Estimating successive pK(a) values of polyprotic acids from ab initio molecular dynamics using metadynamics: the dissociation of phthalic acid and its isomers

Estimation of the dissociation constant, or pK(a), of weak acids continues to be a central goal in theoretical chemistry. Here we show that ab initio Car-Parrinello molecular dynamics simulations in conjunction with metadynamics calculations of the free energy profile of the dissociation reaction can provide reasonable estimates of the successive pK(a) values of polyprotic acids. We use the distance-dependent coordination number of the protons bound to the hydroxyl oxygen of the carboxylic group as the collective variable to explore the free energy profile of the dissociation process. Water molecules, sufficient to complete three hydration shells surrounding the acid molecule, were included explicitly in the computation procedure. Two distinct minima corresponding to the dissociated and un-dissociated states of the acid are observed and the difference in their free energy values provides the estimate for pK(a), the acid dissociation constant. We show that the method predicts the pK(a) value of benzoic acid in good agreement with experiment and then show using phthalic acid (benzene dicarboxylic acid) as a test system that both the first and second pK(a) values as well, as the subtle difference in their values for different isomers can be predicted in reasonable agreement with experimental data.

Review of river fisheries valuation in Central and South America

Unlike Africa and Asia, where a large part of the population are heavily dependent upon fishing for their livelihoods, fishing for a living in the interior of Central and South America (CSA) remains a marginal occupation for all but the most isolated of families. As such, the economics and management of fisheries on the continent have received little attention from within the continent and the rest of the world. This study shows that while a number of studies have been carried out on fishing in the region, they tend to be limited in their geographical focus and time scale. Although fishing of freshwater species may appear to be comparatively insignificant in the region, the rivers of CSA are very important. This report attempts to analyze the literature available on CSA river fisheries and attempts to draw out an economic value of these fisheries. It is divided into a number of sections. First, the authors describe the major river basins on the continent, characterize their fisheries, and place freshwater fisheries in CSA into a global context. Second, the authors provide a review of valuation techniques for fisheries and use this analytical framework to review the principal literature on freshwater fisheries in the region. Then they turn their attention to the economic impact of dams and water abstraction schemes, reviewing the available literature to ascertain how/if economic values are computed for the impact on fisheries. Finally, they offer some conclusions and recommendations on the direction for future studies of freshwater fisheries in CSA.

A comparison of seafloor habitats and associated benthic fauna in areas open and closed to bottom trawling along the central California Continental Shelf

Executive Summary: A number of studies have shown that mobile, bottom-contact fishing gear (such as otter trawls) can alter seafloor habitats and associated biota. Considerably less is known about the recovery of these resources following such disturbances, though this information is critical for successful management. In part, this paucity of information can be attributed to the lack of access to adequate control sites – areas of the seafloor that are closed to fishing activity. Recent closures along the coast of central California provide an excellent opportunity to track the recovery of historically trawled areas and to compare recovery rates to adjacent areas that continue to be trawled. In June 2006 we initiated a multi-year study of the recovery of seafloor microhabitats and associated benthic fauna inside and outside two new Essential Fish Habitat (EFH) closures within the Cordell Bank and Gulf of the Farallones National Marine Sanctuaries. Study sites inside the EFH closure at Cordell Bank were located in historically active areas of fishing effort, which had not been trawled since 2003. Sites outside the EFH closure in the Gulf of Farallones were located in an area that continues to be actively trawled. All sites were located in unconsolidated sands at equivalent water depths. Video and still photographic data collected via a remotely operated vehicle (ROV) were used to quantify the abundance, richness, and diversity of microhabitats and epifaunal macro-invertebrates at recovering and actively trawled sites, while bottom grabs and conductivity/temperature/depth (CTD) casts were used to quantify infaunal diversity and to characterize local environmental conditions. Analysis of still photos found differences in common seafloor microhabitats between the recovering and actively trawled areas, while analysis of videographic data indicated that biogenic mound and biogenic depression microhabitats were significantly less abundant at trawled sites. Each of these features provides structure with which demersal fishes, across a wide range of size classes, have been observed to associate. Epifaunal macro-invertebrates were sparsely distributed and occurred in low numbers in both treatments. However, their total abundance was significantly different between treatments, which was attributable to lower densities at trawled sites. In addition, the dominant taxa were different between the two sites. Patchily-distributed buried brittle stars dominated the recovering site, and sea whips (Halipteris cf. willemoesi) were most numerous at the trawled site though they occurred in only five of ten transects. Numerical classification (cluster analysis) of the infaunal samples also revealed a clear difference between benthic assemblages in the recovering vs. trawled areas due to differences in the relative abundances of component species. There were no major differences in infaunal species richness, H′ diversity, or J′ evenness between recovering vs. trawled site groups. However, total infaunal abundance showed a significant difference attributable to much lower densities at trawled sites. This pattern was driven largely by the small oweniid polychaete Myriochele gracilis, which was the most abundant species in the overall study region though significantly less abundant at trawled sites. Other taxa that were significantly less abundant at trawled sites included the polychaete M. olgae and the polychaete family Terebellidae. In contrast, the thyasirid bivalve Axinopsida serricata and the polychaetes Spiophanes spp. (mostly S. duplex), Prionospio spp., and Scoloplos armiger all had significantly to near significantly higher abundances at trawled sites. As a result of such contrasting species patterns, there also was a significant difference in the overall dominance structure of infaunal assemblages between the two treatments. It is suggested that the observed biological patterns were the result of trawling impacts and varying levels of recovery due to the difference in trawling status between the two areas. The EFH closure was established in June 2006, within a month of when sampling was conducted for the present study, however, the stations within this closure area are at sites that actually have experienced little trawling since 2003, based on National Marine Fishery Service trawl records. Thus, the three-year period would be sufficient time for some post-trawling changes to have occurred. Other results from this study (e.g., similarly moderate numbers of infaunal species in both areas that are lower than values recorded elsewhere in comparable habitats along the California continental shelf) also indicate that recovery within the closure area is not yet complete. Additional sampling is needed to evaluate subsequent recovery trends and persistence of effects. Furthermore, to date, the study has been limited to unconsolidated substrates. Ultimately, the goal of this project is to characterize the recovery trajectories of a wide spectrum of seafloor habitats and communities and to link that recovery to the dynamics of exploited marine fishes. (PDF has 48 pages.)

Competing Ecosystem Services: an Assessment of Carbon and Timber in the Tropical Forests of Central America

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Central area redd project [Ribble, Hodder and Lune catchments]

Redd counting is an integral part of most Fishery Officers duties. The number and distribution of salmonid redds throughout salmonid catchments provides invaluable information on the range and extent of spawning by both salmon and sea trout. A project was initiated by the Fisheries Science and Management Team of Central Area, North West Region in England in liaison with the Flood Defence function. The main objective of this project was to assess redd count data for Central Area and attempt to quantify these data in order to produce a grading system that would highlight key salmonid spawning areas. By showing which were the main areas for salmon and sea trout spawning, better informed decisions could be made on whether or not in-stream Flood Defence works should be given the go-ahead. The main salmonid catchments in Central Area were broken into individual reaches, approximately 1 km in length. The number of redds in these individual reaches were then calculated and a density per lkm value was obtained for each reach. A grading system was devised which involved looking at the range of density per km values and dividing this by five to produce 5 classes, A - E. A sixth class (F) was used where the density per Ion value was 0.00. This grading system was calculated at two levels of detail. Grades for salmon and sea trout were produced for each individual catchment and also on an Area-wide level. Maps were produced using a range of colours to represent the grade for each reach. These maps provide a highly useful overview of the status of salmonid spawning for each catchment over individual years and highlight the key salmon and sea trout spawning areas in each catchment. These maps and the associated summary data should now provide Flood Defence and Fisheries staff with a fairly detailed overview of the status of spawning in any location within the. main salmonid catchments in Central Area. Although these maps are very useful they should only be used as a guide. The current practice of consulting with the local Fishery Officer should be continued to ensure that expert local knowledge is taken into account.

CYCLIC PEPTIDE HEPATOTOXINS FROM FRESH-WATER CYANOBACTERIAL (BLUE-GREEN-ALGAE) WATERBLOOMS COLLECTED IN CENTRAL CHINA

Toxic cyanobacteria (blue-green algae) waterblooms have been found in several Chinese water bodies since studies began there in 1984. Waterbloom samples for this study contained Anabaena circinalis, Microcystis aeruginosa and Oscillatoria sp. Only those waterblooms dominated by Microcystis aeruginosa were toxic by the intraperitoneal (i.p.) mouse bioassay. Signs of poisoning were the same as with known hepatotoxic cyclic peptide microcystins. One toxic fraction was isolated from each Microcystis aeruginosa sample. Two hepatotoxic peptides were purified from each of the fractions by high-performance liquid chromatography and identified by amino acid analysis followed by low and high resolution fast-atom bombardment mass spectrometry (FAB-MS). LD50 i.p. mouse values for the two toxins were 245-mu-g/kg (Toxin A) and 53-mu-g/g (Toxin B). Toxin content in the cells was 0.03 to 3.95 mg/g (Toxin A) and 0.18 to 3.33 mg/kg (Toxin B). The amino acid composition of Toxin A was alanine [1], arginine [2], glutamic acid [1] and beta-methylaspartic acid [1]; for Toxin B it was the same, except one of the arginines was replaced with a leucine. Low- and high-resolution FAB-MS showed that the molecular weights were 1,037 m/z (Toxin A) and 994 m/z (Toxin B), with formulas of C49H76O12N13 (Toxin A) and C49H75O12N10 (Toxin B). It was concluded that Toxin A is microcystin-RR and Toxin B is microcystin-LR, both known cyclic heptapeptide hepatotoxins isolated from cyanobacteria in other parts of the world. Sodium borohydride reduction of microcystin-RR yielded dihydro-microcystin-RR (m/z = 1,039), an important intermediate in the preparation of tritium-labeled toxin for metabolism and fate studies.

Spatial variations of size-fractionated chlorophyll, cyanobacteria and heterotrophic bacteria in the Central and Western Pacific

Geographic and vertical variations of size-fractionated (0.2-1 mu m, 1-10 mu m, and >10 mu m) Chlorophyll a (Chl.a) concentration, cyanobacteria abundance and heterotrophic bacteria abundance were investigated at 13 stations from 4 degrees S, 160 degrees W to 30 degrees N, 140 degrees E in November 1993. The results indicated a geographic distribution pattern of these parameters with instances of high values occurring in the equatorial region and offshore areas, and with instance of low values occurring in the oligotrophic regions where nutrients were almost undetectable. Cyanobacteria showed the highest geographic variation (ranging from 27x10(3) to 16,582x10(3) cell l(-1)), followed by Chl.a (ranging from 0.048 to 0.178 mu g l(-1)), and heterotrophic bacteria (ranging from 2.84x10(3) to 6.50 x 10(5) cell l(-1)). Positive correlations were observed between nutrients and Chl.a abundance. Correspondences of cyanobacteria and heterotrophic bacteria abundances to nutrients were less significant than that of Chl.a. The total Chl.a was accounted for 1.0-30.9%, 35.9-53.7%, and 28.1-57.3% by the >10 mu m, 1-10 mu m and 0.2-1 mu m fractions respectively. Correlation between size-fractionated Chl.a and nutrients suggest that the larger the cell size, the more nutrient-dependent growth and production of the organism. The ratio of pheophytin to chlorophyll implys that more than half of the > 10 mu m and about one third of the 1-10 mu m pigment-containing particles in the oligotrophic region were non-living fragments, while most of the 1-10 mu m fraction was living cells. In the depth profiles, cyanobacteria were distributed mainly in the surface layer, whereas heterotrophic bacteria were abundant from surface to below the euphotic zone. Chl.a peaked at the surface layer (0-20 m) in the equatorial area and at the nitracline (75-100 m) in the oligotrophic regions. Cyanobacteria were not the principle component of the picoplankton. The carbon biomass ratio of heterotroph to phytoplankton was greater than 1 in the eutrophic area and lower than 1 in oligotrophic waters.

Late Holocene climate change in central Sweden inferred from lacustrine stable isotope data

Stable isotopes (delta O-18 and delta C-13) of lacustrine carbonates (Chara spp. algae and Pisidium spp. molluscs) from a lake sedimentary sequence in central Sweden were analysed to infer changes in lake hydrology and climate during the late Holocene. Results from analysis of lake water isotopes (delta O-18 and delta H-2) show that Lake Blektjarnen water isotope composition is responsive to the balance between evaporation and input water (E/l ratio). A high E/l ratio results from a dry and probably warmer climate, decreasing the relative importance of precipitation input. Under such conditions evaporation and atmospheric equilibration probably enrich lake water in O-18 and C-13, respectively, which is reflected in the isotopic composition of the carbonates in the lake. From the relatively positive Chara delta O-18 values we infer that conditions were dry and warm between 4400 and 4000 cal. a BP, whereas more negative values indicate that conditions were wetter and probably cooler between 4000 and 3000 cal. a BP. A drier climate is inferred from more positive values between 2500 and 1000 cal. a BP. However, a successive depletion after ca. 1750 cal. a BP, also detected in several other delta O-18 records (carbonate and diatom), suggest increasingly wetter conditions in Scandinavia after that time, which is probably related to increased strength of the zonal flow.

Isolation basin records of late Quaternary sea-level change, central mainland British Columbia, Canada.

Isolation basin records from the Seymour-Belize Inlet Complex, a remote area of central mainland British Columbia, Canada are used to constrain post-glacial sea-level changes and provide a preliminary basis for testing geophysical model predictions of relative sea-level (RSL) change. Sedimentological and diatom data from three low-lying (<4 m elevation) basins record falling RSLs in late-glacial times and isolation from the sea by ~11,800–11,200 14C BP. A subsequent RSL rise during the early Holocene (~8000 14C BP) breached the 2.13 m sill of the lowest basin (Woods Lake), but the two more elevated basins (sill elevations of ~3.6 m) remained isolated. At ~2400 14C BP, RSL stood at 1.49 ± 0.34 m above present MTL. Falling RSLs in the late Holocene led to the final emergence of the Woods Lake basin by 1604 ± 36 14C BP. Model predictions generated using the ICE-5G model partnered with a small number of different Earth viscosity models generally show poor agreement with the observational data, indicating that the ice model and/or Earth models considered can be improved upon. The best data-model fits were achieved with relatively low values of upper mantle viscosity (5 × 1019 Pa s), which is consistent with previous modelling results from the region. The RSL data align more closely with observational records from the southeast of the region (eastern Vancouver Island, central Strait of Georgia), than the immediate north (Bella Bella–Bella Coola and Prince Rupert-Kitimat) and areas to the north-west (Queen Charlotte Sound, Hecate Strait), underlining the complexity of the regional response to glacio-isostatic recovery.

Market Basket Survey Shows Elevated Levels of As in South Central U.S. Processed Rice Compared to California: Consequences for Human Dietary Exposure:consequences for human dietary exposure

We report the largest market basket survey of arsenic (As) in U.S. rice to date. Our findings show differences in transitional-metal levels between polished and unpolished rice and geographical variation in As and selenium (Se) between rice processed in California and the South Central U.S. The mean and median As grain levels for the South Central U.S. were 0.30 and 0.27 µg As g-1, respectively, for 107 samples. Levels for California were 41% lower than the South Central U.S., with a mean of 0.17 µg As g-1 and a median of 0.16 µg As g-1 for 27 samples. The mean and median Se grain levels for the South Central U.S. were 0.19 µg Se g-1. Californian rice levels were lower, averaging only 0.08 and 0.06 µg Se g-1 for mean and median values, respectively. The difference between the two regions was found to be significant for As and Se (General Linear Model (GLM):? As p < 0.001; Se p < 0.001). No statistically significant differences were observed in As or Se levels between polished and unpolished rice (GLM:? As p = 0.213; Se p = 0.113). No significant differences in grain levels of manganese (Mn), cobalt (Co), copper (Cu), or zinc (Zn) were observed between California and the South Central U.S. Modeling arsenic intake for the U.S. population based on this survey shows that for certain groups (namely Hispanics, Asians, sufferers of Celiac disease, and infants) dietary exposure to inorganic As from elevated levels in rice potentially exceeds the maximum intake of As from drinking water (based on consumption of 1 L of 0.01 mg L-1 In. As) and Californian state exposure limits. Further studies on the transformation of As in soil, grain As bioavailability in the human gastrointestinal tract, and grain elemental speciation trends are critical.

Oxygen isotopes from Phorcus (Osilinus) turbinatus shells as a proxy for sea surface temperature in the central Mediterranean: a case study from Malta.

The marine topshell, Phorcus (Osilinus) turbinatus, is a common component of many archaeological sites in the Mediterranean. This species has been successfully used as a palaeoclimate proxy in Italy. To test whether d18O from P. turbinatus shells can serve as a reliable palaeoclimate archive for other regions of the Mediterranean, we collected live P. turbinatus from the northeast coast of Malta each month for a year. The d18OSHELL values of the outermost growth increments of these live-collected shells ranged between-0.4 and+2.4‰. These values correspond to growing temperatures calculated from shell edge d18O of between 15 °C and 27 °C. Calculated shell edge sea surface temperatures are highly correlated with instrumental records of sea surface temperature recorded over the period of collection. The individuals analysed for this study are smaller than P. turbinatus from populations studied elsewhere in the Mediterranean. Nonetheless, d18OSHELL provides a robust record of sea surface temperatures, suggesting that smaller/younger shells in archaeological deposits can still provide reliable palaeothermometry records. This study extends the upper growth limit P. turbinatus by 2 °C compared with the previous studies of P. turbinatus in the Mediterranean and suggests that, contrary to the previous studies, growth shutdown does not occur in all P. turbinatus when sea surface temperatures exceed 25 °C. This may reflect the higher sample resolution that can be obtained from smaller/faster growing shells, or it may reflect actual higher growth tolerances of P. turbinatus populations in Malta. By showing that P. turbinatus precipitate their shells in d18O equilibrium with surrounding sea water, this study reinforces the potential for the stable isotope chemistry of P. turbinatus shells preserved in Mediterranean archaeological sites to provide a window into the climate and seasonality regimes of the past.

Role of central dopaminergic pathways in the neural control of growth hormone secretion in normal men:Studies with metoclopramide

The aim of this study was to gain further insight into the role that central dopaminergic pathways play in GH neuroregulation in man. Our experimental hypothesis was based on the possibility that most of the controversies on DA role could be due to the fact that the hypothalamic somatotroph rhythm (HSR) was not taken into account when interpreting the GH responses after pharmacological manipulations on dopaminergic pathways. In 10 normal subjects we monitored the effect of central dopaminergic blockade, achieved with metoclopramide (MCP; 10 mg, i.v. Bolus), on the pattern of spontaneous GH secretion and the GH responses to a GHRH challenge (GRF , 1 µg/kg, i.v. bolus) administered together with MCP or 60 min after this drug was given. The study of HSR was made according to our previous postulate. Our results indicate that MCP administration, either prior to or together with the GHRH bolus, significantly increased GHRH-induced GH release during a refractory HSR phase; but not when the GHRH challenge took place during a spotaneous secretory phase. The strong relationship between pre-GHRH plasma GH values and GHRH-elicited GH peaks was lost when MCP was given. These data indicate that MCP was able to disrupt the intrinsic HSR by inhibiting the hypothalamic release of somatostain (SS). While a main conclusion would be that central DA is a secretagogue for SS secretion, our results also suggest that this role could be dependent on its effects on the adrenergic inputs to SS neurons.

Translating Values:Evaluative Concepts in Translation

This collection explores the central importance of values and evaluative concepts in cross-cultural translational encounters. Written by a group of international scholars from a diverse range of linguistic and cultural backgrounds, the chapters in this book consider what it means to translate cultures by examining core values and their relationship to key evaluative concepts (such as authenticity, clarity, home, honour, or justice) and how they influence the complex multidimensional process of translation. This book will be of interest to academics studying cross-cultural and inter-linguistic interactions, to translators and interpreters, students of translation and of modern languages, and all those dealing with multilingual and multicultural settings.

Intraocular pressure, central corneal thickness, and glaucoma in chinese adults: the liwan eye study.

PURPOSE: To describe the distribution of central corneal thickness (CCT), intraocular pressure (IOP), and their determinants and association with glaucoma in Chinese adults.DESIGN: Population-based cross-sectional study.METHODS: Chinese adults aged 50 years and older were identified using cluster random sampling in Liwan District, Guangzhou. CCT (both optical [OCCT] and ultrasound [UCCT]), intraocular pressure (by Tonopen, IOP), refractive error (by autorefractor, RE), radius of corneal curvature (RCC), axial length (AL), and body mass index (BMI) were measured, and history of hypertension and diabetes (DM) was collected by questionnaire. Right eye data were analyzed.RESULTS: The mean values of OCCT, UCCT, and IOP were 512 ± 29.0 μm, 542 ± 31.4 μm, and 15.2 ± 3.1 mm Hg, respectively. In multiple regression models, CCT declined with age (P < .001) and increased with greater RCC (P < .001) and DM (P = .037). IOP was positively associated with greater CCT (P < .001), BMI (P < .001), and hypertension (P < .001). All 25 persons with open-angle glaucoma had IOP <21 mm Hg. CCT did not differ significantly between persons with and without open- or closed-angle glaucoma. Among 65 persons with ocular hypertension (IOP >97.5th percentile), CCT (555 ± 29 μm) was significantly (P = .01) higher than for normal persons.CONCLUSIONS: The distributions of CCT and IOP in this study are similar to that for other Chinese populations, though IOP was lower than for European populations, possibly due to lower BMI and blood pressure. Glaucoma with IOP <21 mm Hg is common in this population. We found no association between glaucoma and CCT, though power (0.3) for this analysis was low.

Pathways of recent fine-grained sediment transport on the central Portuguese continental margin

Com o intuito de estudar as principais vias de transporte de sedimentos finos recentes na zona central da margem continental Oeste Portuguesa, parâmetros geoquímicos, mineralógicos e granulométricos foram analisados em sedimentos superficiais e em matéria particulada colhida em armadilhas de sedimentos e integrados com observações da hidrodinâmica de fundo. Os parâmetros geoquímicos foram também estudados na coluna de sedimentos depositada nos últimos 150 anos e em sedimentos pré-industriais. Os referidos parâmetros determinados foram: concentrações elementares, isótopos estáveis de Pb, teores em materiais litogénicos, carbonato de cálcio e carbono orgânico. Os canhões de Lisboa-Setúbal e Cascais tiveram especial destaque no presente estudo dado que, até à data, encontram-se menos estudados que o Canhão da Nazaré. Os resultados mostram que a distribuição de sedimentos na zona central da margem ocidental Portuguesa é particionada pelos canhões e que a exportação de sedimentos da plataforma para zonas mais profundas da margem é restringida pelas correntes do talude, excepto onde os canhões funcionam como corredores para o transporte de sedimentos. Enquanto no Canhão de Lisboa-Setúbal, e provavelmente no Canhão de Cascais, o transporte de sedimentos até à zona inferior é limitada, provavelmente apenas despoletado por eventos de elevada energia, no Canhão da Nazaré o transporte ao longo do todo o canhão parece eficiente. As zonas superiores dos canhões de Lisboa-Setúbal e Cascais presentemente actuam como armadilhas de sedimentos finos, aprisionando partículas em suspensão provenientes da plataforma adjacente. A introdução directa de sedimentos provenientes das plumas dos rios Tejo e Sado nas zonas superiores dos canhões parece limitada, contudo a resuspensão dos sedimentos do prodelta do Tejo como resultado de ondas de tempestade e ondas de maré interna permite o transporte de sedimentos para os canhões adjacentes. Na plataforma de Lisboa-Setúbal-Sines foram identificadas as assinaturas geoquímicas e mineralógicas de diferentes fontes de sedimentos finos (e.g. estuários do Tejo e Sado, arribas costeiras, lagoas de St. André e Melides). As concentrações elementares pré-industriais são muito semelhantes nos canhões da Nazaré e Lisboa-Setúbal, mas variados graus de enriquecimento antrópico de metais traço estão presentes nos sedimentos recentes. A mais acentuada influência antrópica na última área referida é consistente com a sua proximidade a áreas densamente povoadas e industrializadas e com input de sedimentos originários dos rios Tejo e Sado, potenciais transportadores de partículas poluentes. A dispersão de Pb atmosférico parece também significativa sendo que toda a zona da plataforma continental adjacente aos canhões de Lisboa-Setúbal e Cascais apresenta-se enriquecida. A principal fonte de Pb antrópico identificada através de isótopos estáveis de Pb é consistente com a assinatura das cinzas de incineradoras. No Canhão de Lisboa a imersão de dragados contaminados parece ser também uma potencial importante fonte de metais traço antropogénicos.