An experimental marine ecosystem study of the pelagic biogeochemistry of pentachlorophenol

The marine biogeochemistry of pure pentachlorophenol was studied relative to a control treatment at a scale which provided a good model for the pelagic planktonic environment (70 m³ polyethylene bags). Pentachlorophenol that was dispersed at concentrations of 10 and 100 μg/litre showed identical relative rates of decrease over 25 days to concentrations 32·8% and 31·1%, respectively, of the initial concentrations. No bioaccumulation by phytoplankton or zooplankton was observed and pentachlorophenol removal by adsorption (by particulates, zooplankton or the enclosure walls) was insignificant. The log of the pentachlorophenol concentration was significantly correlated to the hours of bright sunshine up to Day 18, after which the photolysis efficiency decreased as the proportion of pentachlorophenol exposed to sunlight decreased. The results imply a long residence time for pentachlorophenol in deeper waters outside the photolysis zone. A persistent reduction in the primary production and production per unit carbon was observed at 100 μg/litre and, when coupled to the reproducible demise of the centric diatom Skeletonema costatum in culture and the spiked enclosures, suggests that pentachlorophenol inhibits phytoplankton growth.     

Distribution of calcareous nannoplankton in surface sediments along the northern KwaZulu-Natal Bight,South Africa

The coccolith assemblages from seafloor sediments over the inner shelf in the northern region of the KwaZulu- Natal Bight on the east coast of South Africa were identified and their distribution determined. In all, 29 Recent species and taxonomic groups, as well as 29 reworked species were recorded. The distribution of the Recent species appears to be governed by environmental features that have been documented in other studies: temperature, salinity, nutrient concentration and water circulation pattern, which reveals the long-term existence of a circulation cell in the sector between Durban Bay and the Thukela River. The outer edge of the cell consists of nutrient-enriched mixed layers and is characterised by an enhanced abundance of Gephyrocapsa oceanica, whereas the central region consists of a stratified nutrient-depleted water mass with elevated abundance of Umbilicosphaera sibogae, Florisphaera profunda, and a group of umbelliform species. The elevated levels of G. oceanica, coupled with the rarity of U. sibogae, F. profunda and the umbelliform species, confirm the presence of a permanent upwelling cell off Richards Bay. The maximum abundance of F. profunda found between Richards Bay and Lake Nhlabane indicates a region of nutrient-depleted (except for nitrite) conditions.     

Early Proterozoic,basaltic andesite tuff-breaccia: downslope,subaqueous mass transport of phreatomagmatically-generated tephra

At Bear Lake, in the Flin Flon-Snow Lake greenstone belt of Manitoba, 400⁺ m of thick-to very thick-bedded, generally ungraded, basaltic andesite tuff-breccia, breccia, and lapilli-tuff are intercalated with pillowed lava flows in the upper part of an early Proterozoic submarine basaltic andesite shield volcano. The fragmental rocks comprise angular, amygdaloidal blocks and lapilli, many with partial chilled selvages, in a matrix of blocky, non-amygdaloidal to highly amygdaloidal vitric basaltic andesite ash and small lapilli. Minor thin-to medium-bedded, commonly normally graded tuff occurs in the upper part of the sequence. Clasts in fragmental beds consistently have higher amygdule contents than intercalated lava flows. Although similar to pillow-fragment breccias, the Bear Lake fragmental rocks were produced by extended surtseyan-type, phreatomagmatic eruptions, with associated fire fountain activity, at a progressively subsiding, shallow water vent. Periodic tephra slumping generated debris flows that transported particles down the uppe, gentle slope of the volcano to a depositional site at a water depth of less than 1 km. Turbidity currents probably carried much fine tephra to deeper water; tuff was deposited in the preserved section only after explosive volcanism ceased.     

Biota: sediment partitioning of aluminium smelter related PAHs and pulp mill related diterpenes by intertidal clams at Kitimat, British Columbia

The question of polycyclic aromatic hydrocarbon (PAH) bioavailability and its relationship to specific PAH sources with different PAH binding characteristics is an important one, because bioavailability drives PAH accumulation in biota and ultimately the biochemical responses to the PAH contaminants. The industrial harbour at Kitimat (British Columbia, Canada) provides an ideal location to study the bioavailability and bioaccumulation of sediment hydrocarbons to low trophic level biota. Samples of soft shell clams (Mya arenaria) and intertidal sediment collected from multiple sites over six years at various distances from an aluminium smelter and a pulp and paper mill were analysed for 106 PAHs, plant diterpenes and other aromatic fraction hydrocarbons. Interpretation using PAH source ratios and multivariate data analysis reveals six principal hydrocarbon sources: PAHs in coke, pitch and emissions from anode combustion from the aluminium smelter, vascular plant terpenes and aromatised terpenes from the pulp and paper mill, petroleum PAHs from shipping and other anthropogenic activities and PAHs from natural plant detritus. Harbour sediments predominantly contain either pitch or pyrogenic PAHs from the smelter, while clams predominantly contain plant derived PAHs and diterpenes from the adjacent pulp mill. PAHs from the smelter have low bioavailability to clams (Biota-Sediment Accumulation Factors; BSAFs <1 for pitch and coke; <10 for anode combustion, decreasing to ∼0.1 for the mass 300 and 302 PAHs), possibly due to binding to pitch or soot carbon matrices. Decreases in PAH isomer ratios between sediments and clams likely reflect a combination of variation in uptake kinetics of petroleum PAHs and compound specific metabolism, with the importance of petroleum PAHs decreasing with increasing molecular weight. Plant derived compounds exhibit little natural bioaccumulation at reference sites, but unsaturated and aromatised diterpenes released from resins by industrial pulping processes are readily accumulated by the clams (BSAFs >500). Thus while most of the smelter associated PAHs in sediments may not be bioavailable to benthic organisms, the plant terpenes (including retene, totarol, ferruginol, manool, dehydroabietane and other plant terpenes that form the chemical defence mechanism of conifers) released by pulp mills are bioavailable and possess demonstrated toxic properties. The large scale release of plant terpenes by some of the many pulp mills located in British Columbia and elsewhere represents a largely undocumented risk to aquatic biota.     

Structural features and mechanical behaviour of a pyroclastic weak rock

The results of an extensive programme of laboratory testing on intact and reconstituted samples of a pyroclastic weak rock from the volcanic complex of the Colli Albani (Central Italy) are presented. The deposit is known as Pozzolana Nera and may be assimilated to a bonded coarse grained material. The nature of bonds and the micro‐structural features were examined by means of diffractometry, optical and electron microscopy. As bonds are made of the same constituents of grains and aggregates of grains, bond deterioration and particles breakage upon loading are indistinguishable features of the mechanical behaviour. The testing programme consisted mainly of one‐dimensional and drained and undrained triaxial compression tests in a wide range of confining pressures up to 58 MPa. As confining stress increases, the mechanical behaviour of the material changes from brittle and dilatant to ductile and contractant; for both brittle and ductile behaviour failure is associated with the formation of shear surfaces separating the sample in several parts at the end of test. The experimental stress–dilatancy relationships are compared with the classical stress–dilatancy theories for a purely frictional material and for a material with friction and cohesion between particles. The analysis of the data indicates that peak strength results from the interplay between degradation of inter‐particle bonds, increasing friction between particles and increasing rate of dilation. Copyright © 2001 John Wiley & Son, Ltd.     

Alkane and PAH biomarkers as tracers of terrigenous organic carbon in Arctic Ocean sediments

We present the first sedimentary biomarker study encompassing the entire Arctic Ocean. A large data set of organic markers for terrigenous, petroleum and combustion inputs [alkanes, hopanes and steranes, parent and alkyl polycyclic aromatic hydrocarbons (PAHs)] is examined for patterns in space and time using principal components analysis (PCA) and partial least squares (PLS). Biomarker patterns reveal the central Arctic Ocean basin sediments to be compositionally distinct from those of the Mackenzie River/Beaufort Sea and Barents Sea, but similar to those of the Laptev Sea. PAH distributions reflected in PAH ratios and PCA projections demonstrate that Arctic Ocean sediment is dominated by natural inputs to the extent that anthropogenic combustion PAHs are not significant. We find only modest changes between the glacial and post-glacial sediments for atmospherically transported hydrocarbon biomarkers, while particle associated biomarkers were captured strongly at basin edges during the glacial period, and much more evenly transported across basins during the post-glacial period. The orders of magnitude decreases in particle associated petrogenic alkanes and PAHs in central basins during glacial times, coupled with the uniformity of most petrogenic biomarker parameters for most basin and shelf locations, reflect a massive reduction in ice transport that makes the margins the most likely source of petrogenic material for the Pleistocene/Holocene central Arctic basins. The proximity of large coal deposits of various maturity levels along the Lena River, the overlap in PAH and biomarker composition of the Laptev Sea and surficial sediments from the central Arctic Ocean and the location of the Laptev Sea at the origin of the main Transpolar Drift all point to eroded coals from the Lena River/Laptev Sea as the likely source of petrogenic hydrocarbons to the central Arctic Ocean. The ubiquitous presence of allochthonous coal in Arctic Ocean surface sediments provides a major constraint on the use of petrogenic biomarkers to infer the presence of subsurface petroleum reserves.     

Tracing the inputs and fate of marine and terrigenous organic matter in Arctic Ocean sediments: A multivariate analysis of lipid biomarkers

An understanding of the carbon cycle within arctic sediments requires discrimination between the terrigenous and marine components of organic carbon, insight into the removal mechanisms for labile carbon during burial and appreciation of shelf-to-basin processes. Using a large data set of multiple molecular organic markers (alkanes, alkanols, sterols, saturated and unsaturated fatty acids, dicarboxylic acids), we apply (1) principal components analysis (PCA) to obtain a robust comparison of biomarker compositions in Arctic Ocean sediments, (2) geometric mean (GM) linear regression of the PCA variables to estimate the relative contributions of labile/marine and stable/terrigenous sources to each biomarker and (3) the slope of the GM regression of each biomarker with TOC to provide a novel measure of the removal rate of each biomarker relative to phytol. The PCA- and TOC-based indices generally increase together: biomarkers with very high TOC-based removal rates such as the saturated and unsaturated n-alkanoic acids generally have a high labile/marine content from PCA, while the sterols have low removal rates, but exhibit a range of labile/marine content values and the n-alkanes and n-alkanols have low values for both. A dominant feature of all PCA models examined is a progressive decrease in the autochthonous/marine biomarkers with each increase in sediment core depth, which points to a universal diagenetic alteration of organic carbon with depth in the cores. The PCA model also displays a shelf to basin trend that is non-diagenetic and implies the ongoing (centuries or more) delivery of long-chain n-alkanes, n-alcohols and n-alkanoic acids in a matrix that is pre-formed and well-preserved within the sediments. Terrigenous biomarker distributions within the PCA model suggest that atmospheric transport of plant waxes in aerosols and the water borne transport of very fine plant macerals likely have significant roles in the export of these vascular plant biomarkers to the basins. Biomarker ratios and profiles of the PCA-based labile/marine content with core depth indicate that the PCA model is more strongly influenced by the biomarker lability than the marine content, while increases in the marine content are largely responsible for the shifts in composition for near-surface core sections.