Lead isotopes inthe Eastern Equatorial Pacific

The influence of atmospheric dust on climate and biogeochemical cycles in the oceans is well understood but poorly quantified. Glacial atmospheric dust loads were generally greater than those during the Holocene, as shown, for example, by the covariation of dust fluxes in the Equatorial Pacific and Antarctic ice cores. Nevertheless, it remains unclear whether these increases in dust flux were associated with changes in sources of dust, which would in turn suggest variations in wind patterns, climate or paleo-environment. Such questions can be answered using radiogenic isotope tracers of dust provenance. Here, we present a 160-kyr high-precision lead isotope time-series of dust input to the Eastern Equatorial Pacific (EEP) from core ODP Leg 138, Site 849 (0°11.59' N, 110°31.18' W). The Pb isotope record, combined with Nd isotope data, rules out contributions from Northern Hemisphere dust sources, north of the Intertropical Convergence Zone, such as Asia or North Africa/Sahara; similarly, eolian sources in Australia, Central America, the Northern Andes and Patagonia appear insignificant based upon the radiogenic isotope data. Fluctuations in Pb isotope ratios throughout the last 160 kyr show, instead, that South America remained the prevailing source of dusts to the EEP. There are two distinct South American Pb isotope end-members, constrained to be located in the south Central Volcanic Zone (CVZ, 22° S - 27.5° S) and the South Volcanic Zone (SVZ, 33° S - 43° S), with the former most likely originating in the Atacama Desert. Dust availability in the SVZ appears to be related to the weathering of volcanic deposits and the development of ash-derived Andosols, and influenced by local factors that might include vegetation cover. Variations in the dust fluxes from the two sources are in phase with both the dust flux and temperature records from Antarctican ice cores. We show that the forcing of dust provenance over time in the EEP overall is influenced by high-southerly-latitude climate conditions, leading to changes in the latitudinal position and strength of the South Westerlies as well as the coastal winds that blow northward along the Chilean margin. The net result is a modulation of dust emission from the Atacama Desert and the SVZ via a northward migration of the South Westerlies during cold periods and southward retreat during glacial terminations.

Improving the management of water and nitrogen resources in cropping systems by using simulation models

Los modelos de simulación de cultivos permiten analizar varias combinaciones de laboreo-rotación y explorar escenarios de manejo. El modelo DSSAT fue evaluado bajo condiciones de secano en un experimento de campo de 16 años en la semiárida España central. Se evaluó el efecto del sistema de laboreo y las rotaciones basadas en cereales de invierno, en el rendimiento del cultivo y la calidad del suelo. Los modelos CERES y CROPGRO se utilizaron para simular el crecimiento y rendimiento del cultivo, mientras que el modelo DSSAT CENTURY se utilizó en las simulaciones de SOC y SN. Tanto las observaciones de campo como las simulaciones con CERES-Barley, mostraron que el rendimiento en grano de la cebada era mas bajo para el cereal continuo (BB) que para las rotaciones de veza (VB) y barbecho (FB) en ambos sistemas de laboreo. El modelo predijo más nitrógeno disponible en el laboreo convencional (CT) que en el no laboreo (NT) conduciendo a un mayor rendimiento en el CT. El SOC y el SN en la capa superficial del suelo, fueron mayores en NT que en CT, y disminuyeron con la profundidad en los valores tanto observados como simulados. Las mejores combinaciones para las condiciones de secano estudiadas fueron CT-VB y CT-FB, pero CT presentó menor contenido en SN y SOC que NT. El efecto beneficioso del NT en SOC y SN bajo condiciones Mediterráneas semiáridas puede ser identificado por observaciones de campo y por simulaciones de modelos de cultivos. La simulación del balance de agua en sistemas de cultivo es una herramienta útil para estudiar como el agua puede ser utilizado eficientemente. La comparación del balance de agua de DSSAT , con una simple aproximación “tipping bucket”, con el modelo WAVE más mecanicista, el cual integra la ecuación de Richard , es un potente método para valorar el funcionamiento del modelo. Los parámetros de suelo fueron calibrados usando el método de optimización global Simulated Annealing (SA). Un lisímetro continuo de pesada en suelo desnudo suministró los valores observados de drenaje y evapotranspiración (ET) mientras que el contenido de agua en el suelo (SW) fue suministrado por sensores de capacitancia. Ambos modelos funcionaron bien después de la optimización de los parámetros de suelo con SA, simulando el balance de agua en el suelo para el período de calibración. Para el período de validación, los modelos optimizados predijeron bien el contenido de agua en el suelo y la evaporación del suelo a lo largo del tiempo. Sin embargo, el drenaje fue predicho mejor con WAVE que con DSSAT, el cual presentó mayores errores en los valores acumulados. Esto podría ser debido a la naturaleza mecanicista de WAVE frente a la naturaleza más funcional de DSSAT. Los buenos resultados de WAVE indican que, después de la calibración, este puede ser utilizado como "benchmark" para otros modelos para periodos en los que no haya medidas de campo del drenaje. El funcionamiento de DSSAT-CENTURY en la simulación de SOC y N depende fuertemente del proceso de inicialización. Se propuso como método alternativo (Met.2) la inicialización de las fracciones de SOC a partir de medidas de mineralización aparente del suelo (Napmin). El Met.2 se comparó con el método de inicialización de Basso et al. (2011) (Met.1), aplicando ambos métodos a un experimento de campo de 4 años en un área en regadío de España central. Nmin y Napmin fueron sobreestimados con el Met.1, ya que la fracción estable obtenida (SOC3) en las capas superficiales del suelo fue más baja que con Met.2. El N lixiviado simulado fue similar en los dos métodos, con buenos resultados en los tratamientos de barbecho y cebada. El Met.1 subestimó el SOC en la capa superficial del suelo cuando se comparó con una serie observada de 12 años. El crecimiento y rendimiento del cultivo fueron adecuadamente simulados con ambos métodos, pero el N en la parte aérea de la planta y en el grano fueron sobreestimados con el Met.1. Los resultados variaron significativamente con las fracciones iniciales de SOC, resaltando la importancia del método de inicialización. El Met.2 ofrece una alternativa para la inicialización del modelo CENTURY, mejorando la simulación de procesos de N en el suelo. La continua emergencia de nuevas variedades de híbridos modernos de maíz limita la aplicación de modelos de simulación de cultivos, ya que estos nuevos híbridos necesitan ser calibrados en el campo para ser adecuados para su uso en los modelos. El desarrollo de relaciones basadas en la duración del ciclo, simplificaría los requerimientos de calibración facilitando la rápida incorporación de nuevos cultivares en DSSAT. Seis híbridos de maiz (FAO 300 hasta FAO 700) fueron cultivados en un experimento de campo de dos años en un área semiárida de regadío en España central. Los coeficientes genéticos fueron obtenidos secuencialmente, comenzando con los parámetros de desarrollo fenológico (P1, P2, P5 and PHINT), seguido de los parámetros de crecimiento del cultivo (G2 and G3). Se continuó el procedimiento hasta que la salida de las simulaciones estuvo en concordancia con las observaciones fenológicas de campo. Después de la calibración, los parámetros simulados se ajustaron bien a los parámetros observados, con bajos RMSE en todos los casos. Los P1 y P5 calibrados, incrementaron con la duración del ciclo. P1 fue una función lineal del tiempo térmico (TT) desde emergencia hasta floración y P5 estuvo linealmente relacionada con el TT desde floración a madurez. No hubo diferencias significativas en PHINT entre híbridos de FAO-500 a 700 , ya que tuvieron un número de hojas similar. Como los coeficientes fenológicos estuvieron directamente relacionados con la duración del ciclo, sería posible desarrollar rangos y correlaciones que permitan estimar dichos coeficientes a partir de la clasificación del ciclo. ABSTRACT Crop simulation models allow analyzing various tillage-rotation combinations and exploring management scenarios. DSSAT model was tested under rainfed conditions in a 16-year field experiment in semiarid central Spain. The effect of tillage system and winter cereal-based rotations on the crop yield and soil quality was evaluated. The CERES and CROPGRO models were used to simulate crop growth and yield, while the DSSAT CENTURY was used in the SOC and SN simulations. Both field observations and CERES-Barley simulations, showed that barley grain yield was lower for continuous cereal (BB) than for vetch (VB) and fallow (FB) rotations for both tillage systems. The model predicted higher nitrogen availability in the conventional tillage (CT) than in the no tillage (NT) leading to a higher yield in the CT. The SOC and SN in the top layer, were higher in NT than in CT, and decreased with depth in both simulated and observed values. The best combinations for the dry land conditions studied were CT-VB and CT-FB, but CT presented lower SN and SOC content than NT. The beneficial effect of NT on SOC and SN under semiarid Mediterranean conditions can be identified by field observations and by crop model simulations. The simulation of the water balance in cropping systems is a useful tool to study how water can be used efficiently. The comparison of DSSAT soil water balance, with a simpler “tipping bucket” approach, with the more mechanistic WAVE model, which integrates Richard’s equation, is a powerful method to assess model performance. The soil parameters were calibrated by using the Simulated Annealing (SA) global optimizing method. A continuous weighing lysimeter in a bare fallow provided the observed values of drainage and evapotranspiration (ET) while soil water content (SW) was supplied by capacitance sensors. Both models performed well after optimizing soil parameters with SA, simulating the soil water balance components for the calibrated period. For the validation period, the optimized models predicted well soil water content and soil evaporation over time. However, drainage was predicted better by WAVE than by DSSAT, which presented larger errors in the cumulative values. That could be due to the mechanistic nature of WAVE against the more functional nature of DSSAT. The good results from WAVE indicate that, after calibration, it could be used as benchmark for other models for periods when no drainage field measurements are available. The performance of DSSAT-CENTURY when simulating SOC and N strongly depends on the initialization process. Initialization of the SOC pools from apparent soil N mineralization (Napmin) measurements was proposed as alternative method (Met.2). Method 2 was compared to the Basso et al. (2011) initialization method (Met.1), by applying both methods to a 4-year field experiment in a irrigated area of central Spain. Nmin and Napmin were overestimated by Met.1, since the obtained stable pool (SOC3) in the upper layers was lower than from Met.2. Simulated N leaching was similar for both methods, with good results in fallow and barley treatments. Method 1 underestimated topsoil SOC when compared with a 12-year observed serial. Crop growth and yield were properly simulated by both methods, but N in shoots and grain were overestimated by Met.1. Results varied significantly with the initial SOC pools, highlighting the importance of the initialization procedure. Method 2 offers an alternative to initialize the CENTURY model, enhancing the simulation of soil N processes. The continuous emergence of new varieties of modern maize hybrids limits the application of crop simulation models, since these new hybrids should be calibrated in the field to be suitable for model use. The development of relationships based on the cycle duration, would simplify the calibration requirements facilitating the rapid incorporation of new cultivars into DSSAT. Six maize hybrids (FAO 300 through FAO 700) were grown in a 2-year field experiment in a semiarid irrigated area of central Spain. Genetic coefficients were obtained sequentially, starting with the phenological development parameters (P1, P2, P5 and PHINT), followed by the crop growth parameters (G2 and G3). The procedure was continued until the simulated outputs were in good agreement with the field phenological observations. After calibration, simulated parameters matched observed parameters well, with low RMSE in most cases. The calibrated P1 and P5 increased with the duration of the cycle. P1 was a linear function of the thermal time (TT) from emergence to silking and P5 was linearly related with the TT from silking to maturity . There were no significant differences in PHINT between hybrids from FAO-500 to 700 , as they had similar leaf number. Since phenological coefficients were directly related with the cycle duration, it would be possible to develop ranges and correlations which allow to estimate such coefficients from the cycle classification.

Adolescent suicide attempts and adult adjustment

Background: Adolescent suicide attempts are disproportionally prevalent and frequently of low severity, raising questions regarding their long-term prognostic implications. In this study, we examined whether adolescent attempts were asso- ciated with impairments related to suicidality, psychopathology, and psychosocial functioning in adulthood (objective 1) and whether these impairments were better accounted for by concurrent adolescent confounders (objective 2). Method: Eight hundred and sixteen adolescents were assessed using interviews and question- naires at four time points from adolescence to adulthood. We examined whether lifetime suicide attempts in adolescence (by T2, mean age 17) predicted adult out- comes (by T4, mean age 30) using linear and logistic regressions in unadjusted models (objective 1) and adjusting for sociodemographic background, adolescent psychopathology, and family risk factors (objective 2). Results: In unadjusted analyses, adolescent suicide attempts predicted poorer adjustment on all outcomes, except those related to social role status. After adjustment, adolescent attempts remained predictive of axis I and II psychopathology (anxiety disorder, antisocial and borderline personality disorder symptoms), global and social adjustment, risky sex, and psychiatric treatment utilization. However, adolescent attempts no longer predicted most adult outcomes, notably suicide attempts and major depressive disorder. Secondary analyses indicated that associations did not differ by sex and attempt characteristics (intent, lethality, recurrence). Conclusions: Adolescent suicide attempters are at high risk of protracted and wide-ranging im- pairments, regardless of the characteristics of their attempt. Although attempts specifically predict (and possibly influence) several outcomes, results suggest that most impairments reflect the confounding contributions of other individual and family problems or vulnerabilites in adolescent attempters.

Adolescent suicide attempts and adult adjustment

Background: Adolescent suicide attempts are disproportionally prevalent and frequently of low severity, raising questions regarding their long-term prognostic implications. In this study, we examined whether adolescent attempts were asso- ciated with impairments related to suicidality, psychopathology, and psychosocial functioning in adulthood (objective 1) and whether these impairments were better accounted for by concurrent adolescent confounders (objective 2). Method: Eight hundred and sixteen adolescents were assessed using interviews and question- naires at four time points from adolescence to adulthood. We examined whether lifetime suicide attempts in adolescence (by T2, mean age 17) predicted adult out- comes (by T4, mean age 30) using linear and logistic regressions in unadjusted models (objective 1) and adjusting for sociodemographic background, adolescent psychopathology, and family risk factors (objective 2). Results: In unadjusted analyses, adolescent suicide attempts predicted poorer adjustment on all outcomes, except those related to social role status. After adjustment, adolescent attempts remained predictive of axis I and II psychopathology (anxiety disorder, antisocial and borderline personality disorder symptoms), global and social adjustment, risky sex, and psychiatric treatment utilization. However, adolescent attempts no longer predicted most adult outcomes, notably suicide attempts and major depressive disorder. Secondary analyses indicated that associations did not differ by sex and attempt characteristics (intent, lethality, recurrence). Conclusions: Adolescent suicide attempters are at high risk of protracted and wide-ranging im- pairments, regardless of the characteristics of their attempt. Although attempts specifically predict (and possibly influence) several outcomes, results suggest that most impairments reflect the confounding contributions of other individual and family problems or vulnerabilites in adolescent attempters.

Ultrasound Mapping of Nerve Stimulator Response during Sciatic Nerve Blockade and Relation to Postoperative Pain Scores

1.1 Background and Purpose: Ultrasound guided sciatic nerve blockade has rapid onset but at 24 hours pain is greater than nerve stimulator techniques. Injection of the nerve branches or trunk and sub-sheath blockade increase success and reduce onset times but risk injury. This study mapped needle coordinates for sciatic nerve blockade with nerve stimulation and its relation to postoperative pain scores. 1.2 Method: Angle and distance of the needle tip and infusion catheter from the popliteal sciatic nerve at which stimulated plantar flexion occurred were measured. Pain scores at postanesthesia unit discharge and 24 hours were recorded. 1.3 Results: 81% of opioid naïve patients reported immediate analgesia and 20.8% at 24 hours. In opioid tolerant patients 56.8% reported immediate analgesia and 9.1% at 24 hours. Plantar flexion was observed with the needle in the posterior medial quadrant near the sciatic nerve. Opioid tolerant patients reported adequate analgesia when the needle was located more medially and proximally to the sciatic nerve. 1.4 Conclusion: Stimulated plantar flexion is isolated to a narrow angular range in the posterior medial quadrant adjacent to the sciatic nerve. Opioid tolerant patients report adequate analgesia if the needle and catheter are more medial and proximal to the nerve surface.

Differences in analgesia in opioid naïve and tolerant patients with sciatic nerve blockade following elective foot and ankle surgery

1.1 Introduction and Purpose: Adequate postoperative analgesia in the opioid tolerant with chronic non-malignant pain is challenging. Multimodal pain relief regimens include regional anesthesia but opioid tolerant patients report increased postoperative pain and opioid consumption. This study compared analgesia in opioid naïve and tolerant patients receiving postoperative sciatic nerve blockade for foot and ankle surgery. 1.2 Method: Preoperative pain scores, trauma, maintenance and intraoperative opioid doses and following postoperative sciatic nerve blockade, patient self-reported pain scores and opioid consumption at discharge from the post-anesthesia unit and 24 hours were recorded. 1.3 Results: 191 patients enrolled. 40.3% were opioid tolerant and 33% had lower extremity trauma. Preoperative, immediate and delayed postoperative pain scores and intraoperative, immediate and 24 hour postoperative consumption of opioids were increased in opioid tolerant patients. Trauma and continuous infusion in opioid naïve and tolerant groups did not result in differences in 24 hour opioid consumption. 1.4 Limitations: Small subgroups and use of the pain score limited the accuracy of results. 1.5 Conclusion: Opioid tolerant patients require greater analgesic doses following sciatic nerve blockade for foot and ankle surgery. 24 hour opioid consumption for opioid naïve and tolerant patients is neither influenced by lower extremity injury nor continuous infusion.

Skeletal maturity and socio-economic status in portuguese children and youths: the Madeira growth study

Skeletal maturity is used to evaluate biological maturity status. Information about the association between socio-economic status (SES) and skeletal maturity is limited in Portugal. Aims: The aim of this study is to document the skeletal maturity of youths in Madeira and to evaluate variation in maturity associated with SES. Subjects and methods: The study involved 507 subjects (256 boys and 251 girls) from the Madeira Growth Study, a mixed-longitudinal study of five cohorts (8, 10, 12, 14 and 16 years of age) followed at yearly intervals over 3 years (1996–1998). A total of 1493 observations were made. Skeletal age was estimated from radiographs of the hand and wrist using the Tanner–Whitehouse 2 method (TW2). Social class rankings were based on Graffar’s (1956) method. Five social rankings were subsequently grouped into three SES categories: high, average and low. Results: Median for the radius, ulna and short finger bones (RUS scores) in the total sample of boys and girls increased curvilinearly across age whereas median for the 7 (without pisiform) carpal bones (Carpal scores) increased almost linearly. The 20-bone maturity scores demonstrated distinctive trends by gender: the medians for boys increased almost linearly while the medians for girls increased curvilinearly. SES differences were minimal. Only among children aged 10–11 years were high SES boys and girls advanced in skeletal maturity. Madeira adolescents were advanced in skeletal maturity compared with Belgian reference values. Conclusion: The data suggests population variation in TW2 estimates of skeletal maturation. Skeletal maturity was not related to SES in youths from Madeira.

Skeletal maturity and socio-economic status in portuguese children and youths: the Madeira growth study

Skeletal maturity is used to evaluate biological maturity status. Information about the association between socio-economic status (SES) and skeletal maturity is limited in Portugal. Aims: The aim of this study is to document the skeletal maturity of youths in Madeira and to evaluate variation in maturity associated with SES. Subjects and methods: The study involved 507 subjects (256 boys and 251 girls) from the Madeira Growth Study, a mixed-longitudinal study of five cohorts (8, 10, 12, 14 and 16 years of age) followed at yearly intervals over 3 years (1996–1998). A total of 1493 observations were made. Skeletal age was estimated from radiographs of the hand and wrist using the Tanner–Whitehouse 2 method (TW2). Social class rankings were based on Graffar’s (1956) method. Five social rankings were subsequently grouped into three SES categories: high, average and low. Results: Median for the radius, ulna and short finger bones (RUS scores) in the total sample of boys and girls increased curvilinearly across age whereas median for the 7 (without pisiform) carpal bones (Carpal scores) increased almost linearly. The 20-bone maturity scores demonstrated distinctive trends by gender: the medians for boys increased almost linearly while the medians for girls increased curvilinearly. SES differences were minimal. Only among children aged 10–11 years were high SES boys and girls advanced in skeletal maturity. Madeira adolescents were advanced in skeletal maturity compared with Belgian reference values. Conclusion: The data suggests population variation in TW2 estimates of skeletal maturation. Skeletal maturity was not related to SES in youths from Madeira.

Tethering for Selective Synthesis of 2,2′-Biphenols : the Acetal Method

2,2'-Biphenols are a large and diverse group of compounds with exceptional properties both as ligands and bioactive agents. Traditional methods for their synthesis by oxidative dimerisation are often problematic and lead to mixtures of ortho- and para-connected regioisomers. To compound these issues, an intermolecular dimerisation strategy is often inappropriate for the synthesis of heterodimers. The ‘acetal method’ provides a solution for these problems: stepwise tethering of two monomeric phenols enables heterodimer synthesis, enforces ortho regioselectivity and allows relatively facile and selective intramolecular reactions to take place. The resulting dibenzo[1,3]dioxepines have been analysed by quantum chemical calculations to obtain information about the activation barrier for ring flip between the enantiomers. Hydrolytic removal of the dioxepine acetal unit revealed the 2,2′-biphenol target.

Determination of the ethylene oxide adduct S-(2-hydroxyethyl)cysteine by a fluorometric HPLC method in albumin and globin from human blood

A new method has been developed for the quantification of 2-hydroxyethylated cysteine resulting as adduct in blood proteins after human exposure to ethylene oxide, by reversed-phase HPLC with fluorometric detection. The specific adduct is analysed in albumin and in globin. After isolation of albumin and globin from blood, acid hydrolysis of the protein and precolumn derivatisation of the digest with 9-fluorenylmethoxycarbonylchloride, the levels of derivatised S-hydroxyethylcysteine are analysed by RP-HPLC and fluorescence detection, with a detection limit of 8 nmol/g protein. Background levels of S-hydroxyethylcysteine were quantified in both albumin and globin, under special consideration of the glutathione transferase GSTT1 and GSTM1 polymorphisms. GSTT1 polymorphism had a marked influence on the physiological background alkylation of cysteine. While S-hydroxyethylcysteine levels in "non-conjugators" were between 15 and 50 nmol/g albumin, "low conjugators" displayed levels between 8 and 21 nmol/g albumin, and "high conjugators" did not show levels above the detection limit. The human GSTM1 polymorphism had no apparent effect on background levels of blood protein 2-hydroxyethylation.

A semi-alternating direction method for a 2-D fractional FitzHugh–Nagumo monodomain model on an approximate irregular domain

A FitzHugh-Nagumo monodomain model has been used to describe the propagation of the electrical potential in heterogeneous cardiac tissue. In this paper, we consider a two-dimensional fractional FitzHugh-Nagumo monodomain model on an irregular domain. The model consists of a coupled Riesz space fractional nonlinear reaction-diffusion model and an ordinary differential equation, describing the ionic fluxes as a function of the membrane potential. Secondly, we use a decoupling technique and focus on solving the Riesz space fractional nonlinear reaction-diffusion model. A novel spatially second-order accurate semi-implicit alternating direction method (SIADM) for this model on an approximate irregular domain is proposed. Thirdly, stability and convergence of the SIADM are proved. Finally, some numerical examples are given to support our theoretical analysis and these numerical techniques are employed to simulate a two-dimensional fractional Fitzhugh-Nagumo model on both an approximate circular and an approximate irregular domain.

Evaluation of a mobile phone image-based dietary assessment method in adults with type 2 diabetes

Photographic and image-based dietary records have limited evidence evaluating their performance and use among adults with a chronic disease. This study evaluated the performance of a mobile phone image-based dietary record, the Nutricam Dietary Assessment Method (NuDAM), in adults with type 2 diabetes mellitus (T2DM). Criterion validity was determined by comparing energy intake (EI) with total energy expenditure (TEE) measured by the doubly-labelled water technique. Relative validity was established by comparison to a weighed food record (WFR). Inter-rater reliability was assessed by comparing estimates of intake from three dietitians. Ten adults (6 males, age=61.2±6.9 years, BMI=31.0±4.5 kg/m2) participated. Compared to TEE, mean EI was under-reported using both methods, with a mean ratio of EI:TEE 0.76±0.20 for the NuDAM and 0.76±0.17 for the WFR. There was moderate to high correlations between the NuDAM and WFR for energy (r=0.57), carbohydrate (r=0.63, p<0.05), protein (r=0.78, p<0.01) and alcohol (rs=0.85, p<0.01), with a weaker relationship for fat (r=0.24). Agreement between dietitians for nutrient intake for the 3-day NuDAM (ICC = 0.77-0.99) was marginally lower when compared with the 3-day WFR (ICC=0.82-0.99). All subjects preferred using the NuDAM and were willing to use it again for longer recording periods.