Negative effects of humic acid addition on phytoremediation of pyrene-contaminated sediments by mangrove seedlings

Vegetated (with Kandelia candel seedlings) and non-vegetated mangrove microcosms were employed to remove pyrene from contaminated sediments, and the effects of adding 6.7% humic acid (HA) on such removal were investigated. At the end of 6-month treatment, residual pyrene concentrations in surface sediments (0-2 cm) of the contaminated microcosms reduced from an initial 5.82 to 0.63 microg g(-1) dw, and the reduction was less in HA amended microcosms with the residual pyrene concentration remained at 3.12 microg g(-1) dw. The pyrene removal percentages in microcosms with HA amendment were 29% for surface aerobic sediments and 41% for bottom (anaerobic) sediments, while the respective removal percentages in microcosms without HA amendment were 89% (surface sediments) and 53% (bottom sediments). Microcosms planted with K. candel seedlings had a significantly higher pyrene removal when compared to the non-vegetated ones, and the average removal percentages were 70.9% and 61.4%, respectively. However, when humic acid was added, no significant difference was found between vegetated and non-vegetated microcosms in pyrene removal, both had less than 40% removal, probably because plant growth in humic acid amended contaminated microcosms, in terms of total biomass, was reduced by 50%. Roots of K. candel could accumulate pyrene from contaminated microcosms, and pyrene concentrations in roots harvested from microcosms with and without humic acid addition were 6.01 and 3.46 microg g(-1) dw, respectively. These results suggest that the addition of HA to contaminated sediments decreased the mangrove microcosm's ability to remove pyrene as pyrene was more tightly bound to the organic matter and plant growth was reduced.     

Effect of heavy metal stress on antioxidative enzymes and lipid peroxidation in leaves and roots of two mangrove plant seedlings (Kandelia candel and Bruguiera gymnorrhiza)

The effects of multiple heavy metal stress on the activity of antioxidative enzymes and lipid peroxidation were studied in leaves and roots of two mangrove plants, Kandelia candel and Bruguiera gymnorrhiza, grown under control (10 per thousand NaCl nutrient solution) or five levels of multiple heavy metal stress (10 per thousand NaCl nutrient solution containing different concentration of Pb2+, Cd2+, and Hg2+). Leaves and roots of control and heavy metal-stressed plants were harvested after two months. In leaves of heavy metal-stressed plants superoxide dismutase (SOD) and peroxidase (POD) activities fluctuated in different stress levels compared to the control, while catalase (CAT) activity increased with stress levels in K. candel, but remained unchanged in leaves of B. gymnorrhiza. In comparison with the control, the dynamic tendency of SOD, CAT, and POD activities in roots of heavy metal-stressed plants all ascended, and then declined. The increase in enzyme activities demonstrated that K. candel is more tolerant to heavy metals than B. gymnorrhiza. Lipid peroxidation was enhanced only in leaves of heavy metal-stressed B. gymnorrhiza. These results indicate that in heavy-metal stress antioxidative activities may play an important role in K. candel and B. gymnorrhiza and that cell membrane in leaves and roots of K. candel have greater stability than those of B. gymnorrhiza. For pollution monitoring purposes, POD activity in roots and leaves maybe serve as a biomarker of heavy metal stress in K. candel, while lipid peroxidation maybe serve as biomarker in B. gymnorrhiza.     

Spatial variation of heavy metals in surface sediments of Hong Kong mangrove swamps

The degree of heavy metal contamination in the fine-grained (<63 microm) and sand-sized (2 mm-63 microm) fractions of surface sediments in 18 different mangrove swamps (144 random samples) in Hong Kong was examined. Higher concentrations of heavy metals were found in the fine-grained than the sand-sized fractions of the sediment; however, the differences between these two fractions became less significant when the swamp was more contaminated. The principal component analyses show that the 18 mangrove swamps, according to the median concentrations of total heavy metals, were clustered into four groups. The first group included three mangrove swamps in Deep Bay region which are seriously contaminated, with heavy metal concentrations in sediments around 80 microg g(-1) Cu, 240 microg g(-1) Zn, 40 microg g(-1) Cr, 30 microg g(-1) Ni, 3 microg g(-1) Cd and 80 microg g(-1) Pb. The second cluster, made up of another four swamps distributed in different geographical locations (two in Sai Kung district and two in Tolo region), also had elevated levels of Cu, Pb, Ni and Cr in the sediments. Field observation reveals that these seven stands received industrial, livestock and domestic sewage as well as pollution from mariculture activities, suggesting that anthropogenic input is the main source of heavy metal contamination in Hong Kong mangroves. The sediments from other mangrove swamps were relatively uncontaminated.     

Conditions for effective removal of pyrene from an artificially contaminated soil using Pseudomonas aeruginosa 57SJ rhamnolipids

The efficacy of a new rhamnolipid biosurfactants mixture to enhance the removal of pyrene from a soil artificially contaminated was investigated. The molar solubilization ratio (MSR) and the partition coefficient between the micelles and water (log K(m)) were found to be 7.5 x 10(-3) and 5.7, respectively. From soil column studies, the pyrene removal increased linearly with the concentration of the injected biosurfactants solution above the effective critical micellar concentration (0.4 g L(-1)). Flushing with a 5.0 g L(-1) biosurfactants solution increased the pyrene concentration in the effluent by 178 times. At high biosurfactants' concentrations (2.5 and 5.0 g L(-1)), the cumulative pyrene recovery reached 70%. This pyrene remobilization takes place independently of the soil organic carbon solubilization. This study provides a combination of batch and column experiments in order to find the conditions for effective soil remediation using a new rhamnolipids mixture.     

Mercury,zinc, and copper accumulation in mangrove sediments surrounding a large landfill in southeast Brazil

The accumulation of Hg, Zn, and Cu was evaluated in mangrove sediments located between a large, 20-years-old landfill and waters of Guanabara Bay (southeast Brazil). The contamination history of the area provides substantial evidence that metal accumulation in the study site is influenced by past metal emissions from multiple sources (e.g. contaminated rivers and the landfill surrounding the site). At the southern part of the site, metal levels are up to 890 ng g(-1) Hg, 850 microg g(-1) Zn, and 58 microg g(-1) Cu. Enrichment factors and excess (background-deducted) concentration inventories show a high spatial variability of metal contamination and storage in the site, with differences often by a factor higher than two within a sampling station and higher than five between sampling stations. These contrasts are attributable to a coupling between spatial variability of anthropogenic metal input and metal behavior and retention within the sediments. Results indicate that during the last few decades mangrove sediments retained a substantial part of metal emissions to the site, probably reducing the metal transport to Guanabara Bay waters, and suggest the suitability of mangrove ecosystems as physical and biogeochemical barriers to metal contaminant transport.     

Contamination of polycyclic aromatic hydrocarbons in surface sediments of mangrove swamps

The concentrations of total polycyclic aromatic hydrocarbons (sigmaPAHs) and 15 individual PAH compounds in 20 surface sediments collected from four mangrove swamps in Hong Kong were analysed. sigmaPAH concentrations ranged from 356 to 11,098 ng g(-1) dry weight with mean and median values of 1992 and 1,142 ng g(-1), respectively. These values were significantly higher than those of marine bottom sediments of Hong Kong harbours, suggesting that more PAHs were accumulated in mangrove surface sediments. The concentrations of sigmaPAHs as well as individual PAH compound varied significantly among mangrove swamps. The swamps heavily polluted by livestock and industrial sewage, such as Ho Chung and Mai Po, had much higher concentrations of total PAHs and individual PAH than the other swamps. The PAH profiles were similar among four mangrove swamps, and were dominated by naphthalene (two-ring PAH), fluorene and phenanthrene (three-ring PAH). The mangrove sediments had higher percentages of low-molecular-weight PAHs. These indicated that PAHs in mangrove sediments might originate from oil or sewage contamination (petrogenic input). Ratio values of specific PAH compounds such as phenanthrene/anthracene and fluoranthene/ pyrene, were calculated to evaluate the possible source of PAH contamination in mangrove sediments. These ratios varied among samples, suggesting that mangrove sediments might have a mixed pattern of pyrolytic and petrogenic inputs of PAHs. Sediments collected from Ho Chung mangrove swamp appeared to be more dominated by pyrolytic input while those from Tolo showed strong petrogenic contamination.     

Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium enriched from mangrove sediments

The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase microextraction (SPME) combining with gas chromatography–mass spectrometry (GC–MS) method. Seventeen metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene, methyl ester, and phthalic acid were found. The detection of various common and novel metabolites demonstrates that SPME combining with GC–MS is a quick and convenient method for identification as well as monitoring the real time changes of metabolite concentrations throughout the degradation processes. The knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.     

Evaluation of TCDD biodegradability under different redox conditions

Polychlorinated dibenzo-p-dioxins have been generated as unwanted by-products in many industrial processes. Although their widespread distribution in different environmental compartments has been recognized, little is known about their fate in the ultimate environment sinks. The highly stable dioxin isomer 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been called the most toxic compound known to man. In this laboratory microcosm study, TCDD bioavailability was evaluated under five reduction/oxidation (redox) conditions including aerobic biodegradation, aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Activated sludge and aquifer sediments from a TCDD and a pentachlorophenol (PCP) contaminated site were used as the inocula. Acetate, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in cometabolism and reductive dechlorination microcosms. After a 90-day incubation period, microcosms constructed under reductive dechlorination conditions were the only treatment showing promising remediation results. The highest TCDD degradation rate [up to 86% of TCDD removal (with an initial concentration of 96 microg/kg of soil)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cakes as the primary substrates. Except for reductive dechlorination microcosms, no significant TCDD removal was observed in the microcosms prepared under other conditions. Thus, application of an effective primary substrate to enhance the reductive dechlorination process is a feasible method for TCDD bioremediation. Bioremediation expense can be significantly reduced by the supplement of some less expensive alternative substrates (e.g., sludge cakes, cane molasses). Results would be useful in designing a scale-up in situ or on-site bioremediation system such as bioslurry reactor for field application.     

Diffusion of PAH and PCB from contaminated sediments with and without mineral capping; measurement and modelling

A novel laboratory microcosm test was developed to measure the diffusion of native PAHs and PCBs from sediments in the presence and absence of a capping layer. Diffusive flux of 15 PAHs and 7 PCBs from uncapped sediment from Oslo harbour was 3.8+/-0.9 microg m(-2)d(-1) and 0.010+/-0.003 microg m(-2)d(-1), respectively. The flux from sediments capped with 1cm mineral cap (crushed limestone or crushed gneiss (0-2mm)), observed during the first 410 d, was 3.5-7.3% of the flux from uncapped sediments. By measuring freely dissolved pore water concentrations of 10 PAHs the flux in the microcosm was modelled with steady state and transient diffusion models. The measured flux from uncapped sediment was 27-290% of modelled steady state flux. Good agreement was also found between the measured flux of pyrene from capped sediment and the flux modelled with the transient model when fitting only with the distribution coefficients for pyrene between the cap material and water (Kd_pyr). Fitted Kd_pyr, (210 and 23 l kg(-1) for limestone and gneiss, respectively) was in the same order of magnitude as K(d) calculated from organic carbon content in the cap materials (68 and 14 l kg(-1) respectively). Calculation of the efficiency of a hypothetical cap with 10 cm diffusion path shows that the increased diffusion path length alone can yield a flux reduction >99% through a strong increase in the stagnant diffusive boundary layer from <1 to 100mm.     

Bioaccumulation of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene by mussels transplanted in a coastal lagoon

The bioaccumulation of two isomeric non-alternant non-priority polycyclic aromatic hydrocarbons (PAHs), namely cyclopenta[cd]pyrene and benzo[ghi]fluoranthene, was investigated in caged mussels (Mytilus galloprovincialis) exposed for 30 days in three sites of a coastal lagoon (Pialassa Baiona, Ravenna, Italy) contaminated by pyrogenic PAHs. The concentration of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene increased from undetectable levels in reference mussels withdrawn from the Adriatic sea to 10-30 ng g(-1) dry weight in transplanted mussels. Other contaminants bioaccumulated by caged mussels included pyrene, fluoranthene and mercury. Whilst the isomer concentration ratio pyrene/fluoranthene in biota was comparable to that observed in sediments, the cyclopenta[cd]pyrene/benzo[ghi]fluoranthene ratio was much lower in mussels than in sediments. The lower sediment biota accumulation factor of cyclopenta[cd]pyrene with respect to that of benzo[ghi]fluoranthene was tentatively attributed to the greater biological activity of the former compound, which contains a reactive olefinic bond in the cyclopenta fused ring moiety. Given the higher mutagenic activity of cyclopenta[cd]pyrene with respect to other priority PAHs, its bioaccumulation from contaminated sediments may rise considerably the overall toxicity of PAH residues in exposed biota.     

Lead concentrations in soil, sediment and clam samples from the Pungo River peatland area of North Carolina, USA

Lead (Pb) concentrations were measured in samples of peat soils, sediments and clams (Rangia cuneata) collected from the Pungo River region of coastal North Carolina. In peat soils, mean Pb concentrations (dry weight +/- 1 SD) were significantly higher (p<0.05) in surface samples (12.8microg g(-1)+/-7.6) than in samples from depths of 20 cm (2.7microg g(-1)+/-2.7) or 1 m (3.6microg g(-1)+/-3.6). Mean Pb concentrations in surface sediments from canals draining peatlands and from the Pungo River which receives this drainage ranged from 0.1microg g(-1)+/-0.1 to 7.0microg g(-1)+/-0.6. These Pb concentrations are similar to values reported in other studies for areas considered uncontaminated. Fractionation analysis revealed that the majority of the Pb in the peat and sediment samples was associated with the residual fraction, with lesser amounts in the organically-bound fraction, and generally negligible amounts in the water-soluble fraction. These results indicate that the bulk of the Pb in the soils and sediments of this area is relatively immobile and non-bioavailabe. This is supported by the relatively low concentrations of Pb (0.2-0.5 microg g(-1), dry weight) observed in soft tissues of R. cuneata collected from the Pungo River.     

Oil pollution in Qatari coastal sediments

The present study focuses on the areal distribution of petroleum hydrocarbons in the Qatari coastal-belt sediments. Total petroleum hydrocarbons were quantified by ultra-violet fluorescence spectroscopy (UVF) for eighteen surface-sediment samples collected from six different areas along the Qatari coastline. Petroleum hydrocarbons are ubiquitous in the sediments studied, and their concentrations ranged from 48 microg g(-1) dw Kuwaiti-oil equivalents on the eastern side of the peninsula to 248 microg g(-1) dw Kuwaiti-oil equivalents on the western side. Concentrations of petroleum hydrocarbons in Qatari coastal sediments were very heterogeneous from one area to another and showed a decreasing sequence in the following order: Al-Zubarah (215 microg g(-1) dw) > Dukhan (143 microg g(-1) dw) > Ruwais (108 microg g(-1) dw) > Umm Said (89 microg g(-1) dw) > Fuwairet (81 microg g(-1) dw) > Doha (5 microg g(-1) dw Kuwaiti-crude-oil equivalents). This could indicate that the possible sources of oil on the Qatari coasts are mainly external on the western side and local on the eastern one. No significant correlation was found between organic C (0.6-1.4%) and petroleum-hydrocarbon concentrations.     

Dissipation of PAHs in saturated, dredged sediments: a field trial

Sediments dredged from navigable rivers often contain elevated concentrations of recalcitrant, potentially toxic organic compounds such as polychlorinated biphenyls (PCBs) and polyaromatic hydrocarbons (PAHs). The presence of these compounds often requires that the sediments be stored in fully contained disposal facilities. A 3-year field study was conducted at the Jones Island disposal facility in Milwaukee, Wisconsin, to compare bioremediation of PAHs in contaminated dredged sediments in the absence of plants to phytoremediation with Salix nigra (black willow) (SX61), Spartina pectinata (prairie cord grass), Carex aquatalis (lake sedge), Lolium multiflorum (annual rye), and Scirpus fluviatilis (bulrush). Nine PAHs were detected initially in the sediments. Over the 3-year experiment, acenaphthene dissipation ranged from 94% to 100%, whereas anthracene, benzo[a]pyrene and indo[1,2,3-cd]pyrene generally had modest decreases in concentration (0-30% decrease). The remaining five PAHs ranged in degree of disappearance from 23% to 82%. Planted treatments did not enhance PAH dissipation relative to those without plants, but treatments with high biomass yield and high transpiration plant species had significantly less removal of PAHs than unplanted controls. Significant, negative correlations between nitrogen removal and decreases in PAH concentration suggest that competition for nutrients between plants and microorganisms may have impeded the microbial degradation of PAHs in the rhizosphere of the more rapidly growing plant species.     

Mineralization of PAHs in coal-tar impacted aquifer sediments and associated microbial community structure investigated with FISH

The microbial community structure and mineralization of polycyclic aromatic hydrocarbons (PAHs) in a coal-tar contaminated aquifer were investigated spatially using fluorescence in situ hybridization (FISH) and in laboratory-scale incubations of the aquifer sediments. DAPI-detected microbial populations in the contaminated sediments were three orders of magnitude greater than nearby uncontaminated sediments, suggesting growth on coal-tar constituents in situ. Actinobacteria, beta- and gamma-Proteobacteria, and Flavobacteria dominated the in situ aerobic (>1 mg l(-1) dissolved oxygen) microbial community, whereas sulfate-reducing bacteria comprised 37% of the microbial community in the sulfidogenic region of the aquifer. Rapid mineralization of naphthalene and phenanthrene were observed in aerobic laboratory microcosms and resulted in significant enrichment of beta- and gamma-Proteobacteria potentially explaining their elevated presence in situ. Firmicutes, Flavobacteria, alpha-Proteobacteria, and Actinobacteria were also enriched in the mineralization assays, but to a lesser degree. Nitrate- and sulfate-limited mineralization of naphthalene in laboratory microcosms occurred to a small degree in aquifer sediments from locations where groundwater chemistry indicated nitrate- and sulfate-reduction, respectively. Some iron-limited mineralization of naphthalene and phenanthrene was also observed in sediments originating near groundwater measurements of elevated ferrous iron. The results of this study suggest that FISH may be a useful tool for providing a much needed link between laboratory microcosms and groundwater measurements made in situ necessary to better demonstrate the potential for natural attenuation at complex PAH contaminated sites.     

Relationship between copper speciation in sediments and bioaccumulation by marine bivalves of Taiwan

This paper evaluates the relationships between copper species in sediments and accumulation by the purple clam (Hiatula diphos) and venus clam (Gomphina aeguilatera) collected from the field and culture (aquaculture) ponds in the polluted coastal area of Lukang, Taiwan. Sediment was sampled along with the molluscs, including oysters (Crassostrea gigas), purple clams (Hiatula diphos), rock-shells (Thais clavigera), venus clams (Gomphina aeguilatera), and hard clams (Meretrix lusoria), from two unique environments of Lukang during the period from August 1993 to July 1994. The data indicate that the total copper concentrations in sediments from culture ponds (185 microg g(-1)) was higher than those of the field (44.0 microg g(-1)). Copper species in sediments were analyzed by a sequential leaching technique. Results show that concentrations of various copper species in the sediments are in the range of 1.14 +/- 0.59 to 13.2 +/- 22.4 microg g(-1) and 0.36 +/- 0.24 to 133 +/- 36.7 microg g(-1) for the two environments, respectively. Also the exchangeable copper in sediment from culture ponds was 15 times higher than that from the field. In addition, the sum of exchangeable and copper carbonates had the highest percentages of copper in both the pond sediment (86.6 %) and the field sediment (50.7 %). Maximum copper concentrations (309 +/- 35.1 microg g(-1)) in oysters were much higher than those in the other benthic organisms by about 4-127 times. Similarly, the data also showed that copper concentrations in Thais clavigera were 12-32 times higher than those in other benthic organisms. Copper concentrations in various benthic organisms differed significantly (p < 0.05) from that in Thais clavigera. This capacity makes Thais clavigera a potential candidate for monitoring copper in marine sediments. In terms of copper species, the best correlation was generally obtained between copper carbonates in sediments and copper concentrations in Hiatula diphos (r = 0.886*). A strong multiple regression correlation (p < 0.05, r2 = 0.7894) also indicates that the copper carbonates may dominate as the available form of copper to Hiatula diphos from various environments in the Lukang coastal area under natural physicochemical conditions.     

Effects of pig manure compost and nonionic-surfactant Tween 80 on phenanthrene and pyrene removal from soil vegetated with Agropyron elongatum

This paper evaluates the effects of pig manure compost (PMC) and Tween 80 on the removal of phenanthrene (PHE) and pyrene (PYR) from soil cultivated with Agropyron elongatum. Soils spiked with about 300mgkg(-1) of PHE and PYR were individually amended with 0%, 2.5%, 5% and 7.5% (dry wt) of PMC or 0, 20 and 100mgkg(-1) of Tween 80. Unplanted and sterile microcosms were prepared as the controls. PAH concentration, total organic matter (TOM), dissolved organic carbon (DOC), total heterotrophic and PAH degrading microbial populations in soil were quantified before and after 60d period. The results indicated that A. elongatum could significantly enhance PYR removal (from 46% to 61%) but had less impact on PHE removal (from 96% to 97%). Plant uptake of the PAHs was insignificant. Biodegradation was the key mechanism of PAH removals (<3% losses in the sterile control). Increase in PMC or Tween 80 levels increased the removal of PYR but not of PHE. Maximal PYR removal of 79% and 92% were observed in vegetated soil receiving 100mgkg(-1) Tween 80 and 7.5% PMC, respectively. Enhanced PYR removal in soil receiving PMC could be explained by the elevated levels of DOC, TOM and microbial populations as suggested by Pearson correlation test. While the positive effect of Tween 80 on PYR removal could probably due to its capacities to enhance PYR bioavailability in soil. This paper suggests that the addition of either PMC or nonionic-surfactant Tween 80 could facilitate phytoremediation of PAH contaminated soil.     

Uptake of polycyclic aromatic hydrocarbons (PAHs) in salt marsh plants Spartina alterniflora grown in contaminated sediments

Polycyclic aromatic hydrocarbon (PAH) concentrations were measured in Spartina alterniflora plants grown in pots of contaminated sediment, plants grown in native sediment at a marsh contaminated with up to 900 microg/g total PAHs, and from plants grown in uncontaminated control sediment. The roots and leaves of the plants were separated, cleaned, and analyzed for PAHs. PAH compounds were detected at up to 43 microg/g dry weight in the root tissue of plants grown in pots of contaminated soil. PAH compounds were detected at up to 0.2 microg/g in the leaves of plants grown in pots of contaminated soil. Concentrations less than 0.004 microg/g were detected in the leaves of plants grown at a reference site. Root concentration factor (RCF) values ranged from 0.009 to 0.97 in the potted plants, and from 0.004 to 0.31 at the contaminated marsh site. Stem concentration factor (SCF) values ranged from 0.00004 to 0.03 in the potted plants and 0.0002 to 0.04 at the contaminated marsh. No correlation was found between the RCF value and PAH compound or chemical properties such as logKOW. SCF values were higher for the lighter PAHs in the potted plants, but not in the plants collected from the contaminated marsh. PAH concentrations in the roots of the potted plants are strongly correlated with soil concentrations, but there is less correlation for the roots grown in natural sediments. Additional plants were grown directly in PAH-contaminated water and analyzed for alkylated PAH homologs. No difference was found in leaf PAH concentrations between plants grown in contaminated water and control plants.     

Oil spill in the Rio de la Plata estuary, Argentina: 2-hydrocarbon disappearance rates in sediments and soils

The 6-month assessment of the oil spill impact in the Rio de la Plata described in the preceding paper [Colombo, J.C., Barreda, A., Bilos, C., Cappelletti, N., Demichelis, S., Lombardi, P., Migoya, M.C., Skorupka, C., Suarez, G., 2004. Oil spill in the Rio de la Plata estuary, Argentina: 1 - biogeochemical assessment of waters, sediments, soils and biota. Environmental Pollution] was followed by a 13- and 42-month campaigns to evaluate the progress of hydrocarbon decay. Average sediment hydrocarbon concentrations in each sampling include high variability (85-260%) due to contrasting site conditions, but reflect a significant overall decrease after 3 years of the spill: 17 +/- 27, 18 +/- 39 to 0.54 +/- 1.4 microg g(-1) for aliphatics; 0.44 +/- 0.49, 0.99 +/- 1.6 to 0.04 +/- 0.03 microg g(-1) for aromatics at 6, 13 and 42 months, respectively. Average soil hydrocarbon levels are 100-1000 times higher and less variable (61-169%) than sediment values, but display a clear attenuation: 3678 +/- 2369, 1880 +/- 1141 to 6.0 +/- 10 microg g(-1) for aliphatics and 38 +/- 26, 49 +/- 32 to 0.06 +/- 0.04 microg g(-1) for aromatics. Hydrocarbon concentrations modeled to first-order rate equations yield average rate constants of total loss (biotic+abiotic) twice as higher in soils (k = 0.18-0.19 month(-1)) relative to sediments (0.08-0.10 month(-1)). Individual aliphatic rate constants decrease with increasing molecular weight from 0.21 +/- 0.07 month(-1) for isoprenoids and n-C27, similar to hopanes (0.10 +/- 0.05 month(-1)). Aromatics disappearance rates were more homogeneous with higher values for methylated relative to unsubstituted species (0.17 +/- 0.05 vs. 0.12 +/- 0.05 months(-1)). Continued hydrocarbon inputs, either from biogenic (algal n-C15,17; vascular plant n-C27,29) or combustion related sources (fluoranthene and pyrene), appear to contribute to reduced disappearance rate. According to the different loss rates, hydrocarbons showed clear compositional changes from 6-13 to 42 months. Aliphatics disappearance rates and compositional changes support an essentially microbiologically-mediated recovery of coastal sediments to pre-spill conditions in a 3-4 year period. The lower rates and more subtle compositional changes deduced for aromatic components, suggest a stronger incidence of physical removal processes.     

Net methylmercury production as a basis for improved risk assessment of mercury-contaminated sediments

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p < 0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.     

Phytoremediation of pyrene contaminated soils amended with compost and planted with ryegrass and alfalfa

Ryegrass (Lolium perenne) and alfalfa (Medicago sativa) were planted in pots to remediate pyrene contaminated quartz sand (as a control group), alluvial and red soils amended with and without compost. The pyrene degradation percentages in quartz sand, alluvial soil, and red soil amended with compost (5%, w/w) and planted with ryegrass and alfalfa for 90 d growth were 98-99% and 97-99%, respectively, while those of pyrene in the corresponding treatments amended without compost but planted with ryegrass and alfalfa were 91-96% and 58-89%, respectively. Further, those of pyrene in the respective treatments amended with and without compost but unplanted were 54-77% and 51-63%, respectively. Pyrene contents in both roots and aboveground parts of ryegrass and alfalfa after 90 d growth in quartz sand and the two soils amended with or without compost were trace amounts. Statistical analyses for the parameters of ryegrass planted in red and alluvial soils including the concentrations of total water-soluble volatile low molecular weight organic acids, microbial population, pyrene degradation percentage, and spiked pyrene concentration show significant correlations at 5% and mostly 1% probability levels, by the analysis of variance. It was thus suggested that the interactions among the consortia of plant root exudates, microorganisms, and amended compost in rhizosphere soils could facilitate bioavailability of pyrene and subsequently enhance its dissipation.