Seasonal variation of polycyclic aromatic hydrocarbons concentrations in urban streams at Niterói City,RJ, Brazil

Polycyclic aromatic hydrocarbons (PAHs) were determined in water samples collected in two streams and a lake located at Niteroi City, Rio de Janeiro State, Brazil between October 2008 and September 2009. Samples were extracted using liquid–liquid extraction and analyzed using high performance liquid chromatography with fluorescence detection. The limits of quantification were sufficiently low to accomplish PAH determination below the maximum concentration levels established by the Brazilian (50 ng/L) and USEPA legislations, with recoveries larger than 81.6%. Phenanthrene, fluoranthene, pyrene and benz[a]anthracene predominated among PAHs. Total concentrations of PAHs were well correlated with rainfall indicating a possible role of runoff to local pollution of water by PAHs and showed a seasonal variation in wet and dry seasons. Our results highlight the contribution of the widespread streams located around Guanabara Bay to the PAH burden found in its waters.     

The Hydrophobicity of Hydrocarbondissolved Benz (a) pyrene

With carcinogenic benz(a)pyrene as an example the distribution of polycyclic arenes in the hydrocarbon-water system is shown to be independent of the hydrophobicity of hydrocarbon present as their carrier and to be constant for the series of paraffins and benzene studied in both fresh and salt water. The hydrocarbon-carrier hinders the penetration of benz(a)pyrene into water, the free energy of the system increases (~ by 4.5 kJ/mole) due to an increase of the hydrophobic interaction of molecules. The increase in temperature from 20 to 50 °C influences the distribution of benz(a)pyrene in the hydrocarbon-water system insignificantly. Changes in standard thermodynamic parameters of the transition of polycyclic arene from the solution in alkane (benzene) into water (enthalpy Δ H°, entropy Δ S°, and free energy Δ G°) are calculated. Negative values of entropy point to the additional “structurization” of water in the course of the solution of hydrocarbons in it. Mineral salts do not influence the transition of carcinogenic arene into water.     

Polycyclic aromatic hydrocarbons in commercial fish and lobsters from the coastal waters of Madagascar following an oil spill in August 2009

Concentrations of polycyclic aromatic hydrocarbons were determined in species of commercial fish and lobsters following an oil-spill just off the protected Madagascan coastline. Samples were collected along the coastline within and outside the affected area. Summed PAH concentrations ranged from 1.9 μg kg⁻¹ to 63 μg kg⁻¹ wet weight, but with no higher molecular weight PAHs (>202 Da) being detected. All concentrations of benzo[a]pyrene, benz[a]anthracene and dibenz[a,h]anthracene were <0.1 μg kg⁻¹ wet weight, well within the EU and UK set limits for the protection of human health. Additionally, samples were calculated as the benzo[a]pyrene toxic equivalency quotient (TEQ) and found to be well below the level of concern in relation to health of human consumers. Evaluation of the biota PAH data indicated the origin of PAH was predominantly petrogenic with >80% arising from oil sources. Profile studies indicate a low-level multisource petrogenic contamination probably representing a pre-spill background for the area.     

Marine-derived filamentous fungi and their potential application for polycyclic aromatic hydrocarbon bioremediation

Eight marine-derived fungi that were previously selected for their abilities to decolorize RBBR dye were subjected to pyrene and benzo[a]pyrene degradation. The fungus Aspergillus sclerotiorum CBMAI 849 showed the best performance with regard to pyrene (99.7%) and benzo[a]pyrene (76.6%) depletion after 8 and 16 days, respectively. Substantial amounts of benzo[a]pyrene (>50.0%) depletion were also achieved by Mucor racemosus CBMAI 847. Therefore, these two fungal strains were subjected to metabolism evaluation using the HPLC-DAD-MS technique. The results showed that A. sclerotiorum CBMAI 849 and M. racemosus CBMAI 847 were able to metabolize pyrene to the corresponding pyrenylsulfate and were able to metabolize benzo[a]pyrene to benzo[a]pyrenylsulfate, suggesting that the mechanism of hydroxylation is mediated by a cytochrome P-450 monooxygenase, followed by conjugation with sulfate ions. Because these fungi were adapted to the marine environment, the strains that were used in the present study are considered to be attractive targets for the bioremediation of saline environments, such as ocean and marine sediments that are contaminated by PAHs.     

Prediction of dissolved inorganic nitrogen (DIN) concentrations in deep,seasonally stratified lakes based on rates of DIN input and N removal processes

Mean dissolved inorganic nitrogen concentrations ([DIN]) in deep, seasonally stratified lakes with comparable DIN inputs can differ by up to a factor of 3 depending on hydraulic and morphometric properties and/or different trophic states of the lakes. In such lakes, net N sedimentation rates were estimated with two independent methods (sediment core analysis and input-output mass balances). They were higher in eutrophic lakes (Mean: 5.1; SD: ± 1.6 g m^–2 yr^–1; n = 13) than in oligotrophic lakes (1.6 ± 1.0 g m^–2 yr^–1; n = 3), but independent of [DIN]. Gaseous N loss rates to the atmosphere, as calculated from combined N- and P-mass balances from selected lakes, ranged from 0.9 to 37.4 g m^–2 yr^–1 (n = 10) and were positively correlated with [DIN]. Reduction of NO ₃ ^- to N₂ is assumed to be the main cause for gaseous N losses. A simple one-box mass balance model for [DIN], based on DIN input and rates and kinetics of N removal processes (net sedimentation and gaseous N loss) is proposed, and validated with a data base on [DIN] and DIN input in 19 deep, seasonally stratified lakes of central Europe. The model illustrated that the amount of water loading per unit surface area of a lake (called water discharge height q) is the critical parameter determining mean lake [DIN] relative to mean input [DIN]. Lakes with a q > 50 m yr^–1 have average [DIN] similar to the [DIN] of the inflows regardless of their trophic states, because input and outflow exceed lake-internal N removal processes. A high primary production favors DIN removal in lakes with q < 50 m yr^–1. It is concluded that measures to decrease primary production, e.g. by means of P removal programs, lead to an increase of [DIN] in lakes.     

Impacts of stormwater runoff in the Southern California Bight: Relationships among plume constituents

The effects from two winter rain storms on the coastal ocean of the Southern California Bight were examined as part of the Bight ‘03 program during February 2004 and February–March 2005. The impacts of stormwater from fecal indicator bacteria, water column toxicity, and nutrients were evaluated for five major river discharges: the Santa Clara River, Ballona Creek, the San Pedro Shelf (including the Los Angeles, San Gabriel, and Santa Ana Rivers), the San Diego River, and the Tijuana River. Exceedances of bacterial standards were observed in most of the systems. However, the areas of impact were generally spatially limited, and contaminant concentrations decreased below California Ocean Plan standards typically within 2–3 days. The largest bacterial concentrations occurred in the Tijuana River system where exceedances of fecal indicator bacteria were noted well away from the river mouth. Maximum nitrate concentrations (~40 μM) occurred in the San Pedro Shelf region near the mouth of the Los Angeles River. Based on the results of general linear models, individual sources of stormwater differ in both nutrient concentrations and the concentration and composition of fecal indicator bacteria. While nutrients appeared to decrease in plume waters due to simple mixing and dilution, the concentration of fecal indicator bacteria in plumes depends on more than loading and dilution rates. The relationships between contaminants (nutrients and fecal indicator bacteria) and plume indicators (salinity and total suspended solids) were not strong indicating the presence of other potentially important sources and/or sinks of both nutrients and fecal indicator bacteria. California Ocean Plan standards were often exceeded in waters containing greater than 10% stormwater (<28–30 salinity range). The median concentration dropped below the standard in the 32–33 salinity range (1–4% stormwater) for total coliforms and Enterococcus spp. and in the 28–30 salinity range (10–16% stormwater) for fecal coliforms. Nutrients showed a similar pattern with the highest median concentrations in water with greater than 10% stormwater. Relationships between colored dissolved organic matter (CDOM) and salinity and between total suspended solids and beam attenuation indicate that readily measurable, optically active variables can be used as proxies to provide at least a qualitative, if not quantitative, evaluation of the distribution of the dissolved, as well as the particulate, components of stormwater plumes. In this context, both CDOM absorption and the beam attenuation coefficient can be derived from satellite ocean color measurements of inherent optical properties suggesting that remote sensing of ocean color should be useful in mapping the spatial areas and durations of impacts from these contaminants.     

Polynomial approximate solutions to the Boussinesq equation

We provide closed-form approximate solutions to models of horizontal infiltration described by the Boussinesq equation in a semi-infinite aquifer that is initially dry. The approximations preserve such important qualitative properties as scaling and wetting fronts. They are applicable to four types of boundary conditions, two on head and two on flux, enumerated in the paper. All the considered problems admit self-similar variables that allow reduction to boundary value problems for a nonlinear ordinary differential equation. This work extends recent results by Lockington et al. [Lockington DA, Parlange J-Y, Parlange MB, Selker J. Similarity solution of the Boussinesq equation. Adv Water Resour 2000;23(7):725–9] and Telyakovskiy et al. [Telyakovskiy AS, Braga GA, Furtado F. Approximate similarity solutions to the Boussinesq equation. Adv Water Resour 2002;25(2):191–4], with new approximations developed for two of the four cases and a new extension of a previously existing method for a third case. Numerical results extending the work of Shampine [Shampine LF. Some singular concentration dependent diffusion problems. ZAMM 1973;53:421–2] provide a basis for assessing the accuracy of the new methods.     

Ecological Risk Assessment of Benzo[a]pyrene in Yellow River Delta

Ecological risk assessment is of great significance to promoting the rational management effectively for the oil‐polluted areas. A comprehensive evaluation method of ecological risk, including probabilistic risk assessment and regional ecological risk assessment, is developed through employing the contaminant benzo[a]pyrene as an indicator to assess ecological risk of five oil mining plots, respectively in Yellow River Delta. In this study, firstly we evaluate the ecological risk probability of five oil mining plots using overlapping area of probabilistic curves, and the results show that local ecological risk varies between the maximum 0.4 and the minimum 0.01. Then we overlay boundaries of five administrative divisions in Yellow River Delta and the spatial distribution patterns of ecosystems to generate new risk receptor plaques, and calculate the integrated value of 30 specifically classified plaques for comprehensive evaluation of ecological risk. The results, fluctuating within the range of 0.00005 and 0.25, indicate that local government should be vigilant to ecological risk of benzo[a]pyrene to some extent, although the current situation is not severe in whole.     

PAHs contamination and bacterial communities in mangrove surface sediments of the Jiulong River Estuary, China

Sixteen sediment samples collected from eight transects in a mangrove swamp of the Jiulong River Estuary, Fujian, China were investigated for their content of polycyclic aromatic hydrocarbons (PAHs) and the biodegradation potential of the indigenous microorganisms. The bacterial community structures in the mangrove sediments and in enrichment cultures were also investigated. The results showed that the total PAHs concentration of mangrove sediments ranged from 280 to 1074 ng g(-1) dry weight, that the PAHs composition pattern in the mangrove sediments was dominated by high molecular weight PAH components (4-6 rings), and that Benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene were the most dominant at different stations. Abundant PAH-degrading bacteria were found in all the stations, the values of phenanthrene-degrading bacteria ranged from 5.85 x 10(4) to 7.80 x 10(5) CFU g(-1) dry weight, fluoranthene-degrading bacteria ranged from 5.25 x 10(4) to 5.79 x 10(5) CFU g(-1) dry weight, pyrene-degrading bacteria ranged from 3.10 x 10(4) to 6.97 x 10(5) CFU g(-1) dry weight and the benzo(a)pyrene-degrading bacteria ranged from 5.25 x 10(4) to 7.26 x 10(5) CFU g(-1) dry weight. DGGE analysis of PCR-amplified 16S rDNA gene fragments confirmed that there was a remarkable shift in the composition of the bacterial community due to the addition of the different model PAH compound phenanthrene (three ring PAH), fluoranthene(four ring PAH), pyrene(four ring PAH) and benzo(a)pyrene(five ring PAH) during enrichment batch culture. Eleven strains were obtained with different morphology and different degradation ability. The presence of common bands for microbial species in the cultures and in the native mangrove sediment DNA indicated that these strains could be potential in situ PAH-degraders.     

Comet assay for the detection of genotoxicity in blood cells of flounder (Paralichthys olivaceus) exposed to sediments and polycyclic aromatic hydrocarbons

To investigate the genotoxic effect of marine sediments on aquatic organism, sediment samples were collected from 13 sites along the coast of Gwangyang Bay (Korea). Concentrations of polycyclic aromatic hydrocarbons (PAHs) in sediments were determined and the relationship between exposure of flounder blood cells to sediment extracts and DNA single-strand breakage in the blood cells was examined using the comet assay. Levels of DNA damage were proportionally increased by exposure concentration and the highest sediment-associated DNA damage was observed at the station showing the highest PAHs contamination. DNA damage in blood cells exposed to five types of PAHs (benzo[a]pyrene, fluoranthene, anthracene, pyrene and phenanthrene) and in flounder (Paralichthys olivaceus) exposed to benzo[a]pyrene (BaP) for 0, 2 and 4 days were assessed by measuring comet tail length. The tail lengths of five PAHs-exposed groups at 50 and 100 ppb were significantly different from the non-exposed group, and the genotoxic effect of BaP correlated with both concentration and duration of exposure. Throughout the study, significant differences in DNA breakage were recorded between cells exposed to sediment extracts or PAHs and non-exposed control. This study demonstrated the comet assay as a successful tool in monitoring contamination of marine sediments and assessing genotoxicity of PAHs in marine organisms, either in vitro or in vivo.     

Assessment of PAH Pollution in Coastal Areas from the NW Mediterranean through the Analysis of Fish Bile

Polycyclic Aromatic Hydrocarbon (PAH) pollution in coastal areas from the NW Mediterranean has been assessed by measuring bile PAH metabolites in two fish species, the red mullet – Mullus barbatus-and the sea comber – Serranus cabrilla – Bile crude samples were directly analysed by LC-fluorescence at the excitation/emission wavelengths of benzo[a]pyrene (380/430 nm). Subsequently, bile samples were hydrolysed and analysed by (a) LC-fluorescence at the excitation/emission wavelength pairs of naphthol (290/335 nm) and pyrenol (345/395 nm), and (b) gas chromatography–mass spectrometry (GC–MS) for the determination of individual PAHs. Qualitative and quantitative differences were recorded among sampling sites. Both species allowed us to detect different pollution gradients, the highest levels of FACs were observed in organisms caught in the vicinity of big industrial cities, whereas the lowest levels were recorded in organisms from Corsica and Sardinia. The obtained results highlight the usefulness of the LC-fluorescence technique as an initial screening method to assess PAH exposure in coastal fish.     

Heavy metals and polycyclic hydrocarbon compounds in benthic organisms of the Upper Gulf of Thailand

Concentrations of heavy metals and polycyclic aromatic hydrocarbons (PAHs) were measured in bivalves collected in the Upper Gulf of Thailand. PAHs detected included acenaphthene, acenaphthylene, benzo[a]pyrene, fluoranthene, methylphenanthrene, phenanthrene and triphenylene. Benzo[a]pyrene was detected in all species at concentrations varying from 1.0 to 8.2 ng·g^?1. Concentrations of cadmium, cobalt, copper, lead and nickel were significantly lower in bivalves from the Gulf than in green mussels collected from the mouth of the Chao Phraya River. No correlation was found between metal concentrations in animals and sediment, with the exception of copper. Copper concentrations in polychaetes and clams appeared to correlate with the copper:iron ratio of sediments. High rates of degradation were observed when radiolabelled chlorobenzene, phenanthrene and chrysene were added to water and sediment of the Chao Phraya River. Rates were lower in the waters and sediment of the Gulf of Thailand. The calculated half-lives of chlorobenzene in the Gulf of Thailand and the Chao Phraya River were about 130 and 68 days, respectively.     

Suspended particulate grain size dynamics and their implications for trace metal sorption in the Don River

We examined particle size distributions of suspended particulate matter (SPM); physical and environmental influences on the observed distributions; and relationships between particle size and geochemical partitioning of metals, over the fall and winter period in a small urban river (Don River, Toronto, Ontario, Canada). For this dataset, the majority of particles (80%) in suspension were less than 10 µm in size. In addition, while total SPM concentrations showed a positive trend with increasing discharge (Q); the proportions of particles found within given size classes were independent of both SPM concentration and Q. Temperature was the only measured environmental variable related to the particle concentrations within size classes. As water temperature increased, the concentration of particles in the smallest size class (1–4 µm) decreased, while the concentration of silt and/or algae sized particles (10–50 µm) increased. Increasing water temperatures may promote bacterial attachment to particles and their subsequent flocculation into larger sized particles. Decreasing concentrations of leachable (most labile) Cd, Zn and Mn were associated with increasing concentrations of the largest particles (70–150 µm) in suspension. In contrast, higher reducible (oxides) associated concentrations of Cd, Zn and Mn occurred with increasing concentrations of smaller particles (1–10 µm) in suspension. Both of these trends are speculated to reflect the importance of particle surface area for metal sorption reactions.     

Contamination and potential biodegradation of polycyclic aromatic hydrocarbons in mangrove sediments of Xiamen, China

Five stations were established in the Fenglin mangrove area of Xiamen, China to determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) and the numbers of PAH-degrading bacteria in surface sediments. Assessing the biodegradation potential of indigenous microorganisms and isolating the high molecule weight (HMW)-PAH degrading bacteria was also one of the aims of this work. The results showed that the total PAH concentration of sediments was 222.59 ng g(-1) dry weight, whereas the HMW-PAH benzo(a)pyrene (BaP) had the highest concentration among 16 individual PAH compounds. The variation in the numbers of PAH-degrading bacteria was 2.62 x 10(2)-5.67 x 10(4)CFU g(-1) dry weight. The addition of PAHs showed a great influence in increasing the microbial activity in mangrove sediments. A bacterial consortium, which could utilize BaP as the sole source of carbon and energy, and which was isolated from mangrove sediments and enriched in liquid medium for nearly one year degraded 32.8% of BaP after 63 days incubation.     

Shape factor in the drawdown solution for well testing of dual-porosity systems

One of the important parameters in existing commercial dual-porosity reservoir simulators is matrix–fracture shape factor, which is customarily obtained by assuming a constant pressure at the matrix–fracture boundary. In his work, Chang [1] and [2] addressed the impact of boundary conditions at the matrix–fracture interface and presented analytical solutions for the transient shape factor and showed that for a slab-shaped matrix block a constant pressure boundary condition leads to an asymptotic (long-time) shape factor of π²/L², and that a constant volumetric flux leads to an asymptotic shape factor of 12/L². In a recent paper [3], we reconfirmed Chang’s [1] and [2] results using a Laplace transform approach. In this study, we extend our previous analysis and use infinite-acting radial and linear dual-porosity models, where the boundary condition is chosen at the wellbore, as opposed to at the matrix boundary. The coupled equations for fracture and matrix are solved analytically, taking into account the transient exchange between matrix and fracture. The analytical solution that invokes the time dependency of fracture boundary condition under constant rate is then used to calculate the transient shape factors. It is shown that, for a well producing at constant rate from a naturally fractured reservoir, the appropriate value of stabilized shape factor is 12/L². This contrasts with the commonly used shape factor for a slab-shaped matrix block that is subject to a constant pressure boundary condition, which is π²/L². The errors in the matrix–fracture exchange term in a dual-porosity model associated with the use of a shape factor derived based on constant pressure boundary condition at the matrix boundary are then evaluated.     

On the use of UV spectrophotometry to assess dissolved organic carbon origin variations in the Upper Rhône River

To detect temporal changes and the origin of the refractory dissolved organic matter in the Upper Rhône River, UV light absorbance (A) at 285 nm and quantitative dissolved organic carbon (DOC) measurements were carried out. Data from 63 visits to the main channel over a period of two years and from visits to different waterbodies in the alluvial plain before and after a flood are presented. There was a good correlation between A (0.019–0.160) and the DOC content (1.40–9.81 mg/L) for the waterbodies, but not for the river axis with lower A (0.013–0.044) and DOC content (1.13–2.20 mg/L). Due to this good correlation, the DOC content could be quantified for the waterbodies by absorbance measurements only. For the river water this indirect determination of the DOC content was not possible. However, the A/DOC ratio showed changes in the composition of DOC of river water and provided indications about the origin of the dissolved organic matter in the Upper Rhône River.     

Water Quality Assessment Based on Chemical and Biological Characteristics: An Example of Classification of Characteristics for the Cheremushnyi Creek–Yenisey River Water System

A six-class scale for a complex classifier of water quality is applied to the Cheremushnyi Creek–Yenisey River water system. The classifier incorporates a chemical index of water pollution and biological characteristics with autotrophic and heterotrophic periphyton groups and macrozoobenthos used as biological indicators. The oligochaeta index and Woodiwiss biotic index are shown to have low indicator capacity. Bioassay studies were based on recording acute and chronic toxic effects for three test species at different trophic levels. The level of biologically safe dilution is proposed as a quantitative index of toxicity. Saprobity and toxicity (saprotoxobity) characteristics are given for individual species. Water of the Cheremushnyi Creek–Yenisey River water system is referred to the IV–VI quality class.     

Exposure and time dependent DNA strand breakage in hepatopancreas of green-lipped mussels (Perna viridis) exposed to Aroclor 1254, and mixtures of B[a]P and Aroclor 1254

Green-lipped mussels (Perna viridis) were exposed to Aroclor 1254 (0.5, 5 and 50 microgl(-1)) and a mixture of benzo[a]pyrene (B[a]P) and Aroclor 1254 (0.3+0.5 and 3+5 microgl(-1)) for 12 days. On day 0, 1, 3, 6 and 12, the levels of DNA strand breaks in the mussel hepatopancreas were monitored using an alkaline unwinding assay. The results were compared to the findings of a previous study in which the levels of DNA strand breakage in the same species were measured following exposure to various concentrations of B[a]P (0.3, 3 and 30 microgl(-1)). The results indicated that Aroclor 1254 at a concentration 相似文献   

Ecotoxicological evaluation of polycyclic aromatic hydrocarbons using marine invertebrate embryo–larval bioassays

The toxicity of polycyclic aromatic hydrocarbons (PAHs) was determined using mussel, sea-urchin and ascidian embryo–larval bioassays. Fluorescent light exposure enhanced phenanthrene, fluoranthene, pyrene and hydroxypyrene toxicity in comparison with dark conditions, but not naphthalene and fluorene toxicity. The toxicity of PAHs was inversely related to their K_OW values following QSAR models derived for baseline toxicity of general narcotics, whereas the obtained regression using toxicity data from photoactivated PAHs significantly departed from the general narcosis model. Also, the mixture toxicity of five PAHs to the larval growth of the sea-urchin was compared with predictions derived from the concentration addition concept, indicating less than additive effects. Finally, we compared our toxicity data with worst-case environmental concentrations in order to provide a preliminary estimate of the risk to the marine environment. Naphthalene, fluorene and pyrene are not considered to pose a risk to sea-urchin, mussel or ascidian larvae, whilst phenanthrene and fluoranthene may pose a risk for mussel and sea-urchin. Moreover, a higher risk for those species is expected when we consider the photoactivation of the PAHs.