Comparison of methods for the removal of organic carbon and extraction of chromium, iron and manganese from an estuarine sediment standard and sediment from the Calcasieu River estuary, Louisiana, U.S.A.

U.S. National Bureau of Standards (NBS) estuarine sediment 1646 from the Chesapeake Bay, Maryland, and surface sediment collected at two sites in the Calcasieu River estuary, Louisiana, were used to evaluate the dilute hydrochloric acid extraction of Cr, Fe and Mn from air-dried and freeze-dried samples that had been treated by one of three methods to remove organic carbon. The three methods for the oxidation and removal of organic carbon were: (1) 30% hydrogen peroxide; (2) 30% hydrogen peroxide plus 0.25 mM pyrophosphate; and (3) plasma oxidation (low-temperature ashing). There was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the percent of organic carbon removed by the three methods. Generally, there was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the concentration of Cr, Fe and Mn that was extracted, regardless of the extraction technique that was used. Hydrogen peroxide plus pyrophosphate removed the most organic carbon from sediment collected at the site in the Calcasieu River that was upstream from industrial outfalls. Plasma oxidation removed the most organic carbon from the sediment collected at a site in the Calcasieu River close to industrial outfalls and from the NBS estuarine sediment sample. Plasma oxidation merits further study as a treatment for removal of organic carbon. Operational parameters can be chosen to limit the plasma oxidation of pyrite which, unlike other Fe species, will not be dissolved by dilute hydrochloric acid. Preservation of pyrite allows the positive identification of Fe present as pyrite in sediments.     

Recent population trends of sooty and light-mantled albatrosses breeding on Marion Island

Sub-Antarctic Marion Island is one of the few islands where both species of Phoebetria albatrosses breed sympatrically. The last published assessment of their population trends, which reported counts up to 2008, concluded that the numbers of breeding pairs of sooty albatross P. fusca (Endangered) were decreasing, whereas numbers of light-mantled albatross P. palpebrata (Near Threatened) were increasing. Extending the counts to 2014 reversed these trends, with numbers of sooty albatrosses increasing from 2006 to 2014, and numbers of light-mantled albatrosses decreasing from 2007 to 2014. Confidence in island-wide counts is low due to the cryptic nature of the albatrosses on their largely inaccessible cliff-side nest sites, as well as counts for sooty albatrosses taking place late in the incubation period when 10?20% of nests have already failed. Given the greater conservation concern for the sooty albatross, we recommend that dedicated annual counts be conducted during the early incubation period, and be repeated shortly after the chicks hatch (late December), mid-way through the nestling period (late February) and prior to fledging (late April), to give a better idea of breeding success. Count zones also should be revised to facilitate more accurate counts, ensuring more reliable estimates of sooty albatross population trends at Marion Island.     

Characterization of sinking particles from the northwest Mediterranean Sea using advanced solid-state NMR

Sinking particles are the major transporter of organic carbon from surface to the deep ocean, and their chemical composition changes dramatically with depth. However, the exact mechanism controlling the chemical transformation as particles sink is not well understood, and little detail is known about the structural changes. This is mainly due to the paucity of techniques available to analyze the major macromolecular components of sinking particles. Here we applied advanced solid-state NMR techniques, including cross polarization/magic angle spinning (CPMAS), direct polarization/magic angle spinning (DPMAS), two-dimensional ¹H-¹³C heteronuclear correlation (2D HETCOR) and ¹H T₁ inversion recovery, on sinking particles collected in the northwest Mediterranean Sea. The CPMAS ¹³C NMR spectrum of the 200-m particles is significantly different from that of the DPMAS ¹³C NMR spectrum: CPMAS overestimates the NCH and CHO groups, but underestimates the aliphatic components, which is attributed to the high mobility of polymethylene units. Thus DPMAS is more suitable for quantifying organic composition of sinking particles. Using 2D HETCOR with ¹H spin diffusion, we estimated that the size of domains (similar structural entities either physically or chemically grouped together) in the 200-m sinking particles can be as large as tens of nanometers. The results of CPMAS ¹³C NMR and ¹H inversion recovery on sinking particles from 200, 520 and 920 m indicate that the macromolecular heterogeneity observed in surface particles virtually disappears as particles sink into the deep ocean. This suggests that the macromolecular components at depth are different in structural composition than those in surface waters, and may be compositionally homogenized as particles sink.     

Results from regional vibroseis profiling: Appalachian ultra-deep core hole site study

Summary. In 1985, 180 km of regional vibroseis profiles were acquired in the Carolinas and Georgia, southeastern United States, as part of the Appalachian Ultra-Deep Core Hole (ADCOH) Site Study. The data quality is excellent, with large-amplitude reflections from faults and crystalline rocks, lower Palaeozoic shelf strata and from within autochthonous Grenville basement. The profiles image the subsurface more clearly than other available data and allow the possibility of alternative interpretations of important elements of the tectonic framework of the southern Appalachians.
The major points in the interpretation are: 1) The Blue Ridge master decollement is at a depth of 2-3 km beneath the Blue Ridge. This thrust increases in dip just NW of the Brevard fault zone. 2) The Brevard fault zone appears to splay from the master decollement at 6 km (2.2 s) near Westminster, S.C., and defines the base of the crystalline Inner Piedmont allochthon. 3) Below the Blue Ridge thrust sheet are images of duplex and imbricate structures ("duplex tuning wedges") connected by other thrust faults that duplicate shelf strata to a thickness of 4–5 km. 4) Subhorizontal reflections from depths of 6 to 9 km may be from relatively undisturbed lower Palaeozoic strata as suggested by others. 5) Eocambrian-Cambrian(?) rift basins in the Grenville basement are also imaged.
The ADCOH data were originally recorded with 14–56 Hz bandwidth and 8 s length, but an extended Vibroseis correlation was used to produce 17 s data length revealing reflections from within the upper crust. Below 8 s, reflections from within the Grenville basement become weak, but are observable as late as 13 s; however, these Moho (?) reflections are generally short segments.     

Producers'' organizations and devolved fisheries management in the United Kingdom: Collective and individual quota systems

In the United Kingdom responsibility for the management of national catch quotas has since 1984 been extensively devolved to producers' organizations, Institutions created by the European Community in order to implement the common organization of the Community market for fish. The paper describes the development of the UK quota management system and the approaches adopted by different producers' organizations to the internal management of their quota allocations. Because of changes in the UK fishing vessel licensing rules as well as developments in the quota allocation system, there is an emerging market in quotas at both individual and collective levels. The implications of these developments are discussed, including the possible evolution, largely through industry-led innovation, of some sort of individual transferable quota (ITQ) system for the UK.     

Covalent coupling of peptides to humic acids: Structural effects investigated using 2D NMR spectroscopy

Covalent and non-covalent interaction of proteinaceous materials in soils and sediments has been suggested as an important mechanism for immobilizing nitrogen in numerous types of environments. In a previous study (Hsu P.-H., Hatcher, P.G., 2005. New evidence for covalent coupling of peptides to humic acids based on 2D NMR spectroscopy: A means for preservation. Geochimica et Cosmochimica Acta 69, 4521–4533), we provided molecular evidence for covalent, as well as non-covalent, bonding between ¹⁵N-labeled peptides and humic acid molecules using the 2D HSQC (heteronuclear single quantum coherence) NMR technique. In this report, we examine the influence of aromaticity and aliphaticity of peptides and humic materials on these covalent and non-covalent interactions. We use 2D NMR techniques to evaluate bonding interactions of ¹⁵N labeled peptides, having different aromatic and aliphatic properties, with three humic acids that vary in degree of aromaticity. The peptide containing primarily aromatic amino acid residues is observed to form covalent and non-covalent bonds with mainly aromatic-rich humic acids. The peptide composed of aliphatic amino acid residues shows, on the other hand, only bonding interactions with aliphatic-rich humic acids. These observations provide the first direct molecular evidence that aliphatic functional groups are involved in bonding with proteinaceous materials. The process may play an important role in sequestration of proteinaceous materials in sedimentary systems such as marine systems where the humic materials are mainly aliphatic in nature.     

Coalification of organic matter in coal balls of the Pennsylvanian (upper Carboniferous) of the Illinois Basin, United States

An evaluation was made of the degree of coalification of two coal balls from the Illinois Basin of the Pennsylvanian (upper Carboniferous) of the United States. Previous interpretations are mainly misleading and contradictory, primarily because of the assumption that the brown color and exceptional cellular and subcellular preservation typical of American coal balls imply chemical preservation of cellulose and lignin, the primary components of peat. Xylem tissue from a medullosan seed fern contained in a coal ball and the coal attached to the coal ball from the Calhoun coal bed, Mattoon Formation, Illinois, was analyzed by elemental, petrographic, and nuclear magnetic resonance (NMR) techniques to determine the degree of coalification. The NMR and elemental data indicate the lack of cellulose and lignin and a probable rank of high-volatile C bituminous coal. These data corroborate data for a coal ball from the Herrin (No. 6) coal bed (Carbondale Formation, Middle Pennsylvanian) and support our hypothesis that the organic matter in coal balls of the Pennsylvanian strata of the United States is coalified to about the same degree as the surrounding coal. Data presented show a range of lower reflectances for xylem tissue and vitrinite in the analyzed coal balls compared with vitrinite in the attached coal.The data reported indicate that physical preservation of organic matter in coal balls does not imply chemical preservation. Also our study supports the hypothesis that compactional (static load) pressure is not a prerequisite for coalification up to a rank of high-volatile C bituminous coal.A whole-rock analysis of the Calhoun coal ball indicates a similarity to other carbonate coal balls from the United States. It consists primarily of calcium carbonate and 1–2% organic matter; silica and alumina together make up less than 0.5%, indicating the lack of minerals such as quartz and clays.     

Resin rodlets in shale and coal (Lower Cretaceous), Baltimore Canyon Trough

Rodlets, occurring in shale and coal (uppermost Berriasian to middle Aptian, Lower Cretaceous), were identified from drill cuttings taken from depths between 9330 ft (2844 m) and 11, 460 ft (3493 m) in the Texaco et al., Federal Block 598, No. 2 well, in the Baltimore Canyon Trough. Under the binocular microscope, most of the rodlets appear black, but a few are reddish brown, or brownish and translucent on thin edges. They range in diameter from about 0.4 to 1.7 mm and are commonly flattened. The rodlets break with a conchoidal fracture, and some show an apparent cellular cast on their longitudinal surfaces. When polished and viewed in reflected light, the rodlets appear dark gray and have an average random reflectance of less than 0.1% whereas mean maximum reflectances are 0.48–0.55% for vitrinite in the associated shale and coal. These vitrinite reflectances indicate either subbituminous A or high-volatile C bituminous coal. The rodlets fluoresce dull gray yellow to dull yellow. The scanning electron microscope (SEM) and light microscope reveal the presence of swirl-like features in the rodlet interiors. Minerals associated with the rodlets occur as sand-size grains attached to the outer surface, as finely disseminated interior grains, and as fracture fillings. Electron microprobe and SEM-energy-dispersive X-ray (EDX) anlayses indicate that the minerals are dominantly clays (probably illite and chlorite) and iron disulfide; calcium carbonate, silicon dioxide, potassium aluminum silicate (feldspar), titanium dioxide, zinc sulfide, and iron sulfate minerals have been also identified. The rodlets were analyzed directly for C, H, N, O, and total S and are interpreted as true resins on the basis of C and H contents that range from 75.6 to 80.3 and from 7.4 to 8.7 wt. % (dry, ash-free basis), respectively. Elemental and infrared data support a composition similar to that of resinite from bituminous coal. Elements determined to be organically associated in the rodlets include S (0.2–0.5 wt.%), Cl (0.03–0.1 wt.%), and Si (0.05–0.08 wt.%). The ash content of the resin rodlets ranges from 4 to 24 wt.% and averages 12 wt.%. Total sulfur contents range from 1.7 to 3.6 wt.%. Resins of fossil plants are known to have little or no sulfur and ash; therefore, these data and the presence of minerals in fractures indicate that most of the sulfur and mineral matter were introduced into the resin partly or wholly after the time of brittle fracture of the resin. The probable source of the resin rodlets is fossil pinaceous conifer cones, which are known to have resin canals as much as 2400 μm in diameter.     

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji.The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C₁, C₂, etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found.The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal.An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids.