Bioorganic/inorganic hybrid composition of sponge spicules: Matrix of the giant spicules and of the comitalia of the deep sea hexactinellid Monorhaphis

The giant basal spicules of the siliceous sponges Monorhaphis chuni and Monorhaphis intermedia (Hexactinellida) represent the largest biosilica structures on earth (up to 3 m long). Here we describe the construction (lamellar organization) of these spicules and of the comitalia and highlight their organic matrix in order to understand their mechanical properties. The spicules display three distinct regions built of biosilica: (i) the outer lamellar zone (radius: >300 mu m), (ii) the bulky axial cylinder (radius: <75 mu m), and (iii) the central axial canal (diameter: <2 mu m) with its organic axial filament. The spicules are loosely covered with a collagen net which is regularly perforated by 7-10 mu m large holes; the net can be silicified. The silica layers forming the lamellar zone are approximate to 5 mu m thick; the central axial cylinder appears to be composed of almost solid silica which becomes porous after etching with hydrofluoric acid (HF). Dissolution of a complete spicule discloses its complex structure with distinct lamellae in the outer zone (lamellar coating) and a more resistant central part (axial barrel). Rapidly after the release of the organic coating from the lamellar zone the protein layers disintegrate to form irregular clumps/aggregates. In contrast, the proteinaceous axial barrel, hidden in the siliceous axial cylinder, is set up by rope-like filaments. Biochemical analysis revealed that the (dominant) molecule of the lamellar coating is a 27-kDa protein which displays catalytic, proteolytic activity. High resolution electron microscopic analysis showed that this protein is arranged within the lamellae and stabilizes these surfaces by palisade-like pillars. The mechanical behavior of the spicules was analyzed by a 3-point bending assay, coupled with scanning electron microscopy. The load-extension curve of the spicule shows a biphasic breakage/cracking pattern. The outer lamellar zone cracks in several distinct steps showing high resistance in concert with comparably low elasticity, while the axial cylinder breaks with high elasticity and lower stiffness. The complex bioorganic/inorganic hybrid composition and structure of the Monorhaphis spicules might provide the blueprint for the synthesis of bio-inspired material, with unusual mechanical properties (strength, stiffness) without losing the exceptional properties of optical transmission. (C) 2007 Elsevier Inc. All rights reserved.

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze river) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0-2 cm) were 5-10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C-26-C-33 long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC(15) to nC(22) compounds. Long-chain (> C-20) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (< C-20) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk delta(CTOCTOC)-C-13. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four US estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (delta(13)C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble "uncharacterized" organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, delta(13) C and stable nitrogen (delta(15)N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples. a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of delta(13)C and delta(15)N measured for bulk HMW-DOM varied from -22.1 to -30.1parts per thousand and 2.8 to 8.9parts per thousand, respectively and varied among the four estuaries studied as well. Among the Compound classes, TCHO was more enriched in C-13 (delta(13)C = -18.5 to -22.8parts per thousand) compared with THAA (delta(13)C = -20.0 to -29.6parts per thousand) and total lipid (delta(13)C = -25.7 to -30.7parts per thousand). The acid-insoluble organic fractions, in general, had depleted C-13 values (delta(13)C = -23.0 to -34.4parts per thousand). Our results indicate that the observed differences in both delta(13)C and delta(15)N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures. Copyright (C) 2004 Elsevier Ltd.

Bacterial roles in the formation of high-molecular-weight dissolved organic matter in estuarine and coastal waters: Evidence from lipids and the compound-specific isotopic ratios

High-molecular-weight dissolved organic matter (HMW-DOM, > 1,000 Daltons) is actively involved in the global biogeochemical cycling of many elements, but its carbon sources and detailed formation pathways are still not well understood. In this study, we measured bulk stable carbon and nitrogen isotopic ratios, lipid composition, and compound-specific carbon isotopic ratios of HMW-DOM samples collected from four U.S. estuaries (Boston Harbor/Massachusetts Bay, Delaware/Chesapeake Bay, San Diego Bay, and San Francisco Bay). Analytical results show (1) a fraction of HMW-DOM (lipid associated) in estuarine and coastal waters is derived from bacteria and phytoplankton; (2) this fraction of HMW-DOM is formed by various release processes of bacterial membrane components and bacterial reworking of phytoplankton-derived material; (3) this fraction of HMW-DOM is generally present in all samples from different coastal systems despite variable organic matter inputs and environmental conditions, suggesting an important bacterial role in HMW-DOM formation.

Organic geochemical studies of sinking particulate material in China sea area(I) - Organic matter fluxes and distributional features of hydrocarbon compounds and fatty acids

Sinking particulate material collected from Nansha Yongshu reef lagoon and the continental shelf of the East China Sea by sediment traps has been analyzed and studied for the first time using organic geochemical method. The results show that about half of the sinking particulate organic matter in the two study areas are consumed before reaching the depth of 5 m to the sea floor and the degree of this consumption in Yongshu reef lagoon is larger than that in the continental shelf of the East China Sea. The distributions of hydrocarbons and fatty acids indicate that the minor difference of biological sources of sinking particulate organic matter exists between Yongshu reel lagoon and the continental shelf of the East China Sea, but they mainly come from marine plankton. Stronger biological and biochemical transformations of sinking particulate organic matter are also observed and the intensity of this transformation in Yongshu reef lagoon is greater than that in the continental shelf of the East China Sea. It is found that the occurrence of C-25 highly branched isoprenoid (HBI) diene may be related to the composition of diatom species.

Changes in plant biomass and species composition of alpine Kobresia meadows along altitudinal gradient on the Qinghai-Tibetan Plateau

Alpine Kobresia meadows are major vegetation types on the Qinghai-Tibetan Plateau. There is growing concern over their relationships among biodiversity, productivity and environments. Despite the importance of species composition, species richness, the type of different growth forms, and plant biomass structure for Kobresia meadow ecosystems, few studies have been focused on the relationship between biomass and environmental gradient in the Kobresia meadow plant communities, particularly in relation to soil moisture and edaphic gradients. We measured the plant species composition, herbaceous litter, aboveground and belowground biomass in three Kobresia meadow plant communities in Haibei Alpine Meadow Ecosystem Research Station from 2001 to 2004. Community differences in plant species composition were reflected in biomass distribution. The total biomass showed a decrease from 13196.96 +/- 719.69 g/m(2) in the sedge-dominated K. tibetica swamp to 2869.58 +/- 147.52 g/m(2) in the forb and sedge dominated K. pygmaea meadow, and to 2153.08 +/- 141.95 g/m(2) in the forbs and grasses dominated K. humilis along with the increase of altitude. The vertical distribution of belowground biomass is distinct in the three meadow communities, and the belowground biomass at the depth of 0-10 cm in K. tibetica swamp meadow was significantly higher than that in K. humilis and K. pygmaea meadows (P < 0.01). The herbaceous litter in K. tibetica swamp was significantly higher than those in K. pygnaeca and K. humilis meadows. The effects of plant litter are enhanced when ground water and soil moisture levels are raised. The relative importance of litter and vegetation may vary with soil water availability. In the K. tibetica swamp, total biomass was negatively correlated to species richness (P < 0.05); aboveground biomass was positively correlated to soil organic matter, soil moisture, and plant cover (P < 0.05); belowground biomass was positively correlated with soil moisture (P < 0.05). However, in the K. pygnaeca and K. humilis meadow communities, aboveground biomass was positively correlated to soil organic matter and soil total nitrogen (P < 0.05). This suggests that the distribution of biomass coincided with soil moisture and edaphic gradient in alpine meadows.

Effects of forage composition and growing season on methane emission from sheep in the Inner Mongolia steppe of China

Understanding the effects of dietary composition on methane (CH4) production of sheep can help us to understand grassland degradation resulting in an increase of CH4 emission from ruminant livestock and its resulting significance affecting CH4 source/sink in the grazing ecosystem. The objective of this study was to investigate the effect of forage composition in the diet of sheep in July and August on CH4 production by sheep in the Inner Mongolia steppe. The four diet treatments were: (1) Leymus chinensis and Cleistogenes squarrosa (LC), (2) Leymus chinensis, Cleistogenes squarrosa and concentrate supplementation (LCC), (3) Artemisia frigida and Cleistogenes squarrosa (AC), and (4) Artemisia frigida, Cleistogenes squarrosa and concentrate supplementation (ACC). CH4 production was significantly lower in July than in August (31.4 and 36.2 g per sheep-unit per day, respectively). The daily average CH4 production per unit of digestive dry matter (DM), organic matter (OM) and neutral detergent fiber (NDF) increased by 10.9, 11.2 and 42.1% for the AC diet compared with the LC diet, respectively. Although concentrate supplementation in both the AC and LC diets increased total CH4 production per sheep per day, it improved sheep productivity and decreased CH4 production by 14.8, 12.5 and 14.8% per unit of DM, OM and NDF digested by the sheep, respectively. Our results suggested that in degraded grassland CH4 emission from sheep was increased and concentrate supplementation increased diet use efficiency. Sheep-grazing ecosystem seems to be a source of CH4 when the stocking rate is over 0.5 sheep-units ha(-1) during the growing season in the Inner Mongolia steppe.

Effect of microwave treatment on chemical composition and in sacco digestibility of wheat straw in yak cow

Wheat straw was treated with microwave for 4 min and 8 min at a power of 750 W and frequency of 2,450 MHz. Chemical compositions of untreated, 4 min treated and 8 min treated Straws were analyzed and in sacco degradabilities of all these straws in yak rumens were measured. Microwave treatment didn't significantly (p > 0.05) affect the chemical composition of the straw. In sacco dry matter (DM) degradability of the straw after 18 h incubation in rumen was significantly (p < 0.01) improved by microwave treatment. In sacco crude protein (CP) degradability of the straw was not (p > 0.05) affected by microwave treatment. In sacco organic matter (OM) degradability of the straw was increased (p < 0.01) by around 20% for both the 4 min and 8 min microwave treatment, that of acid detergent fibre (ADF) was increased (p < 0.01) by 61.6% and 62.8%, and that of ash free ADF was enhanced by 72.1% and 69.6% for the 4 min and 8 min microwave treatment respectively. No significant difference was observed between the 4 min and 8 min microwave treatment on the degradability of DM, OM, CP, ADF and ash-free ADF of the straw.

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C-18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) = XYZ(0) + mV(1)/100 + spi* + bbeta(m) + aalpha(m), was applied to analyze capacity factors (k'), soil organic partition coefficients (K-oc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control log K-oc, log P, and log k' (on soil and on C-18) are the solute size (V-1/100) and hydrogen-bond basicity (beta(m)). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpha(m)). Log k' on soil and log K-oc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C-18 and log P have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, log k' values on C-18 have good correlations with log P (r > 0.97), while log k' values on soil have good correlations with log K-oc (r > 0.98). Two K-oc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC. (C) 2002 Elsevier Science Ltd. All rights reserved.

Effects of organic modifiers on solute retention and electrokinetic migrations in micellar electrokinetic capillary chromatography

Influences of seven organic modifiers, including urea, methanol (MeOH), dioxane (DIO), tetrahydrofuran (THF), acetonitrile (ACN), 1-propanol (1-PrOH) and 2-propanol (2-PrOH), on the solute retention and the electrokinetic migrations in micellar electrokinetic capillary chromatography (MEKC) are investigated with sodium dodecyl sulfate (SDS) micelle as pseudostationary phase. It is observed that in the limited concentration ranges used in the MEKC systems the effect of organic modifier concentration on the retention can be described by the equation logk'=logk'(w)-SC for most binary aqueous-organic buffer, but deviations from this retention equation are observed at ACN and particularly THF as organic modifiers. With parameter S as a measure of the elutropic strength, the elutropic strength of the organic modifiers is found to follow a general order urea organic modifiers studied. The electroosmotic mobility decreases linearly with increasing modifier concentrations. The strength of modifiers to suppress the electroosmotic mobility follows the order urea < MeOH, ACN < DIO, THF, 1-PrOH, 2-PrOH. The addition of ACN affects the electrophoretic mobility of the SDS micelle in different patterns depending on the buffer composition used, while the addition of the other modifiers leads to a rough linear decrease of the electrophoretic mobility of the SDS micelle. The suppressing strength of THF on the electrophoretic mobility of the SDS micelle is strongly related to the buffer composition, whereas the suppressing strength for the other modifiers follows the sequence urea < MeOH < DIO, 1-PrOH, 2-PrOH. The migration time window is expanded by the use of organic modifiers. Urea and MeOH have the least expanding strength while ACN, DIO, THF, 1-PrOH and 2-PrOH have the highest expanding strength on the migration time window.

Hybrid organic-inorganic phenyl monolithic column for capillary electrochromatography

A novel hybrid organic-inorganic silica-based monolithic column possessing phenyl ligands for reversed-phase (RP) capillary electrochromatography (CEC) is described. The monolithic stationary phase was prepared by in situ co-condensation of tetraethoxysilane (TEOS) with phenyltriethoxysilane (PTES) via a two-step catalytic sol-gel procedure to introduce phenyl groups distributed throughout the silica matrix for chromatographic interaction. The hydrolysis and condensation reactions of precursors were chemically controlled through pH variation by adding hydrochloric acid and dodecylamine, respectively. The structural property of the monolithic column can be easily tailored through adjusting the composition of starting sol solution. The effect of PTES/TEOS ratios on the morphology of the created stationary phases was investigated. A variety of neutral and basic analytes were used to evaluate the column performance. The CEC columns exhibited typical RP chromatographic retention mechanism for neutral compounds and had improved peak shape for basic solutes.