs) in both loci. They were analyzed in 1,651 patients with RA and 1,619 control individuals of Spanish ancestry.Weak evidence of association was found both in the 6q23 intergenic region and in the TNFAIP3 locus. The rs582757 SNP and a common haplotype in the TNFAIP3 locus exhibited association with RA. In the intergenic region, two SNPs were associated, namely rs609438 and rs13207033. The latter was only associated in patients with anti-citrullinated peptide antibodies. Overall, statistical association was best explained by the interdependent contribution of SNPs from the two loci TNFAIP3 and the 6q23 intergenic region.Our data are consistent with the hypothesis that several RA genetic factors exist in the 6q23 region, including polymorphisms in the TNFAIP3 gene, like that previously described for systemic lupus erythematosus.

A combined micropaleontological, geochemical, and sedimentological study of the upper Aptian-Albian succession from the Sergipe basin, northeastern Brazil, has been undertaken. The paleoenvironmental evolution of the basin from the late Aptian to late Albian can be subdivided into three major depositional phases: (1) late Aptian, (2) early to middle Albian; (3) late Albian. A shallow carbonate compensation depth within upper mesopelagic depths (c. 300-500 m) is inferred for the late Aptian-Albian. Intermittent anoxic events, associated with salinity-stratified water masses, occurred in the basin during the late Aptian to Albian. An oxygen minimum (dysaerobic to anoxic conditions) occurred during the late Aptian to earliest Albian, in middle-outer neritic to upper bathyal settings. Waning dysaerobic to oxic conditions are apparent in the late Albian. The foraminiferal assemblages recovered from the upper Aptian marine deposits have a characteristic Tethyan affinity. The microfaunal evidence suggests that this area of the northern South Atlantic had at least some surface water exchange with low-latitude central North Atlantic-western Tethyan Provinces, even possible at intermediate (epipelagic to mesopelagic) water depths. Contribution of microfaunal elements coming from high-latitude northern (Boreal Realm) and/or southern (Austral) regions is also apparent, although of less significance.