Promoted dissipation of phenanthrene and pyrene in soils by amaranth (<Emphasis Type="Italic">Amaranthus tricolor</Emphasis> L.)

A study was conducted to investigate the performance of amaranth, a known hyperaccumulator of cesium, on the promotion of the dissipation of soil phenanthrene and pyrene, which are PAHs (polycyclic aromatic hydrocarbons). Amaranthus tricolor L. een choi was the cultivar used. The presence of Amaranthus tricolor L. evidently enhanced the dissipation of these PAHs in soils with initial phenanthrene concentrations of 7.450–456.5 mg/kg dw (dw, dry weight) and pyrene of 8.010–488.7 mg/kg dw. At the end of the experiment (45 days), the residual concentrations of phenanthrene and pyrene in spiked soils with plants were generally higher than those with no plants. The loss of phenanthrene and pyrene in vegetated soils was 87.85–94.03% and 46.89–76.57% of the soil with these chemicals, which was 2.55–13.66% and 11.12–56.55% larger than the loss in non-vegetated soils, respectively. The accumulation of phenanthrene and pyrene by the plant was evident. Root and shoot concentrations of these chemicals monotonically increased with increasing soil PAH concentrations. Bioconcentration factors (BCFs), defined as the ratio of chemical concentrations in plants and in the soils (on a dry weight basis), of phenanthrene and pyrene by roots were 0.136–0.776 and 0.603–1.425, while by shoots were 0.116–0.951 and 0.082–0.517, respectively. BCFs of phenanthrene and pyrene tended to decrease with the increasing concentrations of soil phenanthrene and pyrene. Plant accumulation only accounted for less than 0.32% (for phenanthrene) and 0.33% (for pyrene) of the total amount enhancement of the dissipated PAHs in vegetated vs. non-vegetated soils. In contrast, plant-promoted microbial biodegradation was the predominant contribution to the plant-enhanced dissipation of soil phenanthrene and pyrene. These results suggested the feasibility of the radionuclide hyperaccumulator in phytoremediating the soil PAH contaminants.     

The role of zooplankton fecal pellets in the sedimentation of polycyclic aromatic hydrocarbons in Dabob Bay,Washington

Polycyclic aromatic hydrocarbon (PAH) compositions were determined in plankton, sediment-trap-collected particulate material and sediment cores from Dabob Bay using a high performance liquid Chromatographie (HPLC)/fluorescence technique. The annual flux of individual PAH measured in a series of sediment traps was compared with the flux of corresponding compounds determined from ²¹⁰Pb dated bottom sediments. Systematic seasonal variations in the fluxes and concentrations of PAH, Al and organic carbon in the trap-collected particulates and seasonally collected plankton were also investigated to determine whether or not PAH are associated with either terrestrial or marine-derived materials.Concentrations of all PAH studied increased tenfold within the last 80–100 yr of sediment deposition, except for perylene which displayed a reasonably constant concentration profile. This suggests at least two sources contribute to the observed sedimentary PAH compositions in Dabob Bay, i.e., anthropogenic combustion and a natural source. Plankton and sediment trap-collected particulates contained PAH mixtures qualitatively similar to underlying surface sediments. Microscopic examination indicated fecal pellets were the major form of particulate material in the sediment traps. The fecal pellets collected in the sediment trap time series quantitatively account for essentially 100% of the PAH fluxes measured in the ²¹⁰Pb dated sediments, implying Zooplankton fecal pellets control the removal of PAH to Dabob Bay sediments. These measurements provide clear evidence that the PAH studied are not produced after sediment deposition. The observed seasonal covariations of PAH and Al in both sediment trap and plankton samples further indicate that PAH originate from terrestrially-based sources, are introduced into the marine environment by runoff and erosion or atmospheric deposition and are not produced by marine plankton.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

Mono- and dicyclic unsaturated triterpenoid hydrocarbons in sediments from Lake Masoko (Tanzania) widely extend the botryococcene family

A mixture of C₃₃–C₃₇ botryococcenes and partially reduced derivatives was isolated from ca. 32,000 year old sediment from Lake Masoko, a freshwater crater lake in the Rungwe Range area (Tanzania). Botryococcenes and derivatives accounted for 246 μg/g dry sediment and for >92% of the hydrocarbon fraction; 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry allowed the structure of the dominant botryococcene (43% of hydrocarbon fraction) to be established, after purification using high performance liquid chromatography (HPLC). The compound is a novel tetraunsaturated dicyclic C₃₄ botryococcene and is named C₃₄ masokocene. Overall, the structures of six other novel botryococcenes and four partially reduced derivatives were tentatively assigned. The structures of the new biomarkers, three dicyclic C₃₄–C₃₆ botryococcenes (or masokocenes) and seven monocyclic C₃₄–C₃₇ analogues are discussed along with their biosynthetic relationship. The high abundance of such polyunsaturated compounds preserved in 32,000 year old sediment from the lake indicates an aquatic ecosystem dominated at the time by the green alga Botryococcus braunii, as well very good preservation of the organic matter.     

Indications for pedogenic formation of perylene in a terrestrial soil profile: Depth distribution and first results from stable carbon isotope ratios

Concentrations and isotope compositions of polycyclic aromatic hydrocarbons (PAHs) were determined in natural soils of Southern Germany. In selected profiles perylene concentrations increased with soil depth when compared to the other PAH compounds present. However, its low solubility made vertical transport by seepage water unlikely. Therefore two mechanisms are discussed that could have caused the unusual distribution of perylene in these soils:

(a) Atmospheric deposition of combustion-derived (i.e. pyrogenic) perylene in the top-soil and

(b) in situ generation in the sub-soil of these specific terrestrial environments. This could have been caused by microbial activities or other catalytic processes yet unknown.

In order to distinguish between pyrogenic and natural generation compound-specific ¹³C/¹²C ratios (δ¹³C) were compared between perylene and other PAHs in samples from the top-soil and sub-soil. Despite successful clean-up of the extracts, low perylene concentrations and peak overlaps with benzo(e)pyrene and benzo(a)pyrene prevented determination of a unique δ¹³C value for perylene in the upper horizon. However, the δ¹³C value of perylene in the sub-soil was 5.7 permille more negative than other equal-mass PAHs (with m/z of 252) in the top-soil, which rather supports in situ generation of perylene in the sub-soil.     

Total mercury and monomethylmercury in water, sediments, and hydrophytes from the rivers, estuary, and bay along the Bohai Sea coast, northeastern China

Mercury contamination in aquatic environments is of worldwide concern because of its high biomagnification factor in food chains and long-range transport. The rivers, estuary and the bay along the northwestern Bohai Sea coast, northeastern China have been heavily contaminated by Hg due to long-term Zn smelting and chlor-alkali production. This work investigated the distributions of total Hg (THg) and monomethylmercury (MMHg) in the water, sediment and hydrophytes from this area. Concentrations of THg in sediment (0.5–64 mg kg⁻¹) and water (39–2700 ng L⁻¹) were elevated by 1–3 orders of magnitude compared to background concentrations, which induced high concentrations of MMHg in these media. The highest concentration of MMHg in sediment reached 35 μg kg⁻¹, which was comparable to that in the Hg mining area, Wanshan, China, and the highest MMHg concentration of 3.0 ng L⁻¹ in the water sample exceeded the MMHg Chinese drinking water guideline of 1.0 ng L⁻¹. Concentrations of THg in a sediment profile from Jinzhou Bay were found to be consistent with annual Hg emission flux from a local Zn smelter (r = 0.74, p < 0.01), indicating that Hg contamination was mainly caused by Zn smelting locally. For some freshwater hydrophytes, concentrations of THg and MMHg ranged from 5.2 to 100 μg kg⁻¹ and 0.15 to 12 μg kg⁻¹, respectively. Compared to sediment, concentrations of THg in hydrophytes were 2–3 orders of magnitude lower but MMHg was comparable or higher, indicating that the bioaccumulation in plants was distinct for the two Hg species studied. The data suggest that a significant load of Hg has been released into the northwestern coastal region of the Bohai Sea.     

Algal pigments in sediments as a measure of eutrophication in the Baltic environment

A method of quantitative comparison of eutrophication of an area is proposed for the Baltic Sea, based on pigment content in sediments. The pigments concerned were chlorins a (i.e. chlorophylls a, b and selected chlorophyll a derivatives) and chlorophylls c. The analyses were performed on 300 samples from different layers of recent (0–10 cm) sediments, collected from about 50 stations, at different sites of the southern Baltic, including the estuaries of the two largest Polish rivers, in different seasons between 1992 and 2001, before and after the great flood of July 1997. The results are related to sampling site, sediment layer and hydrological conditions and also to organic carbon and E_h in sediments, oxygen and salinity in near-bottom waters. Depending on different chlorin a content in 0–1 and 0–10 cm layers, the sampling sites are classified into one of three groups: 1. Szczecin Lagoon and the Deep of Gda sk stations (permanently eutrophic, chl a in 0–1 cm >40 nmol/g, Σchlns a in 0–1 in 0–10 cm layer, Σchlns a_A in Σchlns a=55–65%), 2. Open sea stations (mesotrophic/oligotrophic, chl a in 0–1 cm <10 nmol/g, Σchlns a in 0–1 in 0–10 cm layer, Σchlns a_A in Σchlns a 50%; and 3. Coastal stations (periodically eutrophic, chl a in 0–1 cm 10–40 nmol/g, Σchlns a_A in Σchlns a 40%). The correlation coefficient between chlorophyll a and chlorophylls b and c indicates the classes of algae, which could be the main source of organic matter in the sediments. A high correlation with chlorophylls c is a marker of diatoms; a high correlation with chlorophyll b is a marker of green algae; and low correlation both with chlorophylls b and c—indicates a high blue–green algae input.     

Polycyclic aromatic hydrocarbon (PAH)-phase associations in Washington coastal sediment

Polycyclic aromatic (PAH) and aliphatic hydrocarbon compositions, organic carbon, nitrogen and lignin contents were determined in whole, unfractionated sediment from the Washington continental shelf and in discrete sediment fractions separated by particle size and density. At least 20 to 25% of perylene and PAH derived from pyrolytic processes and 50% of the retene measured in whole sediment are contained within organic C- and lignin-rich panicles of density ≤ 1.9 g/cc. These particles, which include primarily vascular plant remains and bits of charcoal, comprise less than 1% of the total sediment weight. In contrast, a series of methylated phenanthrene homologs, possibly of fossil origin, are concentrated in some component of the more dense, lithic matrix of the sediment. Equilibrium models of PAH sorption/desorption from aqueous phase onto small particles of high surface area do not appear applicable to the behavior of the major PAH types identified in this aquatic environment.     

Polycyclic aromatic hydrocarbons in an anoxic sediment core from the Pettaquamscutt River (Rhode Island,U.S.A.)

Fifteen sections from an anoxic sediment core were analyzed for polycyclic aromatic hydrocarbons (PAH). Two types of PAH were observed: (a) those from combustion sources such as pyrene and chrysene and (b) those from natural sources such as retene and perylene. The combustion PAH levels in core sections dated between 1900 and 1970 were much higher than in earlier sections; this indicated an anthropogenic origin of these PAH at this location. The perylene and retene core profiles show significant anomalies during the period 1850–1880. Organic carbon does not fluctuate markedly but δC-13 of organic carbon shows several unexplained excursions; one of which correlates with the perylene and retene anomalies.     

Polycyclic aromatic hydrocarbons in the soils of technogenic landscapes

An integrated study of qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAH) in the atmospheric precipitation-soil-lysimetric water system of aerotechnogenic polluted landscapes was conducted using high-performance liquid chromatography in a gradient mode. Only low-molecular weight polyarenes (phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, and chrysene) were found in the atmospheric precipitation and lysimetric waters. The growth of PAHs in soils is provided by the input of phenanthrene, fluoranthene, and pyrene with atmospheric precipitation. The absence of heavy PAHs (benzfluoranthenes, benz(a)pyrene, dibenz(a,h)anthracene, benz(ghi) perylene, and indeno[1,2,3-cd]pyrene) in the atmospheric precipitation and their identification in soil give grounds to state that their accumulation was caused mainly by transformation of organic matter during pedogenesis. The technogenic impact was estimated and criterion of the degree of soil pollution by PAH was proposed.     

Effects of physical mixing on the attenuation of polycyclic aromatic hydrocarbons in estuarine sediments

To examine the role of physical disturbance on the long-term preservation of polycyclic aromatic hydrocarbons (PAHs) in sediments, cores were collected from two sites removed from point sources of PAHs and representing contrasting seabed mixing regimes. Although ΣPAH concentrations in sediments over the past 50 years were not significantly different between the two sites, several PAH isomer ratios were significantly different (P<0.05) between the two sites. Downcore changes in PAH isomer ratios resulted from preferential losses of the more linear PAH isomers. Thus, episodic, intense seabed mixing contributes to more efficient removal of selected PAHs. However, PAHs are still sufficiently stable relative to mixing events that historical PAH profiles can be used to reconstruct major resuspension events.     

Sources of polycyclic aromatic hydrocarbons (PAHs) to northwestern Saskatchewan lakes east of the Athabasca oil sands

The past several decades have witnessed a significant expansion of mining activities in the Athabasca oil sands region, raising concerns about their impact on the surrounding boreal forest ecosystem. To better understand the extent to which distal sites are impacted by oil sands-derived airborne contaminants, we examine sources of polycyclic aromatic hydrocarbons (PAHs) in surface sediments and dated sediment cores from Saskatchewan lakes situated ∼100–220 km east–northeast of the main area of bitumen mining activities. The concentrations and fluxes of both parent and alkylated PAHs are low and show considerable variability over the past 70–100 years. Small yet discernible increases in PAH concentrations and fluxes occurred over the past 30 years, a trend which coincides with the rapid growth in bitumen production. However, several lines of evidence point to wildfires as the principal source of PAHs to these lakes: (1) the significant co-variations in most cores between retene (1-methyl-7-isopropyl phenanthrene) and other groups of parent and alkylated PAHs, (2) the similarity in compound specific δ¹³C signatures of the parent PAHs phenanthrene and pyrene in recently deposited surficial sediments and those corresponding to time intervals considerably pre-dating the large scale development of the oil sands and (3) the discernible up-core increases in the proportion of refractory carbon (i.e., char) in Rock-Eval 6 data. The collective evidence points to softwood combustion from boreal forest fires as the principal source of retene in sediments and the general increase in forest fire activity in this region over the past several decades as the source of refractory carbon. Mining activities associated with the Athabasca oil sands are thus not considered a major source of PAHs to these lakes.     

Elemental composition of sediment cores from a mangrove environment using neutron activation analysis

The geochemistry of Sepetiba Bay was studied in four sediment cores using a multi-element approach. Two cores were sampled in the more contaminated eastern part of the bay and two cores were sampled in the western region. The aim was to determine whether less common elements like the rare earths or the actinides are associated with contaminant metals like zinc in the Bay. Samples were analysed by instrumental neutron activation analysis that permits the quantification of total concentrations of metals (Ba, Co, Cr, Cs, Fe, Hf, Rb, Sc, Zn), rare earth elements (Ce, Eu, La, Lu, Sm and Yb), actinides (Th, U), non-metals and semi-metals (As, Br). Organic carbon and total sulphur were also analysed. The results show very strong zinc contamination in the top layers (more than 1000 μg g⁻¹) and background concentrations in the bottom (15 μg g⁻¹). Elements like chromium which would be expected to be released by the heavy industries of Sepetiba Bay, did not show a contamination profile, and concentrations remained close to those of natural environments. No evidence of any association between the zinc and other potential contaminant elements could be identified in this work.     

Nature of sedimentary organic matter in the lower reaches of the Godavari River basin, India

The distribution and nature of sedimentary organic matter (OM) have been examined in sediment cores collected from the lower reaches, including estuary, of the Godavari River in order to understand sedimentation patterns, sources, and diagenesis of OM. The samples were analyzed for organic carbon (Corg), total nitrogen, amino acids and hexosamines. The observed irregular trends in Corg distribution with depth indicate the unstable nature of bed sediment in the lower reaches of the river. Yet, in the lower estuarine region, regular trends in Corg distribution with depth reflect the deposition of sediment. The atomic ratio of Corg and total nitrogen (C/N; 10.5–16.1) also supported this observation. The distribution of amino acids and diagenetic indicators (β-ala+γ-aba mol.%, AA/HA and Glc-NH₂/Gal-NH₂) in individual cores revealed the post-depositional changes in the OM. In the core sediment from the lower reaches, there was no clear cut trend in amino acid content with depth. In the estuarine region, however, amino acid content was very low (50.5 and 186.5 μg g⁻¹) in the upper layers compared to that in the lower layers (558.5 and 1099.3 μg g⁻¹). Reactivity index (range 0.3–3.7) revealed that OM in the upper few centimeters, especially in the lower estuarine region, was more reactive relative to that in the deeper layers.     

Climate signals in sediment mineralogy of Lake Baikal and Lake Hovsgol during the LGM-Holocene transition and the 1-Ma carbonate record from the HDP-04 drill core

Modeling the bulk sediment XRD patterns allows insight into the environmental and depositional histories of two neighboring rift lake basins within the Baikal watershed. Parallel ¹⁴C-dated LGM-Holocene records in Lakes Baikal and Hovsgol are used to discuss the mineralogical signatures of regional climate change. In both basins, it is possible to distinguish ‘glacial’ and ‘interglacial’ mineral associations. Clay minerals comprise in excess of 50% of layered silicates in bulk sediment.The abundance of smectite (expandable) layers in mixed-layer illite–smectites and the total illite abundance are the main paleoclimatic indices in the clay mineral assemblage. Both indices exhibit coherent responses to the Bølling–Allerød and the Younger Dryas. The smectite layer index is not equivalent to the abundance of illite–smectite, because illite–smectite tends to transform into illite. Repeated wetting–drying cycles in soils and high abundance of expandable layers in illite–smectites (>42%) favor the process of illitization. This relationship is clearly shown in both Baikal and Hovsgol records for the first time. The opposite late Holocene trends in illite abundance in Lake Baikal and Lake Hovsgol records suggest that a sensitive optimal regime may exist for illite formation in the Baikal watershed with regard to warmth and effective moisture.The Lake Hovsgol sediments of the last glacial contain carbonates, suggesting a positive trend in the lake's water budget. A progressive change towards lower Mg content in carbonates indicates lowering mineralization of lake waters. This trend is consistent with the lithologic evidence for lake-level rise in the Hovsgol basin.The pattern of mineralogical changes during the past 20 ka is used to interpret bulk sediment and carbonate mineralogy of the long 81-m Lake Hovsgol drill core (HDP-04) with a basal age of 1 Ma. The interglacial-type silicate mineral associations are confined to several thin intervals; most of the sediment record is calcareous. Carbonates are represented by six main mineral phases: calcite, low-Mg calcite, intermediate/high-Mg calcite, dolomite, excess-Ca dolomite and metastable monohydrocalcite. These mineral phases tend to form stratigraphic successions indicative of progressive changes in lake water chemistry. Five sediment layers with abundant Mg-calcites in the HDP-04 section suggest deposition in a low standing lake with high mineralization (salinity) and high Mg/Ca ratios of lake waters. Lake Hovsgol sediments contain the oldest known monohydrocalcite, found tens of meters below lake bottom in sediments as old as 800 ka. This unusual find is likely due to the conditions favorable to preservation of this metastable carbonate.     

Compositional fractionation of polyaromatic hydrocarbons in the karst soils, South China

This study aims to explore the condensation and fractionation trends of persistent organic pollutants (POPs) in the karst soils. The tiankeng is a karst surface expression that can act as a focal point for introduction of contaminants to a karst aquifer, which may serve both as condenser for vapor phase POPs and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs in soils from the upper rim and floor of tiankeng is of interest in understanding the role of tiankeng in the long-distance transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in the surface soils from the upper rim and floor of Dashiwei tiankeng in Southern China were analyzed. The total PAH concentrations in soils were 23.40–190 ng g⁻¹, with phenanthrene being the most abundant. The distribution patterns of PAH compounds in the soil samples matched well with their properties. It indicated the heavy PAHs were susceptible to retention by the floor soils of tiankeng than light PAHs. A plot of Cfloor/Crim against PAH molecular weight gave a good positive relationship in the molecular weight range of 152–276. It is suggested that the floor soils can be focal points of more concentrated PAH and deserve attention. The concentrations of total PAHs in the floor soils (43.40–190 ng g⁻¹, mean 87.76 ng g⁻¹) were higher than those in the upper rim (23.40–88.94 ng g⁻¹, mean 57.74 ng g⁻¹). In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation is proposed as the major mechanism for the compositional fractionation of PAHs in the soils from the upper rim and floor of tiankeng.     

Distribution of hydrocarbons in the estuarine area of the Northern Dvina River during seasonal flood

Heavy contaminant load released into the Northern Dvina River during flooding increased the concentrations of aliphatic (AHC) and polcyclic aromatic (PAH) hydrocarbons in water and bottom sediments. The composition of hydrocarbons was different from that of the summer low flow season. The concentrations of dissolved and particulate AHC ranged from 12 to 106 and from 192 to 599 μg/l, respectively, and bottom sediments contained from 26.2 to 329 μg/g AHC and 4 to 1785 ng/g PAH. As the transformation of AHC occurred at low spring temperatures, the alkane composition was shown to be dominated by terrigenous compounds, whereas more stable PAH showed elevated contents of petrogenic and pyrogenic compounds. It was also shown that the Northern Dvina-Dvina Bay geochemical barrier prevents contaminant input into the White Sea, i.e., acts as a marginal filter.     

The effect of biodegradation on polycyclic aromatic hydrocarbons in reservoired oils from the Liaohe basin, NE China

The occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) has been studied in oil columns from the Liaohe basin, NE China, characterized by varied degrees of biodegradation. The Es3 oil column has undergone light to moderate biodegradation – ranging from levels 2 to 5 on the [Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide: Interpreting Molecular Fossils in Petroleum and Ancient Sediments. Prentice Hall, Englewood Cliffs, NJ, p. 363] scale (abbreviated as ‘PM level’) – while the shallower Es1 column has undergone more severe biodegradation, ranging from PM level 5 to 8. Both columns show excellent vertical biodegradation gradients, with degree of biodegradation increasing with increasing depth toward the oil–water contact (OWC). The compositional gradients in the oil columns imply mass transport control on degradation rates, with degradation occurring primarily at the OWC. The diffusion of hydrocarbons to the OWC zone will be the ultimate control on the maximum degradation rate. The chemical composition and physical properties of the reservoired oils, and the ‘degradation sequence’ of chemical components are determined by mixing of fresh oil with biodegraded oil.The PAH concentrations and molecular distributions in the reservoired oils from these biodegraded columns show systematic changes with increasing degree of biodegradation. The C₃₊-alkylbenzenes are the first compounds to be depleted in the aromatic fraction. Concentrations of the C_0–5-alkylnaphthalenes and the C_0–3-alkylphenanthrenes decrease markedly during PM levels 3–5, while significant isomer variations occur at more advanced stages of biodegradation (>PM level 4).The degree of alkylation is a critical factor controlling the rate of biodegradation; in most cases the rate decreases with increasing number of alkyl substituents. However, we have observed that C₃-naphthalenes concentrations decrease faster than those of C₂-naphthalenes, and methylphenanthrenes concentrations decrease faster than that of phenanthrene. Demethylation of a substituted compound is inferred as a possible reaction in the biodegradation process.Differential degradation of specific alkylated isomers was observed in our sample set. The relative susceptibility of the individual dimethylnaphthalene, trimethylnaphthalene, tetramethylnaphthalene, pentamethylnaphthalene, methylphenanthrene, dimethylphenanthrene and trimethylphenanthrene isomers to biodegradation was determined. The C₂₀ and C₂₁ short side-chained triaromatic steroid hydrocarbons are degraded more readily than their C_26–28 long side-chained counterparts. The C_21–22-monoaromatic steroid hydrocarbons (MAS) appear to be more resistant to biodegradation than the C_27–29-MAS.Interestingly, the most thermally stable PAH isomers are more susceptible to biodegradation than less thermally stable isomers, suggesting that selectivity during biodegradation is not solely controlled by thermodynamic stability and that susceptibility to biodegradation may be related to stereochemical structure. Many commonly used aromatic hydrocarbon maturity parameters are no longer valid after biodegradation to PM level 4 although some ratios change later than others. The distribution of PAHs coupled with knowledge of their biodegradation characteristics constitutes a useful probe for the study of biodegradation processes and can provide insight into the mechanisms of biodegradation of reservoired oil.     

Spatial variation in pore water geochemistry in a mangrove system (Pai Matos island, Cananeia-Brazil)

Spatial variation in salinity, pH, redox potential, and in the concentrations of dissolved Mn, Fe²⁺ and sulphides in pore water were investigated in a mangrove system in the state of São Paulo (Brazil). Total organic C (TOC), S, Fe and Mn were analyzed in the solid phase, along with acid volatile sulphide (AVS), density of roots and percentage of sand. Five zones, situated along the length of a 180 m transect were considered in the study. Four of these were colonized by different species of vascular plants (Spartina, Laguncularia, Avicennia and Rhizophora) and were denominated soils; the other was not colonized by vegetation, and was denominated sediment. The results indicated important differences between the physicochemical conditions of the pore water in the vegetated zones and the sediment. In the former, two geochemical environments were identified, based on soil depths. The upper 20 cm contained the largest quantity of roots, and the conditions were oxic (Eh > 350 mV) or suboxic (Eh: 100–350 mV), acidic, and with high concentrations of Fe and Mn in the pore water. Below this depth, the soil became anoxic, the concentration of sulphides (HS⁻) increased significantly and the concentrations of dissolved Fe and Mn decreased significantly. The total S and the AVS fraction increased with depth, while TOC concentrations decreased, indicating that the decreases in Fe and Mn were due to the precipitation of metal sulphides. However, clear differences among the vegetated zones were not observed. The sediment was always anoxic, but with low concentrations of sulphide in the interstitial water, and was neutral or slightly alkaline. As in the soils, the concentrations of sulphides and total S increased significantly with depth, indicating that the conditions favoured the synthesis and stability of metal sulphides.