Direct conversion of calcium carbonate to C-1-C-3 hydrocarbons

With the objective of investigating the direct conversion of inorganic carbonates such as CaCO3 to hydrocarbons, assisted by transition metal ions, we have carried out studies on CaCO3 in an intimate admixture with iron oxides (FeCaCO) with a wide range of Fe/Ca mole ratios (x), prepared by co-precipitation. The hydrogen reduction of FeCaCO at 673 K gives up to 23% yield of the hydrocarbons CH4, C2H4, C2H6 and C3H8, leaving solid iron residues in the form of iron metal, oxides and carbide particles. The yield of hydrocarbons increases with x and the conversion of hydrocarbons occurs through the formation of CO. While the total yield of hydrocarbons obtained by us is comparable to that in the Fischer-Tropsch synthesis, the selectivity for C-2-C-3 hydrocarbons reported here is noteworthy.

A coat of many scents: Cuticular hydrocarbons in multitrophic interactions of fig wasps with ants

The fig fig wasp system of Ficus racemosa constitutes an assemblage of galler and parasitoid wasps in which tritrophic interactions occur. Since predatory ants (Oecophylla smaragdina and Technomyrmex albipes) or mostly trophobiont-tending ants (Myrmicaria brunnea) were previously shown to differentially use volatile organic compounds (VOCs) from figs as proximal cues for predation on fig wasps, we examined the response of these ants to the cuticular hydrocarbons (CHCs) of the wasps. CHC signatures of gallers were distinguished from those of parasitoids by the methyl-branched alkanes 5-methylpentacosane and 13-methylnonacosane which characterised trophic group membership. CHC profiles of wasp predator and wasp prey were congruent suggesting that parasitoids acquire CHCs from their prey; the CHC composition of the parasitoid Apocrypta sp 2 clustered with that of its galler host Apocryptophagus fusca, while the CHC profile of the parasitoid Apocryptophagus agraensis clustered with its galler prey, the fig pollinator Ceratosolen fusciceps. In behavioural assays with ants, parasitoid CHC extracts evoked greater response in all ant species compared to galler extracts, suggesting that parasitoid CHC extracts contain more elicitors of ant behaviour than those of plant feeders. CHCs of some wasp species did not elicit significant responses even in predatory ants, suggesting chemical camouflage. Contrary to earlier studies which demonstrated that predatory ants learned to associate wasp prey with specific fig VOCs, prior exposure to fig wasp CHCs did not affect the reaction of any ant species to these CHCs. (C) 2015 Elsevier Masson SAS. All rights reserved.

Sediment Quality in Puget Sound Year 3 - Southern Puget Sound

As a component of a three-year cooperative effort of the Washington State Department of Ecology and the National Oceanic and Atmospheric Administration, surficial sediment samples from 100 locations in southern Puget Sound were collected in 1999 to determine their relative quality based on measures of toxicity, chemical contamination, and benthic infaunal assemblage structure. The survey encompassed an area of approximately 858 km2, ranging from East and Colvos Passages south to Oakland Bay, and including Hood Canal. Toxic responses were most severe in some of the industrialized waterways of Tacoma’s Commencement Bay. Other industrialized harbors in which sediments induced toxic responses on smaller scales included the Port of Olympia, Oakland Bay at Shelton, Gig Harbor, Port Ludlow, and Port Gamble. Based on the methods selected for this survey, the spatial extent of toxicity for the southern Puget Sound survey area was 0% of the total survey area for amphipod survival, 5.7% for urchin fertilization, 0.2% for microbial bioluminescence, and 5- 38% with the cytochrome P450 HRGS assay. Measurements of trace metals, PAHs, PCBs, chlorinated pesticides, other organic chemicals, and other characteristics of the sediments, indicated that 20 of the 100 samples collected had one or more chemical concentrations that exceeded applicable, effects-based sediment guidelines and/or Washington State standards. Chemical contamination was highest in eight samples collected in or near the industrialized waterways of Commencement Bay. Samples from the Thea Foss and Middle Waterways were primarily contaminated with a mixture of PAHs and trace metals, whereas those from Hylebos Waterway were contaminated with chlorinated organic hydrocarbons. The remaining 12 samples with elevated chemical concentrations primarily had high levels of other chemicals, including bis(2-ethylhexyl) phthalate, benzoic acid, benzyl alcohol, and phenol. The characteristics of benthic infaunal assemblages in south Puget Sound differed considerably among locations and habitat types throughout the study area. In general, many of the small embayments and inlets throughout the study area had infaunal assemblages with relatively low total abundance, taxa richness, evenness, and dominance values, although total abundance values were very high in some cases, typically due to high abundance of one organism such as the polychaete Aphelochaeta sp. N1. The majority of the samples collected from passages, outer embayments, and larger bodies of water tended to have infaunal assemblages with higher total abundance, taxa richness, evenness, and dominance values. Two samples collected in the Port of Olympia near a superfund cleanup site had no living organisms in them. A weight-of-evidence approach used to simultaneously examine all three “sediment quality triad” parameters, identified 11 stations (representing 4.4 km2, 0.5% of the total study area) with sediment toxicity, chemical contamination, and altered benthos (i.e., degraded sediment quality), 36 stations (493.5 km2, 57.5% total study area) with no toxicity or chemical contamination (i.e., high sediment quality), 35 stations (274.1 km2, 32.0% total study area) with one impaired sediment triad parameter (i.e., intermediate/high sediment quality), and 18 stations (85.7km2, 10.0% total study area) with two impaired sediment parameters (i.e., intermediate/degraded quality sediments). Generally, upon comparison, the number of stations with degraded sediments based upon the sediment quality triad of data was slightly greater in the central Puget Sound than in the northern and southern Puget Sound study areas, with the percent of the total study area degraded in each region decreasing from central to north to south (2.8, 1.3 and 0.5%, respectively). Overall, the sediments collected in Puget Sound during the combined 1997-1999 surveys were among the least contaminated relative to other marine bays and estuaries studied by NOAA using equivalent methods. (PDF contains 351 pages)

Survey of sediment quality in Sabine Lake, Texas and vicinity

The toxicity of sediments in Sabine Lake, Texas, and adjoining Intracoastal Waterway canals was determined as part of bioeffects assessment studies managed by NOAA’s National Status and Trends Program. The objectives of the survey were to determine: (1) the incidence and degree of toxicity of sediments throughout the study area; (2) the spatial patterns (or gradients) in chemical contamination and toxicity, if any, throughout the study area; (3) the spatial extent of chemical contamination and toxicity; and (4) the statistical relationships between measures of toxicity and concentrations of chemicals in the sediments. Surficial sediment samples were collected during August, 1995 from 66 randomly-chosen locations. Laboratory toxicity tests were performed as indicators of potential ecotoxicological effects in sediments. A battery of tests was performed to generate information from different phases (components) of the sediments. Tests were selected to represent a range in toxicological endpoints from acute to chronic sublethal responses. Toxicological tests were conducted to measure: reduced survival of adult amphipods exposed to solid-phase sediments; impaired fertilization success and abnormal morphological development in gametes and embryos, respectively, of sea urchins exposed to pore waters; reduced metabolic activity of a marine bioluminescent bacteria exposed to organic solvent extracts; and induction of a cytochrome P-450 reporter gene system in exposures to solvent extracts of the sediments. Chemical analyses were performed on portions of each sample to quantify the concentrations of trace metals, polynuclear aromatic hydrocarbons, and chlorinated organic compounds. Correlation analyses were conducted to determine the relationships between measures of toxicity and concentrations of potentially toxic substances in the samples. Based upon the compilation of results from chemical analyses and toxicity tests, the quality of sediments in Sabine Lake and vicinity did not appear to be severely degraded. Chemical concentrations rarely exceeded effects-based numerical guidelines, suggesting that toxicant-induced effects would not be expected in most areas. None of the samples was highly toxic in acute amphipod survival tests and a minority (23%) of samples were highly toxic in sublethal urchin fertilization tests. Although toxic responses occurred frequently (94% of samples) in urchin embryo development tests performed with 100% pore waters, toxicity diminished markedly in tests done with diluted pore waters. Microbial bioluminescent activity was not reduced to a great degree (no EC50 <0.06 mg/ml) and cytochrome P-450 activity was not highly induced (6 samples exceeded 37.1 ug/g benzo[a]pyrene equivalents) in tests done with organic solvent extracts. Urchin embryological development was highly correlated with concentrations of ammonia and many trace metals. Cytochrome P450 induction was highly correlated with concentrations of a number of classes of organic compounds (including the polynuclear aromatic hydrocarbons and chlorinated compounds). (PDF contains 51 pages)

Sampling and analytical methods of the National Status and Trends Program Mussel Watch Project: 1993-1996 Update

Polycyclic aromatic hydrocarbons, butyltins, polychlorinated biphenyls, DDT and metabolites, other chlorinated pesticides, trace and major elements, and a number of measures of contaminant effects are quantified in bivalves and sediments collected as part of the NOAA National Status and Trends (NS&T) Program. This document contains descriptions of some of the sampling and analytical protocols used by NS&T contract laboratories from 1993 through 1996. (PDF contains 257 pages)

Exciplexes in fluorescence quenching of aromatic hydrocarbons by tertiary aliphatic amines

Strong quenching of the fluorescence of aromatic hydrocarbons by tertiary aliphatic amines has been observed in solution at room temperature. Accompanying the fluorescence quenching of aromatic hydrocarbons, an anomalous emission is observed. This new emission is very broad, structureless and red-shifted from the original hydrocarbon fluorescence.

Kinetic studies indicate that this anomalous emission is due to an exciplex formed by an aromatic hydrocarbon molecule in its lowest excited singlet state with an amine molecule. The fluorescence quenching of the aromatic hydrocarbons is due to the depopulation of excited hydrocarbon molecules by the formation of exciplexes, with subsequent de-excitation of exciplexes by either radiative or non-radiative processes.

Analysis of rate constants shows the electron-transfer nature of the exciplex. Through the study of the effects on the frequencies of exciplex emissions of substituents on the hydrocarbons, it is concluded that partial electron transfer from the amine molecule to the aromatic hydrocarbon molecule in its lowest excited singlet state occurs in the formation of exciplex. Solvent effects on the exciplex emission frequencies further demonstrate the polar nature of the exciplex.

A model based on this electron-transfer nature of exciplex is proposed and proves satisfactory in interpreting the exciplex emission phenomenon in the fluorescence quenching of aromatic hydrocarbons by tertiary aliphatic amines.

Analysis of soils and sediments for organic pollutants

20 samples of soil or sediment (7 of which were predominantly sand) from various locations were received for analysis of their content of organic pollutants. These analyses were performed using a capillary column gas chromatograph equipped with an electron impact (E.I.) mass spectrometer as detector and using computerised data storage. In addition to the target compounds, the full scan data were examined to determine the composition of natural organic products and a series of diagnostic fragment ions was used to search for additional anthropogenic products. Organic-rich environmental samples are notoriously difficult to analyse for pollutant organics owing to the presence of high concentrations of many natural organic compounds. A single procedure for extraction and clean-up was adopted. It was designed for chlorinated aliphatic and aromatic hydrocarbons and other pesticides containing acidic functional groups and was based on published methods for the determination of organic pollutants in soils and sediments. 4 soils and 2 sands showed levels of one or two groups of PCBs slightly in excess of the detection limit, one sample showed a similar level of 2,4-D and 3 samples contained dieldrin at or just above the detection limit.

Petroleum hydrocarbons in fresh waters: a preliminary desk study and bibliography

A literature survey was carried out into the effects of petroleum hydrocarbons in freshwater, from the toxicity, biodegradability and concentration aspects. It was supplemented by a selective search on hydrocarbons in the marine environment for comparison. The aim was to determine the major inputs of these hydrocarbons, their accumulation, effects and fate in freshwaters. The search was confined to the period 1965-1978. The bibliography contains 390 references, divided by subject.

Measurement of polycyclic aromatic hydrocarbons in ambient air by fluorescence spectroscopic techniques

250 p. + anexos

Research on operating conditions at the catalytic reactor for the combined removal of NOx and PCDD/PCDFs from MWI plants

The management of municipal solid waste (MSW), particularly the role of incineration, is currently a subject of public debate. Incineration shows to be a good alternative of reducing the volume of waste and eliminating certain infectious components. Moreover, Municipal Waste Incinerators (MWI), are reported to be highly hygienic and apart from that MWIs are immediately effective in terms of transport (incinerators can be built close to the waste sources) and incineration's nature. Nevertheless, the emissions of many hazardous substances make the Municipal Waste Incineration (MWI) plants to be unpopular. Metals (especially lead, manganese, cadmium, chromium and mercury) are concentrated in fly and bottom ashes. Furthermore, incomplete combustion produces a wide variety of potentially hazardous organic compounds, such as aldehydes, polycyclic aromatic hydrocarbons (PAH), chlorinated hydrocarbons including polychlorinated dibenzodioxins (PCDD) and dibenzofurans (PCDF), and even acid gases, including NOx. Many of these hazardous substances are carcinogenic and some have direct systemic toxicity.

Concentrations of Polychlorinated Biphenyls (PCB’s), Chlorinated Pesticides, and Heavy Metals and Other Elements in Tissues of Belugas, Delphinapterus leucas, from Cook Inlet

Tissues from Cook Inlet beluga whales, Delphinapterus leucas, that were collected as part of the Alaska Marine Mammal Tissue Archival Project were analyzed for polychlorinated biphenyls (PCB’s), chlorinated pesticides, and heavy metals and other elements. Concentrations of total PCB’s (ΣPCB’s), total DDT (ΣDDT), chlordane compounds, hexachlorobenzene (HCB), dieldrin, mirex, toxaphene, and hexachlorocyclohexane (HCH) measured in Cook Inlet beluga blubber were compared with those reported for belugas from two Arctic Alaska locations (Point Hope and Point Lay), Greenland, Arctic Canada, and the highly contaminated stock from the St. Lawrence estuary in eastern Canada. The Arctic and Cook Inlet belugas had much lower concentrations (ΣPCB’s and ΣDDT were an order of magnitude lower) than those found in animals from the St. Lawrence estuary. The Cook Inlet belugas had the lowest concentrations of all (ΣPCB’s aver-aged 1.49 ± 0.70 and 0.79 ± 0.56 mg/kg wet mass, and ΣDDT averaged 1.35 ± 0.73 and 0.59 ± 0.45 mg/kg in males and females, respectively). Concentrations in the blubber of the Cook Inlet males were significantly lower than those found in the males of the Arctic Alaska belugas (ΣPCB’s and ΣDDT were about half). The lower levels in the Cook Inlet animals might be due to differences in contaminant sources, food web differences, or different age distributions among the animals sampled. Cook Inlet males had higher mean and median concentrations than did females, a result attributable to the transfer of these compounds from mother to calf during pregnancy and during lactation. Liver concentrations of cadmium and mercury were lower in the Cook Inlet belugas (most cadmium values were <1 mg/kg and mercury values were 0.704–11.42 mg/kg wet mass), but copper levels were significantly higher in the Cook Inlet animals (3.97–123.8 mg/kg wet mass) than in Arctic Alaska animals and similar to those reported for belugas from Hudson Bay. Although total mercury levels were the lowest in the Cook Inlet population, methylmercury concentrations were similar among all three groups of the Alaska animals examined (0.34–2.11 mg/kg wet mass). As has been reported for the Point Hope and Point Lay belugas, hepatic concentrations of silver were re