(Table 1) Organic geochemistry at DSDP Leg 71 Holes

Forty-three core samples from Sites 511 through 514 of DSDP Leg 71 were analyzed geochemically. The black shales at the bottom of Hole 511, in the basin province of the Falkland Plateau, contain an average of 1590 ppm extractable organic matter (EOM) and 120 ppm hydrocarbons. Whereas molecular type-carbon number distributions of mono- and polynuclear aromatic hydrocarbons and their sulphur and oxygen analogues in the black shale "aromatic hydrocarbon" fractions are very similar to those of many crude oils, other data - gas chromatography (GC) fingerprint, pyrolysis GC, visual kerogen analysis, H/C ratio - suggest the black shale section is thermally immature. Together, these observations imply that many of the hydrocarbons were deposited with the original sediments or are diagenetic products of other biological compounds. Pyrograms of the humic acid and kerogen fractions from the black shale interval are typical of geopolymers derived from marine algal material. It appears that these humic acids and kerogens are derived from the same lipid stock.

(Table 1) Lithological and organic-geochemical compositions of bottom sediments from the Southwestern Indian Ocean (Mozambique Basin)

Geochemical changes in organic matter of bottom sediments from the Mozambique Basin at the river-sea barrier from the mouths of the Zambezi and Limpopo rivers toward the pelagic zone are discussed. Changes in bitumen, hydrolyzable material, humic acids, amino acids, n-alkanes, and polycyclic aromatic compounds resulting from genetic and diagenetic factors are described. This information is significant for paleoceanology reconstructions and for knowing ways of organic matter transformation into fossil forms.

Composition of organic matter in bottom sediments from the Antarctic sector of the Atlantic Ocean

We identify geochemical features of sedimentary organic matter in various morphostructural zones of the Antarctic sector of the Atlantic. We present background geochemical organic parameters for shelf and deep-sea sediments from the Weddell and Scotia Seas and the Bransfield Strait. Geochemical organic parameters are good indicators of environmental and facial variations in sediments and could be used for environmental monitoring of the World Ocean.

Accumulation rates and composition of organic matter in sediments off Peru

Deep-sea sediment samples from three Ocean Drilling Program (ODP) Leg 112 sites on the Peru continental margin were investigated, using a number of organic geochemical and organic petrographic techniques, for amounts and compositions of the organic matter preserved. Preliminary results include mass accumulation rates of organic carbon at Site 679 and characteristics of the organic facies for sediments from Sites 679, 681, and 684. Organic-carbon contents are high, with few exceptions. Particularly high values were determined in the Pliocene interval at Site 684 (4%-7.5%) and in the early Pliocene to Quaternary section of Hole 679D (2%-9%). Older sediments at this site have distinctively lower organic-carbon contents (0.2%-2.5%). Mass accumulation rates of organic matter at Site 679 are 0.02 to 0.07 g carbon/cm**2/k.y. for late Miocene to early Pliocene sediments and higher by a factor of 5 to 10 in the Quaternary sediments. The organic matter in all samples has a predominantly marine planktonic and bacterial origin, with minor terrigenous contribution. Organic particle sizes are strikingly small, so that only a minor portion is covered by visual maceral analysis. Molecular organic-geochemical data were obtained for nonaromatic hydrocarbons, aromatic hydrocarbons (including sulfur compounds), alcohols, ketones, esters, and carboxylic acids. Among the total extractable lipids, long-chain unsaturated ketones from Prymnesiophyte algae strongly predominate among the gas chromatography (GC) amenable components. Steroids are major constituents of the ketone and free- and bound-alcohol fractions. Perylene is the most abundant aromatic hydrocarbon, whereas in the nonaromatic hydrocarbon fractions, long-chain n-alkanes from higher land plants predominate, although the total terrigenous organic matter proportion in the sediments is small.

Investigation at Markham illegal dumping site : Markham, Cook County, Illinois.

"July 2010."

Estimating the Extent of Soil Contamination During a Redevelopment Excavation

From October 2014 to March 2015, I provided excavation oversight services at a property with substantial environmental concerns. The property in question is located near downtown Seattle and was formerly occupied by the Washington’s first coal gasification plant. The plant operated from 1888 to 1908 and produced coal gas for municipal use. A coal tar like substance with a characteristically high benzene concentration was a byproduct of the coal gasification process and heavily contaminated at or below the surface grade of the plant as shown in previous investigations on the property. Once the plant ceased operation in 1908 the property was left vacant until 1955 when the site was filled in and a service station was built on the property. The main goal of the excavation was not to achieve cleanup on the property, but to properly remove what contaminated soil was encountered during the redevelopment excavation. Areas of concern were identified prior to the commencement of the excavation and an estimation of the extent of contamination on the property was developed. “Hot spots” of contaminated soil associated with the fill placed after 1955 were identified as areas of concern. However, the primary contaminant plume below the property was likely sourced from the coal gasification plant, which operated at an approximate elevation of 20 feet. We planned to constrain the extents of the soil contamination below the property as the redevelopment excavation progressed. As the redevelopment excavation was advanced down to an elevation of approximately 20 feet, soil samples were collected to bound the extents of contamination in the upper portion of the site. The hot spots, known pockets of carcinogenic polycyclic aromatic hydrocarbons (cPAH) located above 20 feet elevation, were excavated as part of the redevelopment excavation. Once a hot spot was excavated, soil samples were collected from the north, south, east, west and bottom sidewalls of the hot spot excavation to check for remaining cPAH. Additionally, four underground storage tanks (USTs) associated with the service station were discovered and subsequently removed. Soil samples were also collected from the resulting UST excavation sidewalls to check for remaining petroleum hydrocarbons. Once the excavation reached its final excavation depth of 20 to 16 feet in elevation, bottom of excavation samples were collected on a 35 foot by 35 foot grid to test for concentrations of contaminants remaining onsite. Once the redevelopment excavation was complete, soils observed from borings drilled for either structural elements, geotechnical wells, or environmental wells were checked for any evidence of contamination using field screening techniques. Evidence of contamination was used to identify areas below the final excavation grade which had been impacted by the operation of the coal gasification plant. Samples collected from the excavation extents of hot spots and USTs show that it was unlikely that any contamination traveled from the post-1955 grade down to the pre-1955 grade. Additionally, the lack of benzene in the bottom of excavation samples suggests that a release from the coal gasification plant occurred below the redevelopment excavation final elevations of 20 to 16 feet. Qualitative data collected from borings for shoring elements and wells indicated that the spatial extent of the subsurface contaminant plume was different than initially estimated. Observations of spoils show that soil contamination extends further to the southwest and not as far to the east and north than originally estimated. Redefining the extent of the soil contamination beneath the property will allow further subsurface investigations to focus on collecting quantitative data in areas that still represent data gaps on the property, and passing over areas that have shown little signs of contamination. This information will help with the formation of a remediation plan should the need to clean up the site arise in the future.

Reactions catalyzed by bacterial cytochromes P450

The cytochromes P450 are a large family of oxidative haemoproteins that are responsible for a wide variety of oxidative transformations in a variety of organisms. This review focuses upon the reactions catalyzed specifically by bacterial enzymes, which includes aliphatic hydroxylation, alkene epoxidation, aromatic hydroxylation, oxidative phenolic coupling, heteroatom oxidation and dealkylation, and multiple oxidations including C-C bond cleavage. The potential for the practical application of the oxidizing power of these enzymes is briefly discussed.

Field-based evaluation of semipermeable membrane devices (SPMDs) as passive air samplers of polyaromatic hydrocarbons (PAHs)

Semipermeable membrane devices (SPMDs) have been used as passive air samplers of semivolatile organic compounds in a range of studies. However, due to a lack of calibration data for polyaromatic hydrocarbons (PAHs), SPMD data have not been used to estimate air concentrations of target PAHs. In this study, SPMDs were deployed for 32 days at two sites in a major metropolitan area in Australia. High-volume active sampling systems (HiVol) were co-deployed at both sites. Using the HiVol air concentration data from one site, SPMD sampling rates were measured for 12 US EPA Priority Pollutant PAHs and then these values were used to determine air concentrations at the second site from SPMD concentrations. Air concentrations were also measured at the second site with co-deployed HiVols to validate the SPMD results. PAHs mostly associated with the vapour phase (Fluorene to Pyrene) dominated both the HiVol and passive air samples. Reproducibility between replicate passive samplers was satisfactory (CV < 20%) for the majority of compounds. Sampling rates ranged between 0.6 and 6.1 m(3) d(-1). SPMD-based air concentrations were calculated at the second site for each compound using these sampling rates and the differences between SPMD-derived air concentrations and those measured using a HiVol were, on average, within a factor of 1.5. The dominant processes for the uptake of PAHs by SPMDs were also assessed. Using the SPMD method described herein, estimates of particulate sorbed airborne PAHs with five rings or greater were within 1.8-fold of HiVol measured values. (C) 2004 Elsevier Ltd. All rights reserved.

Monitoring PAHs in the Brisbane River and Moreton Bay, Australia, using semipermeable membrane devices and EROD activity in yellowfin bream, Acanthopagrus australis

Two water quality monitoring strategies designed to sample hydrophobic organic contaminants have been applied and evaluated across an expected concentration gradient in PAHs in the Moreton region. Semipermeable membrane devices (SPMDs) that sequester contaminants via passive diffusion across a membrane were used to evaluate the concentration of PAHs at four and five sites in spring and summer 2001/2002, respectively. In addition, induction of hepatic cytochrome P4501, EROD activity, in yellowfin bream, Acanthopagrus australis, captured in the vicinity of SPMD sampling sites following deployment in summer was used as a biomarker of exposure to PAHs and related chemicals. SPMDs identified a clear and reproducible gradient in PAH contamination with levels increasing from east to west in Moreton Bay and upstream in the Brisbane River. The highest PAH concentrations expressed as B(a)P-toxicity equivalents (TEQs) were found in urban areas, which were also furthest upstream and experienced the least flushing. Cytochrome P4501 induction in A. australis was similar at all sites. The absence of clear trends in EROD activity may be attributable to factors not measured in this study or variable residency time of A. australis in contaminated areas. It is also possible that fish in the Moreton region are displaying enzymatic adaptation, which has been reported previously for fish subjected to chronic exposure to organic contaminants. These potential interferences complicate interpretation of EROD activity from feral biota. It is, therefore, suggested that future monitoring combine the two methods by applying passive sampler extracts to in vitro EROD assays. (C) 2004 Elsevier Ltd. All rights reserved.